Renewable & Sustainable Energy

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Manuscript Draft

Manuscript Number: RSER-D-18-02996R1

Title: Renewable energy in cement manufacturing: A quantitative

assessment of energy and environmental efficiency of food residue
biofuels

Article Type: Original Research Article

Section/Category: Bioenergy

Keywords: Bioenergy; solid biofuels; renewable fuels; cement

manufacturing; household food waste; fossil fuel substitution.

Abstract: The present work investigates solid fuel, derived from

household food waste (food residue biofuel, FRB) as a potential source of
bioenergy in the cement industry. Up-to-date investigations of household
food waste as a solid fuel focused on composition and heating value, yet
no results are available regarding impact on plant efficiency and
emissions upon utilization. A multidimensional model based on fundamental
principles (mass and enthalpy balances) is used together with actual data
from fossil fuel operation to identify and quantitatively asses the
impacts on plant performance, product quality and atmospheric emissions.
Τhe energy needed to prepare low moisture FRBs is determined and suitable
processes are singled out. Key issues of cement plant operation are
identified and quantitatively assessed via simulation in an actual dry-
process plant, when FRBs substitute 20% of thermal energy (provided by
petcoke). The facility utilizes 1.65x105 tpa of fossil fuels to produce
1.5x106 tpa clinker. It is found that energy efficiency falls and
clinker production diminishes by about 0.5t clinker/t FRB. Refractory
thermal rating and main blower capacity constraints remain satisfied.
Non-biogenic green-house-gas emissions are reduced by ~60 kg/t clinker.
Emitted concentrations slightly increase for several pollutants, mainly
nitrogen oxides (NOx) hydrogen chloride (HCl) and metals; they decrease
for sulphur dioxide (SO2) and particulates. Maximum emission limits are
observed for all regulated pollutants but NOx,. Incombustible chlorine
and inclusions of alkalis in cement increase by ~9%. To reap the
bioenergy benefits and mitigate impacts, blends of FRB (~80%wt) with
paper residues (~20%wt) are investigated. Conforming to plant
operational constraints and product specifications, the blends ensure
production level, environmental compliance and reduced emission rates.
The results direct towards customer-tailored FRB blends with
lignocellulosic residues, that best suit the design, specific quarry raw
materials, operating conditions and individual parameters of the cement
plant, towards more sustainable cement manufacturing.

Response to Reviewers: Detailed Response to reviewers is included in a

separate file.
Detailed Response to Reviewers

Ms. Ref. No.: RSER-D-18-02996

Renewable & Sustainable Energy Reviews

Title: Renewable energy in cement manufacturing: A quantitative assessment of energy and

environmental efficiency of food residue biofuels

Reviewer #1:
1. Abstract
The abstract should be improved. There is a lack of clearly identified problem. Author could
include one sentence clearly sating what is the current knowledge gap (e.g., what is the research
question) addressed by the research, one sentence explaining how this knowledge gap is
addressed and drawing broader and more general conclusions.
Answer
The ABSTRACT has been improved according to the suggestions by the reviewer. The problem is
identified in the ABSTRACT and in the INTRODUCTION.

2. Introduction
The introduction section is developed in the adequate form. However, the introduction misses
significant information such as: what makes the multidimensional model suitable and superior in
comparison to existing studies? What is the expected new insight gained by applying the
methodolody/model? What is the research question or hypothesis?

Answer
The information has been added in the INTRODUCTION as follows: the model is discussed in the
INTRODUCTION (stressing the novelty of the analysis based on the multidimensional model) in
Section 3, in Appendices A, B and C and in the Supplementary Information in the Web.

The following were added in the INTRODUCTION in the revised manuscript regarding the
multidimensional model.

A multidimensional model[18,19] will be employed to this purpose, based on the combined mass and
enthalpy balance of the kiln, which enables simulation of concurrent utilization of multiple biofuels
and fossil fuels and provides more accurate results than models based solely on stoichiometry.
Expressed in linear algebraic form (i.e. in terms of vectors and matrices) the model decouples the
impact of feeding rates of the various fuels in a linear fashion. It also isolates the impact of
combustion air (excess air, oxygen enrichment, air moisture) allowing explicit evaluation of their
impact if used for kiln control. Enabling explicit utilization of hard core data from actual operation
under fossil fuels, the model provides an holistic quantitative description, reflecting production,
capacity constraints, atmospheric emissions and environmental compliance, as well as inclusions of
chlorines, alkalis and metals in the clinker and impact on cement quality. With the vector of feed
rates, f, as the sought variable, it enables direct application of the vast array of optimization methods
towards determining superior combinations of renewable fuel blends. .

3. Results and Discussions

The paper misses a proper Discussion section. Such a section must contain: (i) two sentences
repeating the most important results, (ii) discussing strengths and shortcomings of this analysis,
(iii) the meaning of results in comparison with literature findings and a short outlook on further
research requirements and possible research extensions.

Answer
A DISCUSSION section was added (Section 5) along the suggestions of the reviewer.

4. Conclusions
A conclusion should summarize the paper, briefly review the purpose, goals, major topics, and
suggestions, as well as discuss implications for future research, action and the potential influence
of limitations on the paper itself. This conclusion did not follow this well-established format, and
was both confusing and inappropriate.

Answer

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The CONCLUSIONS section has been modified according to the structure suggested by the reviewer
(purpose, goals, major topics, suggestions, limitations, further implications and potential influence of
limitations on the paper itself).

The authors should also pay attention to the following editorial issues
1. Page 2, line 20 capitalize a to read Paris Agreement
2. Page 3, line 55, A, B and C should be in small letters
3. Page 4, line 52, write APCS in full
4. Page 5, line 43 (… 700 kWe/tonne MSW) e should be subscripted
5. Page 5, line 57 your number referencing should be consistent, e.g. instead of [17]-[18], use [17, 18],
and [20]-[21], use [20,21]
6. Page 9, line 24 - Please clarify whether it reads " Alternative Scenaria" of "Alternative Scenario"
7. Page 12, line 26….. measured emitted concentrations are standardized to standard conditions () via
multiplication by the standardization factors (SF), in order to be reported. Please recast this sentence
8. Page 13, line 47, simulated scenaria or scenario, line 54 in concord with enacted legislation. Replace
with in "compliance with"
9. Page 16, line 9, replace with 1.5 x 106
10. Page 16, line 21, write % thermal participation in full
11. Page 17, line 2……… or a hot oil (or steam) dyer, replace with dryer
12. Page 18, line 57 the word concord has been overused
13. Page 21, line 18, clarify if the word ratii has been misspelled with ratio, line 21,, windrose
(magenda). I think it should be magenta
I wish that these comments can help the author to improve the paper.

Answer
All the above editorial issues have been rectified in the revised manuscript.

#7 has been modified as follows:

Reported emitted concentrations are obtained from measured emitted concentrations via
standardization. Standardization to standard conditions (normal temperature and pressure, dry and
10% oxygen) is performed via multiplication by the standardization factor SF.

Reviewer #2:
(1) Page 3, lines 3-25: The authors related to the data such as "rated at 1 kWe/capita", "9 billion",
and "37%" should be given some references in the manuscript.
Answer
The statement was improved and references (new) were provided.

(2) Page 3, lines 33-37: I don't quite understand the meaning of the sentence. Do the authors mean
that the biowastes can not competitive with the food? However, the energy crops could occupy a
large amount of land, resulting in a reduction in crop cultivation? I think the authors should make the
sentence more be clear.
Answer
The statement has been changed as follows:

In contrast to energy crops targeted to biofuel/bioenergy production, biowastes are not competitive
to food crops when used as biofuels. Consequently, use of solid biofuels, produced from food waste,
may be crucial towards a sustainable low carbon economy, by reducing the dependence on depleting
fossil fuels without restricting food produce.

(3) Page 5, line 27: What's the means of the sentence? The authors mean that the food waste has
been burned by waste-to-energy facilities?
Answer
The sentence has been rectified as follows:

About 20% of household food waste is used in mass burn, waste-to-energy facilities [23] as part of
commingled, or residual waste.

2
 (4) Page 5, lines 31-40: Key references should be given for the data.
Answer
References have been given in the revised version.

(5) Part of 2.1 Disposal and valorization: The part summarizes the management of food waste, but
the authors only described their application on energy. In fact, there were various methods to reuse
the food waste. Although the main purpose of the manuscript was aim to utilization of energy, the
authors should also describe other aspects of the application of food waste.
Answer
A discussion of other potential valorization routes of food waste was added towards the end of
section 2.1. It includes biochemicals, enzymes, biopesticides, biomaterials, proteins, biofuels and
fertilizers and many additional references.

(6) Section of 2.2 Pretreatment and preparation of solid biofuel from food residues: In my opinion,
some of the contents in the part were not supported by literatures. For example, the main
components of biomass were clear. However, the components of food waste were different, and have
more complex as compared with biomass components. It was not appropriate for the authors to
describe some related technologies of biomass pretreatment on food waste.
Answer
The critique is correct. We have amended this point by focusing on household food waste and
production of solid biofuel. The pretreatment methods discussed were (a) drying and (b)
torrefaction. The latter has found no industrial application yet and therefore the discussion in the
revised version has been shortened and targeted mainly on food waste torrefaction. The alternative
drying technologies are brought forth since the domain of efficient drying of food waste for
preparation of a stable product is open and consists a key pretreatment stage. Some of the drying
technologies discussed come from the food industry (e.g. olive pomace drying, or fruit drying) others
from the waste industry (biosludge drying)

(7) The main components of various food residues should be described in detail before pretreatment
technologies.
Answer
Table 1 in the revised version includes the main components of food residues. Reference to the
Table is done in the INTRODUCION (Section 1), i.e. , i.e., prior to the discussion of the pretreatment
technologies (Section 2.2).

(8) Page 8, lines 27-48: This part putted forward many questions about industrial drying. However,
there were no literatures to cite.
Answer
Some references are included in the revised version. Olive pomace driers are described according to
our own experience in the local industry.

(9) As described by the author (See Page 3, lines 43-47), some food residue content more than
70% moisture. In my opinion, the easiest way to get rid of this moisture was to filter or settle at
rest. Unfortunately, the author did not cover it in this section.
Answer
Removing part of the moisture by gravity is an interesting option saving energy and further
valorizing FRB. The balance is as follows:

moisture ww total water dry water removed check

78% 100 78% 22,5%
63% 60,81 38,31 22,50 39,19 0,63
1,10% 22,75 0,25 22,50 38,06 0,011

We have included the following short discussion of this point.

Regarding drying, since about half of the water content of the original FW (78%ww moisture)
corresponds to 63% moisture ww, a first stage drying can be performed by filtering or settling at

3
 rest. This may cut in half the energy required for drying; a thorough analysis must take into account
settling and filtering times, due to the rapid decomposition of food waste.

(10) I have some question about Section 3 and 4: In this section, the evaluation methods used in
this study were described by authors. My questions were that was the evaluation method the only
one to evaluate? What was its advantage? Why should be choose this evaluation method, and
whether it was rigorous?
Answer
The evaluation can be performed using other methods as well, e.g. via the ASPEN simulator. Based
on the multidimensional model which entails the combined mass and enthalpy balances, the
proposed method offers insight and particular capabilities which are discussed in the INTRODUCTION
and Section 3 and demonstrated in the Case study of an actual plant in the revised version.

(11) This paper was not like a research review, but more like an engineering application project
book.
Answer
The paper aimed at establishing a concrete methodology in practical thermal energy applications,
namely, assessing the suitability and impacts of using solid biofuel derived from household food
residues in cement kilns. Using an actual Case study it quantified the strong and weak points
regarding plant operation, quantity and quality of clinker, greenhouse gas emissions and atmospheric
pollution impacts. It concluded that this is a feasible valorization route for food waste, requiring
customer tailored preparation of blends of dried food residue with other biogenic wastes.

(12) The conclusion and Abstract should be concise and clear.

Answer
Both sections have been made more clear. The CONCLUSIONS section has been made more
focused, while conforming the comments of Reviewer 1 as well.

Reviewer #4:
1.P5, L40: "Waste-to-energy plants achieve high availability (>90%) enhanced controllability,
compensating for waste variability, high net power efficiency (~ 700kWhe/tonne MSW) and consistently
low emissions".
What are the characteristics of the MSW considered here? If it contains a high proportion of plastics, it
cannot be compared directly with biowaste-based energy production plants.

Answer
Indeed, the characteristics are those of commingled or residual waste which includes plastics. It cannot
be compared with biowaste based energy production plants. However this is a practical efficiency figure
and we think it appropriate to include it. The sentence has been modified as follows in order to conform
to the critique by the review:

Utilizing commingled waste which includes plastic and paper, waste-to-energy plants achieve high
availability ….

2.P6, L8: "Despite common belief, they feature significantly larger (~50%) greenhouse gas emissions
than direct waste-to-energy valorization, if energy efficiency is taken into account."

How this value has been calculated? If GHG emissions are estimated before CH4 combustion, it
cannot be compared with biowaste combustion technologies. In the case of anaerobic digestion, all
the carbon extracted from biomass is converted into CO2 at the end. I don't see how it can be 50%
higher than a direct combustion.

Answer
GHG emissions have been calculated after CH4 combustion (i.e., including CO2 contained in biogas
and CO2 from CH4 combustion) and taking into account the CO2 released from aerobic stabilization
(composting) of the digestate (enforced by legislation). Also, our figure includes the displaced CO2
emissions from production of the same amount of energy coal power plants. Direct combustion in
actual plants converts all combustibles (and carbon) into CO2. Anaerobic digestion of food waste in

4
 practice converts about 80% of volatile solids which amount to 90% of total solids [12]. This gives
around 380-450 Nlt CH4 /kg VS or 340-400 Nlt CH4 /kg TS or 55-73 Nlt CH4 /kg FW.

Considering the median figure the anaerobic digestion (AD) gives

64 lt CH4/kg FW x 16/22.4 gr/lt x1/1000 kg /gr x 50 MJ/kg CH4 =2.29 MJ/kg FW.

For the FRB option:

FRB1.5 18.2 MJ/kg FRB1.5
Or 4.1 MJ/kg FW

Then. since 1MJ= 0.2778 kWh it follows that

AD 2.29 MJ/kg FW =545 kWh/t FW

FRB 4.1 MJ/kg FW = 1035 kWh/t/FW

If electrical energy requirements of anaerobic digestion (30-70 kWh/t FW) and thermal requirements
of subsequent composting of the digestate (20-60 kWh/t) are taken into account, the net energy
from anaerobic digestion of FW is at 40-170 kWhe/t and 180-380kWh/t thermal. Also, if drying
energy requirements for FRB are taken into account,

Drying 2 MJ/kg FW or net 2.05 MJ/kg FW = 582 kWh/t/FW

Then net
AD 455 kWh/t FW (electric + thermal)
FRB 582 kWh/t/FW (thermal)

3. P6, L25: "Impediments to wide scale applicability of anaerobic digestion to organic municipal
solid wastes, including food wastes, stem from the high lignocellulosic content and the presence of
phenolic and other recalcitrant organic species and inhibitors."

Food waste contain very low amounts of lignocellulosic compounds. They are mainly composed of
carbohydrates, proteins and lipids which are all biodegradable without any pretreatment. Please
correct this statement or provide a reference. For more information, the authors can refer to:
Food waste valorization via anaerobic processes: a review (https://doi.org/10.1007/s11157-016-
9405-y)

Answer
The sentence is corrected in the revised version as follows.

Anaerobic digestion of organic municipal solid wastes, including food wastes has been investigated
extensively in the last decade with significant improvements in the conversion efficiency to biogas.
Yields exceeding 520 Nlt biogas/kg VS with methane content up to 70% have been reported [11].
Industrial scale applications in state of the art plants, feature about 240-550 Nlt biogas/kg VS [44],
with the upper figure corresponding to animal manure and with methane content at 60% vol,
whereas older plants treating municipal organic wastes do not exceed 300 Nlt biogas/kg VS [45] .
With the use of biogas engines and combined cycle, this gives a net electrical efficiency around 100
kWhe/tonne of biowaste. Digestion of leached extracts from biowastes circumvents the operational
issues mentioned above, at the cost of even lower efficiencies, (~80 Nm3 biogas/tone of
biowaste[43]).

4. P6, L38: "All in all, biogas yields range around 400ml/gr volatile solids [26], with the content of
volatile solids at 23%, the ratio of volatile solids over total solids at 84-87% and the ratio C/N at 14.8."

Higher value of 400 NmL-biogas/gVS are usually obtained from food wastes as they are almost
entirely biodegradable. The reference cited here is almost 10 years old while many research projects
have focused on food waste conversion into methane since then. For instance, values as high as 529

5
 NmL-CH4/gVS have been reported when food waste from a university restaurant was used (it
corresponds to about 750 NmL-biogas/gVS if a ratio of 70%CH4 is considered). Moreover, if food
waste are almost completely biodegradable, it means the most the chemical energy is recovered as
methane.
Ref: Food waste valorization via anaerobic processes: a review (https://doi.org/10.1007/s11157-
016-9405-y)

Answer
Indeed higher values have been reported reaching 546 Nml CH4/g/VS. However in practical
industrial applications including plants by DRANCO, VALORGAS, COMPOGASS, BEACON, BIOCELL the
values are between 340 and 450 Nml CH4/g/VS (see also Answer to point 2, above) and therefore
our figure is correct.

5. P6, L45: "With the use of biogas engines and combined cycle, this gives a net electrical efficiency
around 200 kWhe/tonne of biowaste"

This value of electrical energy production (which includes the cogeneration yield) cannot be readily
compared with a thermal energy production as in the cement production process proposed by the
authors. Biogas can also be injected in the grid instead of natural gas or directly used to produce
thermal energy. Moreover, there is no need to dry biowastes prior anaerobic digestion. It would be
interesting to compare the potential thermal energy recovered from methane in an anaerobic
digester with the actual energy recovered from FRBs when drying is taken into account.

Answer
The reviewer’s critique is correct. However the point was not aimed at direct comparison between
thermal energy and electrical energy. Comparison should be on the same basis. The sentence is
modified as follows in the revised version.

With the use of biogas engines and combined cycle, this gives a net electrical efficiency around 100
kWhe/tonne of biowaste. Digestion of leached extracts from biowastes circumvents the operational
issues mentioned above, at the cost of even lower efficiencies, (~80 Nm3 biogas/tone of
biowaste[43]). .

6. P7, L10: "For instance, high efficiency plasma gasification[32] recovers about 95% of the biofuel's
energy content in the form of chemical energy of syngas, enabling efficiencies 40% to electric power
production, via combined cycle."

Do these values take into account the energy spent for gasification? What is the actual energy yield
of the overall process?

Answer
Based on the patents cited, the energy requirement for the plasma torch is about 4% of the energy
of the fuel. Most of the enthalpy of the hot syngas exiting the gasifier is recovered in a waste heat
boiler adding steam to the heat recovery steam generator of the cogeneration unit. Therefore our
figure is correct. The gross efficiency figure of 40% is also correct. It is noted that new
developments in plasma gasification including microwave plasma gasifiers and use of supercritical
steam in the gasification zone further improve syngas quality by increasing the hydrogen molar
fraction and lead to higher overall energy production. The sentence is improved as follows in the
revised manuscript.

For instance, high efficiency plasma gasification[32] with combined cycle and recuperation of the
syngas heat from the gasifier, recovers about 95% of the biofuel's energy content in the form of
chemical energy of syngas, enabling gross efficiencies of 40% to electric power production. new
developments in plasma gasification including microwave plasma gasifiers and use of supercritical
steam in the gasification zone further improve syngas quality by increasing the hydrogen molar
fraction and lead to higher overall energy production.

6
7. P7, L45: "Although a stable product of consistent quality is obtained by torrefaction, the method
requires relatively high temperatures (optimal for food residues is around 300oC) and reduces the
energy yield of the produced FRB by about 30%."
What is the energy considered here (thermal, electrical)? At the end, what is the energy yield value
per ton foodwaste?

Answer
The energy for torrefaction is electrical and the results regard lab scale torrefaction of food waste as
in the cited reference. The energy yield value per ton of food waste is lower than the corresponding
energy yield of the FRB investigated which was produced by drying at 90 o C. The point is made
clearer in the revision by rephrasing as follows:

Although a stable product of consistent quality is obtained by torrefaction, the method requires
relatively high temperatures (optimal for food residues is around 300 oC) and reduces the energy
content of the end product to about 10 MJ/kg.

8. P7, L54: "Pretreatment via thermal drying at 90 oC for about 4-9 hours produces stable FRBs at
moisture levels down to 1.1%w"
Is it possible to provide quantitative values of energy yields when using this method?

Answer
The energy yield information is given in fig. 1 in the original version (same figure in the revision).

9. P7, L57: "Volatilization of organics is limited to highly volatile compounds and thus the product
(FRB) almost maintains the energy yield of the original material."
Is it possible to add quantitative values? I wonder if the loss of organic matter is really negligible,
especially considering that food waste usually starts to be fermented (producing volatile fatty acids)
before collection.

Answer
The critique is rightful. Volatiles are reduced to 75.3-78.1% w/w down from 88-90% of the original
food waste. The statement has been improved as follows.

Drying for 5-9 hours leads to 1.1% w/w moisture and partial volatilization of volatile organic
compounds (from 88-90% originally, to 75-78%).

10. P16, L26: "Elemental composition of food residues are given in Table 1, revealing small
deviations depending on the collection and preparation method."
It seems to me that these deviations are not small. For instance, the LHV for food residues range
from 668 to 4919 kcal/kgDM. Is this incertitude considered in the different scenarios? It would be
interesting to carry out a sensitivity analysis to strengthen the different conclusions drown from the
case study.

Answer
The critique is correct. The significant deviation is due to the different basis: the figure 668 kcal/kg
is reported from the literature (gross heating value of FW) and the figure 4919 kcal/kg to the LHV of
the dry matter. The sentence has been corrected in the revised manuscript as follows.

Elemental composition of food residues are given in Table 4, revealing deviations depending on the
collection and preparation method (e.g., LHV). Uncertainty, as expressed by large variability of key
variables such as the LHV of any fuel, (particularly of the prepared FRB via drying of FW) can be
readily investigated using our multidimensional model (the vector of LHVs, λ, explicitly appears in eq.
4 and eqs A16 and A18 in the Supplementary Information in the Web).

11. P16, L53: "As clearly manifested, the thermal energy need is about 55% of the LHV of the
respective FRB"
I am surprised that this ratio does not decrease when the moisture content of FRB increases from 1.5
to 15%. Is it possible to check these values?

Answer

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 The ratio increases slightly with moisture in the range 1% to 15%. The difference between 1.1%
moisture and 15% moisture is small since the largest part of moisture is removed in going from 75%
moisture to 15%.

moisture ww total water dry water removed

78% 100 78% 22.5%
15% 26.47 3.97 22.50 73.53
1.10% 22.75 0.25 22.50 3.72

12. P17, L6: "About 70% of FRB is required under 80% efficiency, leaving 30% of FRB for other
uses, e.g., as solid biofuel."
This value means that the global energy yield for dried FRB combustion is very low. Is it possible to
comment in the manuscript (especially in comparison with the energy yields of processes mentioned
in Section 2).

Answer
The following comment is added in the manuscript.

Apparently such a self-sustained use implies a lower overall energy yield (~175 kWh/t FW) than self-
sustained anaerobic digestion which reaches 455 kWh/t FW, (electric + thermal).

13. P17, L10: "In this case 100% of FRB is available for use as a solid biofuel."
Is it possible to provide a quantitative assessment of this statement (e.g. in the supplementary
material)?

Answer
The following comment is added in the manuscript.

Based on fig. 1, the energy needed for drying 65000t/y of FW (20% thermal substitution of by
petcoke by FRB with 1.5% moisture) is 6.4 x105 Mcal/y which is more than an order of magnitude
lower than the enthalpy released by cooling the kiln-soil mill offgases from 140 0C to 130 0C, i.e., by
10 0C, (9.4 x106 Mcal/y).

14. P17, L40: "For instance, FRB with 10% moisture (FRB 10%) leads to losses of about 30 000
tonnes clinker per annum (tpa) fig. 5b, i.e., lower production due to lower energy efficiency by about
2%."
Is this 2% value significant? Again, I think that a sensitivity analysis should be carried out.

Answer
As stated in the case study and the ABSTRACT losses are at 0.5t clinker/t FRB10% with respect to
baseline. The value is significant (it exceeds income benefits from lower GHG emissions) and this is a
main reason for investigating blends of FRB with paper residues (FPRBs). The latter feature small or
no clinker production losses. A major outcome of our work is that such renewable fuel blends are
necessary for enhanced performance of the cement plant, for emissions compliance and no
deterioration of cement quality or process equipment, and that the superior blends depend on plant
characteristics, and the procedure for selecting such blends requires analytical investigation as the
one presented in the manuscript. Regarding sensitivity analysis we have investigated the cases with
20% and 10% thermal substitution of petcoke and found that the deviations from linearity are small,
i.e. in the range of 10% to 20% thermal substitution of petcoke by FRB10% clinker production losses
will be around 0.5t clinker/t FRB10%. Fig. 5 presents the full quantitative figures and clearly
manifests the impact of FRB moisture on the loss level. For instance, losses corresponding to
FRB1.5% (70 000 t/y FRB1.5% for 20% thermal substitution of petcoke) are at 25 000 t/y whereas CO2
emissions are reduced by 48 kg/t clinker or 70000 t CO2/y. In contrast, FPRB1.5%features no clinker losses
and lower CO2 emissions by 10 kg/t clinker or 15250 t CO2/y.

A short discussion of the above observations is included in the Case study (section on Plant operability,
GHG emissions and product quality).
.

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 15. P21, L5: "Energy and environmental performance: Wind rose diagrams and snapshot evaluation"
I found this section and the related figures difficult to read. Instead of radar diagrams, I would
recommend adding a Table summarizing all the quantitative results from the case study. Moreover,
providing ratios is insightful to compare the results to the baseline, but it is difficult to get actual
yields values which could be compared to other food waste valorisation processes. Is it possible to
provide these values and to comment them in the manuscript (at least the energy yields)?

Answer
The values are given in Table in the Supplementary Information. The energy yields are summarized
in Table 2 in the revised version of the manuscript and commented in the Case study.

16. Other topics:

- I would recommend adding a Table to summarize important information provided in Section 2.
This table could contain a line for each food waste valorisation technology along with the pros and
the cons and ranges for energy yields (under the same assumption).
Answer
Table 2 in the revised version presents this information.

- Is it possible to add a discussion about ashes management? My understanding is it more ashes

will be produced during the proposed process. If not, it should be clearly stated in the manuscript.
Answer
Ashes are incorporated in the clinker and in the cement matrix. The manuscript thoroughly
discusses the impact of crucial inclusions such as chlorines, alkalis and heavy metals in the Case
Study.

- Is it possible to remove "circular economy" from the key words? The process described in this
manuscript does not cycle any of the N-P-K or trace elements loop. It is a process using less fossil
fuel which is not equivalent to circular economy.
Answer
The key word circular economy was removed from the key words. It is noted however that the
concept is utilized for energy recovery (reference 13].

- Is it possible to add a discussion about food waste valorisation as bulk chemicals though green
chemistry? I think this is an important topic which is gaining importance and is directly competing
with the process proposed by the authors.

Answer
The following short discussion was added in Section 2.1.

Apart from methane [52], specific products include bulk chemicals and biomaterials, such as pectin [53]
volatile fatty acids [11, 54,55] lactate, ethanol and hydrogen[56] biofuels [proteins, peptides, lactose,
glucose, galactose, yeast [57], enzymes, bio-pesticides and bioplastics[58] succinic acid [59,60]. Critical
issues are comparability and compatibility of use with fossil fuel derived compounds, while ecological
repercussions should not be taken for granted. Two major threats of emerging biorefineries utilizing food
waste[61,62] are eased via the FRB route investigated herein, namely (a) stable, non decomposing FRB
via drying, readily stored for long periods and thus no longer requiring infrastructural and expensive
storage and conditioning to avert the rapid decomposition of raw food waste and (b) small variations in
composition and quality of household food waste within a district or country circumventing the high
variety of quality and volume of food waste.
- Please provide references for the following statements:
P3, L43: "Ranging at 0.3kg/capita day food residues (precooked and leftover) from the entire
food supply chain (food processing industries, households and hospitality sector) consist the wet
fraction of municipal solid waste (moisture content about 70-75%)."
P3, L46: "Estimated at 1.3 billion tonnes per annum (tpa) in 2015, food residues are escalating
rapidly at a global scale."
P4, L35: "As one of the largest fossil fuel consumers, cement manufacturing averages around
0.85 Mcal/t clinker. With the global cement production at 4.1 x109 metric tpa (50% of which in

9
 China) this amounts to about 5 x 108 tpa, i.e., half a billion tpa of fossil fuels globally."
P5, L32: "Electric energy recovery is reaching about 25% of the feedstock's lower heating value
(LHV)."
P6, L8: "Despite common belief, they feature significantly larger (~50%) greenhouse gas
emissions than direct waste-to-energy valorization, if energy efficiency is taken into account."
P6, L14: "The end product (compost) from commingled refuse still contains xenobiotic
substances that inhibit wide scale application as soil amendment."
P6, L25: "Impediments to wide scale applicability of anaerobic digestion to organic municipal
solid wastes, including food wastes, stem from the high lignocellulosic content and the presence
of phenolic and other recalcitrant organic species and inhibitors."
P7, L57: "Volatilization of organics is limited to highly volatile compounds and thus the product
(FRB) almost maintains the energy yield of the original material."
Answer
The revisions regarding this point are shown in the following Table.
LINE REVISED
P3, L43: References provided
P3, L46: References provided
P4, L35: References provided
P5, L32: References provided and improvement of the statement
P6, L8: References provided and improvement of the statement
P6, L14: References provided and improvement of the statement
P6, L25: References provided and improvement of the statement
P7, L57: References provided and improvement of the statement

10
*Marked Version of revised manuscript

Renewable energy in cement manufacturing: A quantitative assessment of energy and

environmental efficiency of food residue biofuels

by
Aristeides Tsiligiannis

and

Christos Tsiliyannis#
ANION Environmental Ltd
26 Lykoudi Str., Athens GR 11141
Tel. / fax: 0030-210-2285650
email: anion@otenet.gr

Submitted for publication to:

Renewable and Sustainable Energy Reviews

August 28, 2018

Revised: February 15, 2019

1
ABSTRACT

The present work investigates solid biofuel, derived from household food waste (food residue
biofuel, FRB) as a potential bioenergy source in cement manufacturing. Up-to-date
investigations of household food waste as a solid fuel focused on composition and heating
value, yet no results are available regarding impact on plant efficiency and emissions upon
utilization. A multidimensional model based on fundamental principles (mass and enthalpy
balances) is used together with actual data from fossil fuel operation to identify and
quantitatively asses the impacts on plant performance, product quality and atmospheric
emissions. Τhe energy needed to prepare low moisture FRBs is determined and suitable
processes are singled out. Key issues of cement plant operation are identified and
quantitatively assessed via simulation in an actual dry-process plant, when FRBs substitute
20% of thermal energy (provided by petcoke). The facility utilizes 1.65x105 tpa of fossil fuels
to produce 1.5x106 tpa clinker. It is found that energy efficiency falls and clinker production
diminishes by about 0.5t clinker/t FRB. Refractory thermal rating and main blower capacity
constraints remain satisfied. Non-biogenic green-house-gas emissions are reduced by ~60
kg/t clinker. Emitted concentrations slightly increase for several pollutants, mainly nitrogen
oxides (NOx) hydrogen chloride (HCl) and metals; they decrease for sulphur dioxide (SO2) and
particulates. Maximum emission limits are observed for all regulated pollutants but NOx,
necessitating revamping of the deNOx system. Incombustible chlorine and inclusions of
alkalis in cement increase by ~9%. To reap the bioenergy benefits and mitigate impacts,
blends of FRB (~80%wt) with paper residues (~20%wt) are investigated. Guidelines are
obtained for preparing Conforming to plant operational constraints and product specifications,
the blends ensure production level, environmental compliance and reduced emission rates.
The results direct towards customer-tailored FRB blends with lignocellulosic residues, that
best suit the design, specific quarry raw materials, operating conditions and individual
parameters of the cement plant towards more sustainable cement manufacturing.

Further that blends of FRBs are suitable as fossil fuel substitutes with slight sacrifice of
energy efficiency and production level. Benefits include lower greenhouse gas emissions, and
lower emissions of sulphur and volatile metals (mercury). The results lay the ground for
extended substitution of fossil fuels by FRB and other refuse derived renewable fuels at a
global scale.

Key words: Bioenergy; biofuels; renewable fuels; cement manufacturing; household food
waste; fossil fuel substitution.

2
INTRODUCTION

Rated at 2 MWhe/capita [1], annual electric energy consumption is rising globally at a fast pace,
as energy needs grow with increasing population. Cement and coal power plants are the
prime consumers of solid fossil fuels. Coal fired power plants supply 37% of global electricity
(~2500 gigawats)[2] using about 9 billion metric tonnes of coal[2]. Energy consumption for
manufacturing energy intensive products, such as cement and steel, grows steadily.
Agriculture uses up higher amounts of energy every year. Global energy consumption
increases also due to rising standards of living worldwide, to growing transport and to
escalating use of energy consuming devices in every-day life. Products that consume energy
in the use phase include vehicles, electric appliances and rechargeable electronic devices
such as data storing and communication units (tablets, cellular phones, etc). Attributed to
fossil fuels, the growing threat to sustainability due to climate change has compelled the Paris
Agreement, which aims at combating fossil carbon emissions and restricting global
temperature increase below 2°C by 2050[3]. Visions of energy metamorphosis via global
phasing–out of fossil fuels and 100% renewable energy supply are expressed and supported.
Biomass is regarded as an essential component in the transition to a 100% renewable
society[4]. In the practical arena, biofuels and bioenergy are already a commercial reality
towards the 2050 climate goals. Cyclic economy[5] and industrial symbiosis[6] contribute to
sustainability by using urban, agricultural and industrial residues and byproducts, including
biowastes, as raw materials in manufacturing, or as energy sources. In contrast to energy
crops targeted to biofuel/bioenergy production, biowastes are not competitive to food crops
when used as biofuels. Consequently, use of solid biofuels, produced from food waste, may
be crucial towards a sustainable low carbon economy, by reducing the dependence on
depleting fossil fuels without restricting food produce. The scope of the present work is to
investigate use of household food waste (FW) as an alternative solid fuel in cement plants,
partly substituting for fossil fuels.

Estimated at 1.3 billion tonnes per annum (tpa) in 2012[7], food residues are escalating rapidly
at a global scale. More than one third of the world’s food production is discarded[7,8], mostly
from urban centers. The loss fraction is higher for developed countries[9]. Food waste or food
loss from the entire food supply chain (agriculture, food processing industries, households and
hospitality sector) is at 0.49 kg/capita day[8] in the EU. Food residues are expected to rise in
Europe to 126 million tonnes by 2020 and in Asia from 278 to 416 million tonnes by 2025 [8,9].
Household food residues (precooked and leftover) range at 0.22kg/capita day[8] in the EU and
consist the wet fraction of municipal solid waste (moisture content about 70-75%).

3
Practical use of solid, food residue biofuels (FRBs) faces serious challenges. (a) The high
moisture content of food residues (about 70-75%) casts doubts on self-sustained combustion,
rendering pretreatment and water removal a sine-qua-non[10], or directing towards anaerobic
[9-11,12] [13]
digestion and biogas production or to production of biodiesel , or production of
[10, 13,14]
bioplastics or bulk chemicals via green chemistry . (b) Logistics costs for mobilization
of biogenic feedstock, and cost reduction along its supply chain and (c) Favorable reception
by flexible production facilities, which can use a variety of alternative solid biofuels as
substitutes of coal or petcoke. In regard to (a) drying may provide a low moisture FRB;
energy is required for this purpose. Regarding (b) mobilization and supply chain efficiency can
be addressed through separation of food residues at source and use of transfer station
systems as for municipal wastes. The challenge is more intricate regarding the third issue.
Licensing and widespread acceptance of biofuels and particularly of solid biofuels derived
from biomass and solid organic residues, including FRBs, touch on key issues of combustor
and plant performance, of environmental compliance and of conformance of end-products to
quality specifications (e.g., cement mineralogy and properties). It is of interest to develop
mechanisms and methods identifying appropriate biofuels, or biofuel blends for specific
industries and individual plants. To this end, several key aspects must be taken into account
for biogenic feedstocks with limited practical applications thus far, such as FRBs. They
include process design of existing plants and fuel utilization methods, energy efficiency,
characteristics of the combustion/energy production system and impact on process
equipment, in association with energy integration, mass recycle and recircuiting. The impact
on air-pollution control efficiency and final (offgas) emissions must also be evaluated.

Low cost, well established methods for preparation of solid FRBs from household food waste
(Table 1) are to be assessed herein. The aim is to partially substitute thermal energy from sold
fossil fuels in large-scale applications and particularly in cement plants, where substitution of
[33, 34]
fossil fuels by alternative fuels, including non-renewable fuels, is reaching 14% globally .
The evaluation method could be general enough to apply to the dominant user of solid fossil
fuels globally, namely coal power plants as well. As one of the largest fossil fuel consumers,
[15]
cement manufacturing averages around 0.85 Mcal/t clinker . With the global cement
production at 4.2 x109 metric tpa (50% of which in China) [16] this amounts to about 5 x 108
tpa, i.e., half a billion tpa of fossil fuels globally. A novel feature of the present attempt in
comparison to previous works is that it aims beyond assessing the fuel per se, in terms of its
composition and heating value, or merely in terms of combustion stoichiometry[17]. Instead,
based on fundamental principles and on actual data obtained under fossil fuel operation, it will
attempt to assess cement plant performance when FRBs are used. Operating conditions to

4
be investigated will include compound operation (fig. F1 in the Supplementary material in the
Web) that is when the soil mill is on for preparation of the raw-meal and the soil mill air is
cleaned together with the majority of the kiln fluegases in the air pollution control system
(APCS). (The raw meal is the inert raw material originating from lime quarries, which is
ground and fed to the cement kiln, where it is transformed to clinker through calcination, at
temperatures exceeding 1450o C). A multidimensional model[18,19] will be employed to this
purpose, based on the combined mass and enthalpy balance of the kiln, which enables
simulation of concurrent utilization of multiple biofuels and fossil fuels and provides more
accurate results than models based solely on stoichiometry. Expressed in linear algebraic
form (i.e. in terms of vectors and matrices) the model decouples the impact of feeding rates of
the various fuels in a linear fashion. It also isolates the impact of combustion air (excess air,
oxygen enrichment, air moisture) allowing explicit evaluation of their impact if used for kiln
control. Enabling explicit utilization of hard core data from actual operation under fossil fuels,
the model provides a holistic quantitative description, reflecting production, capacity
constraints, atmospheric emissions and environmental compliance, as well as inclusions of
chlorines, alkalis and metals in the clinker and impact on cement quality. With the vector of
feed rates, f, as the sought variable, it enables direct application of the vast array of
optimization methods towards determining superior combinations of renewable fuel blends.
Section 2 reviews the status of food waste treatment; section 3 presents the evaluation
method and framework, followed by quantitative assessment via a Case study in section 4.

2. REVIEW OF UP-TO-DATE MANAGEMENT OF FOOD RESIDUES AND

PRETREATMENT TECHNOLOGIES

2.1 Disposal and valorization

With unreasonably low landfill costs until the beginning of this century (not including
externalities from environmental repercussions) most of food waste (>60%) has been dumped
or landfilled. Land-disposal of non-stabilized biowastes, including food waste, is gradually
banned[20,211]. It has been recognized as another menace to sustainability due to high green-
house gas (GHG) emissions, mainly CH4 and CO2 and also, due to emissions of halogenated
and sulphonated organic pollutants[22].

About 20% of household food waste is used in mass burn, waste-to-energy facilities[23] as part
of commingled, or residual waste. Significant innovations in the long proved energy-from-
waste technology allow efficient valorization, together with other richer (of higher heating

5
value) fractions of municipal wastes (paper, plastics). Opponents of waste-to-energy invoke
arguments of atmospheric pollution[24], hinging on the heterogeneous and varying feedstock,
which contains heavy metals and precursors of persistent organic pollutants (POPs) such as
PCDD/Fs. A small portion of POPs, not removed from the fluegases in the APCS is released
with the offgases, even though emissions are maintained within the maximum limits[25,26].
Utilizing commingled waste, which includes plastic and paper, waste-to-energy plants achieve
high availability (>90%) enhanced controllability, compensating for waste variability, high net
power efficiency (~ 700kWhe/tonne MSW, which is ~25% of the feedstock’s lower heating
value (LHV)[27] and consistently low emissions [28]
. State-of-the-art technology [29,30]
is
employed to this end, with reverse acting grate, overfire air system with multiple nozzle rows -
e.g., "4-row stitching", combustion control system activated by infrared thermography, on-line
feedback control of fluegas recirculation, heat recovery and oxygen enrichment of combustion
air. Emitted concentrations of regulated pollutants have fallen to one or more orders of
[25, 26]
magnitude lower than emission limits set by legislation . With new high capacity facilities
[30]
under construction in the Far East , the total capacity of energy from waste facilities is
expected to rise to 260 million tonnes per annum (tpa)[32, 33], which is about 20% of global
[34]
municipal waste arisings by 2025 . The corresponding analogy of global food waste
directed to energy-from-waste facilities is slightly lower.

Another 10% of food residues are biologically treated either aerobically, via slow oxidation to
produce compost, or SRF via biodrying for use in power stations and cement plants, or
[35, 36]
anaerobically, via digestion, to produce biogas for energy recovery in gas power units .
Due to long residence times, biological treatment technologies are volume-intensive,
compelling, also, large footprints. Even with complete combustion of nonoxidized products
(CH4) they feature greenhouse gas emissions due to CO2 release and biostabilazation of
organic residuals compelled by enacted legislation. Composting and biodrying plants are
associated with odor problems, since they release high volumes of potentially infectious
bioaerosols. The end product (compost) from commingled refuse still contains xenobiotic
[37]
substances that inhibit wide scale application as soil amendment . Important studies have
brought forth the potential for cyclic valorization of food waste for industrial use in the chemical
and material industry, or via biogas-to-energy[9-14,38]. With residence times at ~4 weeks[36] and
relatively large volumes of bioreactors, biogas-to-energy is now at a mature technological
stage, having resolved operational, stability and process control problems. It has been widely
applied in agro-industries with slurry or sludge biowastes (e.g., swine and cattle farm wastes)
and in some food wastes (e.g., dairy wastes). Several large scale applications of municipal
[39,40,41]
organic wastes that include food and kitchen residues are in operation . Operational
issues relate to the heterogeneous substrate from municipal wastes in the digester which may

6
lead to foaming, reduced bioreactor volumes and decreasing yields[42]. As a result, cleanup
maintenance is frequent, resulting in low availability, <75%[43]. An additional problem is the
large quantities of biosludge, which must be stabilized and disposed of.

Impediments to wide scale applicability of anaerobic digestion to organic municipal solid

wastes, including food wastes, stem from the high lignocellulosic content and the presence of
phenolic and other recalcitrant organic species and inhibitors. The heterogeneous substrate of
food residues from municipal wastes in the digester leads to foaming, reduced bioreactor
volumes and decreasing yields[26]. As a result, cleanup maintenance is frequent, resulting in
low availability, <75%[27]. With residence times at ~4 weeks[24], applications of anaerobic
digestion in food and kitchen residues are limited. An additional problem of anaerobic
digestion is the large quantities of biosludge, which must be stabilized and disposed of. All in
[26]
all, biogas yields range around 400ml/gr volatile solids , with the content of volatile solids at
23%, the ratio of volatile solids over total solids at 84-87% and the ratio C/N at 14.8. The
above lead to yields that are lower than 120 Nm3 biogas per tonne of biowastes[27-28].
Considering the methane content to be ~73%, the energy content reaches 37.3 MJ/m3.

Anaerobic digestion of organic municipal solid wastes, including food wastes has been
investigated extensively in the last decade with significant improvements in the conversion
efficiency to biogas. Yields exceeding 520 Nlt biogas/kg VS with methane content up to 70%
[11]
have been reported . Industrial scale applications in state of the art plants, feature about
[44]
240-550 Nlt biogas/kg VS , with the upper figure corresponding to animal manure and with
methane content at 60% vol, whereas older plants treating municipal organic wastes do not
[45]
exceed 300 Nlt biogas/kg VS . With the use of biogas engines and combined cycle, this
gives a net electrical efficiency around 100 kWhe/tonne of biowaste. Digestion of leached
extracts from biowastes circumvents the operational issues mentioned above, at the cost of
even lower efficiencies, (~80 Nm3 biogas/tone of biowaste[43]). The typical power output for a
100 tpd biowaste facility is around 0.7 MWe.

[35]
Biogas yields from food waste range around 400ml/gr volatile solids , with the content of
volatile solids at 21-23%, the ratio of volatile solids over total solids at 84-87% and the ratio
C/N at 14.8. Anaerobic digestion of food waste in practice converts about 80% of volatile
[12]
solids which amount to 90% of total solids . This gives around 380-450 Nlt CH4 /kg VS or
[45,46,47]
340-400 Nlt CH4 /kg TS or 55-73 Nlt CH4 /kg FW . If electrical energy requirements of
anaerobic digestion (30-70 kWhe/t FW) and thermal requirements of subsequent composting

7
 [45]
of the digestate (20-60 kWh/t FW) are taken into account , the net energy potential of
methane from anaerobic digestion of FW is at 40-170 kWhe/t and 180-380kWh/t thermal.

Considering the methane content to be ~73%, the energy content reaches 37.3 MJ/m3.
As a result, considerable subsidies amounting to 230 E/MWhe supplied to the grid are needed
to render biogas projects viable.

The main constituents of FW are as in Table 1[11, 12]. The energy content of the household FRB
[48-51]
produced via drying of FW is around 4 MJ/kg FW or 1000 kWh/t/FW . Recognizing the
feasibility of thermal valorization of household food residues, part of the EU support to biogas-
to energy is now directed to solid and liquid biofuels[44,49], while the waste management
hierarchy[20] is maintained. Food residues and FRBs are now viewed as promising sources of
biochemicals, biomaterials and bioenergy[37], via direct energy production, or transformation to
solid and liquid biofuels, with the aid of innovative technology.

[52]
Apart from methane , specific products include bulk chemicals and biomaterials, such as
[53] [11, 54,55]
pectin volatile fatty acids lactate, ethanol and hydrogen[56] biofuels [proteins,
[57]
peptides, lactose, glucose, galactose, yeast , enzymes, bio-pesticides and bioplastics[58]
[59,60]
succinic acid . Critical issues are comparability and compatibility of use with fossil fuel
derived compounds, while ecological repercussions should not be taken for granted. Two
major threats of emerging biorefineries utilizing food waste[61,62] are eased via the FRB route
investigated herein, namely (a) stable, non decomposing FRB via drying, readily stored for
long periods and thus no longer requiring infrastructural and expensive storage and
conditioning to avert the rapid decomposition of raw food waste and (b) small variations in
composition and quality of household food waste within a district or country circumventing the
high variety of quality and volume of food waste.

Other notable examples include: (i) production of syngas via gasification[63] followed by
production of liquid biodiesel, biokerosene, or naptha fuels via Fisher-Tropsch liquefaction, (ii)
production of bioethanol and biomethanol (iii) production of biochemicals including fatty acids
and biopolymers, biomethanol, bioethanol, or of fertilizers via the Bosh-Bashke method
featuring zero carbon footprint, (iv) production of hythane. For instance, high efficiency
[64]
plasma gasification with combined cycle and recuperation of the syngas heat from the
gasifier, recovers about 95% of the biofuel's energy content in the form of chemical energy of
syngas, enabling gross efficiencies of 40% to electric power production. This figure is about

8
70% higher than direct waste-to-energy recovery. At about the same CAPEX and OPEX as
waste-to-energy, these promising biorefinery technologies are yet to entertain large scale
implementation. New developments in plasma gasification including microwave plasma
gasifiers and use of supercritical steam in the gasification zone further improve syngas quality
by increasing the hydrogen molar fraction and lead to higher overall energy production.
Bridging the “development gap” from pilot plants to operational first-of-a-kind industrial plants
is a main bottleneck for biofuels, particularly challenging for single-product start-ups.

2.2 Pretreatment and preparation of solid biofuel from food residues

In regard to pretreatment and preparation, two methods have been attested thus far for
biomass and organic wastes: torrefaction[48, 65,66] and long established thermal drying. Lab
and pilot scale torrefaction of food waste[65] takes place under anoxic conditions (nitrogen
atmosphere) in temperatures ranging from 150 oC to 600 oC and residence times varying up to
50 min. It can produce a free-of-volatiles, solid biomass fuel for combustion gasification or
pyrolysis. The torrefied solid FRB features increased energy density, while the strong fibers of
the biomass become brittle, improving grindability, ignitability, reactivity and efficiency.
Industrial scale applications of torrefaction are yet to appear. The method requires relatively
high temperatures (optimal for food residues is around 300oC) and reduces the energy yield of
the produced FRB by about 30% [66].

Pretreatment of FW with main constituents as in Table 1 via thermal drying at 90 oC for about
4-9 hours produces stable FRBs at moisture levels down to 1.1%w (fig. 1)[49, 67] and partial
volatilization of volatile organic compounds (from 88-90% originally, to 75-78%). The
characteristic brown colored product has a negligible, rather pleasant odor of dried food (e.g.,
soup cubes). Volatilization of organics is limited to highly volatile compounds and thus the
product (FRB) almost maintains the energy yield of the original material. Pilot scale
[67]
applications can use electric driers of up to 1.2 tpd to produce a stable product of consistent
[49]
quality, easily grindable and pressed to pellets . Industrial scale drying via heat convection
may be applied as in direct thermal dryers, that is, by directing the fluegases to the material
along its course on suitable belt conveyors, or in rotating drums (fig. 2). Long established for
drying olive pomaces, rotary drums use the hot drying gases produced from combustion of
residual exhausted olive cake (a solid biofuel) to dry the fresh pomace. The olive cake is
obtained from the dried fatty pomaces after the pomace oil is extracted using solvents
(cyclohexane). The product (pomace) to be dried and the hot drying gases are introduced co-

9
currently at high temperatures (400°C to 800°C) in the rotary drum. Low moisture is reached
with direct rotary driers: pomace can be dried down to 1.5% wt moisture. Alternatively, plate
heat exchangers can be employed using hot air, hot oil, or steam. Hot air can be blown
directly to the material, as in rotating drums with co-current air flow; the material is thus dried
by heat convection as in food drying applications. Hot oil or steam may be used in heat
conduction driers circulating in an inner axis of rotating paddles as in waste-water-treatment
plant biosludge drying [68].

Given the aforementioned potential for direct applicability of industrial drying, specific
questions of interest in this respect are (i) what are the energy needs and the final energy
content of FRBs (ii) are there any adverse effects regarding production level and profits when
FRBs substitute for fossil fuels, e.g., petcoke (iii) which are, if any, the benefits from fossil fuel
substitution, e.g., cost savings (iv) how much are greenhouse gas emissions reduced per
tonne clinker (v) are there any plant operation limitations, stemming from plant capacity
constraints (vi) is the product detrimentally affected by inclusions of trace elements such as
alkalis and leachable metals? (vii) what is the impact of chlorines form food salt on plant
operation and emissions (viii) is emissions compliance ensured for regulated pollutants and
are the actual emission rates maintained at the same levels as under baseline (fossil fuel)
operation? (ix) how does the final moisture content of FRBs affect economic performance of
cement-plants, product quality and emissions? The answers to the above questions may
provide guidelines for suitable, customer-made blends of FRBs with other bioresidues, e.g.,
paper detrita, since paper cannot be recycled more than seven times.

3. ASSESSMENT METHOD: ENERGY EFFICIENCY, PRODUCTION LEVEL, CEMENT

QUALITY AND ATMOSPHERIC EMISSIONS

The evaluation method investigates the following (fig. 3): (i) satisfaction of main constraints of
process operation: thermal load should not exceed heat rating of kiln refractory and overall
offgas volumetric flowrates should not exceed main blower capacity, (ii) level of clinker
production (directly related to cement sales), (iii) non-biogenic CO2 emissions (analogous to
CO2 pollution rights), (iv) emitted concentrations of regulated pollutants and compliance, (v)
actual rates of pollutant emissions, (vi) trace metal inclusions remaining within acceptable
limits and (vii) chlorine presence in the process equipment and in the APCS.

10
Quantitative evaluation is based on actual data from baseline operation used in a multiple fuel
combustion model. The model entails process stoichiometry and mass and enthalpy balances
of the kiln and recircuiting systems[18,19,69] (depicted in fig. F1, Appendix F in the
Supplementary information in the Web). It enables simultaneous consideration of
multicomponent mixtures of fossil fuels and/or renewable fuels and decouples the varying
parts due to fuel variability, or due to manipulation of process parameters (e.g., excess air) by
the plant operator, from the parts that remain invariant. Several alternative scenaria can be
evaluated using one or more biofuels and comparatively assessed. The key expressions
represent the following:
1) Clinker level in the kiln and required raw meal level.
2) Kiln fluegas species’ flowrates, including CO2 from lime dissociation.
3) Biogenic, non-biogenic and overall CO2 flowrate.
4) Gas species flowrates prior to the main air pollution control system (APCS) under
direct operation and, also, after mixing part of the kiln fluegases with soil mill air
(compound operation) prior to the APCS.
5) Overall kiln / soil mill offgas flowrates.
6) Gas species flowrates and overall flowrate at the fuel mill APCS, after diverting the
remaining part of the kiln fluegases to the fuel mill to maintain inert atmosphere and to
heat up the fuel.
7) Pollutant emission rates, taking into account the removal efficiency in the main APCS
(kiln – soil mill APCS) as established from baseline operation.

Common characteristics featured by the key expressions of (1)–(7) above are the following:
(i) they entail linear expressions in terms of the fuel charging rates fi, i.e., of the vector
f   f1 f2 ... fn .

(ii) if the types and compositions of the candidate renewable fuels are known, then, under
constant excess air and oxygen enrichment, the coefficients of the linear expressions remain
constant; if a renewable fuel (e.g., fuel 3) is not present in the fuel mixture, then it suffices to
simply set f3=0 while maintaining the same linearity coefficients.
(iii) under manipulated (known) excess air and/or oxygen enrichment the linearity coefficients
change, yet they can be known a priori in terms of the values of plant parameters and of
excess air (%) or oxygen enrichment (e.g., oxygen at 28%v instead of 21%v).

Specific energy consumption in the kiln

For instance, the energy released by the fuels is given by the scalar product  f , where
T

11
f = fuel mass feedrate vector, that is the n-dimensional column vector f, each component of
which is the mass feedrate of one of the n fuels, coal (i=1), petcoke (i=2) and so on for
i=3,4,...,n, including the renewable fuels, e.g., FRB, paper, saw dust, or others and λ is the
vector of the lower heating values of the fuels (e.g., λ1= λcoal = 6 146 kcal/kg, λ2= λ petcoke =8
Τ
342 kcal/kg, etc. denotes the transpose (row) of a (column) vector and thus λT is a row

vector. The specific energy consumption to produce clinker is given by  f k , where k is

T

the mass (flowrate) of the clinker produced. Evidently, even under isothermal substitution

(constant  f ) if the clinker level changes, the specific energy consumption will be different
T

and thus it is not a constant design parameter or an invariable parameter of process operation
when some fuels are substituted by other fuels.

Kin fluegases
The mass flowrates of individual kiln fluegas species (mfgi, i=1,2…,9 for CO2, H2O, O2, N2,
SO2, HCl, P2O5, HBr, HF respectively) are given by the scalar expression

m fg ,i  c fg ,i  c fg ,i f
T
(1)

where cfg,i is a scalar, cfg,i is a vector (Appendix A). The scalar cfg,i, and the vector cfg,i entering
eq. 1 are independent of f. In particular, they are independent of the fuel types (composition,
LHV) and of the fuel charging rates fi and depend only on process design and operation
parameters (e.g., CaO yield from CaCO3).

Nonbiogenic CO2 emissions

Regarding CO2 emissions, the non-biogenic CO2 mass flowrate is given by

Nonbiogenic CO2 mass flowrate m fg ,CO2  c fg ,CO2  c fg ,CO2

T
f  f 
b
(2)

where fb=biogenic fuel mass feedrate vector, that is the vector f with zeroes in the entries
corresponding to fossil (non-biogenic) fuels. The scalar c fg ,CO2 and the vector c fg ,CO2 entering

eq. 2 are independent of the fuel types (composition, LHV) and of the fuel charging rates fi of f
and fb, and depend only on process parameters. The analytic expressions for the scalar
c fg ,CO2 and the vector c fg ,CO2 are given in Appendix A.

Atmospheric emissions of main offgas species

12
The volumetric flowrates of the main species in the fluegases are determined from the mass
flowrates (eq. 1). Then the overall kiln fluegas volumetric flowrate is found, from which in turn,
concentrations of main species in the overall fluegas can be determined (Appendix A).
Regarding offgases and stack emissions, under direct operation the main blower directs (kiln)
fluegases to the APCS and thus the fluegas flow increases merely by the blower induced air
draft (false air). Under compound operation (fig. F1, Supplementary Information) the majority
of the kiln fluegases are cleaned together with the soil mill air. Mass and volumetric flowrates
of the various species in the kiln soil-mill gas stream are given by expressions of similar form
that take into account the soil mill air, as well as the false air drawn by the APCS blower.

Vk ,sm,i  ck ,sm,i  c k ,sm,,i f

T
Offgas species i volumetric flowrate: (3).

The analytic expressions for the scalar ck ,sm,i and the vector c k ,sm,,i are given in Appendix A.

Clinker production level

Obtained directly from the kiln enthalpy balance, using the stoichiometric mass balance
described above, the key relation that quantifies operational efficiency is the explicit
expression for the clinker level, directly related to profits and economic performance,

k    f
T
(4).

Overall offgas volumes

Regarding stack emissions, the expression for the overall offgas flowrate (resulting from eq. 3)
which directly relates to main APCS blower costs is eq. 5:

Vk , sm  v  v f
T
(5).

The scalar κ and the (row) vector κΤ in eq. 4 and the scalar v and the vector vT in eq. 5 (A,
Supplementary Information in the Web) are independent of the fuel types (composition, LHV)
and of the fuel charging rates fi and depend only on process parameters. The process
parameters are independent of the fuels (composition, LHV and feedrates) as well. The
factors v (scalar) and the vector v in eq. 5 explicitly depend on κ and κΤ. In this way, the
parameters v and v constitute the link between performance (clinker level) and two key
objectives of operation: (a) satisfaction of main blower capacity constraint Vk , sm  Vk , sm,max and

(b) environmental constraints and particularly emissions’ compliance, since (i) environmental

13
compliance is assessed in terms of emitted pollutant concentrations and (ii) pollutant removal
efficiency depends on the offgas volumetric flowrate, Vk,sm. Larger values of Vk,sm reduce the
residence time and increase the pressure drop in the APCS, thus reducing the removal
efficiency, y (fraction) and increasing the non-removed fraction (1-y) which is released in the
atmosphere with the offgases.

Emissions compliance and actual emission rates of regulated pollutants

Reported emitted concentrations are obtained from measured emitted concentrations via
standardization. Standardization to standard conditions (normal temperature and pressure,
dry and 10% oxygen) is performed via multiplication by the standardization factor SF. In fact,
a necessary and sufficient emissions compliance condition[43] is expressed via the compliance
factors (1  y ) SFxin, APCS / xl , where xl is the emissions limit under utilization of waste derived

fuels and xin, APCS is the pollutant concentration entering the APCS, which can be determined

analytically for several pollutants via the model and stoichiometry (e.g., HX, SO2, NOx). The
SF is directly determined from the plant model and in particular from the offgas flowrates
(given in Table S1 in the Supplementary information in the Web) of oxygen and water.
Compliance is ensured for any regulated pollutant, if and only if, the following condition is
satisfied[68]:

  1 (6)
where
xl , 0 SF xin, APCS
 :  A (7)
xl SF0 xin, APCS , 0

is the dimensionless ratio of compliance factors with respect to baseline conditions, i.e.
compliance factor under use of FRB / compliance factor under use of stand alone fossil fuels,
 A  1  y  1  y0  is the ratio of removal efficiencies in the APCS with respect to baseline
operation,
xl , 0
μ (also dimensionless) is defined as the ratio   , that is the ratio of the maximum limit of
xs 0
emitted concentrations under fossil fuel (baseline operation) set by enacted legislation[70,71],
xl,0, with respect to reported actual standardized emissions xs,0, also under baseline operation;
μ refers only to baseline conditions and is independent of the biofuel assessed.

14
The ratio φ/μ represents emissions compliance with regard to the respective maximum
emissions limit. Named thereof emissions compliance index, it includes the impact of possibly
differing emission limits for refuse or waste derived fuels, the impact of standardization factors
and the impact of removal efficiencies in the APCS, which are affected by offgas volumes and
by the presence of other species (see the discussion for SO2 and chlorines below). For
instance, if for a certain pollutant φ/μ=0.6, then emitted concentrations of the specific pollutant
are at 60% of the maximum allowed value. The inverse μ/φ represents the emissions safety
factor, i.e., how many times the emitted concentration can be increased without violating the
maximum limit. For instance, if μ/φ =1.4, then emitted concentration should be increased by
40% in order to reach the maximum limit. Evidently, φ/μ depends on the types of renewable
fuels and on the overall fuel mixture, on the emissions’ limit under alternative fuel utilization xl
SF
(it may be lower or higher than xl,0) on the ratio of the standardization factors, and on the
SF0

ratio of removal efficiencies in the APCS,  A  1  y  1  y 0  . Condition 6 is necessary and

sufficient, i.e., non-excessive. For regulated pollutants not entering the stoichiometry (TSP,
TOC, volatile and non-volatile metals and PCDD/Fs) the ratio can be approximated or
bounded, leading to sufficient conditions for emissions compliance. When condition 6 is
applied to an actual cement plant, data from actual operation entering condition 6 via the
parameters φ and μ include: the actual removal efficiency y0, the actual concentration
measurements, xS,0 (standardized) and the actual standardization factor, SF0. The maximum
emission limits, xl and xl,0 are known a priori. The values of the rest of the parameters in
condition 6 are determined from the model equations. In this way the simulated scenaria
under use of FRBs are tied to the actual plant performance via hard-core evidence. It is noted
that condition 6 under baseline conditions reduces to the trivial condition μ≥1.

Apart from emitted concentrations addressed via the emissions’ compliance index, φ/μ, in
compliance with enacted legislation, the actual burden to the environment is assessed via the
ratio of emission rates with respect to baseline conditions:

moffg xin, APCS Vksm x SF0 Vksm

A  l (8).
moffg,0 xin, APCS ,0 Vksm,0 xl ,0 SF Vksm,0

Inclusions of trace elements in cement

Trace elements, alkalis, volatile and non-volatile metals and halogens included in the final
product, affect cement strength, leachability, integrity and lifetime. The impact of inclusions is

15
assessed by the ratio of inclusions per tonne clinker with respect to baseline operation, given
the raw meal content. For instance, inclusion of alkalis per tonne clinker is assessed by eq. 9:

 Na  K , r r   Na  Kl , f T f  moffg, Na  K k0
( Na  K ) inclusions ratio  (9)
 Na  K , r r0   Na  K , f ,0 f 0  moffg,0, Na  K
T
k

where  Na  K ,r r   Na  Kl , f f is the overall alkali generation rate by raw meal (r) and fuels;
T

βNa+K,r is the specific alkali generation rate in the kiln, originating from the raw meal (raw meal
feedrate = r tpa); and
βNa+K,f is the specific alkali generation rate in the kiln originating from the fuels;
moffg, Na+K is the emission (mass) rate of alkalis in the offgases, found in terms of the overall
offgas flow and emitted concentration data. Similar expressions are used for mercury,
cadmium and thallium and non-volatile metals (A, Supplementary Information).

Chlorine impact on emissions, inclusions and corrosive deposits on process

equipment
With a specific content of 1 wt% in food residues the fate of halogens (mainly Cl) is a serious
consideration in FRBs. Chlorine is a precursor of PCDD/Fs[72-75] and it inhibits removal of
volatile metals in the APCS, incurring increased emissions of Hg, Cd and Tl and other metals.
Thus, the presence of chlorine ought to be assessed both in the kiln /precalciner/preheater
system (i.e., in the kiln fluegases) and in the APCS (offgases). Food residues contain the
[48l]
majority of chlorine in household waste (45%-50% ) the rest attributed to plastics, mainly
PVC (45%). Not all chlorine in the fuel becomes hydrogen chloride however[76,77]. Due to
higher binding energy of NaCl and KCl in food residues, alkali salts give rise to incombustible
chlorine, which is incorporated in Friedel’s salt[78] in waste incinerator ash in waste-to-energy
plants, or incorporated in the mass of clinker in cement kilns. A typical ratio is combustible
chlorine/incombustible chlorine =1.5[79]. Thus, the emission rates of HCl are expected to be
lower under use of FRBs than under use of alternative fuels derived from plastic residues,
which, in addition, are non-biogenic and non-renewable. Nevertheless, at the high
temperatures (1500oC to 2000oC) prevailing in the kiln, incombustible chlorine is present in the
form of water-soluble alkali chloride salts, which as the fluegases are cooled down (along their
course from the kiln to the precalciner and the preheater) are deposited on equipment and
pipes contributing significantly to high temperature corrosion in process equipment (kiln-
precalciner, riser and preheater) and, also, on piping and ducts[80]. Recent studies[81] have
shown that the presence of sulphur favors chloride becoming HCl and reduces vaporized salts
in the furnace/kiln. Since the petcoke content in sulphur is about one order of magnitude

16
larger than FRB (Table 3) the impact of SO2 on the presence of hydrogen chlorides must be
taken into account (fig. 4). This can be done by assuming that the fraction of combustible
chlorines over hydrogen chlorides as given by stoichiometry (reaction a, Supplementary
Information, A) follows first order kinetics with the kiln SO2 concentration (Appendix C) after
taking into account the detainment of hydrogen chloride by the (alkaline) clinker in the kiln,
which acts as a huge scrubber. The presence of incombustible chlorines can be subsequently
m fg , HCl
assessed via the ratio , which is found from the fluegas chlorine mass balance
m fg , HCl , 0

(incombustible + combustibles chlorines in the kiln are equal to the overall chlorines in the kiln
fluegases) in conjunction with the stoichiometry (reaction a, Supplementary Information, A).
Then, chlorine presence in the kiln/precalciner/preheater and in the APCS is assessed via eqs
10a – 10c (Appendix C).

[ HCl ] fg m fg , HCl V fg , 0 g HCl V fg , 0

Chlorine in kiln/precalciner/preheater:    C S (10a)
[ HCl ] fg , 0 m fg , HCl , 0 V fg g HCl , 0 V fg

x HCl ,in, APCS g HCl Vk , sm, 0

Chlorine in main theAPCS:   C S (10b)
x HCl ,in, APCS , 0 g HCl , 0 Vk , sm

[Cl ] fg m fg ,Cl V fg , 0 g HCl V fg , 0

Incombustible chlorine:   C S (10c)
[Cl ] fg , 0 m fg ,Cl , 0 V fg g HCl , 0 V fg

where, similarly to γΑ, γC is the ratio of nonremoved fraction of chlorines by the clinker, with
respect to baseline, based on first order adsorption kinetics and γS is the ratio of fractions of

incombustible chlorines with respect to baseline. The factor  S is found from the chlorine

mass balance in the kiln. The expressions for γC, γS and  S are included in the model

(Appendix C). The complete model is given in the Supplementary information in the Web.
Eqs (1)-(10) constitute the core of the evaluation method applied to a Case study in the next
section.

4. CASE STUDY

An actual dry kiln process plant producing 1.5 x 106 tonnes clinker per annum (tpa) and
utilizing 1.65 105 tpa fossil fuels is investigated under compound operation. Direct and

17
compound operation, key process flows and emissions are represented via the model in the
Supplementary information. Current (baseline) operation corresponds to a thermal load
distribution 30% coal and 70% petcoke. The overall heat rating is 1.244 x 106 Gcal/annum.
The limiting flowrate of the main APCS (kiln/soil mill) is 578.000 Nm3/h. Separate use of
FRB and blends with paper residues, or FPRBs, is assessed via simulation of various
scenaria, each one under twenty percent isothermal substitution of petcoke (i.e. the quantity
of FRB or FPRB supplies 20% of the thermal energy in the kiln, while the quantity of petcoke
is reduced equivalently). The percentage of thermal participation of coal in the fuel mixtures
remains constant at 30%, since coal inhibits PCDD/PCDF emissions. An additional reason for
not increasing coal to higher levels is that it may favour reactions with different metals in raw
meal and increase their release with the flue gases. Elemental composition of food residues
are given in Table 3, revealing deviations (e.g., in the LHV) depending on the collection and
preparation method. Uncertainty, as expressed by large variability of key variables such as
the LHV of any fuel, (particularly of the prepared FRB via drying of FW) can be readily
investigated using our multidimensional model (the vector of LHVs, λ, explicitly appears in eq.
4 and eqs A16 and A18 in the Supplementary Information in the Web). Notably, the ash
[82]
content is below 10%, in line with the new EU regulation on food-waste pellets (though >
than the 2% maximum ash content required for woody biomass pellets). The elemental
[49]
composition used in the model is from Papanikola et al., . Clinker exit temperature is
Tk  2000 o C and preheater temperature T p  450o C . Plant parameter values and other

baseline operating conditions are as in Table 4. The essential characteristics and efficiency of
FRBs with moisture contents 1.5%wt, 10% wt and 15% wt is assessed with respect to (a)
clinker production, k, (b) offgas volumetric flowrate, Vk , sm , (c) GHG emissions (d) inclusions of

trace elements and (e) atmospheric emissions of pollutants are revealed. Actual data from
baseline operation are used, including stack measurements of pollutant concentrations.

Evaluation
Energy requirements for FRB preparation. Fig. 1 presents the thermal energy
requirements for producing FRB at various moisture levels. As clearly manifested, the thermal
energy need is about 55% of the LHV of the respective FRB. This is a marginal figure if
electric energy stand-alone is used for drying (taking into account an average efficiency of
30% of transforming chemical energy to electricity). It becomes attractive if cogeneration is
employed (fig. 2). For instance, a 1 MW e natural gas or diesel generator can be combined
with a direct fluegas dryer for drying 20 tpd of food residues down to 1.1%. Alternatively, a hot
air-dryer (with the recirculated air heated in a heat exchanger) or a hot oil (or steam) dryer can
be used, in which the recirculated hot oil is heated by the fluegases in a heat exchanger. Fig.

18
1 also reveals the feasibility of an self-sustained, autonomous process, using part of FRB as
fuel in a dedicated thermal dryer. About 70% of FRB is required under 80% efficiency, leaving
30% of FRB for other uses, e.g., as solid biofuel. The prospect of drying the food residues
using the enthalpy of the cement plant offgases is also attractive. In this case 100% of FRB is
available for use as a solid biofuel. Based on fig. 1, the energy needed for drying 65 000t/y of
FW (20% thermal substitution of by petcoke by FRB 1.5%) is 6.4 x105 Mcal/y, which is more
than an order of magnitude lower than the enthalpy released by cooling the kiln-soil mill
offgases from 140 0C to 130 0C, i.e., by 10 0C, (9.4 x106 Mcal/y). This option commands a
rigorous feasibility assessment by the cement plant management, including CAPEX, gate fees
of FRBs and environmental benefits or drawbacks as well.

Plant operability, GHG emissions and product quality

The key relations (1) – (10) are used to identify the benefits and challenges of the use of FRB
in cement kilns when substituting 20% of the thermic contribution of petcoke in accordance
with fig. 3. The feedrates of FRBs and of blends of FRB with paper residues (FPRBs) are
shown in fig. 5a: about 65 000 tpa of FRB or 52 000 tpa of FPRBs (80% wt FRB and 20% wt
paper residues) substitute 29 829 tpa of petcoke, keeping the respective fossil carbon in the
ground. Notably, FPRB feedrates are about 20% lower than FRB feedrates at the same
moisture level, leading to lower kiln fluegas volumes.

Regarding operability, the refractory thermal rating constraint is satisfied, since FRB
contributes the same amount of thermal energy as the substituted petcoke. The main blower
capacity constraint is also satisfied in all scenaria, since offgas volumetric flowrates are
between 565 135 Nm3/h and 570 639 Nm3/h. As to clinker production, it is seen that use of
FRB results in lower production levels. For instance, FRB with 10% moisture (FRB 10%) leads
to losses of about 30 000 tonnes clinker per annum (tpa) fig. 5b, i.e., lower production due to
lower energy efficiency by about 2%. This amounts to about 0.46 tonnes of clinker per tonne
of FRB with moisture level 10%wt (FRB 10%). In contrast, use of blends of FRB (80%wt) and
paper residues (20%wt) raises clinker production level and increases energy efficiency. The
blend with the lowest moisture content (FPRB 1.5%) corresponds to the highest gains (27 000
tpa) or ~0.58 tonnes of clinker/tonne of FRB 10% (fig. 5b). The reason is that the mass of kiln
fluegases is lower, resulting in lower enthalpy discharge with the fluegases, which, in turn,
enables higher clinker volumes. Going back to blower capacity and offgas flowrates, it is now
apparent that offgas volumes are about equal, despite the fact that kiln fluegas flowrates
under FRBs are about 20% higher than FPRBs. This is due to the higher clinker production
levels associated with FPRBs, which imply higher soil mill air, higher volumes of CO2 from

19
lime dissociation and higher false air drawn and cleaned together with the kiln fluegases in the
main APCS.

Greenhouse gas emissions are assessed as emissions of non-biogenic CO2 originating from
the fuels, per tonne clinker. They are reduced by about 20% under use of FRB (~equal to the
substituted fraction of fossil fuels) and by about 23% under use of blends of FRB with paper
residues. The blend FPRB1.5% features the lowest non-biogenic GHG emissions (266.85 kgr/t
clinker, versus 267.66 kgr/t clinker of FPRB10% and 268.22 kgr/t clinker of FPRB15%). Fig. 5
presents the full quantitative figures and clearly manifests the impact of moisture on the loss
level. For instance, losses corresponding to FRB1.5% (70 000 t/y FRB1.5% for 20% thermal
substitution of petcoke) are at 25 000 t/y, whereas CO2 emissions are reduced by 48 kg/t
clinker or 70 800 t CO2/y. In contrast, FPRB1.5% features no clinker losses and lower CO2
emissions by 10 kg/t clinker or 15 250 t CO2/y.

Product quality, as reflected by inclusion of alkalis, leachable and volatile metals is presented
in fig. 5c via the inclusion ratios per tonne clinker with respect to baseline conditions.
Inclusions of alkalis when using FRBs are higher by about 10% due to the sodium from
kitchen salt in food residues. The blends of FRB with paper residues feature lower inclusions
than FRBs, though still larger than baseline K+Na inclusions by about 7%. Combustible
chlorine concentrations (HCl), as quantified by eq. 10a, rise by 11%, 13% and 16% for
FRB1.5%, FRB10% and FRB15% respectively. They fall by 13%, 11% and 9% for FPRB1.5%,
FPRB10% and FPRB15% respectively. Incombustible chlorine concentrations (eq. 10c) and
resulting halide deposits in equipment and pipes are predicted to be higher than baseline by
22% for FRB1.5%, by 26% for FRB 10% and by 30% for FRB15%. This is due to the higher feeding
rate of chlorines with the FRBs in conjunction with the lower SO2 concentrations (resulting
from 29 829 tpa lower petcoke feedrate than baseline) which shifts the chlorine vapor
equilibrium to alkali halides, favoring chlorine deposits. Another factor is the lower quantity of
clinker produced, implying a lower overall quantity of chlorine adsorbed by the clinker in the
kiln. In contrast, incombustible chlorine is lower under use of FPRBs and, more specifically,
by 8% for FPRB1.5%, by 6% for FPRB10%, and by 4% for FPRB15%. This is attributed to the
lower charging of chlorines with the FPRBs (FPRBs are blends consisting of 80%wt FRB,
20%wt paper, while paper chlorine content is at 1/3 of FRB chlorine content, Table 3[48-51,83-86])
and, also, to the higher quantity of clinker produced.

Inclusions of volatile metals Cd +Tl per t clinker are equal to baseline for FRBs and FPRB
blends (fig. 5c), due to the counteracting effects of chlorines (favoring higher releases to the
atmosphere, i.e., lower inclusions) and of the quantity of clinker. In other words, the increase

20
due to the lower clinker quantity is balanced by the decrease of inclusions due to slightly
higher Cd+Tl emissions, which, in turn, are induced by the higher concentrations of
combustible chlorines. These observations and reasoning are in accordance with the
description above and, also, with fig. 8a depicting HX emissions. For mercury, inclusions per t
clinker are slightly lower (by about 1.5%) than baseline for FRBs and slightly higher (by about
1%) for FPRB blends, despite the increased clinker levels. This is due to the impact of
combustible chlorines shown in fig. 4 (as affected by sulphur (figs 4 and 6c) since the feedrate
of petcoke is the same as for FRBs, i.e., 29 829 tpa lower than baseline). Chlorines are lower
under FPRBs than FRBs (fig. 8a), thus resulting in lower Hg emissions for FPRBs than FRBs
(Hg emissions depicted in fig. 6b). From the Hg mass balance, if Hg emissions fall, then Hg
inclusions must rise by the same amount. Thus, acting in parallel, these two mechanisms,
that is, (i) lower combustible and higher incombustible chlorine than FRBs and (ii) lower Hg
emissions, counterbalance the impact of higher clinker quantity for FPRBs on Hg inclusions/t
clinker.

Environmental compliance and actual emission rates

Regarding environmental compliance and actual emission rates the following are noted. At
first the emissions limits, xl , for SO2, TSPs and NOx, are different under fossil fuel operation
and under use of waste derived fuels (A, Supplementary Information). In particular,
xl ,SO2 ,baseline  60mg / Nm3 versus xl ,SO2 , FRB  50mg / Nm3 , xl ,TSP,baseline  20mg / Nm3 versus

xl ,TSP, FRB  30mg / Nm3 and xl , NOx ,baseline  800mg / Nm3 versus xl , NOx , FRB  500mg / Nm3 (fig.
6a). The stricter limits, rendering compliance more strenuous, are fully reflected in condition
(6), which requires (necessary and sufficient) φ/μ <1 for compliance.

It is seen that, under 20% thermal substitution of petcoke by FRB, compliance condition (6) is
satisfied for all regulated pollutants but NOx (fig.6a). In particular, the ratio φ/μ for NOx is at
(φ/μ)NOx =0.78 under baseline conditions. When FRBs and FPRBs are used, the ratio φ/μNOx
ranges between 1.28 and 1.45, showing that emissions exceed the maximum limits by 28%
and 45% respectively, with the lower values corresponding to blends of FRB with paper
residues. It is also noted (fig. 6a) that actual emission rates of NOx increase by about 20%
with respect to baseline, mo ffg, NO
x
mo ffg, NOx ,0 =1.20. This is attributed to the higher N-content of

FRBs compared to the N-content of the substituted petcoke. Thus, the NOx emissions
compliance problem revealed under utilization of FRBs is not due only to the lower emissions
limit, but to the increased rates of NOx emissions as well, originating from the biogenic fuel
itself (fuel nitrogen)[89-94]. In contrast, under use of blends of FRBs with paper residues

21
(FPRBs) the NOx emission rates remain at baseline levels (despite the increased clinker
production levels) and thus, the violation of the compliance limit under use of FPRBs is solely
due to the stricter emissions limit (800 mg/Nm3 versus 500 mg/Nm3). It is deduced that
additional N-removal effort is required for NOx. The NOx emissions compliance problem can
be addressed by revamping of the deNOx system or, by increasing the catalyst rate in catalytic
nitrogen removal systems, or by increasing the levels of added urea in selective non catalytic
nitrogen removal systems (SNCR) [92-93].

The compliance index (ratio φ/μ= ratio of compliance factors) for Hg under baseline conditions
is at (φ/μ)Hg =0.53, i.e., the emitted concentrations of mercury are at 53% of the maximum limit
set by the legislation (fig. 6b). It ranges between 0.62 and 0.68, under use of FRBs and
between 0.41 and 0.47 under use of FPRBs, i.e., lower than baseline. Actual emissions of
mercury are also lower than baseline; again the lowest emission rate corresponds to FPRB
with 1.5% moisture. The lower Hg emissions of the paper and food residue blends, compared
to stand alone FRBs, are due to the lower halogen levels, which imply lower combustible
chlorine in the offgases and therefore higher removal efficiencies of volatile metals from the
offgases. The same is true regarding other volatile metals (Cd and Tl, fig. 7b). SO2 emitted
concentrations and emission rates are lower, both under use of FRBs and of FPRBs (fig. 6c),
due to the lower sulphur content in FRBs than petcoke. The compliance index, φ/μ, is slightly
higher than baseline, due to the lower maximum limit xl , SO2 ,baseline . The lower sulphur presence

in the kiln favors incombustible chlorine, i.e., chloride deposits and incorporation of chlorines
in the clinker mass as salts. Regarding PCDD/Fs, nonvolatile metals and the volatile metals,
cadmium and thallium (Cd and Tl) the compliance indices φ/μ, and emission rates are ~10%
higher than baseline for FRBs and ~10% lower for FPRBs (fig. 7). It is noted that emitted
concentrations of PCDD/Fs are more than two orders of magnitude times lower than
maximum limits set by legislation in all scenaria. The high compliance margin (low compliance
index) under baseline conditions (φ/μd= 0.009, φ/μCd, Tl= 0.12 and φ/μdm= 0.25) ensure ample
compliance under use of FRBs. The multifaceted impact of chlorines in regard to emissions of
volatile metals, PCDD/Fs and on corrosive chlorine deposits could be addressed by regulated
injection of activated carbon to the fluegases[95] right after the precalciner, where FRBs are
likely to be fired.

Halogen emitted concentrations are higher by about 16% than baseline when FRBs are used,
yet lower (by about 20%) under use of FPRBs (fig. 8a). This is due to lower chlorine charging
with FPRBs and to higher clinker levels. Emission rates follow the same trend. Particulate
emissions are higher by about 3% under FRBs but lower by ~2% under FPRBs. A similar

22
trend is observed for TOC emissions, i.e., they increase under use of FRBs but decrease
under use of FPRBs (fig. 8b). Regarding TSPs, the lower maximum limit set by legislation
under use of refuse derived fuels renders compliance easier, i.e., under use of any of FRBs
and FPRBs the ratio φ/μ is lower and the compliance margin larger than baseline (fig. 8c).
Emission rates are slightly higher under FPRBs due to the higher levels of clinker, which
require higher quantities of raw meal to be processed in the soil mill, leading to higher
emission rates of particulates.

Energy and environmental performance: Wind rose diagrams and snapshot evaluation
Evaluation can be readily perceived via a single picture depicting the relative values of all
important criteria included in fig. 3, as given by eqs 1-10: economic performance, product
quality and environmental performance as reflected by both compliance to emission standards
and actual emission rates to the environment. Such a comprehensive evaluation is depicted
via the wind rose, or radar graphs in figs 9-11. Figs 9a and 9b depict performance under
baseline conditions. Environmental performance is depicted in fig 9a, economic performance
in fig. 9b. The environmental evaluation of NOx and Hg emissions are shown in fig. 9b as
well. As expected, the ratios of emission rates (green line) take the value one (1) (fig. 9a).
The compliance index, i.e., the ratio φ/μ for NOx is at (φ/μ)NOx =0.78 and for Hg is (φ/μ)Hg =0.53.
The internal wind rose (magenta) refers to the compliance indices, i.e., the ratios (φ/μ). In line
with figs 6-8, the compliance indices are all below one (data included on the graph), reflecting
the conformance of emitted concentrations to the maximum limits of emitted concentrations
set by enacted legislation. Also, in accord with fig. 5, all scaled economic performance
indicators take the value one (1) under baseline conditions (fig. 9b). Figs 9c-9d depict the
performance when using FRB, dried at 1.5%: the ratio φ/μ for Hg is (φ/μ)Hg =0.65 and for NOx
(φ/μ)NOx =1.46. Emitted concentrations are within maximum limits set by legislation except
from NOx, yet emission rates are higher compared to baseline. Sulphur dioxide (SO2)
emission rates are lower than baseline. Regarding economic performance, fossil fuel cost
and non-biogenic CO2 emissions are at 80% of baseline. Fig. 10 presents the same
information for FRB at 10%w moisture and FRB 15%wt moisture level. As expected, FRB1.5%
features better economic and environmental performance. Fig. 11 depicts the windrose
evaluation diagram for FPRB blends. It is seen that in all scenaria (FPRB1.5%, FPRB10% and
FPRB15%) emitted concentrations of all regulated pollutants but NOx conform to maximum
limits, while emission rates of pollutants are equal or lower than under baseline conditions.
FPRB1.5% features the best economic performance and lowest emissions. As previously
stated, the issue of NOx compliance can be readily addressed by revamping of the deNOx
system via catalytic or non-catalytic deNOx system. Based on the above discussion it is
evident that the windrose diagrams allow prompt, yet holistic depiction of energy efficiency,

23
economic opportunities and costs, and also, of environmental repercussions from FRB use in
cement plants. Obtained via model simulations and used for licensing the specific cement
plant, the results are to be further validated via actual trials, with FRB obtained from source
separation programs in a large urban center located nearby (10 km) the cement plant and
pretreated (thermally dried) at a municipal biowaste facility.

5. DISCUSSION

Food waste has been investigated in existing literature as a solid fuel based on its
composition and heating value. The novelty of the present work lies in assessing dried
household food waste via simulations as an alternative fuel in cement kilns, based on actual
plant performance (clinker production level), operability (satisfaction of operational constraints)
atmospheric emissions, potential impact on product quality and process equipment. Using a
model founded on mass and enthalpy balances, the method showed that thermal substitution
of petcoke by 20% in a local plant implies lower production level by about 2%, higher volumes
of offgases and increased inclusions of alkalis and trace metals. Lower moisture resulted in
higher performance and improved emissions. In contrast, blends of FRB with paper detrita -a
biogenic fuel as well- improved plant performance and emissions. Limitations of the analysis
and results include the specific source (kitchen food residues, country and area of origin) and
composition, potential additives and blends. Food waste from agricultural production was not
included. Another limitation is the specific plant evaluated, which revealed the crucial role of
plant design and operational parameters. Further research can be directed towards assessing
FRBs from various sources worldwide. Identification of appropriate blends with other
renewable fuels (paper, biosludges, wood residues), custom tailored for specific plants
emerges as a key research issue.

suggestions, limitations, further implications and potential influence of limitations on the paper itself

6. CONCLUSIONS

Half a billion metric tonnes of coal and petcoke per year (2017) are consumed globally in
cement plants. Food residues (classified as non-dangerous wastes according to European
Commission Decision 2014/955) are projected globally at 1.5 billion tonnes per annum (tpa)
by year 2025. The purpose of the present work was to evaluate potential use of household
food residue biofuels (FRBs) as a substitute for fossil fuels in cement kilns. The major goals of

24
the evaluation were to assess the impact on plant operation and performance, and on product
quality and emissions as compared to conventional operation that uses fossil fuels (baseline
operation). Based on simulations of an actual dry-process plant, via a multidimensional model
which utilizes actual data as well, the analysis divulged that if dried at low moisture (<15% wt)
household FRBs are abundant, biogenic resources, which, could substitute fossil fuels in
cement kilns as renewable fuels. A method was presented for assessing on the basis of
operational efficiency and environmental performance of the cement plant and of the impact
on product quality as well. Applied via simulations in a case study, Besides Lower clinker
production level, lower greenhouse gas emissions, lower emissions of sulphur and volatile
metals (mercury) but increased chlorine presence and slightly higher emission rates for
several pollutants were revealed at 20% isothermal substitution of petcoke. Compliance to
environmental regulation was maintained for all pollutants but NOx. Use of that blends
consisting of 80%wt FRB and 20%wt paper residues (FPRB blends) is suggested since they
lead to improved performance and emissions. The feature increased clinker production by
~2%, ensuring emissions compliance (emitted concentrations below maximum limits set by
legislation) lower actual emission rates than baseline operation and no significant degradation
of product quality (small increase of inclusions). In practice, this means that in a medium scale
cement plant such as that of the case study, about 38 000 tpa of FRB could be used,
originating from about 170 000 tpa of household food wastes. A further implication of using
such blends is that lower effort for revamping the deNOx system, or lower levels of additional
urea are required for NOx compliance, compared to stand alone FRB utilization. Limitations of
the evaluation method include the steady state lumped model used. Limitations of the results
include the specific food waste investigated (composition and heating value) and the specific
cement plant analyzed, albeit the method can be applied to any plant and various food wastes
from differing countries with different characteristics. The method presented may also be
useful in evaluating agriculture FRBs and identifying superior blends with other low VS
biogenic residues, (high cellulose and lignine, e.g., saw dust, wood detrita). Such blends
could be tailor-made for cement plants under specific modes of operation (e.g., direct or
compound) or fit to process design, operating conditions (e.g., combustion excess air, use of
oxygen enrichment) and raw material characteristics (CaO yield from quarry lime CaCO 3).
Addressing successfully the main economic and ecological challenges, including high content
of chlorine and alkalis and impact on emissions and process equipment, such blends may lay
the ground towards higher substitution rates of fossil fuels by renewable fuels in cement kilns.
unleash the potential FRBs. For instance, 20% isothermal substitution of petcoke by FRB
dried at 1.5% wt moisture and paper (FPRB 1.5%) in cement plants at a global scale requires
104 million tonnes of FRB emanating from 500 million tonnes of foodwaste; 55% worldwide

25
substitution would devour the entire global production of foodwaste. Partial substitution of
coal by FRB in power plants is to be evaluated next along similar lines.

26
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Nomenclature
-1
A inverse of the pxp diagonal matrix of atomic weights A =
{diag (AW)j}, of the chemical elements in the
fuels, in the order C, H, O, S, N, Cl, P, Br, F, Si, Ca, Mg, Na, Fe, Al, Ti
a = vector giving the oxygen and nitrogen molar flows from total air molar flow in
T
the order of the flue gas vector constituents, a = (0, 0, 0.21, 0.79, 0,….0)
b specific energy requirement per t of clinker (Kcal/kg clinker) or TJ/t clinker,
bk   f
T

Cmxn matrix C =: DS A–1 W + η u1 (b-1 λΤ - σΤ)

cfg,i  M u1  =ith component of the vector M u1 =scalar in eq. 1, which gives the
mass flowrates of kiln fluegas i
cfg,i  1
 T T

= M DSA W  u 1 (   ) =vector multiplying the vector of fuel feeding
rates, f, in eq. 1
cp vector of heat capacities of the flue gases (cp1 = cpCO2, cp2 = cpH2O, cp3 = cpO2, cp4=
o
cpN2, cp5 = cpSO2, cp6 = cpHCl2, cp7 = cpP2O5 in kca/kg K
o
cp clinker clinker heat capacity in kca/kg K
o
cpf fuel heat capacity vector, in kca/kg K
o
cp rm raw meal heat capacity in kca/kg K
D acid detainment matrix by clinker (impact on fluegases) due to neutralization
T
e orthodiagonal vector e =[1, 1,…,1],
f fuel mass flowrate vector (fi in t /y),
g generation rate from raw meal and fuels, tpa, e.g., g SO2   SO2 r  m fg ,SO2
h air moisture, molal fraction
In nxn identity matrix
k total clinker production level, (t/y) = b-1 λΤ f
kA APCS adsorption rate constant
1
clinker adsorption rate constant, e.g. for SO2: k C  1.2 * 10
3
kC Nm /tn found from
baseline SO2 detainment factor, e.g. 1  exp(  k C r0 / V fg , 0 )  68% (Case study),
km = (b-1 λΤ - σΤ) f = raw meal clinker production (t/y) (not including fuel ash)
LHV lower heating value of fuels
mfg vector of the mass of flue gases produced = mass flows of (CO2, H2O,
O2, N2, SO2, HCl, P2O5). mfg = total mass flowrate of kiln flue gases
= m fg , SO  u 5 m fg ,0
T
m fg , SO fluegas mass flowrate of SO2
2 2

msm air total mass of soil mill air driven to the kiln/soil mill APCS
mfm air total mass of fuel mill air driven to the fuel mill APCS
Mmxm = diag {MW(CO2), MW(CO), MW(H2O), MW(O2), MW(N2), MW(NO), MW(N2O),
MW(SO2), MW(HCl), MW(P2O5), MW(HBr), MW(HF),…} =
diag {44, 28, 18, 32, 28, 30, 44, 64, 36.5, 142,...)
Mair =MW air = molecular weight of air = 28.84
M1 molecular weight of CO2 = ΜW(CO2) = 44
P pressure
R universal gas constant = 0.08206 (atm Lt) /(mol K)
r raw meal feed rate, r  (1  M 1 )   (  T

 ) f ,
T

Smxm stoichiometry matrix of fuel conversion to flue gas products

Sb part of stoichiometry matrix independent of excess air and oxygen enrichment
sa part of stoichiometry matrix independent of excess air and oxygen enrichment
s fraction of hot clinker enthalpy not recovered by secondary and tertiary air
T temperature, Tkiln:kiln, Ts:ambient, Tr:heat of reaction reference, Tp: preheater
th
ui i unit vector (0, 0, 0,…1, 0, 0)
3
Vfg kiln flue gas volumetric flowrate (Nm /h)
3
Vk sm kiln / soil mill gas volumetric flowrate (Nm /h)
th
Wrxn rxn matrix of net fuel weight composition, without the slag: the i
th
column of W is the % weight as received composition of the i fuel in the
th
combustible elements, multiplied by the net combustible content (1- σi) of the i
T
fuel, W j = (1- σi) % (C, H, O, S, N, Cl, P, Br, F, Si, Ca, Mg, Na, Fe, Al, Ti)
x pollutant concentration
xin APCS pollutant concentration in kiln/soil mill gases entering the APCS
yA  
= exp  k A / Vk , sm , APCS pollutant removal efficiency by the APCS
z vector dependent on excess air and oxygen enrichment (affects the stoichiometry
matrix, Smxm). 31
GREEK

αsm air drawn in the soil mill, kg per kg clinker

th
βi,r factor for i pollutant rate, originating from raw meal (produced in the kiln), t/t
th
βf vector of production rate of i pollutant from the fuels utilized, t/t
γA dimensionless APCS non-adsorption ratio,  A 
1 y
1  y0
  1
 exp k A Vk ,sm, 0  Vk ,sm
1

γC dimensionless kiln non-adsorption ratio  C  exp kC r0 / V fg ,0  r / V fg 
ΔH = enthalpy with respect to a reference level
δ power in law for effect of halogen hindrance on metal detainment by the clinker
δ’ power in law for effect of metal concentration on metal detainment by the clinker
O 2
oxygen enrichment, v% , O2 air vol composition = ( 20.95   O2 )%

ζ ζ is the ww fraction of raw meal in CaO, typically ζ is between 0.4 – 0.5.

-1
η η = ζ/56 (1-M1 ζ/56) , # kmols of CO2 produced via lime dissociation (reaction b) per kg of
clinker from raw meal, krm
θ fraction of flue gas cleaned in the kiln/soil mill APCS
krm annual clinker quantity originating from the raw meal
κ constant term in clinker level, independent of the fuel, given in eq. A11
κ vector independent of fuels, (eq. A12), element κi=marginal clinker production per t of fuel i
λ vector of lower heating values of the various fuels, 1,2,…,n, i.e. λT f is
the total (annual) thermal load of the kiln /precalciner system
μ dimensionless ratio of standardized pollutant emission to maximum allowed limit
ν dimensionless ratio in necessary and sufficient compliance condition 12
-1
ρ vector incorporating kiln fluegas split and pseudo air (θI + Mair ψ M) e that is component ρi=
[θ+ ψ (MW i / MW air)], e.g. ρ1 = θ+ψ (MW CO2/MW air), etc.
t
σi w% of noncombustible solids contained in the i fuel,
υ specific molal flue gas volume under P, T conditions = RT/P
φ dimensionless emission compliance ratio
ψ mass fraction of induced air draft (pseudo or intrusion air) with respect to kiln flue gas

Subscripts
0 refers to the baseline case with conventional fossil fuels
1 refers to CO2
l limit imposed by legislation

s standard conditions, 10% oxygen, dry, STP

M actual measurement, past the APCS, (offgas)

A APCS

C clinker

Superscripts
T
transpose of a vector or a matrix

Symbols
=:
equal by definition
[] molar concentration
Abbreviations
AF alternative fuel
APCS air pollution control system
FPRB food and paper residue biofuel
FRB food residue biofuel
LHV lower heating value
PCDD/F dibenzo-p-dioxins and dibenzo furans
SF standardization factor
SM Supplementary Material
tpa, tpd tones per annum, tones per day
TOC, TSP total organic carbon, total solid particulates

32
 FRB (kg / tn food residue)
265
260
255
(kg/tn food residue)

250
245
FRB

240
235
230
225
220
0.0% 5.0% 10.0% 15.0%
Moisture of FRB

FRB LHV(MJ/kg)
Energy for water evap.(MJ / kg FRB)
Energy for water evap. (MJ/ kg food residue)

18
16
14
Energy (Mj/kg)

12
10
8
6
4
2
0
0.0% 5.0% 10.0% 15.0%
Moisture of FRB

Fig. 1. Food residue biofuel (FRB) yield of food residues (food waste) and associated drying
energy and energy content (LHV) of produced FRB.

33
 Exhaust
900kWe gases
Hot Cooled
fluegases fluegases
Rotating
Natural NG or diesel drum. Cyclone
gas or electricity Direct heat decanter
diesel generator convection.
FRB
Food
residues 5 tpd
20 tpd 1.5% Ash
75% moist. moist.

Cooled
Hot fluegases Air and
Hot Air moisture
fluegases Heat
Air heat convection, Condenser
exchanger Drier belt
Make up Food FRB
Air residues Water,
75% moist. volatiles

Condenser
Food
residues Water,
Cooled volatiles
Exhaust
fluegases Hot Oil
Hot
FRB
fluegases Oil (or
Steam)
heat
exchanger Cooled FRB
Oil
Make up Archimedean screw, mixer /
oil or Food drier / heat exchanger featuring
water residues two counter rotating axes with
heated paddles and axial
circulation of heating agent.

Fig. 2. Flowdiagrams of drying processes for producing FRBs. Top: Direct drying in rotating drum
using the fluegases of a diesel generator. Middle: air drying via heat convection to the FRB on a drier
belt. Bottom: drying via heat conduction (oil or steam circulating in the counter rotating axes of the
Archimedean screws with paddles).

34
 Plant Product
operability: Feasibility of use quality
Heat rating, of biogenic fuels within
blower limit in cement plants specs

Direct economic
benefits.

Economic: Economic:
clinker production level. CO2 eq pollution rights.

Economic: Economic:
Income from gate fees & Product quality/price due to
Reduced fossil fuel inclusions of alkalis and
Sustainability trace metals.
costs. assessment of
renewable
fuels in
cement plants Environmental:
Environmental:
Pollutant emissions Reduced greenhouse gas
(a) compliance kiln emissions,
(b) actual emissions rates. (lower non-biogenic CO2 eq,
t/t clinker).

Environmental: Environmental:
Resource preservation. Prevention of biowaste
(Substitution of depleting disposal (high BOD leachates
fossil fuels). & high GHG emissions).

Emissions compliance.
Social acceptance.
Green labeling of
cement product &
indirect economic benefits.

Fig. 3. Evaluation of food residue biofuels for substituting fossil fuels in cement plants,
including economic performance, product quality and environmental performance

35
 Higher emissions of
PCDD/Fs

Higher fuel Combustible

sulphur chlorine Higher emissions of
Hg, Cd and Tl

FRB
chlorine Increased corrosive
deposits of chlorine

Lower fuel Non

sulphur or combustible Higher inclusions of
lower chlorine alkalis and chlorine in
feedrate of cement.
petcoke
Higher inclusions of
volatile metals, mainly
Hg, in cement.

Fig. 4. The fate of FRB chlorine in cement plants and consequences when substituting FRBs for
petcoke.

36
 70 000
biofuel, (t/y) 60 000
50 000
40 000
30 000
20 000
10 000
0

5%

%
%

%
5%

lin

10

15
10

15

1.
1.

se

B
B

B
ba
B

R
FR

FR

R
FR

(a)

FP

FP
FP
clinker, tn/y Non Biogenic fuel CO2 (gr/tn clinker) Vksm (Nm3/h)

1 550 000 800 000

(gr/tn clinker), Vksm (Nm3/h)

700 000

Non Biogenic fuel CO2,

1 500 000
600 000
clinker, (t/y)

1 450 000
500 000
1 400 000
400 000
324 213
1 350 000 276 103 277 288 278 120 266 847 267 654 268 217 300 000

1 300 000 200 000

e

5%

%
%

%
5%

lin

10

15
10

15

1.
1.

se

B
B

B
ba
B

(b)
R

R
FR

FR

R
FR

FP

FP
FP

Ratio of combustible chlorines Inclusions ratio (Na+K)/t clinker

Inclusions ratio (nonvol metals)/t clinker Inclusions ratio (Cd,Tl)/t clinker
Inclusions ratio (Hg)/t clinker ratio of noncombustible chlorines

1.30
1.25
Hydrogen halides

1.20
Inclusions,

1.15
1.10
1.05
1.00
0.95
0.90
0.85
e
5%

5%

%
%

lin

10

15
10

15

1.
1.

se

B
B

ba

B
B

FR

FR

R
FR

(c)
FP

FP
FP

6
Fig. 5. Case study: Economic performance of a 1.5 x 10 tpa dry clinker facility under 20%
thermal substitution of petcoke by food residue biofuels (FRBs) or food (80%w) and paper
(20%w) residue biofuels (FPRBs) at various moisture levels. Baseline: fossil fuel operation with
70% petcoke and 30% coal, thermal contribution (a) FRB and FPRB federates (b) Performance
criteria: clinker production level, main blower load (V k.sm) and nonbiogenic CO2 emissions per
tonne clinker (c) Combustible chlorines, incombustible chlorines in process equipment and pipes
and product quality assessed by inclusions of alkalis and leachable metals per tonne clinker
(ratios with respect to baseline conditions).

37
 moffg,NOx/moffg,NOx,0 φ NOx / μ NOx
xl,NOx, (mg/Nm3) xs,NOx, (mg/Nm3)

1.6 900
1.4 800

xl.ΝΟx, xs.ΝΟx
700
moffg,NOx/moffg,NOx,0
1.2

(mg/m3)
1.0 600
φNOx / μNOx,

500
0.8
400
0.6 300
0.4 200
0.2 100
0.0 0

e
5%

FP .5%

%
FR %

FP elin

10

15
10

15
1.

1
s

B
B

ba

B
B

(a)
FR

R
FR

FP
moffg,m,Hg/moffg,m,Hg,0 φ Hg / μHg
xl,Hg (mg/Nm3) xs,Hg, (mg/Nm3)

1.4 0.06
moffg,,Hg/moffg,Hg,0

1.2 0.05

xl.Hg, xs.Hg
φHg/μHg,

1.0

(mg/m )
0.04

3
0.8
0.03
0.6
0.4 0.02
0.2 0.01
0.0 0.00
e
5%

5%

%
%

lin

10

15
10

15

1.
1.

se

B
B

ba

B
B

(b)
FR

FR

R
FR

FP

FP
FP

moffg,SO2/moffg,SO2,0 φSO2 / μSO2

xl,SO2, (mg/Nm3) xs,SO2, (mg/Nm3)

1.20 60
moffg,SO2/moffg,SO2,0

1.00 50
xl,SO2, xso,SO2
φSO2/ μSO2,

(mg/m )

0.80 40
3

0.60 30
0.40 20
0.20 10
0.00 0
e
5%

5%

%
%

lin

10

15
10

15

1.
1.

se

B
B

ba

B
B

FR

FR

R
FR

FP

FP
FP

(c)

Fig. 6. Case study: 20% isothermal substitution of petcoke by FRB and FPRB at various
moisture levels. Environmental performance: NOX, Hg and SO2. (A) Compliance to
maximum allowed limits is assessed via the compliance margin ratio with respect to
baseline operation, (φ/μ): compliance is ensured if and only if φ/μ <1. (B) ratio of actual
offgas emission rates (emitted pollutant mass/s) with respect to baseline conditions,
moffg/moffg,0.

38
 moffg,d/moffg,d,0 φd / μd xs,d, (ng/Nm3) xl,d, (ng/Nm3)

1.15 0.12

xl.d, xs.d (ng/m3)

1.10 0.10
moffg,d/moffg,d,0

1.05

φ d/ μ d,
0.08
1.00
0.06
0.95
0.04
0.90
0.85 0.02

0.80 0.00

e
5%

5%

%
%

lin

10

15
10

15

1.
1.

se

B
B

ba

B
B

FR

FR

R
FR

R
(a)

FP

FP
FP

moffg,m,Cd, Tl/moffg,m,Cd, Tl,0 φm, Cd, Tl / μm, Cd, Tl

xl,m,Cd, Tl (mg/Nm3) xs,Cd,Tl, (mg/Nm3)
1.4 0.06
moffg,Cd,Tl/moffg,Cd,Tl,0

1.2
φm, Cd, Tl/ μm,Cd,Tl ,

0.05

xs.m,Cd,Tl (mg/m 3)
1.0
0.04

xl.m,Cd,Tl,
0.8
0.03
0.6
0.02
0.4
0.2 0.01
0.0 0.00
e
5%

5%

%
%

lin

10

15
10

15

1.
1.

se

B
B

ba

B
B

FR

FR

R
FR

FP

FP
FP

(b)

moffg,m/moffg,m,0 φm / μm
xl,m (mg/Nm3) xs,m, (mg/Nm3)
1.4 0.50
xl.m, xs.m (mg/m )
3

1.2 0.45
moffg,m/moffg,m,0

0.40
φm / μm ,

1.0 0.35
0.8 0.30
0.25
0.6 0.20
0.4 0.15
0.10
0.2 0.05
0.0 0.00
e
5%

5%

%
%

lin

10

15
10

15

1.
1.

se

B
B

ba

B
B

FR

FR

R
FR

FP

FP
FP

(c)

Fig. 7. Case study: 20% isothermal substitution of petcoke by FRB and FPRB at various
moisture levels. Environmental performance: PCDD/Fs, volatile metals (Cd, Tl) and
nonvolatile metals.

39
 moffg,HX/moffg,HX,0 φHX / μΗΧ
xl,HX, (mg/Nm3) xs,HX, (mg/Nm3)

moffg,HX/moffg,HX,0 1.8 10
1.6 9

xl,HX, xso,HX,
φHX / μHX,

1.4 8

(mg/m3)
1.2 7
1.0 6
5
0.8 4
0.6 3
0.4 2
0.2 1
0.0 0

e
5%

5%

%
%

lin

10

15
10

15

1.
1.

se

B
B

ba

B
B

FR

FR

R
FR

FP

FP
FP
(a)

moffg,TOC/moffg,TOC,0 φ TOC / μ TOC

xl,TOC, (mg/Nm3) xs,TOC, (mg/Nm3)
1.10 12
1.05

xl.TOC, xs.TOC (mg/m3)

10
moffg,TOC/moffg,TOC,0

1.00
φTOC/ μTOC,

8
0.95
0.90 6
0.85
4
0.80
2
0.75
0.70 0
e
5%

5%

%
%

lin

10

15
10

15

1.
1.

se

B
B

ba

B
B

FR

FR

R
FR

FP

FP
FP

(b)

moffg,TSP/moffg,TSP,0 φTSP / μTSP

xl,TSP, (mg/Nm3) xs,TSP, (mg/Nm3)

1.20 35
30
xl.TSP, xs.TSP (mg/m3)
moffg,TSP/moffg,TSP,0

1.00
25
φTSP/ μTSP,

0.80
20
0.60
15
0.40
10
0.20 5
0.00 0
5%

%
%

5%
e
lin

10

15
10

15
1.

1.
se

B
B

B
B

B
ba

R
FR

FR
FR

FP

FP

(c)
FP

Fig. 8. Case study: 20% isothermal substitution of petcoke by FRB and FPRB at various
moisture levels. Environmental performance: HX, TOC and TSP.

40
 moffg/moffg,0 φ/μ Baseline Baseline

SO2
clinker level
2
FRB drying energy / 2
Hg HX offgas volume
LHV
1.000
1 1 1.000
0.53 0.38 fossil fuel cost Hg, φ/μ
Cd, Tl 0.23 TOC 1.000
0.533
0.10 0 0.75 0
0.090.01 1.000 0.779
0.75 nb CO2 NOx, φ/μ
1.000 1.000
nv metals 0.78 TSP 1.000
kiln Cl nv metal inclusions

PCDD/Fs NOx Na+K inclusions

moffg/moffg,0 φ/μ FRB 1.5% FRB 1.5%

SO2
2.0 clinker level
FRB drying energy /
2.0
Hg 1.5 HX offgas volume
LHV 1.5
1.0
1.0
fossil fuel cost Hg, φ/μ
Cd, Tl
0.5
TOC 0.5
0.0 0.0
nb CO2 NOx, φ/μ

nv metals TSP
kiln Cl nv metal inclusions

PCDD/Fs NOx Na+K inclusions

Fig. 9. Wind rose (radar) graphs depicting economic and environmental performance of FRBs and
FPRBs at 20% thermal substitution of petcoke, compared to baseline operation. Shown in fig. 9:
baseline operation (top) and operation under use of FRB with 1.5% moisture (bottom). Economic
performance (blue line, right column graphs) includes, production (clinker) level, ratio of offgas
volumetric flowrates (must be lower than main blower capacity) drying energy compared to energy
content (LHV) of the renewable biofuel, savings from substituted fossil fuels, savings from
greenhouse gas pollution rights (non-biogenic CO2), product quality as reflected by inclusions of
volatile and leachable metals and alkalis. Relative presence of chlorines in process equipment, pipes
and ducts is also depicted. Environmental performance (left column) is assessed by the ratio of
compliance factors with respect to baseline operation, φ/μ, which must be lower than one, φ/μ <1 for
compliance (magenta line) and by the ratio of actual emission rates, moffg/moffg,0 (green line) which
reflects the actual burden to the environment.

41
 moffg/moffg,0 φ/μ FRB 10% FRB 10%
SO2 clinker level
2.0
FRB drying 2.0
Hg HX offgas volume
1.5 energy / LHV 1.5
1.0 1.0
fossil fuel cost Hg, φ/μ
0.5
0.5
Cd, Tl TOC 0.0
0.0
nb CO2 NOx, φ/μ

nv metal
nv metals TSP kiln Cl
inclusions
Na+K inclusions
PCDD/Fs NOx

moffg/moffg,0 φ/μ FRB 15% FRB 15%

SO2 clinker level
2.0
2.0 FRB drying energy /
offgas volume
Hg HX LHV 1.5
1.5
1.0
1.0 fossil fuel cost Hg, φ/μ
0.5
0.5
Cd, Tl TOC 0.0

0.0
nb CO2 NOx, φ/μ

nv metals TSP kiln Cl nv metal inclusions

Na+K inclusions
PCDD/Fs NOx

Fig. 10. Wind rose (radar) graphs depicting economic and environmental performance of FRBs for
20% thermal substitution of petcoke, compared to baseline operation: use of FRB with 10%
moisture (top) and use of FRB with 15% moisture (bottom).

42
 moffg/moffg,0 φ/μ FPRB 1.5% FPRB 1.5%
clinker level
SO2 2.0
2.0 FRB drying energy /
offgas volume
LHV 1.5
Hg 1.5 HX
1.0
1.0 fossil fuel cost 0.5
Hg, φ/μ

0.5 0.0
Cd, Tl TOC
0.0
nb CO2 NOx, φ/μ

nv metals TSP kiln Cl nv metal inclusions

Na+K inclusions
PCDD/Fs NOx

moffg/moffg,0 φ/μ FPRB 10% FPRB 10%

SO2 clinker level
2.0 2.0
FRB drying energy /
offgas volume
Hg 1.5 HX LHV 1.5

1.0
1.0
fossil fuel cost 0.5
Hg, φ/μ
0.5
Cd, Tl TOC 0.0
0.0
nb CO2 NOx, φ/μ

nv metals TSP
kiln Cl nv metal inclusions

Na+K inclusions
PCDD/Fs NOx

moffg/moffg,0 φ/μ FPRB 15% FPRB 15%

SO2 clinker level
2.0 2.0
FRB drying energy /
Hg HX offgas volume
1.5 LHV 1.5

1.0 1.0
fossil fuel cost Hg, φ/μ
0.5 0.5
Cd, Tl TOC
0.0 0.0

nb CO2 NOx, φ/μ

nv metals TSP
kiln Cl nv metal inclusions

PCDD/Fs NOx Na+K inclusions

Fig. 11. Wind rose (radar) graphs depicting the superior economic and environmental performance
of FPRBs (80%w FRB and 20%w paper residues) for 20% thermal substitution of petcoke,
compared to baseline operation. The top blend FPRB1.5% (1.5%w moisture) features enhanced
economic performance (slightly higher clinker level than baseline) without increasing emissions
(apart from NOx emissions which can be improved by revamping the deNOx system) and without
impairing product quality.

43
APPENDIX

A. Cement Plant Model and constants (independent of fuel feedrates) in eqs 1-5.

Combustion fluegases mass flowrates

MDSA 1W f (A1)
Kiln fluegas mass
flowrates 
m fg  M DSA 1W f  u1   (   ) f  T T
 (A2)

T
Fuel ash in clinker σ f (A3)

Lime dissociation CO2 mCO 2 , lime  M 1   (   ) f  T T

 M 1  MWCO2  44 (A4)

  M 1 
 1   , (A5)
MWCaO  MWCaO 
Nonbiogenic CO2
mass flowrate 
M 1  M 1 (   )  u1 MDSA 1W B f
T T T
 (A6)

B = diagonal matrix with ii diagonal element equal to 1 if i corresponds to non-

biogenic fuel and 0 to biogenic fuel

Raw meal r  (1  M 1 )   (   ) f  T T
 (A7)
Offgas species’
volumetric flowrates  1 1

V k , sm   I  M air a e M C f  M air a sm (1  M 1 )   (   ) f (A8)
T T T
 
Vk , sm  v  v f
T
Overall offgas

vol. flowrate 
v   1  M air  sm (1  M 1 )
1

     
1
DSA W  1  M air  sm (1  M 1 ) (   )
1
T T T T
v (A9)

k    f
T
Clinker level (A10)
  c p rm (1  M 1 )(Tr  Ts )  (T p  Tr )c p1 M 1  sc p clin ker (Tki ln  Tr ) 1 L (A11)
 T  c p rm (1  M 1 )(Tr  Ts )  (T p  Tr )c p1 M 1  sc p clin ker (Tki ln  Tr ) 1 x
T
{  (Tr  Ts )c pf  c p rm (1  M 1 ) (Tr  Ts )
T T

 (T p  Tr )c p MDSA 1W  (T p  Tr )c p1 M 1 }

T T
(A12)

Model calculations performed in EXCEL software via the function MMULT.

B. Emission rates.
xin, APCS 1  y A Vk , sm  Vk , sm  V
1  y A,0  Vk ,sm,0 1 k ,sm   xl SF0 k ,sm
moffg xin, APCS V
 
moffg,0 xin, APCS ,0 1  y A,0 Vk , sm,0 xin, APCS ,0 Vk , sm,0 xl ,0 SF Vk , sm,0
(B1)

44
C. Presence of chlorines in equipment and APCS
As already discussed at high temperatures, a fraction of chlorine depending on the
concentration of sulphur is in the form of incombustible chlorines. Assuming that combustible
chlorines follow first order kinetics with respect to concentrations of SO2 in the
kiln/precalaciner/preheater, it follows that


m fg , HCl  g HCl exp  k C r / V fg exp  k HCl ,SO2 / x fg ,SO2  (C1)

The constant k HCL ( SO2 ) is found from baseline conditions,

k HCl ,SO2   x fg ,SO2 , 0 ln m fg , HCl , 0 g HCl , 0   k C r0 / V fg , 0  (C2)

and assuming m fg , HCl , 0 g HCl , 0  2 / 5 [52] it follows that k HCL ( SO2 )   x fg ,SO2 ,0 ln 2 / 5  kC r0 / V fg ,0 .  
Then, from eq. C2 it follows that

[ HX ] fg x fg , HCl g HCl V fg , 0
   C S (C3)
[ HX ] fg , 0 x fg , HCl , 0 g HCl , 0 V fg

which is eq. 10a with

 S  exp k HCl , SO x fg , SO 0  x fg.SO 0 

2 2 2
(C4).

If [Cl]fg, denotes the molar concentration of alkali chlorines in the fluegases, then taking into
account the detainment by the clinker in the kiln, it follows from the chlorine mass balance that


m fg ,Cl  g HCl exp  k C r / V fg   g HCl exp  k C r / V fg exp  k HCl , SO2 / x fg , SO2  (C5)

or
 
m fg ,Cl  g HCl exp  k C r / V fg  1  exp  k HCl , SO2 / x fg , SO2  (C6)

Then,
[Cl ] fg m fg ,Cl  
g HCl exp  k C r / V fg  1  exp  k HCl , SO2 / x SO2  V fg ,0 g HCl V fg ,0
   C S
[Cl ] fg ,0 m fg ,Cl ,0 g HCl ,0 exp  k C r0 / V fg ,0 1  exp  k HCl , SO2 / x SO2 ,0  V fg g HCl ,0 V fg
or
[Cl ] fg g HCl V fg , 0
 C S (C7)
[Cl ] fg , 0 g HCl , 0 V fg

45
which is equation 10c with

S 
1  exp  k HCl , SO2 / x SO2 
1  exp  k HCl , SO2 / x SO2 ,0  (C8).

Consequentlym the ratio of chlorine concentrations in APCS is given by eq. 10b,

x HCi ,n, APCS g HCi Vk ,sm,0
  C S (C9)
x HCl ,in, APCS ,0 g HCi , 0 Vk ,sm
g HX   HX r  m fg , HX  (C10)


 HX  r0 1  xs , HX ,0Vk ,sm,0

exp k C r0 / V fg , 0 exp k HCl ,SO2 / x fg ,SO2 , 0 m 
 (C11)
SF0 (1  y A, HX , 0 )
fgHX , 0 
 
xs,HCl ,0  2.25mg / Nm3 , xl ,HCl ,0  xl ,HCl  10mg / Nm3 xl , HF ,0  xl , HF  1mg / Nm3 (C12).

46
Table 1. Main constituents of food waste

Fruits and Pasta, rice, bread, Meat, fish, eggs Dairy products Drinks Meals Other food Other food Other
vegetables bakery, cereals (biodegradables)
54-71 1.5-10.2 2.4-4.5 0.3-1 0.3-0.4 0.2-1.5 - 23-30 -

Table 2. Characteristics of food waste energy valorization technologies

Energy content Self-sustained: Electricity via combined Byproducts and residues
of biofuel Energy content cycle
product (kWh / of biofuel
kg/FW) product (kWh /
kg/FW)
Anaerobic digestion 545 455 150 Digestate – needs stabilization (aerobic – composting)
Drying for use as solid 1035 582 145 Ashes (noncombustibles) incorporated in cement
biofuel (FRB) matrix
Plasma Gasification 950 550 220 Complete disintegration of organics, Very low amounts
(syngas) of vitrified solid residues from inorganics (recyclable as
inerts).
Mass burn in WTE plants 582 582 145 Bottom and flying ash to be disposed in ash monofils
(FW)

47
Table 3. Ultimate analysis (weight fraction) of fossil fuels and food residue biofuels
[85] [86]
Coal PC (as Food residues Food resi- Food res- Food resi- Food resi- Food resi- Paper
[48] , [84] [66] [50] [ 66] [83] [49] [85]-[86]
as received received) (dry basis) dues (d.b.) idues (d.b.) dues (d.b.) dues(d.b.) dues (d.b.)
C 0.6696 0,8809 0.4557 0.4826 0.480 0.480 0.389 0.484 0.421
H 0.0452 0,0350 0.0676 0.0568 0.064 0.064 0.040 0.063 0.056
O 0.1093 0,0130 0.3619 0.4202 0.376 0.376 0.513 0.342 0.381
S 0.0031 0,0430 0.0001 0.0039 0.004 0.004 0.001 0.002 0.005
N 0.0172 0,0230 0.0261 0.0255 0.026 0.026 0.026 0.023 0.005
Cl 0.0002 0 0.0088 0 0 0 0.001 0.0055 0.002
P 0.0000 0,0001 0 0 0 0 0 0 0.000
0.1556 0.0050
Ash 0.0828 0.011 0.05 0.05 0.030 0.081 0.130
0.0763 0.005 0.075
moisture 0.790 0.770 0.750 0.650 0.609 0.778
LHV 6146 8342 668 4325 1 631.3 4330.1 3500
(kcal/kg) 4919 4169.2
- - -
Cd, ppm 0.11 - 0.7295 n.d. 0.096
- - -
Tl, ppm 0.00 - 0.1000 n.d. 0.00
- - -
Hg, ppm 0.11 - 0.0290 n.d. 0.00
- - -
As , ppm 3.30 - 2.00 <2,00 0.00
- - -
Pb, ppm 8.58 15 - 12,1 2.40
- - -
Cr , ppm 21.58 25 4.07 4.25 0.00
- - -
Co, ppm 5.52 30 2 2.13 0.00
- - -
Cu , ppm 13.24 - 6.79 7.19 29.90
- - -
Mn , ppm 49.04 50 21.5 21.4 0.00
- - -
Ni , ppm 13.61 255 5.9 6.05 1.50
- - -
V, ppm 0.00 250 2.00 <2,00 0.00
- - -
Zn, ppm 15.57 - 19.0 20.9 3.70
- - -
F, ppm 0.00 - <1000 0.00
- - -
K, ppm 1 845 70 16000 16000 14 400
- - -
Na, ppm 868.00 340 4100 4100 89.00
Non vol. - - - -
metals 261 620 53

48
Case Study: Table 4. Cement plant operating parameters (compound operation)

Cement Plant Parameters η= θ=0.85 ζ =0.43 αsm=1.66 ψ= 0.15 E= 20% ε=0

0.0116

49
*Clean Version of revised manuscript
Click here to view linked References

1
2
3
4
5
6
7 Renewable energy in cement manufacturing: A quantitative assessment of energy and
8 environmental efficiency of food residue biofuels
9
10
11
12
13
14
15 by
16
17 Aristeides Tsiligiannis
18
19
20 and
21
22
23 Christos Tsiliyannis#
24
25 ANION Environmental Ltd
26
27 26 Lykoudi Str., Athens GR 11141
28 Tel. / fax: 0030-210-2285650
29
30 email: anion@otenet.gr
31
32
33
34
35
36
37 Submitted for publication to:
38
39
40 Renewable and Sustainable Energy Reviews
41
42
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48
August 28, 2018
49
50 Revised: February 15, 2019
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52
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64 1
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 ABSTRACT
1
2
3 The present work investigates solid biofuel, derived from household food waste (food residue
4
5 biofuel, FRB) as a potential bioenergy source in cement manufacturing. Up-to-date
6
7 investigations of household food waste as a solid fuel focused on composition and heating
8 value, yet no results are available regarding impact on plant efficiency and emissions upon
9
10 utilization. A multidimensional model based on fundamental principles (mass and enthalpy
11
12 balances) is used together with actual data from fossil fuel operation to identify and
13 quantitatively asses the impacts on plant performance, product quality and atmospheric
14
15 emissions. Τhe energy needed to prepare low moisture FRBs is determined and suitable
16
17 processes are singled out. Key issues of cement plant operation are identified and
18 quantitatively assessed via simulation in an actual dry-process plant, when FRBs substitute
19
20 20% of thermal energy (provided by petcoke). The facility utilizes 1.65x105 tpa of fossil fuels
21
22 to produce 1.5x106 tpa clinker. It is found that energy efficiency falls and clinker production
23 diminishes by about 0.5t clinker/t FRB. Refractory thermal rating and main blower capacity
24
25 constraints remain satisfied. Non-biogenic green-house-gas emissions are reduced by ~60
26
27 kg/t clinker. Emitted concentrations slightly increase for several pollutants, mainly nitrogen
28 oxides (NOx) hydrogen chloride (HCl) and metals; they decrease for sulphur dioxide (SO2) and
29
30 particulates. Maximum emission limits are observed for all regulated pollutants but NOx,.
31
32 Incombustible chlorine and inclusions of alkalis in cement increase by ~9%. To reap the
33 bioenergy benefits and mitigate impacts, blends of FRB (~80%wt) with paper residues
34
35 (~20%wt) are investigated. Conforming to plant operational constraints and product
36
37 specifications, the blends ensure production level, environmental compliance and reduced
38
emission rates. The results direct towards customer-tailored FRB blends with lignocellulosic
39
40 residues, that best suit the design, specific quarry raw materials, operating conditions and
41
42 individual parameters of the cement plant towards more sustainable cement manufacturing.
43
44
45
46
47 Key words: Bioenergy; biofuels; renewable fuels; cement manufacturing; household food
48
waste; fossil fuel substitution.
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64 2
65
 INTRODUCTION
1
2
3 Rated at 2 MWhe/capita [1], annual electric energy consumption is rising globally at a fast pace,
4
5 as energy needs grow with increasing population. Cement and coal power plants are the
6
7 prime consumers of solid fossil fuels. Coal fired power plants supply 37% of global electricity
8 (~2500 gigawats)[2] using about 9 billion metric tonnes of coal[2]. Energy consumption for
9
10 manufacturing energy intensive products, such as cement and steel, grows steadily.
11
12 Agriculture uses up higher amounts of energy every year. Global energy consumption
13 increases also due to rising standards of living worldwide, to growing transport and to
14
15 escalating use of energy consuming devices in every-day life. Products that consume energy
16
17 in the use phase include vehicles, electric appliances and rechargeable electronic devices
18 such as data storing and communication units (tablets, cellular phones, etc). Attributed to
19
20 fossil fuels, the growing threat to sustainability due to climate change has compelled the Paris
21
22 Agreement, which aims at combating fossil carbon emissions and restricting global
23
temperature increase below 2°C by 2050[3]. Visions of energy metamorphosis via global
24
25 phasing–out of fossil fuels and 100% renewable energy supply are expressed and supported.
26
27 Biomass is regarded as an essential component in the transition to a 100% renewable
28
29
society[4]. In the practical arena, biofuels and bioenergy are already a commercial reality
30 towards the 2050 climate goals. Cyclic economy[5] and industrial symbiosis[6] contribute to
31
32 sustainability by using urban, agricultural and industrial residues and byproducts, including
33
34 biowastes, as raw materials in manufacturing, or as energy sources. In contrast to energy
35 crops targeted to biofuel/bioenergy production, biowastes are not competitive to food crops
36
37 when used as biofuels. Consequently, use of solid biofuels, produced from food waste, may
38
39 be crucial towards a sustainable low carbon economy, by reducing the dependence on
40 depleting fossil fuels without restricting food produce. The scope of the present work is to
41
42 investigate use of household food waste (FW) as an alternative solid fuel in cement plants,
43
44 partly substituting for fossil fuels.
45
46
47 Estimated at 1.3 billion tonnes per annum (tpa) in 2012[7], food residues are escalating rapidly
48
49 at a global scale. More than one third of the world’s food production is discarded[7,8], mostly
50 from urban centers. The loss fraction is higher for developed countries[9]. Food waste or food
51
52 loss from the entire food supply chain (agriculture, food processing industries, households and
53
54 hospitality sector) is at 0.49 kg/capita day[8] in the EU. Food residues are expected to rise in
55 Europe to 126 million tonnes by 2020 and in Asia from 278 to 416 million tonnes by 2025 [8,9].
56
57 Household food residues (precooked and leftover) range at 0.22kg/capita day[8] in the EU and
58
59 consist the wet fraction of municipal solid waste (moisture content about 70-75%).
60
61
62
63
64 3
65
 Practical use of solid, food residue biofuels (FRBs) faces serious challenges. (a) The high
1
2 moisture content of food residues (about 70-75%) casts doubts on self-sustained combustion,
3 rendering pretreatment and water removal a sine-qua-non[10], or directing towards anaerobic
4
[9-11,12] [13]
5 digestion and biogas production or to production of biodiesel , or production of
6 [10, 13,14]
7 bioplastics or bulk chemicals via green chemistry . (b) Logistics costs for mobilization
8 of biogenic feedstock, and cost reduction along its supply chain and (c) Favorable reception
9
10 by flexible production facilities, which can use a variety of alternative solid biofuels as
11
12 substitutes of coal or petcoke. In regard to (a) drying may provide a low moisture FRB;
13 energy is required for this purpose. Regarding (b) mobilization and supply chain efficiency can
14
15 be addressed through separation of food residues at source and use of transfer station
16
17 systems as for municipal wastes. The challenge is more intricate regarding the third issue.
18 Licensing and widespread acceptance of biofuels and particularly of solid biofuels derived
19
20 from biomass and solid organic residues, including FRBs, touch on key issues of combustor
21
22 and plant performance, of environmental compliance and of conformance of end-products to
23 quality specifications (e.g., cement mineralogy and properties). It is of interest to develop
24
25 mechanisms and methods identifying appropriate biofuels, or biofuel blends for specific
26
27 industries and individual plants. To this end, several key aspects must be taken into account
28 for biogenic feedstocks with limited practical applications thus far, such as FRBs. They
29
30 include process design of existing plants and fuel utilization methods, energy efficiency,
31
32 characteristics of the combustion/energy production system and impact on process
33 equipment, in association with energy integration, mass recycle and recircuiting. The impact
34
35 on air-pollution control efficiency and final (offgas) emissions must also be evaluated.
36
37
38
39 Low cost, well established methods for preparation of solid FRBs from household food waste
40 (Table 1) are to be assessed herein. The aim is to partially substitute thermal energy from sold
41
42 fossil fuels in large-scale applications and particularly in cement plants, where substitution of
43 [33, 34]
44 fossil fuels by alternative fuels, including non-renewable fuels, is reaching 14% globally .
45
The evaluation method could be general enough to apply to the dominant user of solid fossil
46
47 fuels globally, namely coal power plants as well. As one of the largest fossil fuel consumers,
48 [15]
49 cement manufacturing averages around 0.85 Mcal/t clinker . With the global cement
50
production at 4.2 x109 metric tpa (50% of which in China) [16] this amounts to about 5 x 108
51
52 tpa, i.e., half a billion tpa of fossil fuels globally. A novel feature of the present attempt in
53
54 comparison to previous works is that it aims beyond assessing the fuel per se, in terms of its
55
composition and heating value, or merely in terms of combustion stoichiometry[17]. Instead,
56
57 based on fundamental principles and on actual data obtained under fossil fuel operation, it will
58
59 attempt to assess cement plant performance when FRBs are used. Operating conditions to
60
61
62
63
64 4
65
 be investigated will include compound operation (fig. F1 in the Supplementary material in the
1
2 Web) that is when the soil mill is on for preparation of the raw-meal and the soil mill air is
3 cleaned together with the majority of the kiln fluegases in the air pollution control system
4
5 (APCS). (The raw meal is the inert raw material originating from lime quarries, which is
6
7 ground and fed to the cement kiln, where it is transformed to clinker through calcination, at
8 temperatures exceeding 1450o C). A multidimensional model[18,19] will be employed to this
9
10 purpose, based on the combined mass and enthalpy balance of the kiln, which enables
11
12 simulation of concurrent utilization of multiple biofuels and fossil fuels and provides more
13 accurate results than models based solely on stoichiometry. Expressed in linear algebraic
14
15 form (i.e. in terms of vectors and matrices) the model decouples the impact of feeding rates of
16
17 the various fuels in a linear fashion. It also isolates the impact of combustion air (excess air,
18 oxygen enrichment, air moisture) allowing explicit evaluation of their impact if used for kiln
19
20 control. Enabling explicit utilization of hard core data from actual operation under fossil fuels,
21
22 the model provides a holistic quantitative description, reflecting production, capacity
23 constraints, atmospheric emissions and environmental compliance, as well as inclusions of
24
25 chlorines, alkalis and metals in the clinker and impact on cement quality. With the vector of
26
27 feed rates, f, as the sought variable, it enables direct application of the vast array of
28 optimization methods towards determining superior combinations of renewable fuel blends.
29
30 Section 2 reviews the status of food waste treatment; section 3 presents the evaluation
31
32 method and framework, followed by quantitative assessment via a Case study in section 4.
33
34
35
36
37 2. REVIEW OF UP-TO-DATE MANAGEMENT OF FOOD RESIDUES AND
38 PRETREATMENT TECHNOLOGIES
39
40
41
42 2.1 Disposal and valorization
43
44
45 With unreasonably low landfill costs until the beginning of this century (not including
46
47 externalities from environmental repercussions) most of food waste (>60%) has been dumped
48
or landfilled. Land-disposal of non-stabilized biowastes, including food waste, is gradually
49
50 banned[20,211]. It has been recognized as another menace to sustainability due to high green-
51
52 house gas (GHG) emissions, mainly CH4 and CO2 and also, due to emissions of halogenated
53
54
and sulphonated organic pollutants[22].
55
56
57 About 20% of household food waste is used in mass burn, waste-to-energy facilities[23] as part
58
59
of commingled, or residual waste. Significant innovations in the long proved energy-from-
60 waste technology allow efficient valorization, together with other richer (of higher heating
61
62
63
64 5
65
 value) fractions of municipal wastes (paper, plastics). Opponents of waste-to-energy invoke
1
2 arguments of atmospheric pollution[24], hinging on the heterogeneous and varying feedstock,
3 which contains heavy metals and precursors of persistent organic pollutants (POPs) such as
4
5 PCDD/Fs. A small portion of POPs, not removed from the fluegases in the APCS is released
6
7 with the offgases, even though emissions are maintained within the maximum limits[25,26].
8 Utilizing commingled waste, which includes plastic and paper, waste-to-energy plants achieve
9
10 high availability (>90%) enhanced controllability, compensating for waste variability, high net
11
12 power efficiency (~ 700kWhe/tonne MSW, which is ~25% of the feedstock’s lower heating
13 value (LHV)[27] and consistently low emissions [28]
. State-of-the-art technology [29,30]
is
14
15 employed to this end, with reverse acting grate, overfire air system with multiple nozzle rows -
16
17 e.g., "4-row stitching", combustion control system activated by infrared thermography, on-line
18 feedback control of fluegas recirculation, heat recovery and oxygen enrichment of combustion
19
20 air. Emitted concentrations of regulated pollutants have fallen to one or more orders of
21 [25, 26]
22 magnitude lower than emission limits set by legislation . With new high capacity facilities
23 under construction in the Far East [30]
, the total capacity of energy from waste facilities is
24
25 expected to rise to 260 million tonnes per annum (tpa)[32, 33], which is about 20% of global
26 [34]
27 municipal waste arisings by 2025 . The corresponding analogy of global food waste
28 directed to energy-from-waste facilities is slightly lower.
29
30
31
32 Another 10% of food residues are biologically treated either aerobically, via slow oxidation to
33 produce compost, or SRF via biodrying for use in power stations and cement plants, or
34
[35, 36]
35 anaerobically, via digestion, to produce biogas for energy recovery in gas power units .
36
37 Due to long residence times, biological treatment technologies are volume-intensive,
38
compelling, also, large footprints. Even with complete combustion of nonoxidized products
39
40 (CH4) they feature greenhouse gas emissions due to CO2 release and biostabilazation of
41
42 organic residuals compelled by enacted legislation. Composting and biodrying plants are
43
associated with odor problems, since they release high volumes of potentially infectious
44
45 bioaerosols. The end product (compost) from commingled refuse still contains xenobiotic
46 [37]
47 substances that inhibit wide scale application as soil amendment . Important studies have
48
brought forth the potential for cyclic valorization of food waste for industrial use in the chemical
49
50 and material industry, or via biogas-to-energy[9-14,38]. With residence times at ~4 weeks[36] and
51
52 relatively large volumes of bioreactors, biogas-to-energy is now at a mature technological
53
54
stage, having resolved operational, stability and process control problems. It has been widely
55 applied in agro-industries with slurry or sludge biowastes (e.g., swine and cattle farm wastes)
56
57 and in some food wastes (e.g., dairy wastes). Several large scale applications of municipal
58 [39,40,41]
59
organic wastes that include food and kitchen residues are in operation . Operational
60 issues relate to the heterogeneous substrate from municipal wastes in the digester which may
61
62
63
64 6
65
 lead to foaming, reduced bioreactor volumes and decreasing yields[42]. As a result, cleanup
1
2 maintenance is frequent, resulting in low availability, <75%[43]. An additional problem is the
3 large quantities of biosludge, which must be stabilized and disposed of.
4
5
6
7 Anaerobic digestion of organic municipal solid wastes, including food wastes has been
8 investigated extensively in the last decade with significant improvements in the conversion
9
10 efficiency to biogas. Yields exceeding 520 Nlt biogas/kg VS with methane content up to 70%
11 [11]
12 have been reported . Industrial scale applications in state of the art plants, feature about
13 [44]
240-550 Nlt biogas/kg VS , with the upper figure corresponding to animal manure and with
14
15 methane content at 60% vol, whereas older plants treating municipal organic wastes do not
16 [45]
17 exceed 300 Nlt biogas/kg VS . With the use of biogas engines and combined cycle, this
18 gives a net electrical efficiency around 100 kWhe/tonne of biowaste. Digestion of leached
19
20 extracts from biowastes circumvents the operational issues mentioned above, at the cost of
21
22 even lower efficiencies, (~80 Nm3 biogas/tone of biowaste[43]).
23
24
25 The main constituents of FW are as in Table 1[11, 12]. Biogas yields from food waste range
26 [35]
27 around 400ml/gr volatile solids , with the content of volatile solids at 21-23%, the ratio of
28 volatile solids over total solids at 84-87% and the ratio C/N at 14.8. Anaerobic digestion of
29
30 food waste in practice converts about 80% of volatile solids which amount to 90% of total
31 [12]
32 solids . This gives around 380-450 Nlt CH4 /kg VS or 340-400 Nlt CH4 /kg TS or 55-73 Nlt
33 CH4 /kg FW [45,46,47]. If electrical energy requirements of anaerobic digestion (30-70 kWhe/t FW)
34
35 and thermal requirements of subsequent composting of the digestate (20-60 kWh/t FW) are
36 [45]
37 taken into account , the net energy potential of methane from anaerobic digestion of FW is
38
at 40-170 kWhe/t and 180-380kWh/t thermal. The energy content of the household FRB
39
[48-51]
40 produced via drying of FW is around 4 MJ/kg FW or 1000 kWh/t/FW . Recognizing the
41
42 feasibility of thermal valorization of household food residues, part of the EU support to biogas-
43
to energy is now directed to solid and liquid biofuels[44,49], while the waste management
44
45 hierarchy[20] is maintained. Food residues and FRBs are now viewed as promising sources of
46
47 biochemicals, biomaterials and bioenergy[37], via direct energy production, or transformation to
48
solid and liquid biofuels, with the aid of innovative technology.
49
50
51 [52]
52 Apart from methane , specific products include bulk chemicals and biomaterials, such as
53
54
pectin[53] volatile fatty acids [11, 54,55]
lactate, ethanol and hydrogen[56] biofuels [proteins,
[57]
55 peptides, lactose, glucose, galactose, yeast , enzymes, bio-pesticides and bioplastics[58]
56 [59,60]
57 succinic acid . Critical issues are comparability and compatibility of use with fossil fuel
58
59
derived compounds, while ecological repercussions should not be taken for granted. Two
60 major threats of emerging biorefineries utilizing food waste[61,62] are eased via the FRB route
61
62
63
64 7
65
 investigated herein, namely (a) stable, non decomposing FRB via drying, readily stored for
1
2 long periods and thus no longer requiring infrastructural and expensive storage and
3 conditioning to avert the rapid decomposition of raw food waste and (b) small variations in
4
5 composition and quality of household food waste within a district or country circumventing the
6
7 high variety of quality and volume of food waste.
8
9
10 Other notable examples include: (i) production of syngas via gasification[63] followed by
11
12 production of liquid biodiesel, biokerosene, or naptha fuels via Fisher-Tropsch liquefaction, (ii)
13 production of bioethanol and biomethanol (iii) production of biochemicals including fatty acids
14
15 and biopolymers, biomethanol, bioethanol, or of fertilizers via the Bosh-Bashke method
16
17 featuring zero carbon footprint, (iv) production of hythane. For instance, high efficiency
18 plasma gasification[64] with combined cycle and recuperation of the syngas heat from the
19
20 gasifier, recovers about 95% of the biofuel's energy content in the form of chemical energy of
21
22 syngas, enabling gross efficiencies of 40% to electric power production. This figure is about
23 70% higher than direct waste-to-energy recovery. At about the same CAPEX and OPEX as
24
25 waste-to-energy, these promising biorefinery technologies are yet to entertain large scale
26
27 implementation. New developments in plasma gasification including microwave plasma
28 gasifiers and use of supercritical steam in the gasification zone further improve syngas quality
29
30 by increasing the hydrogen molar fraction and lead to higher overall energy production.
31
32 Bridging the “development gap” from pilot plants to operational first-of-a-kind industrial plants
33 is a main bottleneck for biofuels, particularly challenging for single-product start-ups.
34
35
36
37
38
39 2.2 Pretreatment and preparation of solid biofuel from food residues
40
41
42 In regard to pretreatment and preparation, two methods have been attested thus far for
43
44 biomass and organic wastes: torrefaction[48, 65,66] and long established thermal drying. Lab
45
46 and pilot scale torrefaction of food waste[65] takes place under anoxic conditions (nitrogen
47 atmosphere) in temperatures ranging from 150 oC to 600 oC and residence times varying up to
48
49 50 min. It can produce a free-of-volatiles, solid biomass fuel for combustion gasification or
50
51 pyrolysis. The torrefied solid FRB features increased energy density, while the strong fibers of
52
the biomass become brittle, improving grindability, ignitability, reactivity and efficiency.
53
54 Industrial scale applications of torrefaction are yet to appear. The method requires relatively
55
56 high temperatures (optimal for food residues is around 300oC) and reduces the energy yield of
57
the produced FRB by about 30% [66].
58
59
60
61
62
63
64 8
65
 Pretreatment of FW with main constituents as in Table 1 via thermal drying at 90 oC for about
1
2 4-9 hours produces stable FRBs at moisture levels down to 1.1%w (fig. 1)[49, 67] and partial
3 volatilization of volatile organic compounds (from 88-90% originally, to 75-78%). The
4
5 characteristic brown colored product has a negligible, rather pleasant odor of dried food (e.g.,
6
7 soup cubes). Pilot scale applications can use electric driers of up to 1.2 tpd[67] to produce a
8 stable product of consistent quality, easily grindable and pressed to pellets[49]. Industrial
9
10 scale drying via heat convection may be applied as in direct thermal dryers, that is, by
11
12 directing the fluegases to the material along its course on suitable belt conveyors, or in
13 rotating drums (fig. 2). Long established for drying olive pomaces, rotary drums use the hot
14
15 drying gases produced from combustion of residual exhausted olive cake (a solid biofuel) to
16
17 dry the fresh pomace. The olive cake is obtained from the dried fatty pomaces after the
18 pomace oil is extracted using solvents (cyclohexane). The product (pomace) to be dried and
19
20 the hot drying gases are introduced co-currently at high temperatures (400°C to 800°C) in the
21
22 rotary drum. Low moisture is reached with direct rotary driers: pomace can be dried down to
23 1.5% wt moisture. Alternatively, plate heat exchangers can be employed using hot air, hot oil,
24
25 or steam. Hot air can be blown directly to the material, as in rotating drums with co-current air
26
27 flow; the material is thus dried by heat convection as in food drying applications. Hot oil or
28 steam may be used in heat conduction driers circulating in an inner axis of rotating paddles as
29
30 in waste-water-treatment plant biosludge drying [68].
31
32
33 Given the aforementioned potential for direct applicability of industrial drying, specific
34
35 questions of interest in this respect are (i) what are the energy needs and the final energy
36
37 content of FRBs (ii) are there any adverse effects regarding production level and profits when
38
FRBs substitute for fossil fuels, e.g., petcoke (iii) which are, if any, the benefits from fossil fuel
39
40 substitution, e.g., cost savings (iv) how much are greenhouse gas emissions reduced per
41
42 tonne clinker (v) are there any plant operation limitations, stemming from plant capacity
43
constraints (vi) is the product detrimentally affected by inclusions of trace elements such as
44
45 alkalis and leachable metals? (vii) what is the impact of chlorines form food salt on plant
46
47 operation and emissions (viii) is emissions compliance ensured for regulated pollutants and
48
are the actual emission rates maintained at the same levels as under baseline (fossil fuel)
49
50 operation? (ix) how does the final moisture content of FRBs affect economic performance of
51
52 cement-plants, product quality and emissions? The answers to the above questions may
53
54
provide guidelines for suitable, customer-made blends of FRBs with other bioresidues, e.g.,
55 paper detrita, since paper cannot be recycled more than seven times.
56
57
58
59
60
61
62
63
64 9
65
 3. ASSESSMENT METHOD: ENERGY EFFICIENCY, PRODUCTION LEVEL, CEMENT
1
2 QUALITY AND ATMOSPHERIC EMISSIONS
3
4
The evaluation method investigates the following (fig. 3): (i) satisfaction of main constraints of
5
6 process operation: thermal load should not exceed heat rating of kiln refractory and overall
7
8 offgas volumetric flowrates should not exceed main blower capacity, (ii) level of clinker
9
10
production (directly related to cement sales), (iii) non-biogenic CO2 emissions (analogous to
11 CO2 pollution rights), (iv) emitted concentrations of regulated pollutants and compliance, (v)
12
13 actual rates of pollutant emissions, (vi) trace metal inclusions remaining within acceptable
14
15
limits and (vii) chlorine presence in the process equipment and in the APCS.
16
17
18
19 Quantitative evaluation is based on actual data from baseline operation used in a multiple fuel
20 combustion model. The model entails process stoichiometry and mass and enthalpy balances
21
22 of the kiln and recircuiting systems[18,19,69] (depicted in fig. F1, Appendix F in the
23
24 Supplementary information in the Web). It enables simultaneous consideration of
25 multicomponent mixtures of fossil fuels and/or renewable fuels and decouples the varying
26
27 parts due to fuel variability, or due to manipulation of process parameters (e.g., excess air) by
28
29 the plant operator, from the parts that remain invariant. Several alternative scenaria can be
30 evaluated using one or more biofuels and comparatively assessed. The key expressions
31
32 represent the following:
33
34 1) Clinker level in the kiln and required raw meal level.
35 2) Kiln fluegas species’ flowrates, including CO2 from lime dissociation.
36
37 3) Biogenic, non-biogenic and overall CO2 flowrate.
38
39 4) Gas species flowrates prior to the main air pollution control system (APCS) under
40 direct operation and, also, after mixing part of the kiln fluegases with soil mill air
41
42 (compound operation) prior to the APCS.
43
44 5) Overall kiln / soil mill offgas flowrates.
45
6) Gas species flowrates and overall flowrate at the fuel mill APCS, after diverting the
46
47 remaining part of the kiln fluegases to the fuel mill to maintain inert atmosphere and to
48
49 heat up the fuel.
50
7) Pollutant emission rates, taking into account the removal efficiency in the main APCS
51
52 (kiln – soil mill APCS) as established from baseline operation.
53
54
55
Common characteristics featured by the key expressions of (1)–(7) above are the following:
56
57 (i) they entail linear expressions in terms of the fuel charging rates fi, i.e., of the vector
58
59 f   f1 f2 ... fn .
60
61
62
63
64 10
65
 (ii) if the types and compositions of the candidate renewable fuels are known, then, under
1
2 constant excess air and oxygen enrichment, the coefficients of the linear expressions remain
3 constant; if a renewable fuel (e.g., fuel 3) is not present in the fuel mixture, then it suffices to
4
5 simply set f3=0 while maintaining the same linearity coefficients.
6
7 (iii) under manipulated (known) excess air and/or oxygen enrichment the linearity coefficients
8 change, yet they can be known a priori in terms of the values of plant parameters and of
9
10 excess air (%) or oxygen enrichment (e.g., oxygen at 28%v instead of 21%v).
11
12
13
Specific energy consumption in the kiln
14
For instance, the energy released by the fuels is given by the scalar product  f , where
15 T
16
17
18 f = fuel mass feedrate vector, that is the n-dimensional column vector f, each component of
19 which is the mass feedrate of one of the n fuels, coal (i=1), petcoke (i=2) and so on for
20
21 i=3,4,...,n, including the renewable fuels, e.g., FRB, paper, saw dust, or others and λ is the
22
23 vector of the lower heating values of the fuels (e.g., λ1= λcoal = 6 146 kcal/kg, λ2= λ petcoke =8
24 Τ
342 kcal/kg, etc. denotes the transpose (row) of a (column) vector and thus λT is a row
25
vector. The specific energy consumption to produce clinker is given by  f k , where k is
26 T
27
28 the mass (flowrate) of the clinker produced. Evidently, even under isothermal substitution
29
30 (constant  f ) if the clinker level changes, the specific energy consumption will be different
T
31
32
and thus it is not a constant design parameter or an invariable parameter of process operation
33
34 when some fuels are substituted by other fuels.
35
36
37
38
Kin fluegases
39 The mass flowrates of individual kiln fluegas species (mfgi, i=1,2…,9 for CO2, H2O, O2, N2,
40
41 SO2, HCl, P2O5, HBr, HF respectively) are given by the scalar expression
42
43
44
m fg ,i  c fg ,i  c fg ,i f
T
(1)
45
46
47
48 where cfg,i is a scalar, cfg,i is a vector (Appendix A). The scalar cfg,i, and the vector cfg,i entering
49
50 eq. 1 are independent of f. In particular, they are independent of the fuel types (composition,
51
LHV) and of the fuel charging rates fi and depend only on process design and operation
52
53 parameters (e.g., CaO yield from CaCO3).
54
55
56
57
Nonbiogenic CO2 emissions
58 Regarding CO2 emissions, the non-biogenic CO2 mass flowrate is given by
59
60
61
62
63
64 11
65
 1
Nonbiogenic CO2 mass flowrate m fg ,CO2  c fg ,CO2  c fg ,CO2
T
f  f 
b
(2)

2
3
4 where fb=biogenic fuel mass feedrate vector, that is the vector f with zeroes in the entries
5
6 corresponding to fossil (non-biogenic) fuels. The scalar c fg ,CO2 and the vector c fg ,CO2 entering
7
8 eq. 2 are independent of the fuel types (composition, LHV) and of the fuel charging rates fi of f
9
10
and fb, and depend only on process parameters. The analytic expressions for the scalar
11 c fg ,CO2 and the vector c fg ,CO2 are given in Appendix A.
12
13
14
15 Atmospheric emissions of main offgas species
16
17 The volumetric flowrates of the main species in the fluegases are determined from the mass
18
19
flowrates (eq. 1). Then the overall kiln fluegas volumetric flowrate is found, from which in turn,
20 concentrations of main species in the overall fluegas can be determined (Appendix A).
21
22 Regarding offgases and stack emissions, under direct operation the main blower directs (kiln)
23
24
fluegases to the APCS and thus the fluegas flow increases merely by the blower induced air
25 draft (false air). Under compound operation (fig. F1, Supplementary Information) the majority
26
27 of the kiln fluegases are cleaned together with the soil mill air. Mass and volumetric flowrates
28
29 of the various species in the kiln soil-mill gas stream are given by expressions of similar form
30 that take into account the soil mill air, as well as the false air drawn by the APCS blower.
31
32
33
Vk ,sm,i  ck ,sm,i  c k ,sm,,i f
T
34 Offgas species i volumetric flowrate: (3).
35
36
37
38 The analytic expressions for the scalar ck ,sm,i and the vector c k ,sm,,i are given in Appendix A.
39
40
41 Clinker production level
42
43 Obtained directly from the kiln enthalpy balance, using the stoichiometric mass balance
44
45 described above, the key relation that quantifies operational efficiency is the explicit
46 expression for the clinker level, directly related to profits and economic performance,
47
48
49
k    f
T
50 (4).
51
52
53 Overall offgas volumes
54 Regarding stack emissions, the expression for the overall offgas flowrate (resulting from eq. 3)
55
56 which directly relates to main APCS blower costs is eq. 5:
57
58
59
Vk , sm  v  v f
T
60 (5).
61
62
63
64 12
65
 1
2 The scalar κ and the (row) vector κΤ in eq. 4 and the scalar v and the vector vT in eq. 5 (A,
3 Supplementary Information in the Web) are independent of the fuel types (composition, LHV)
4
5 and of the fuel charging rates fi and depend only on process parameters. The process
6
7 parameters are independent of the fuels (composition, LHV and feedrates) as well. The
Τ
8 factors v (scalar) and the vector v in eq. 5 explicitly depend on κ and κ . In this way, the
9
10 parameters v and v constitute the link between performance (clinker level) and two key
11
12 objectives of operation: (a) satisfaction of main blower capacity constraint Vk , sm  Vk , sm,max and
13
14 (b) environmental constraints and particularly emissions’ compliance, since (i) environmental
15
16 compliance is assessed in terms of emitted pollutant concentrations and (ii) pollutant removal
17 efficiency depends on the offgas volumetric flowrate, Vk,sm. Larger values of Vk,sm reduce the
18
19 residence time and increase the pressure drop in the APCS, thus reducing the removal
20
21 efficiency, y (fraction) and increasing the non-removed fraction (1-y) which is released in the
22 atmosphere with the offgases.
23
24
25
26 Emissions compliance and actual emission rates of regulated pollutants
27 Reported emitted concentrations are obtained from measured emitted concentrations via
28
29 standardization. Standardization to standard conditions (normal temperature and pressure,
30
31 dry and 10% oxygen) is performed via multiplication by the standardization factor SF. In fact,
32 a necessary and sufficient emissions compliance condition[43] is expressed via the compliance
33
34 factors (1  y ) SFxin, APCS / xl , where xl is the emissions limit under utilization of waste derived
35
36 fuels and xin, APCS is the pollutant concentration entering the APCS, which can be determined
37
38
analytically for several pollutants via the model and stoichiometry (e.g., HX, SO2, NOx). The
39
40 SF is directly determined from the plant model and in particular from the offgas flowrates
41
42 (given in Table S1 in the Supplementary information in the Web) of oxygen and water.
43
44
Compliance is ensured for any regulated pollutant, if and only if, the following condition is
45 satisfied[68]:
46
47
48
49   1 (6)
50
51 where
52 xl , 0 SF xin, APCS
53  :  A (7)
54 xl SF0 xin, APCS , 0
55
56
57
58 is the dimensionless ratio of compliance factors with respect to baseline conditions, i.e.
59 compliance factor under use of FRB / compliance factor under use of stand alone fossil fuels,
60
61
62
63
64 13
65
  A  1  y  1  y0  is the ratio of removal efficiencies in the APCS with respect to baseline
1
2 operation,
3
4 xl , 0
5 μ (also dimensionless) is defined as the ratio   , that is the ratio of the maximum limit of
6
xs 0
7
8 emitted concentrations under fossil fuel (baseline operation) set by enacted legislation[70,71],
9 xl,0, with respect to reported actual standardized emissions xs,0, also under baseline operation;
10
11 μ refers only to baseline conditions and is independent of the biofuel assessed.
12
13
14 The ratio φ/μ represents emissions compliance with regard to the respective maximum
15
16 emissions limit. Named thereof emissions compliance index, it includes the impact of possibly
17
18 differing emission limits for refuse or waste derived fuels, the impact of standardization factors
19
and the impact of removal efficiencies in the APCS, which are affected by offgas volumes and
20
21 by the presence of other species (see the discussion for SO2 and chlorines below). For
22
23 instance, if for a certain pollutant φ/μ=0.6, then emitted concentrations of the specific pollutant
24
are at 60% of the maximum allowed value. The inverse μ/φ represents the emissions safety
25
26 factor, i.e., how many times the emitted concentration can be increased without violating the
27
28 maximum limit. For instance, if μ/φ =1.4, then emitted concentration should be increased by
29
40% in order to reach the maximum limit. Evidently, φ/μ depends on the types of renewable
30
31 fuels and on the overall fuel mixture, on the emissions’ limit under alternative fuel utilization xl
32
33 SF
34 (it may be lower or higher than xl,0) on the ratio of the standardization factors, and on the
SF0
35
ratio of removal efficiencies in the APCS,  A  1  y  1  y 0  . Condition 6 is necessary and
36
37
38
39 sufficient, i.e., non-excessive. For regulated pollutants not entering the stoichiometry (TSP,
40 TOC, volatile and non-volatile metals and PCDD/Fs) the ratio can be approximated or
41
42 bounded, leading to sufficient conditions for emissions compliance. When condition 6 is
43
44 applied to an actual cement plant, data from actual operation entering condition 6 via the
45 parameters φ and μ include: the actual removal efficiency y0, the actual concentration
46
47 measurements, xS,0 (standardized) and the actual standardization factor, SF0. The maximum
48
49 emission limits, xl and xl,0 are known a priori. The values of the rest of the parameters in
50 condition 6 are determined from the model equations. In this way the simulated scenaria
51
52 under use of FRBs are tied to the actual plant performance via hard-core evidence. It is noted
53
54 that condition 6 under baseline conditions reduces to the trivial condition μ≥1.
55
56
57
58
59
60
61
62
63
64 14
65
 Apart from emitted concentrations addressed via the emissions’ compliance index, φ/μ, in
1
2 compliance with enacted legislation, the actual burden to the environment is assessed via the
3 ratio of emission rates with respect to baseline conditions:
4
5
6
moffg xin, APCS Vksm x SF0 Vksm
7 A  l (8).
8 moffg,0 xin, APCS ,0 Vksm,0 xl ,0 SF Vksm,0
9
10
11
12
13
14 Inclusions of trace elements in cement
15 Trace elements, alkalis, volatile and non-volatile metals and halogens included in the final
16
17 product, affect cement strength, leachability, integrity and lifetime. The impact of inclusions is
18
19 assessed by the ratio of inclusions per tonne clinker with respect to baseline operation, given
20 the raw meal content. For instance, inclusion of alkalis per tonne clinker is assessed by eq. 9:
21
22
23
24  Na  K , r r   Na  Kl , f T f  moffg, Na  K k0
25 ( Na  K ) inclusions ratio  (9)
26  Na  K , r r0   Na  K , f ,0 f 0  moffg,0, Na  K
T
k
27
28
29
where  Na  K ,r r   Na  Kl , f f is the overall alkali generation rate by raw meal (r) and fuels;
T
30
31
32 βNa+K,r is the specific alkali generation rate in the kiln, originating from the raw meal (raw meal
33
34 feedrate = r tpa); and
35
36 βNa+K,f is the specific alkali generation rate in the kiln originating from the fuels;
37 moffg, Na+K is the emission (mass) rate of alkalis in the offgases, found in terms of the overall
38
39 offgas flow and emitted concentration data. Similar expressions are used for mercury,
40
41 cadmium and thallium and non-volatile metals (A, Supplementary Information).
42
43
44 Chlorine impact on emissions, inclusions and corrosive deposits on process
45
equipment
46
47 With a specific content of 1 wt% in food residues the fate of halogens (mainly Cl) is a serious
48
49 consideration in FRBs. Chlorine is a precursor of PCDD/Fs[72-75] and it inhibits removal of
50
51
volatile metals in the APCS, incurring increased emissions of Hg, Cd and Tl and other metals.
52 Thus, the presence of chlorine ought to be assessed both in the kiln /precalciner/preheater
53
54 system (i.e., in the kiln fluegases) and in the APCS (offgases). Food residues contain the
55 [48l]
56
majority of chlorine in household waste (45%-50% ) the rest attributed to plastics, mainly
57 PVC (45%). Not all chlorine in the fuel becomes hydrogen chloride however[76,77]. Due to
58
59 higher binding energy of NaCl and KCl in food residues, alkali salts give rise to incombustible
60
61
62
63
64 15
65
 chlorine, which is incorporated in Friedel’s salt[78] in waste incinerator ash in waste-to-energy
1
2 plants, or incorporated in the mass of clinker in cement kilns. A typical ratio is combustible
3 chlorine/incombustible chlorine =1.5[79]. Thus, the emission rates of HCl are expected to be
4
5 lower under use of FRBs than under use of alternative fuels derived from plastic residues,
6
7 which, in addition, are non-biogenic and non-renewable. Nevertheless, at the high
8 temperatures (1500oC to 2000oC) prevailing in the kiln, incombustible chlorine is present in the
9
10 form of water-soluble alkali chloride salts, which as the fluegases are cooled down (along their
11
12 course from the kiln to the precalciner and the preheater) are deposited on equipment and
13 pipes contributing significantly to high temperature corrosion in process equipment (kiln-
14
15 precalciner, riser and preheater) and, also, on piping and ducts[80]. Recent studies[81] have
16
17 shown that the presence of sulphur favors chloride becoming HCl and reduces vaporized salts
18 in the furnace/kiln. Since the petcoke content in sulphur is about one order of magnitude
19
20 larger than FRB (Table 3) the impact of SO2 on the presence of hydrogen chlorides must be
21
22 taken into account (fig. 4). This can be done by assuming that the fraction of combustible
23 chlorines over hydrogen chlorides as given by stoichiometry (reaction a, Supplementary
24
25 Information, A) follows first order kinetics with the kiln SO2 concentration (Appendix C) after
26
27 taking into account the detainment of hydrogen chloride by the (alkaline) clinker in the kiln,
28 which acts as a huge scrubber. The presence of incombustible chlorines can be subsequently
29
30 m fg , HCl
31 assessed via the ratio , which is found from the fluegas chlorine mass balance
32 m fg , HCl , 0
33
34 (incombustible + combustibles chlorines in the kiln are equal to the overall chlorines in the kiln
35
36 fluegases) in conjunction with the stoichiometry (reaction a, Supplementary Information, A).
37
Then, chlorine presence in the kiln/precalciner/preheater and in the APCS is assessed via eqs
38
39 10a – 10c (Appendix C).
40
41
42
43 [ HCl ] fg m fg , HCl V fg , 0 g HCl V fg , 0
44 Chlorine in kiln/precalciner/preheater:    C S (10a)
[ HCl ] fg , 0 m fg , HCl , 0 V fg g HCl , 0 V fg
45
46
47
48 x HCl ,in, APCS g HCl Vk , sm, 0
49 Chlorine in main theAPCS:   C S (10b)
50 x HCl ,in, APCS , 0 g HCl , 0 Vk , sm
51
52
53
54 [Cl ] fg m fg ,Cl V fg , 0 g HCl V fg , 0
55 Incombustible chlorine:   C S (10c)
[Cl ] fg , 0 m fg ,Cl , 0 V fg g HCl , 0 V fg
56
57
58
59 where, similarly to γΑ, γC is the ratio of nonremoved fraction of chlorines by the clinker, with
60 respect to baseline, based on first order adsorption kinetics and γS is the ratio of fractions of
61
62
63
64 16
65
 incombustible chlorines with respect to baseline. The factor  S is found from the chlorine
1
2
3 mass balance in the kiln. The expressions for γC, γS and  S are included in the model
4
5 (Appendix C). The complete model is given in the Supplementary information in the Web.
6 Eqs (1)-(10) constitute the core of the evaluation method applied to a Case study in the next
7
8 section.
9
10
11
12
13 4. CASE STUDY
14
15
16 An actual dry kiln process plant producing 1.5 x 106 tonnes clinker per annum (tpa) and
17 utilizing 1.65 105 tpa fossil fuels is investigated under compound operation. Direct and
18
19 compound operation, key process flows and emissions are represented via the model in the
20
21 Supplementary information. Current (baseline) operation corresponds to a thermal load
22 distribution 30% coal and 70% petcoke. The overall heat rating is 1.244 x 106 Gcal/annum.
23
24 The limiting flowrate of the main APCS (kiln/soil mill) is 578.000 Nm3/h. Separate use of
25
26 FRB and blends with paper residues, or FPRBs, is assessed via simulation of various
27
scenaria, each one under twenty percent isothermal substitution of petcoke (i.e. the quantity
28
29 of FRB or FPRB supplies 20% of the thermal energy in the kiln, while the quantity of petcoke
30
31 is reduced equivalently). The percentage of thermal participation of coal in the fuel mixtures
32
remains constant at 30%, since coal inhibits PCDD/PCDF emissions. An additional reason for
33
34 not increasing coal to higher levels is that it may favour reactions with different metals in raw
35
36 meal and increase their release with the flue gases. Elemental composition of food residues
37
are given in Table 3, revealing deviations (e.g., in the LHV) depending on the collection and
38
39 preparation method. Uncertainty, as expressed by large variability of key variables such as
40
41 the LHV of any fuel, (particularly of the prepared FRB via drying of FW) can be readily
42
43
investigated using our multidimensional model (the vector of LHVs, λ, explicitly appears in eq.
44 4 and eqs A16 and A18 in the Supplementary Information in the Web). Notably, the ash
45
[82]
46 content is below 10%, in line with the new EU regulation on food-waste pellets (though >
47
48 than the 2% maximum ash content required for woody biomass pellets). The elemental
49 [49]
composition used in the model is from Papanikola et al., . Clinker exit temperature is
50
51 Tk  2000 o C and preheater temperature T p  450o C . Plant parameter values and other
52
53 baseline operating conditions are as in Table 4. The essential characteristics and efficiency of
54
55 FRBs with moisture contents 1.5%wt, 10% wt and 15% wt is assessed with respect to (a)
56
57 clinker production, k, (b) offgas volumetric flowrate, Vk , sm , (c) GHG emissions (d) inclusions of
58
59
60
61
62
63
64 17
65
 trace elements and (e) atmospheric emissions of pollutants are revealed. Actual data from
1
2 baseline operation are used, including stack measurements of pollutant concentrations.
3
4
5 Evaluation
6
7 Energy requirements for FRB preparation. Fig. 1 presents the thermal energy
8 requirements for producing FRB at various moisture levels. As clearly manifested, the thermal
9
10 energy need is about 55% of the LHV of the respective FRB. This is a marginal figure if
11
12 electric energy stand-alone is used for drying (taking into account an average efficiency of
13 30% of transforming chemical energy to electricity). It becomes attractive if cogeneration is
14
15 employed (fig. 2). For instance, a 1 MW e natural gas or diesel generator can be combined
16
17 with a direct fluegas dryer for drying 20 tpd of food residues down to 1.1%. Alternatively, a hot
18 air-dryer (with the recirculated air heated in a heat exchanger) or a hot oil (or steam) dryer can
19
20 be used, in which the recirculated hot oil is heated by the fluegases in a heat exchanger. Fig.
21
22 1 also reveals the feasibility of an self-sustained, autonomous process, using part of FRB as
23 fuel in a dedicated thermal dryer. About 70% of FRB is required under 80% efficiency, leaving
24
25 30% of FRB for other uses, e.g., as solid biofuel. The prospect of drying the food residues
26
27 using the enthalpy of the cement plant offgases is also attractive. In this case 100% of FRB is
28 available for use as a solid biofuel. Based on fig. 1, the energy needed for drying 65 000t/y of
29
30 FW (20% thermal substitution of by petcoke by FRB 1.5%) is 6.4 x105 Mcal/y, which is more
31
32 than an order of magnitude lower than the enthalpy released by cooling the kiln-soil mill
33 offgases from 140 0C to 130 0C, i.e., by 10 0C, (9.4 x106 Mcal/y). This option commands a
34
35 rigorous feasibility assessment by the cement plant management, including CAPEX, gate fees
36
37 of FRBs and environmental benefits or drawbacks as well.
38
39
40 Plant operability, GHG emissions and product quality
41
42 The key relations (1) – (10) are used to identify the benefits and challenges of the use of FRB
43
in cement kilns when substituting 20% of the thermic contribution of petcoke in accordance
44
45 with fig. 3. The feedrates of FRBs and of blends of FRB with paper residues (FPRBs) are
46
47 shown in fig. 5a: about 65 000 tpa of FRB or 52 000 tpa of FPRBs (80% wt FRB and 20% wt
48
paper residues) substitute 29 829 tpa of petcoke, keeping the respective fossil carbon in the
49
50 ground. Notably, FPRB feedrates are about 20% lower than FRB feedrates at the same
51
52 moisture level, leading to lower kiln fluegas volumes.
53
54
55 Regarding operability, the refractory thermal rating constraint is satisfied, since FRB
56
57 contributes the same amount of thermal energy as the substituted petcoke. The main blower
58
59
capacity constraint is also satisfied in all scenaria, since offgas volumetric flowrates are
60 between 565 135 Nm3/h and 570 639 Nm3/h. As to clinker production, it is seen that use of
61
62
63
64 18
65
 FRB results in lower production levels. For instance, FRB with 10% moisture (FRB 10%) leads
1
2 to losses of about 30 000 tonnes clinker per annum (tpa) fig. 5b, i.e., lower production due to
3 lower energy efficiency by about 2%. This amounts to about 0.46 tonnes of clinker per tonne
4
5 of FRB with moisture level 10%wt (FRB 10%). In contrast, use of blends of FRB (80%wt) and
6
7 paper residues (20%wt) raises clinker production level and increases energy efficiency. The
8 blend with the lowest moisture content (FPRB 1.5%) corresponds to the highest gains (27 000
9
10 tpa) or ~0.58 tonnes of clinker/tonne of FRB 10% (fig. 5b). The reason is that the mass of kiln
11
12 fluegases is lower, resulting in lower enthalpy discharge with the fluegases, which, in turn,
13 enables higher clinker volumes. Going back to blower capacity and offgas flowrates, it is now
14
15 apparent that offgas volumes are about equal, despite the fact that kiln fluegas flowrates
16
17 under FRBs are about 20% higher than FPRBs. This is due to the higher clinker production
18 levels associated with FPRBs, which imply higher soil mill air, higher volumes of CO2 from
19
20 lime dissociation and higher false air drawn and cleaned together with the kiln fluegases in the
21
22 main APCS.
23
24
25 Greenhouse gas emissions are assessed as emissions of non-biogenic CO2 originating from
26
27 the fuels, per tonne clinker. They are reduced by about 20% under use of FRB (~equal to the
28 substituted fraction of fossil fuels) and by about 23% under use of blends of FRB with paper
29
30 residues. The blend FPRB1.5% features the lowest non-biogenic GHG emissions (266.85 kgr/t
31
32 clinker, versus 267.66 kgr/t clinker of FPRB10% and 268.22 kgr/t clinker of FPRB15%). Fig. 5
33 presents the full quantitative figures and clearly manifests the impact of moisture on the loss
34
35 level. For instance, losses corresponding to FRB1.5% (70 000 t/y FRB1.5% for 20% thermal
36
37 substitution of petcoke) are at 25 000 t/y, whereas CO2 emissions are reduced by 48 kg/t
38
clinker or 70 800 t CO2/y. In contrast, FPRB1.5% features no clinker losses and lower CO2
39
40 emissions by 10 kg/t clinker or 15 250 t CO2/y.
41
42
43
Product quality, as reflected by inclusion of alkalis, leachable and volatile metals is presented
44
45 in fig. 5c via the inclusion ratios per tonne clinker with respect to baseline conditions.
46
47 Inclusions of alkalis when using FRBs are higher by about 10% due to the sodium from
48
kitchen salt in food residues. The blends of FRB with paper residues feature lower inclusions
49
50 than FRBs, though still larger than baseline K+Na inclusions by about 7%. Combustible
51
52 chlorine concentrations (HCl), as quantified by eq. 10a, rise by 11%, 13% and 16% for
53
54
FRB1.5%, FRB10% and FRB15% respectively. They fall by 13%, 11% and 9% for FPRB1.5%,
55 FPRB10% and FPRB15% respectively. Incombustible chlorine concentrations (eq. 10c) and
56
57 resulting halide deposits in equipment and pipes are predicted to be higher than baseline by
58
59
22% for FRB1.5%, by 26% for FRB 10% and by 30% for FRB15%. This is due to the higher feeding
60 rate of chlorines with the FRBs in conjunction with the lower SO2 concentrations (resulting
61
62
63
64 19
65
 from 29 829 tpa lower petcoke feedrate than baseline) which shifts the chlorine vapor
1
2 equilibrium to alkali halides, favoring chlorine deposits. Another factor is the lower quantity of
3 clinker produced, implying a lower overall quantity of chlorine adsorbed by the clinker in the
4
5 kiln. In contrast, incombustible chlorine is lower under use of FPRBs and, more specifically,
6
7 by 8% for FPRB1.5%, by 6% for FPRB10%, and by 4% for FPRB15%. This is attributed to the
8 lower charging of chlorines with the FPRBs (FPRBs are blends consisting of 80%wt FRB,
9
10 20%wt paper, while paper chlorine content is at 1/3 of FRB chlorine content, Table 3[48-51,83-86])
11
12 and, also, to the higher quantity of clinker produced.
13
14
15 Inclusions of volatile metals Cd +Tl per t clinker are equal to baseline for FRBs and FPRB
16
17 blends (fig. 5c), due to the counteracting effects of chlorines (favoring higher releases to the
18 atmosphere, i.e., lower inclusions) and of the quantity of clinker. In other words, the increase
19
20 due to the lower clinker quantity is balanced by the decrease of inclusions due to slightly
21
22 higher Cd+Tl emissions, which, in turn, are induced by the higher concentrations of
23 combustible chlorines. These observations and reasoning are in accordance with the
24
25 description above and, also, with fig. 8a depicting HX emissions. For mercury, inclusions per t
26
27 clinker are slightly lower (by about 1.5%) than baseline for FRBs and slightly higher (by about
28 1%) for FPRB blends, despite the increased clinker levels. This is due to the impact of
29
30 combustible chlorines shown in fig. 4 (as affected by sulphur (figs 4 and 6c) since the feedrate
31
32 of petcoke is the same as for FRBs, i.e., 29 829 tpa lower than baseline). Chlorines are lower
33 under FPRBs than FRBs (fig. 8a), thus resulting in lower Hg emissions for FPRBs than FRBs
34
35 (Hg emissions depicted in fig. 6b). From the Hg mass balance, if Hg emissions fall, then Hg
36
37 inclusions must rise by the same amount. Thus, acting in parallel, these two mechanisms,
38
that is, (i) lower combustible and higher incombustible chlorine than FRBs and (ii) lower Hg
39
40 emissions, counterbalance the impact of higher clinker quantity for FPRBs on Hg inclusions/t
41
42 clinker.
43
44
45 Environmental compliance and actual emission rates
46
47 Regarding environmental compliance and actual emission rates the following are noted. At
48
first the emissions limits, xl , for SO2, TSPs and NOx, are different under fossil fuel operation
49
50 and under use of waste derived fuels (A, Supplementary Information). In particular,
51
52 xl ,SO2 ,baseline  60mg / Nm3 versus xl ,SO2 , FRB  50mg / Nm3 , xl ,TSP,baseline  20mg / Nm3 versus
53
54 xl ,TSP, FRB  30mg / Nm3 and xl , NOx ,baseline  800mg / Nm3 versus xl , NOx , FRB  500mg / Nm3 (fig.
55
56
6a). The stricter limits, rendering compliance more strenuous, are fully reflected in condition
57
58 (6), which requires (necessary and sufficient) φ/μ <1 for compliance.
59
60
61
62
63
64 20
65
 It is seen that, under 20% thermal substitution of petcoke by FRB, compliance condition (6) is
1
2 satisfied for all regulated pollutants but NOx (fig.6a). In particular, the ratio φ/μ for NOx is at
3 (φ/μ)NOx =0.78 under baseline conditions. When FRBs and FPRBs are used, the ratio φ/μNOx
4
5 ranges between 1.28 and 1.45, showing that emissions exceed the maximum limits by 28%
6
7 and 45% respectively, with the lower values corresponding to blends of FRB with paper
8 residues. It is also noted (fig. 6a) that actual emission rates of NOx increase by about 20%
9
10 with respect to baseline, mo ffg, NO
x
mo ffg, NOx ,0 =1.20. This is attributed to the higher N-content of
11
12 FRBs compared to the N-content of the substituted petcoke. Thus, the NOx emissions
13
14 compliance problem revealed under utilization of FRBs is not due only to the lower emissions
15
16 limit, but to the increased rates of NOx emissions as well, originating from the biogenic fuel
17 itself (fuel nitrogen)[89-94]. In contrast, under use of blends of FRBs with paper residues
18
19 (FPRBs) the NOx emission rates remain at baseline levels (despite the increased clinker
20
21 production levels) and thus, the violation of the compliance limit under use of FPRBs is solely
22 due to the stricter emissions limit (800 mg/Nm3 versus 500 mg/Nm3). It is deduced that
23
24 additional N-removal effort is required for NOx. The NOx emissions compliance problem can
25
26 be addressed by revamping of the deNOx system or, by increasing the catalyst rate in catalytic
27 nitrogen removal systems, or by increasing the levels of added urea in selective non catalytic
28
29 nitrogen removal systems (SNCR) [92-93].
30
31
32 The compliance index (ratio φ/μ= ratio of compliance factors) for Hg under baseline conditions
33
34 is at (φ/μ)Hg =0.53, i.e., the emitted concentrations of mercury are at 53% of the maximum limit
35
36 set by the legislation (fig. 6b). It ranges between 0.62 and 0.68, under use of FRBs and
37
between 0.41 and 0.47 under use of FPRBs, i.e., lower than baseline. Actual emissions of
38
39 mercury are also lower than baseline; again the lowest emission rate corresponds to FPRB
40
41 with 1.5% moisture. The lower Hg emissions of the paper and food residue blends, compared
42
to stand alone FRBs, are due to the lower halogen levels, which imply lower combustible
43
44 chlorine in the offgases and therefore higher removal efficiencies of volatile metals from the
45
46 offgases. The same is true regarding other volatile metals (Cd and Tl, fig. 7b). SO2 emitted
47
48
concentrations and emission rates are lower, both under use of FRBs and of FPRBs (fig. 6c),
49 due to the lower sulphur content in FRBs than petcoke. The compliance index, φ/μ, is slightly
50
51 higher than baseline, due to the lower maximum limit xl , SO2 ,baseline . The lower sulphur presence
52
53 in the kiln favors incombustible chlorine, i.e., chloride deposits and incorporation of chlorines
54
55 in the clinker mass as salts. Regarding PCDD/Fs, nonvolatile metals and the volatile metals,
56
cadmium and thallium (Cd and Tl) the compliance indices φ/μ, and emission rates are ~10%
57
58 higher than baseline for FRBs and ~10% lower for FPRBs (fig. 7). It is noted that emitted
59
60 concentrations of PCDD/Fs are more than two orders of magnitude times lower than
61
62
63
64 21
65
 maximum limits set by legislation in all scenaria. The high compliance margin (low compliance
1
2 index) under baseline conditions (φ/μd= 0.009, φ/μCd, Tl= 0.12 and φ/μdm= 0.25) ensure ample
3 compliance under use of FRBs. The multifaceted impact of chlorines in regard to emissions of
4
5 volatile metals, PCDD/Fs and on corrosive chlorine deposits could be addressed by regulated
6
7 injection of activated carbon to the fluegases[95] right after the precalciner, where FRBs are
8 likely to be fired.
9
10
11
12 Halogen emitted concentrations are higher by about 16% than baseline when FRBs are used,
13 yet lower (by about 20%) under use of FPRBs (fig. 8a). This is due to lower chlorine charging
14
15 with FPRBs and to higher clinker levels. Emission rates follow the same trend. Particulate
16
17 emissions are higher by about 3% under FRBs but lower by ~2% under FPRBs. A similar
18 trend is observed for TOC emissions, i.e., they increase under use of FRBs but decrease
19
20 under use of FPRBs (fig. 8b). Regarding TSPs, the lower maximum limit set by legislation
21
22 under use of refuse derived fuels renders compliance easier, i.e., under use of any of FRBs
23 and FPRBs the ratio φ/μ is lower and the compliance margin larger than baseline (fig. 8c).
24
25 Emission rates are slightly higher under FPRBs due to the higher levels of clinker, which
26
27 require higher quantities of raw meal to be processed in the soil mill, leading to higher
28 emission rates of particulates.
29
30
31
32 Energy and environmental performance: Wind rose diagrams and snapshot evaluation
33 Evaluation can be readily perceived via a single picture depicting the relative values of all
34
35 important criteria included in fig. 3, as given by eqs 1-10: economic performance, product
36
37 quality and environmental performance as reflected by both compliance to emission standards
38
and actual emission rates to the environment. Such a comprehensive evaluation is depicted
39
40 via the wind rose, or radar graphs in figs 9-11. Figs 9a and 9b depict performance under
41
42 baseline conditions. Environmental performance is depicted in fig 9a, economic performance
43
in fig. 9b. The environmental evaluation of NOx and Hg emissions are shown in fig. 9b as
44
45 well. As expected, the ratios of emission rates (green line) take the value one (1) (fig. 9a).
46
47 The compliance index, i.e., the ratio φ/μ for NOx is at (φ/μ)NOx =0.78 and for Hg is (φ/μ)Hg =0.53.
48
The internal wind rose (magenta) refers to the compliance indices, i.e., the ratios (φ/μ). In line
49
50 with figs 6-8, the compliance indices are all below one (data included on the graph), reflecting
51
52 the conformance of emitted concentrations to the maximum limits of emitted concentrations
53
54
set by enacted legislation. Also, in accord with fig. 5, all scaled economic performance
55 indicators take the value one (1) under baseline conditions (fig. 9b). Figs 9c-9d depict the
56
57 performance when using FRB, dried at 1.5%: the ratio φ/μ for Hg is (φ/μ)Hg =0.65 and for NOx
58
59
(φ/μ)NOx =1.46. Emitted concentrations are within maximum limits set by legislation except
60 from NOx, yet emission rates are higher compared to baseline. Sulphur dioxide (SO2)
61
62
63
64 22
65
 emission rates are lower than baseline. Regarding economic performance, fossil fuel cost
1
2 and non-biogenic CO2 emissions are at 80% of baseline. Fig. 10 presents the same
3 information for FRB at 10%w moisture and FRB 15%wt moisture level. As expected, FRB1.5%
4
5 features better economic and environmental performance. Fig. 11 depicts the windrose
6
7 evaluation diagram for FPRB blends. It is seen that in all scenaria (FPRB1.5%, FPRB10% and
8 FPRB15%) emitted concentrations of all regulated pollutants but NOx conform to maximum
9
10 limits, while emission rates of pollutants are equal or lower than under baseline conditions.
11
12 FPRB1.5% features the best economic performance and lowest emissions. As previously
13 stated, the issue of NOx compliance can be readily addressed by revamping of the deNOx
14
15 system via catalytic or non-catalytic deNOx system. Based on the above discussion it is
16
17 evident that the windrose diagrams allow prompt, yet holistic depiction of energy efficiency,
18 economic opportunities and costs, and also, of environmental repercussions from FRB use in
19
20 cement plants. Obtained via model simulations and used for licensing the specific cement
21
22 plant, the results are to be further validated via actual trials, with FRB obtained from source
23 separation programs in a large urban center located nearby (10 km) the cement plant and
24
25 pretreated (thermally dried) at a municipal biowaste facility.
26
27
28
29
30 5. DISCUSSION
31
32
33 Food waste has been investigated in existing literature as a solid fuel based on its
34
35 composition and heating value. The novelty of the present work lies in assessing dried
36
37 household food waste via simulations as an alternative fuel in cement kilns, based on actual
38
plant performance (clinker production level), operability (satisfaction of operational constraints)
39
40 atmospheric emissions, potential impact on product quality and process equipment. Using a
41
42 model founded on mass and enthalpy balances, the method showed that thermal substitution
43
of petcoke by 20% in a local plant implies lower production level by about 2%, higher volumes
44
45 of offgases and increased inclusions of alkalis and trace metals. Lower moisture resulted in
46
47 higher performance and improved emissions. In contrast, blends of FRB with paper detrita -a
48
biogenic fuel as well- improved plant performance and emissions. Limitations of the analysis
49
50 and results include the specific source (kitchen food residues, country and area of origin) and
51
52 composition, potential additives and blends. Food waste from agricultural production was not
53
54
included. Another limitation is the specific plant evaluated, which revealed the crucial role of
55 plant design and operational parameters. Further research can be directed towards assessing
56
57 FRBs from various sources worldwide. Identification of appropriate blends with other
58
59
renewable fuels (paper, biosludges, wood residues), custom tailored for specific plants
60 emerges as a key research issue.
61
62
63
64 23
65
 1
2
3 suggestions, limitations, further implications and potential influence of limitations on the paper itself
4
5
6 6. CONCLUSIONS
7
8
9
10 Half a billion metric tonnes of coal and petcoke per year (2017) are consumed globally in
11 cement plants. Food residues (classified as non-dangerous wastes according to European
12
13 Commission Decision 2014/955) are projected globally at 1.5 billion tonnes per annum (tpa)
14
15 by year 2025. The purpose of the present work was to evaluate potential use of household
16
food residue biofuels (FRBs) as a substitute for fossil fuels in cement kilns. The major goals of
17
18 the evaluation were to assess the impact on plant operation and performance, and on product
19
20 quality and emissions as compared to conventional operation that uses fossil fuels (baseline
21
operation). Based on simulations of an actual dry-process plant, via a multidimensional model
22
23 which utilizes actual data as well, the analysis divulged that dried at low moisture (<15% wt)
24
25 household FRBs could substitute fossil fuels in cement kilns as renewable fuels. Lower
26
clinker production level, lower greenhouse gas emissions, lower emissions of sulphur and
27
28 volatile metals (mercury) but increased chlorine presence and slightly higher emission rates
29
30 for several pollutants were revealed at 20% isothermal substitution of petcoke. Compliance to
31
32
environmental regulation was maintained for all pollutants but NOx. Use of that blends
33 consisting of 80%wt FRB and 20%wt paper residues (FPRB blends) is suggested since they
34
35 lead to increased clinker production by ~2%, ensuring emissions compliance (emitted
36
37
concentrations below maximum limits set by legislation) lower actual emission rates than
38 baseline operation and no significant degradation of product quality (small increase of
39
40 inclusions). In practice, this means that in a medium scale cement plant such as that of the
41
42 case study, about 38 000 tpa of FRB could be used, originating from about 170 000 tpa of
43 household food wastes. A further implication of using such blends is that lower effort for
44
45 revamping the deNOx system, or lower levels of additional urea are required for NOx
46
47 compliance, compared to stand alone FRB utilization. Limitations of the evaluation method
48 include the steady state lumped model used. Limitations of the results include the specific
49
50 food waste investigated (composition and heating value) and the specific cement plant
51
52 analyzed, albeit the method can be applied to any plant and various food wastes from differing
53 countries with different characteristics. The method may be useful in evaluating agriculture
54
55 FRBs and identifying superior blends with other low VS biogenic residues, (high cellulose and
56
57 lignine, e.g., saw dust, wood detrita). Such blends could be tailor-made for cement plants
58 under specific modes of operation (e.g., direct or compound) or fit to process design,
59
60 operating conditions (e.g., combustion excess air, use of oxygen enrichment) and raw material
61
62
63
64 24
65
 characteristics (CaO yield from quarry lime CaCO3). Addressing successfully the main
1
2 economic and ecological challenges, including high content of chlorine and alkalis and impact
3 on emissions and process equipment, such blends may lay the ground towards higher
4
5 substitution rates of fossil fuels by renewable fuels in cement kilns.
6
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49
50
51
52
53
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55
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 Nomenclature
-1
A inverse of the pxp diagonal matrix of atomic weights A =
{diag (AW)j}, of the chemical elements in the
fuels, in the order C, H, O, S, N, Cl, P, Br, F, Si, Ca, Mg, Na, Fe, Al, Ti
1 a = vector giving the oxygen and nitrogen molar flows from total air molar flow in
T
2 the order of the flue gas vector constituents, a = (0, 0, 0.21, 0.79, 0,….0)
3 b specific energy requirement per t of clinker (Kcal/kg clinker) or TJ/t clinker,
bk   f
T
4
5
Cmxn matrix C =: DS A–1 W + η u1 (b-1 λΤ - σΤ)
 M u1  =ith component of the vector
6
7 cfg,i M u1 =scalar in eq. 1, which gives the
8 mass flowrates of kiln fluegas i
9
10
cfg,i   T T

= M DSA W  u 1 (   ) =vector multiplying the vector of fuel feeding
1

11 rates, f, in eq. 1
12 cp vector of heat capacities of the flue gases (cp1 = cpCO2, cp2 = cpH2O, cp3 = cpO2, cp4=
o
13 cpN2, cp5 = cpSO2, cp6 = cpHCl2, cp7 = cpP2O5 in kca/kg K
o
14 cp clinker clinker heat capacity in kca/kg K
o
15 cpf fuel heat capacity vector, in kca/kg K
o
16 cp rm raw meal heat capacity in kca/kg K
17 D acid detainment matrix by clinker (impact on fluegases) due to neutralization
T
18 e orthodiagonal vector e =[1, 1,…,1],
19 f fuel mass flowrate vector (fi in t /y),
20 g generation rate from raw meal and fuels, tpa, e.g., g SO2   SO2 r  m fg ,SO2
21
22 h air moisture, molal fraction
23 In nxn identity matrix
24 k total clinker production level, (t/y) = b-1 λΤ f
25 kA APCS adsorption rate constant
1
clinker adsorption rate constant, e.g. for SO2: k C  1.2 * 10
3
26 kC Nm /tn found from
27
baseline SO2 detainment factor, e.g. 1  exp(  k C r0 / V fg , 0 )  68% (Case study),
28
29 km = (b-1 λΤ - σΤ) f = raw meal clinker production (t/y) (not including fuel ash)
30 LHV lower heating value of fuels
31 mfg vector of the mass of flue gases produced = mass flows of (CO2, H2O,
32 O2, N2, SO2, HCl, P2O5). mfg = total mass flowrate of kiln flue gases
33
= m fg , SO  u 5 m fg ,0
T
34 m fg , SO fluegas mass flowrate of SO2
2 2
35 msm air total mass of soil mill air driven to the kiln/soil mill APCS
36 mfm air total mass of fuel mill air driven to the fuel mill APCS
37 Mmxm = diag {MW(CO2), MW(CO), MW(H2O), MW(O2), MW(N2), MW(NO), MW(N2O),
38 MW(SO2), MW(HCl), MW(P2O5), MW(HBr), MW(HF),…} =
39
40 diag {44, 28, 18, 32, 28, 30, 44, 64, 36.5, 142,...)
41 Mair =MW air = molecular weight of air = 28.84
42 M1 molecular weight of CO2 = ΜW(CO2) = 44
43 P pressure
R universal gas constant = 0.08206 (atm Lt) /(mol K)
 
44
raw meal feed rate, r  (1  M 1 )   (  ) f ,
T T
45 r
46
Smxm stoichiometry matrix of fuel conversion to flue gas products
47
48 Sb part of stoichiometry matrix independent of excess air and oxygen enrichment
49 sa part of stoichiometry matrix independent of excess air and oxygen enrichment
50 s fraction of hot clinker enthalpy not recovered by secondary and tertiary air
51 T temperature, Tkiln:kiln, Ts:ambient, Tr:heat of reaction reference, Tp: preheater
th
52 ui i unit vector (0, 0, 0,…1, 0, 0)
3
53 Vfg kiln flue gas volumetric flowrate (Nm /h)
3
54 Vk sm kiln / soil mill gas volumetric flowrate (Nm /h)
th
55 Wrxn rxn matrix of net fuel weight composition, without the slag: the i
th
56 column of W is the % weight as received composition of the i fuel in the
th
57 combustible elements, multiplied by the net combustible content (1- σi) of the i
T
58 fuel, W j = (1- σi) % (C, H, O, S, N, Cl, P, Br, F, Si, Ca, Mg, Na, Fe, Al, Ti)
59 x pollutant concentration
xin APCS pollutant concentration in kiln/soil mill gases entering the APCS
 
60
61 yA = exp  k A / Vk , sm , APCS pollutant removal efficiency by the APCS
62
z vector dependent on excess air and oxygen enrichment (affects the stoichiometry
63
matrix, Smxm). 30
64
65
 GREEK

αsm air drawn in the soil mill, kg per kg clinker

th
βi,r factor for i pollutant rate, originating from raw meal (produced in the kiln), t/t
th
βf vector of production rate of i pollutant from the fuels utilized, t/t
  
1
1 y 1 1
2 γA dimensionless APCS non-adsorption ratio,  A   exp k A Vk ,sm, 0  Vk ,sm
3 1  y0
4 γC dimensionless kiln non-adsorption ratio  C  exp kC r0 / V fg ,0  r / V fg 
5
6 ΔH = enthalpy with respect to a reference level
7 δ power in law for effect of halogen hindrance on metal detainment by the clinker
8 δ’ power in law for effect of metal concentration on metal detainment by the clinker
9 O 2
oxygen enrichment, v% , O2 air vol composition = ( 20.95   O2 )%
10
11 ζ ζ is the ww fraction of raw meal in CaO, typically ζ is between 0.4 – 0.5.
-1
12 η η = ζ/56 (1-M1 ζ/56) , # kmols of CO2 produced via lime dissociation (reaction b) per kg of
13 clinker from raw meal, krm
14 θ fraction of flue gas cleaned in the kiln/soil mill APCS
15 krm annual clinker quantity originating from the raw meal
16 κ constant term in clinker level, independent of the fuel, given in eq. A11
17 κ vector independent of fuels, (eq. A12), element κi=marginal clinker production per t of fuel i
18 λ vector of lower heating values of the various fuels, 1,2,…,n, i.e. λT f is
19 the total (annual) thermal load of the kiln /precalciner system
20 μ dimensionless ratio of standardized pollutant emission to maximum allowed limit
21 ν dimensionless ratio in necessary and sufficient compliance condition 12
-1
22 ρ vector incorporating kiln fluegas split and pseudo air (θI + Mair ψ M) e that is component ρi=
23 [θ+ ψ (MW i / MW air)], e.g. ρ1 = θ+ψ (MW CO2/MW air), etc.
t
24 σi w% of noncombustible solids contained in the i fuel,
25 υ specific molal flue gas volume under P, T conditions = RT/P
26 φ dimensionless emission compliance ratio
27 ψ mass fraction of induced air draft (pseudo or intrusion air) with respect to kiln flue gas
28
29 Subscripts
30
31 0 refers to the baseline case with conventional fossil fuels
32 1 refers to CO2
33 l limit imposed by legislation
34
35 s standard conditions, 10% oxygen, dry, STP
36 M actual measurement, past the APCS, (offgas)
37
38 A APCS
39
40
C clinker
41
42
43 Superscripts
44 T
45 transpose of a vector or a matrix
46
47 Symbols
=:
48 equal by definition
49 [] molar concentration
50 Abbreviations
51 AF alternative fuel
52 APCS air pollution control system
53 FPRB food and paper residue biofuel
54 FRB food residue biofuel
55 FW food waste
56
LHV lower heating value
57
58 PCDD/F dibenzo-p-dioxins and dibenzo furans
59 SF standardization factor
60 SM Supplementary Material
61 tpa, tpd tones per annum, tones per day
62 TOC, TSP total organic carbon, total solid particulates
63
64 31
65
 1
2
3 FRB (kg / tn food residue)
4
5 265
6
260
7
8 255
(kg/tn food residue)

9
10 250
11
245
FRB

12
13 240
14
15 235
16
230
17
18 225
19
20 220
21 0.0% 5.0% 10.0% 15.0%
22 Moisture of FRB
23
24
FRB LHV(MJ/kg)
25
26 Energy for water evap.(MJ / kg FRB)
27 Energy for water evap. (MJ/ kg food residue)
28
29 18
30
31 16
32 14
Energy (Mj/kg)

33
34 12
35
10
36
37 8
38
39 6
40 4
41
42 2
43 0
44
45 0.0% 5.0% 10.0% 15.0%
46 Moisture of FRB
47
48
49
50
51 Fig. 1. Food residue biofuel (FRB) yield of food residues (food waste) and associated drying
52 energy and energy content (LHV) of produced FRB.
53
54
55
56
57
58
59
60
61
62
63
64 32
65
 Exhaust
1 900kWe gases
2 Hot Cooled
3 fluegases fluegases
4 Rotating
5 Natural NG or diesel drum. Cyclone
6 electricity
7
gas or Direct heat decanter
8 diesel generator convection.
9
FRB
Food
10 residues 5 tpd
11 20 tpd 1.5% Ash
12 75% moist. moist.
13
14
15
16
17 Cooled
18 fluegases
19 Hot Air and
Hot Air moisture
20 fluegases Heat
21
22
Air heat convection, Condenser
23 exchanger Drier belt
24 Make up
25 Food FRB
26 Air residues Water,
27 75% moist. volatiles
28
29
30
31
32
33
34 Condenser
35 Food
36 residues Water,
37 volatiles
38 Cooled Exhaust
39 fluegases Hot Oil
40 Hot
41 FRB
fluegases Oil (or
42
43 Steam)
44 heat
45 exchanger Cooled FRB
46
Oil
47
48 Make up Archimedean screw, mixer /
49 oil or Food drier / heat exchanger featuring
50 water two counter rotating axes with
51 residues
52 heated paddles and axial
53 circulation of heating agent.
54
55
56 Fig. 2. Flowdiagrams of drying processes for producing FRBs. Top: Direct drying in rotating drum
57 using the fluegases of a diesel generator. Middle: air drying via heat convection to the FRB on a drier
58 belt. Bottom: drying via heat conduction (oil or steam circulating in the counter rotating axes of the
59 Archimedean screws with paddles).
60
61
62
63
64 33
65
 1
2
3 Plant Product
operability: Feasibility of use quality
4
Heat rating, of biogenic fuels within
5 in cement plants
6 blower limit specs
7
8
9
Direct economic
10 benefits.
11
12
13
14
15 Economic: Economic:
clinker production level. CO2 eq pollution rights.
16
17
18
19 Economic:
20 Economic:
Income from gate fees & Product quality/price due to
21 inclusions of alkalis and
Reduced fossil fuel Sustainability
22 costs. trace metals.
23 assessment of
renewable
24
fuels in
25 cement plants
Environmental: Environmental:
26
Pollutant emissions Reduced greenhouse gas
27 kiln emissions,
28 (a) compliance
(b) actual emissions rates. (lower non-biogenic CO2 eq,
29 t/t clinker).
30
31
32
33 Environmental: Environmental:
34 Resource preservation. Prevention of biowaste
35 (Substitution of depleting disposal (high BOD leachates
fossil fuels). & high GHG emissions).
36
37
38
39
40 Emissions compliance.
41 Social acceptance.
42 Green labeling of
43 cement product &
44 indirect economic benefits.
45
46
47
48
49
50 Fig. 3. Evaluation of food residue biofuels for substituting fossil fuels in cement plants,
51 including economic performance, product quality and environmental performance
52
53
54
55
56
57
58
59
60
61
62
63
64 34
65
 1
2
3
4
5
6
7 Higher emissions of
8 PCDD/Fs
9
10 Higher fuel Combustible
11 sulphur chlorine Higher emissions of
12
Hg, Cd and Tl
13
14
15
FRB
16 chlorine Increased corrosive
17 deposits of chlorine
18
19 Lower fuel Non
20 sulphur or combustible Higher inclusions of
21 alkalis and chlorine in
22
lower chlorine
feedrate of cement.
23
24 petcoke
25
26 Higher inclusions of
27 volatile metals, mainly
28 Hg, in cement.
29
30
31
32
33
34
35
36 Fig. 4. The fate of FRB chlorine in cement plants and consequences when substituting FRBs for
37 petcoke.
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64 35
65
 1 70 000
2 60 000
3
biofuel, (t/y)
50 000
4 40 000
5
30 000
6
20 000
7
10 000
8
0
9

5%

%
%

%
5%

10

lin

10

15
10

15

1.
1.

se
11

B
B

B
ba
B

R
FR

FR

R
FR

12 (a)

FP

FP
FP
13
14
15 clinker, tn/y Non Biogenic fuel CO2 (gr/tn clinker) Vksm (Nm3/h)
16
17
1 550 000 800 000
18

(gr/tn clinker), Vksm (Nm3/h)

19 700 000

Non Biogenic fuel CO2,

1 500 000
20
600 000
clinker, (t/y)

21 1 450 000
22 500 000
23 1 400 000
24 400 000
324 213
25 1 350 000 276 103 277 288 278 120 266 847 267 654 268 217 300 000
26
27 1 300 000 200 000
28
e

5%

%
%

%
5%

lin

29
10

15
10

15

1.
1.

se

B
B

30
B
ba
B

(b)
R

R
FR

FR

R
FR

FP

FP
FP

31
32
33 Ratio of combustible chlorines Inclusions ratio (Na+K)/t clinker
34 Inclusions ratio (nonvol metals)/t clinker Inclusions ratio (Cd,Tl)/t clinker
35 Inclusions ratio (Hg)/t clinker ratio of noncombustible chlorines
36
37 1.30
38 1.25
Hydrogen halides

39 1.20
Inclusions,

40 1.15
41 1.10
42 1.05
43 1.00
44 0.95
45 0.90
46
0.85
47
e
5%

5%

48
%

lin

10

15
10

15

1.
1.

se

49
B

B
B

ba

B
B

FR

FR

R
FR

50 (c)
FP

FP
FP

51
52 6
53 Fig. 5. Case study: Economic performance of a 1.5 x 10 tpa dry clinker facility under 20%
54 thermal substitution of petcoke by food residue biofuels (FRBs) or food (80%w) and paper
55 (20%w) residue biofuels (FPRBs) at various moisture levels. Baseline: fossil fuel operation with
56 70% petcoke and 30% coal, thermal contribution (a) FRB and FPRB federates (b) Performance
57 criteria: clinker production level, main blower load (V k.sm) and nonbiogenic CO2 emissions per
58 tonne clinker (c) Combustible chlorines, incombustible chlorines in process equipment and pipes
59 and product quality assessed by inclusions of alkalis and leachable metals per tonne clinker
60 (ratios with respect to baseline conditions).
61
62
63
64 36
65
 moffg,NOx/moffg,NOx,0 φ NOx / μ NOx
1
2 xl,NOx, (mg/Nm3) xs,NOx, (mg/Nm3)
3
4 1.6 900
5 800
1.4

xl.ΝΟx, xs.ΝΟx
6 700
moffg,NOx/moffg,NOx,0
1.2

(mg/m3)
7 600
8 1.0
φNOx / μNOx,

500
9 0.8
400
10 0.6 300
11 0.4 200
12 0.2 100
13 0.0 0
14

e
5%

FP .5%

%
FR %

FP elin
15

10

15
10

15
1.

1
s
16

B
B

ba

B
B

(a)
FR

R
FR

FP
17
18
19
20 moffg,m,Hg/moffg,m,Hg,0 φ Hg / μHg
21 xl,Hg (mg/Nm3) xs,Hg, (mg/Nm3)
22
23 1.4 0.06
moffg,,Hg/moffg,Hg,0

24
1.2 0.05
25

xl.Hg, xs.Hg
φHg/μHg,

1.0

(mg/m )
0.04

3
26
27 0.8
0.03
28 0.6
29 0.4 0.02
30 0.2 0.01
31 0.0 0.00
32
e
5%

5%

%
%

33
lin

10

15
10

15

1.
1.

se

34
B

B
B

ba

B
B

(b)
FR

FR

R
FR

35
FP

FP
FP

36
37
38 moffg,SO2/moffg,SO2,0 φSO2 / μSO2
39 xl,SO2, (mg/Nm3) xs,SO2, (mg/Nm3)
40
41
1.20 60
moffg,SO2/moffg,SO2,0

42
43 1.00 50
xl,SO2, xso,SO2
φSO2/ μSO2,

44
(mg/m )

0.80 40
3

45
46 0.60 30
47 0.40 20
48
0.20 10
49
50 0.00 0
51
e
5%

5%

%
%

lin

10

15
10

15

52
1.
1.

se

B
B

ba

B
B

53
FR

FR

R
FR

FP

FP
FP

54 (c)
55
56 Fig. 6. Case study: 20% isothermal substitution of petcoke by FRB and FPRB at various
57 moisture levels. Environmental performance: NO X, Hg and SO2. (A) Compliance to
58 maximum allowed limits is assessed via the compliance margin ratio with respect to
59 baseline operation, (φ/μ): compliance is ensured if and only if φ/μ <1. (B) ratio of actual
60 offgas emission rates (emitted pollutant mass/s) with respect to baseline conditions,
61 moffg/moffg,0.
62
63
64 37
65
 1
2 moffg,d/moffg,d,0 φd / μd xs,d, (ng/Nm3) xl,d, (ng/Nm3)
3
4
5 1.15 0.12

xl.d, xs.d (ng/m3)

6 1.10 0.10
moffg,d/moffg,d,0

7
8 1.05

φ d/ μ d,
0.08
9 1.00
10 0.06
11 0.95
12 0.04
0.90
13
0.85 0.02
14
15 0.80 0.00
16
e
5%

5%

%
%

17
lin

10

15
10

15

1.
1.

se

18

B
B

ba

B
B

FR

FR

R
FR

R
19 (a)

FP

FP
FP

20
21 moffg,m,Cd, Tl/moffg,m,Cd, Tl,0 φm, Cd, Tl / μm, Cd, Tl
22
23 xl,m,Cd, Tl (mg/Nm3) xs,Cd,Tl, (mg/Nm3)
24 1.4 0.06
25
moffg,Cd,Tl/moffg,Cd,Tl,0

1.2
φm, Cd, Tl/ μm,Cd,Tl ,

0.05

xs.m,Cd,Tl (mg/m 3)
26
27 1.0
0.04

xl.m,Cd,Tl,
28
0.8
29 0.03
30 0.6
31 0.02
0.4
32
33 0.2 0.01
34 0.0 0.00
35
e
5%

5%

%
%

36
lin

10

15
10

15

1.
1.

se

37
B

B
B

ba

B
B

FR

FR

R
FR

38
FP

FP
FP

(b)
39
40
moffg,m/moffg,m,0 φm / μm
41
42 xl,m (mg/Nm3) xs,m, (mg/Nm3)
43 1.4 0.50
xl.m, xs.m (mg/m )
3

44 1.2 0.45
moffg,m/moffg,m,0

45 0.40
φm / μm ,

1.0 0.35
46
0.8 0.30
47 0.25
48 0.6 0.20
49 0.4 0.15
50 0.10
0.2 0.05
51
52 0.0 0.00
53
e
5%

5%

%
%

lin

10

15
10

15

54
1.
1.

se

B
B

ba

B
B

55
FR

FR

R
FR

FP

FP
FP

56 (c)
57
58 Fig. 7. Case study: 20% isothermal substitution of petcoke by FRB and FPRB at various
59 moisture levels. Environmental performance: PCDD/Fs, volatile metals (Cd, Tl) and
60 nonvolatile metals.
61
62
63
64 38
65
 moffg,HX/moffg,HX,0 φHX / μΗΧ
1
2 xl,HX, (mg/Nm3) xs,HX, (mg/Nm3)
3
4 moffg,HX/moffg,HX,0 1.8 10
1.6 9

xl,HX, xso,HX,
φHX / μHX,

5 1.4 8

(mg/m3)
6 1.2 7
1.0 6
7 5
8 0.8 4
9 0.6 3
0.4 2
10 0.2 1
11 0.0 0
12

e
5%

5%

%
%

lin
13

10

15
10

15

1.
1.

se
14

B
B

ba

B
B

FR

FR

R
FR

FP

FP
FP
15 (a)
16
17 moffg,TOC/moffg,TOC,0 φ TOC / μ TOC
18
19 xl,TOC, (mg/Nm3) xs,TOC, (mg/Nm3)
20
1.10 12
21
1.05

xl.TOC, xs.TOC (mg/m3)

22 10
moffg,TOC/moffg,TOC,0

23 1.00
24
φTOC/ μTOC,

8
25 0.95
26 0.90 6
27 0.85
28 4
29 0.80
2
30 0.75
31 0.70 0
32
e
5%

5%

%
%

33
lin

10

15
10

15

1.
1.

se

34
B

B
B

ba

B
B

FR

FR

R
FR

FP

FP

35
FP

(b)
36
37
moffg,TSP/moffg,TSP,0 φTSP / μTSP
38
39 xl,TSP, (mg/Nm3) xs,TSP, (mg/Nm3)
40
41 1.20 35
42 30
xl.TSP, xs.TSP (mg/m3)
moffg,TSP/moffg,TSP,0

1.00
43
25
φTSP/ μTSP,

44 0.80
45 20
46 0.60
47 15
48 0.40
10
49 0.20
50 5
51 0.00 0
52
5%

%
%

5%
e
lin

53
10

15
10

15
1.

1.
se

B
B

54
B

B
ba

R
FR

FR
FR

FP

FP

(c)
FP

55
56
57
58 Fig. 8. Case study: 20% isothermal substitution of petcoke by FRB and FPRB at various
59 moisture levels. Environmental performance: HX, TOC and TSP.
60
61
62
63
64 39
65
 1 moffg/moffg,0 φ/μ Baseline Baseline
2
SO2
3 2
clinker level
4 FRB drying energy / 2
Hg HX offgas volume
5 LHV
1.000
6 1 1 1.000
7 0.53 0.38 fossil fuel cost Hg, φ/μ
8 Cd, Tl 0.23 TOC 1.000
0.533
0.10 0 0.75 0
9
0.090.01 1.000 0.779
10 nb CO2 NOx, φ/μ
0.75
11 1.000 1.000
12 nv metals 0.78 TSP 1.000
13 kiln Cl nv metal inclusions
14
PCDD/Fs NOx Na+K inclusions
15
16
17
moffg/moffg,0 φ/μ FRB 1.5% FRB 1.5%
18 SO2
19 2.0 clinker level
20 FRB drying energy /
2.0
Hg 1.5 HX offgas volume
21 LHV 1.5
22 1.0
1.0
23 fossil fuel cost Hg, φ/μ
24 Cd, Tl
0.5
TOC 0.5
25 0.0 0.0
26
nb CO2 NOx, φ/μ
27
28 nv metals TSP
29 kiln Cl nv metal inclusions
30
31 PCDD/Fs NOx Na+K inclusions
32
33
34
35 Fig. 9. Wind rose (radar) graphs depicting economic and environmental performance of FRBs and
36 FPRBs at 20% thermal substitution of petcoke, compared to baseline operation. Shown in fig. 9:
37 baseline operation (top) and operation under use of FRB with 1.5% moisture (bottom). Economic
38 performance (blue line, right column graphs) includes, production (clinker) level, ratio of offgas
39 volumetric flowrates (must be lower than main blower capacity) drying energy compared to energy
40 content (LHV) of the renewable biofuel, savings from substituted fossil fuels, savings from
41 greenhouse gas pollution rights (non-biogenic CO2), product quality as reflected by inclusions of
42 volatile and leachable metals and alkalis. Relative presence of chlorines in process equipment, pipes
43 and ducts is also depicted. Environmental performance (left column) is assessed by the ratio of
44 compliance factors with respect to baseline operation, φ/μ, which must be lower than one, φ/μ <1 for
45 compliance (magenta line) and by the ratio of actual emission rates, m offg/moffg,0 (green line) which
46 reflects the actual burden to the environment.
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64 40
65
 moffg/moffg,0 φ/μ FRB 10% FRB 10%
1 SO2 clinker level
2.0
2 FRB drying 2.0
3 Hg HX offgas volume
1.5 energy / LHV 1.5
4
5 1.0 1.0
fossil fuel cost Hg, φ/μ
6 0.5
0.5
7 Cd, Tl TOC 0.0
8 0.0
9 nb CO2 NOx, φ/μ
10
11 nv metal
nv metals TSP kiln Cl
12 inclusions
13 Na+K inclusions
14 PCDD/Fs NOx
15
16
moffg/moffg,0 φ/μ FRB 15% FRB 15%
17 SO2 clinker level
2.0
18 2.0 FRB drying energy /
19 offgas volume
Hg HX LHV 1.5
1.5
20 1.0
21 1.0 fossil fuel cost Hg, φ/μ
0.5
22
23 0.5
Cd, Tl TOC 0.0

24 0.0
25 nb CO2 NOx, φ/μ
26
27 nv metals TSP kiln Cl nv metal inclusions
28
29 Na+K inclusions
30 PCDD/Fs NOx
31
32
33
34 Fig. 10. Wind rose (radar) graphs depicting economic and environmental performance of FRBs for
35 20% thermal substitution of petcoke, compared to baseline operation: use of FRB with 10%
36 moisture (top) and use of FRB with 15% moisture (bottom).
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64 41
65
 1 moffg/moffg,0 φ/μ FPRB 1.5% FPRB 1.5%
2 clinker level
SO2 2.0
3 2.0 FRB drying energy /
offgas volume
4 LHV 1.5
Hg 1.5 HX
5 1.0
6 1.0 fossil fuel cost Hg, φ/μ
0.5
7
0.5 0.0
8 Cd, Tl TOC
9 0.0
nb CO2 NOx, φ/μ
10
11
12 nv metals TSP kiln Cl nv metal inclusions
13
14 Na+K inclusions
PCDD/Fs NOx
15
16
moffg/moffg,0 φ/μ FPRB 10% FPRB 10%
17
18 SO2 clinker level
2.0 2.0
19 FRB drying energy /
offgas volume
20 Hg 1.5 HX LHV 1.5
21 1.0
1.0
22 fossil fuel cost Hg, φ/μ
0.5
23 0.5
Cd, Tl TOC 0.0
24
0.0
25
nb CO2 NOx, φ/μ
26
27
nv metals TSP
28 kiln Cl nv metal inclusions
29
30 Na+K inclusions
PCDD/Fs NOx
31
32
moffg/moffg,0 φ/μ FPRB 15% FPRB 15%
33
34 SO2 clinker level
2.0 2.0
35 FRB drying energy /
Hg HX offgas volume
36 1.5 LHV 1.5
37 1.0 1.0
38 fossil fuel cost Hg, φ/μ
39 0.5 0.5
Cd, Tl TOC
40 0.0 0.0
41
42 nb CO2 NOx, φ/μ

43 nv metals TSP
44
kiln Cl nv metal inclusions
45
46 PCDD/Fs NOx Na+K inclusions
47
48
49
50
51 Fig. 11. Wind rose (radar) graphs depicting the superior economic and environmental performance
52 of FPRBs (80%w FRB and 20%w paper residues) for 20% thermal substitution of petcoke,
53 compared to baseline operation. The top blend FPRB1.5% (1.5%w moisture) features enhanced
54 economic performance (slightly higher clinker level than baseline) without increasing emissions
55 (apart from NOx emissions which can be improved by revamping the deNOx system) and without
56 impairing product quality.
57
58
59
60
61
62
63
64 42
65
 APPENDIX
1
2
A. Cement Plant Model and constants (independent of fuel feedrates) in eqs 1-5.
3
4
5 Combustion fluegases mass flowrates
6 MDSA 1W f (A1)
7
Kiln fluegas mass
  
8
m fg  M DSA 1W f  u1   (   ) f
T T
9 flowrates (A2)
10
11
T
12 Fuel ash in clinker σ f (A3)
13
14
15
Lime dissociation CO2 mCO 2 , lime  M 1   (   ) f  T T
 M 1  MWCO2  44 (A4)

16   M 1 
17  1   , (A5)
18
MWCaO  MWCaO 
Nonbiogenic CO2
 
19
M 1  M 1 (   )  u1 MDSA 1W B f
T T T
20 mass flowrate (A6)
21
22 B = diagonal matrix with ii diagonal element equal to 1 if i corresponds to non-
23 biogenic fuel and 0 to biogenic fuel
24
25
26 Raw meal r  (1  M 1 )   (   ) f  T T
 (A7)
27 Offgas species’
   
28 1 1
V k , sm   I  M air a e M C f  M air a sm (1  M 1 )   (   ) f (A8)
T T T
29 volumetric flowrates
30
Vk , sm  v  v f
T
31 Overall offgas

 
32
1
33 vol. flowrate v   1  M air  sm (1  M 1 )
     
34 1
DSA W  1  M air  sm (1  M 1 ) (   )
1
T T T T
35 v (A9)
36
k    f
T
37 Clinker level (A10)
38   c p rm (1  M 1 )(Tr  Ts )  (T p  Tr )c p1 M 1  sc p clin ker (Tki ln  Tr ) 1 L (A11)
39
40  T  c p rm (1  M 1 )(Tr  Ts )  (T p  Tr )c p1 M 1  sc p clin ker (Tki ln  Tr ) 1 x
41
T
42
{  (Tr  Ts )c pf  c p rm (1  M 1 ) (Tr  Ts )
T T
43
 (T p  Tr )c p MDSA 1W  (T p  Tr )c p1 M 1 }
44 T T
(A12)
45
46
47 Model calculations performed in EXCEL software via the function MMULT.
48
49
50
51 B. Emission rates.
52
xin, APCS 1  y A Vk , sm  Vk , sm  V
1  y A,0  Vk ,sm,0 1 k ,sm   xl SF0 k ,sm
moffg xin, APCS V
53
 
54 moffg,0 xin, APCS ,0 1  y A,0 Vk , sm,0 xin, APCS ,0 Vk , sm,0 xl ,0 SF Vk , sm,0
55
56 (B1)
57
58
59
60
61
62
63
64 43
65
 1 C. Presence of chlorines in equipment and APCS
2
3 As already discussed at high temperatures, a fraction of chlorine depending on the
4
5 concentration of sulphur is in the form of incombustible chlorines. Assuming that combustible
6
chlorines follow first order kinetics with respect to concentrations of SO2 in the
7
8 kiln/precalaciner/preheater, it follows that
9
10
11
12

m fg , HCl  g HCl exp  k C r / V fg exp  k HCl ,SO2 / x fg ,SO2  (C1)
13
14
15 The constant k HCL ( SO2 ) is found from baseline conditions,
16
k HCl ,SO2   x fg ,SO2 , 0 ln m fg , HCl , 0 g HCl , 0   k C r0 / V fg , 0  (C2)
17
18

 
19
20 and assuming m fg , HCl , 0 g HCl , 0  2 / 5 [52] it follows that k HCL ( SO2 )   x fg ,SO2 ,0 ln 2 / 5  kC r0 / V fg ,0 .
21
22
23 Then, from eq. C2 it follows that
24
25
26 [ HX ] fg x fg , HCl g HCl V fg , 0
27    C S (C3)
28 [ HX ] fg , 0 x fg , HCl , 0 g HCl , 0 V fg
29
30
31
which is eq. 10a with
32
33

 S  exp k HCl , SO x fg , SO 0  x fg.SO 0 

34
35 2 2 2
(C4).
36
37
38 If [Cl]fg, denotes the molar concentration of alkali chlorines in the fluegases, then taking into
39
40
account the detainment by the clinker in the kiln, it follows from the chlorine mass balance that
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44

m fg ,Cl  g HCl exp  k C r / V fg   g HCl exp  k C r / V fg exp  k HCl , SO2 / x fg , SO2  (C5)

45 or
 
m fg ,Cl  g HCl exp  k C r / V fg  1  exp  k HCl , SO2 / x fg , SO2 
46
47 (C6)
48
49
50
51 Then,
52 [Cl ] fg m fg ,Cl  
g HCl exp  k C r / V fg  1  exp  k HCl , SO2 / x SO2  V fg ,0 g HCl V fg ,0
   C S
g HCl ,0 exp  k C r0 / V fg ,0 1  exp  k  V
53
54 [Cl ] fg ,0 m fg ,Cl ,0 HCl , SO2 / x SO2 ,0 fg g HCl ,0 V fg
55
56 or
57
58 [Cl ] fg g HCl V fg , 0
59  C S (C7)
60
[Cl ] fg , 0 g HCl , 0 V fg
61
62
63
64 44
65
 1
2 which is equation 10c with
3
4
5
S 
1  exp  k HCl , SO2 / x SO2 
1  exp  k 
6 (C8).
7 HCl , SO2 / x SO2 ,0
8
9
10
11 Consequentlym the ratio of chlorine concentrations in APCS is given by eq. 10b,
12 x HCi ,n, APCS g HCi Vk ,sm,0
13   C S (C9)
14 x HCl ,in, APCS ,0 g HCi , 0 Vk ,sm
g HX   HX r  m fg , HX 
15
(C10)
16
17
18
19
20 
 HX  r0 1  xs , HX ,0Vk ,sm,0

exp k C r0 / V fg , 0 exp k HCl ,SO2 / x fg ,SO2 , 0 m 
 (C11)
21 SF0 (1  y A, HX , 0 )
fgHX , 0 
22  
23
24 xs,HCl ,0  2.25mg / Nm3 , xl ,HCl ,0  xl ,HCl  10mg / Nm3 xl , HF ,0  xl , HF  1mg / Nm3 (C12).
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64 45
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 1
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3 Table 1. Main constituents of food waste
4
5 Fruits and Pasta, rice, bread, Meat, fish, eggs Dairy products Drinks Meals Other food Other food Other
6 vegetables bakery, cereals (biodegradables)
7 54-71 1.5-10.2 2.4-4.5 0.3-1 0.3-0.4 0.2-1.5 - 23-30 -
8
9
10
11
12
13
14
15
16 Table 2. Characteristics of food waste energy valorization technologies
17 Energy content Self-sustained: Electricity via combined Byproducts and residues
18 of biofuel Energy content cycle
19 product (kWh / of biofuel
20 kg/FW) product (kWh /
21 kg/FW)
22 Anaerobic digestion 545 455 150 Digestate – needs stabilization (aerobic – composting)
23
24 Drying for use as solid 1035 582 140 Ashes (noncombustibles) incorporated in cement
25 biofuel (FRB) matrix
26 Plasma Gasification 950 550 200 Complete disintegration of organics, Very low amounts
27 (syngas) of vitrified solid residues from inorganics (recyclable as
28 inerts).
29 Mass burn in WTE plants 582 582 145 Bottom and flying ash to be disposed in ash monofils
30 (FW)
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 1
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3 Table 3. Ultimate analysis (weight fraction) of fossil fuels and food residue biofuels
[85] [86]
4 Coal PC (as Food residues Food resi- Food res- Food resi- Food resi- Food resi- Paper
[48] , [84] [66] [50] [ 66] [83] [49] [85]-[86]
5 as received received) (dry basis) dues (d.b.) idues (d.b.) dues (d.b.) dues(d.b.) dues (d.b.)
6 C 0.6696 0,8809 0.4557 0.4826 0.480 0.480 0.389 0.484 0.421
7
H 0.0452 0,0350 0.0676 0.0568 0.064 0.064 0.040 0.063 0.056
8
9 O 0.1093 0,0130 0.3619 0.4202 0.376 0.376 0.513 0.342 0.381
10 S 0.0031 0,0430 0.0001 0.0039 0.004 0.004 0.001 0.002 0.005
11
N 0.0172 0,0230 0.0261 0.0255 0.026 0.026 0.026 0.023 0.005
12
13 Cl 0.0002 0 0.0088 0 0 0 0.001 0.0055 0.002
14
P 0.0000 0,0001 0 0 0 0 0 0 0.000
15
0.1556 0.0050
16 Ash 0.0828 0.011 0.05 0.05 0.030 0.081 0.130
17 0.0763 0.005 0.075
moisture 0.790 0.770 0.750 0.650 0.609 0.778
18
LHV 6146 8342 668 4325 1 631.3 4330.1 3500
19
(kcal/kg) 4919 4169.2
20 - - -
21 Cd, ppm 0.11 - 0.7295 n.d. 0.096
22 - - -
Tl, ppm 0.00 - 0.1000 n.d. 0.00
23
- - -
24 Hg, ppm 0.11 - 0.0290 n.d. 0.00
25 - - -
As , ppm 3.30 - 2.00 <2,00 0.00
26
- - -
27 Pb, ppm 8.58 15 - 12,1 2.40
28 - - -
Cr , ppm 21.58 25 4.07 4.25 0.00
29
- - -
30 Co, ppm 5.52 30 2 2.13 0.00
31 - - -
32 Cu , ppm 13.24 - 6.79 7.19 29.90
- - -
33 Mn , ppm 49.04 50 21.5 21.4 0.00
34 - - -
35 Ni , ppm 13.61 255 5.9 6.05 1.50
36 - - -
V, ppm 0.00 250 2.00 <2,00 0.00
37 - - -
38 Zn, ppm 15.57 - 19.0 20.9 3.70
39 - - -
F, ppm 0.00 - <1000 0.00
40 - - -
41 K, ppm 1 845 70 16000 16000 14 400
42 - - -
Na, ppm 868.00 340 4100 4100 89.00
43 Non vol. - - - -
44 metals 261 620 53
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3 Case Study: Table 4. Cement plant operating parameters (compound operation)
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5
6 Cement Plant Parameters η= θ=0.85 ζ =0.43 αsm=1.66 ψ= 0.15 E= 20% ε=0
7 0.0116
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Supplementary File
Click here to download Supplementary File: Food residue biofuels in cement kilns Supplementary Information Revised.doc
*Highlights

Ms. Ref. No.: RSER-D-18-02996

Renewable & Sustainable Energy Reviews

Renewable energy in cement manufacturing: A quantitative assessment of energy

and environmental efficiency of food residue biofuels

by
Aristeides Tsiligiannis
and
#
Christos Tsiliyannis
ANION Environmental Ltd
26 Lykoudi Str., Athens GR 11141
Tel. / fax: 0030-210-2285650
email: anion@otenet.gr

HIGHLIGHTS
Food waste can be valorized to biochemicals and biofuels, including solid fuels.
Drying to ≤15% moisture gives stable, nonhazardous food residue biofuels (FRBs).
Substitution of petcoke by FRBs in cement kilns decreases clinker level.
Lower CO2, SO2 and mercury but higher chlorines and NOx emissions result.
Superior blends of FRB with paper residues improve clinker production and
emissions.