Calorific Values and Proximate Analysis of

67C Chemical 8ngineering 7tudent -esearch 9nnual %)&)

Sargassum spp. and Ulva spp.

Carlo S. Alburo, Radzwell H. Conje, Maria "n#r. Patric$ %. &an'
Department of Chemical Engineering, University of San Carlos, 6000 Cebu City, Philippines *Corresponding uthor!

racelda !. Pino,

Abstract The potential of seaweeds, Sargassum spp" and Ulva spp., as biomass for energy production was investigated based on their calorific values. Further, calorific values were correlated with the proximate analysis, which covers moisture, ash, volatile matter and fixed carbon contents of the seaweeds, using multiple linear regression. The calorific value was measured using bomb calorimetry while the proximate analysis was conducted using gravimetric method. The seaweed samples were taken from three different spots in Mactan Island, namely, Cordova, uaya, and Maribago. It was found that the calorific values of Sargassum spp" range from !"#$.%& k'(kg to &%#"".") k'(kg while Ulva spp" have a mean calorific value of &*"++."&k'(kg on dry basis. This shows that the seaweeds have comparable calorific values with those of the conventional biomass fuels like bagasse, rice husks and corn cobs. Correlation between calorific values and proximate analysis was finally established in this study as, with -% . ).!). #ey$ords! Calorific %alues, Pro&imate nalysis, Sea$eeds, 'ultiple (inear Correlations (. )ntroduction )")" Sea$eeds as *iofuels The /hilippines has an abundant supply of biomass resources which include agricultural crops 0rice hulls, coconut husk and meat, cocoa, cassava and bagasse1, saw mill 0forest logs1 and furniture residues 0sawn timber1. ut these biomass resources readily compete with food production and agricultural land 2&3. To address these constraints, a potentially viable alternative is to use a4uatic biomass, such as algae, as the feedstock for second5generation biofuel and bioenergy production.

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6sing macroalgae 0or seaweeds1 as biofuel has the advantage of higher growth rates compared to terrestrial crops and and avoids competing with the agricultural land. Moreover, seaweeds can mitigate greenhouse gases emission since C:% from flue gas can be utili;ed as carbon source in algae growth. 9side from that, wastewater can be used to provide nutrients for seaweed growth 2%3. /ast attempts in utili;ing seaweed as source of fuel started in &#+)<s oil crisis. 9mong the programs started to compensate for the energy crisis, the =iant >elp /rogram of 6nited 7tates used the brown seaweed 'acrocystis pyrifera as energy crop. ?owever the program was discontinued when it was thought that the crisis was over 2*3. ut with the serious problems posed by global warming and the rapid depletion of oil reserves today, the use of a4uatic biomass energy is now being reconsidered as a means of C:% mitigation. /rocesses that are now considered for energy generation from a4uatic biomass include direct combustion, anaerobic digestion, fermentation to alcohol, thermal li4uefaction, thermal gasification, and pyrolysis 2"3. In =ermany, studies are ongoing for the closed cycle 7olar :xygen Fuel Turbine 07:FT1 in which dried seaweeds 0specifically Ulva spp"1 are combusted in a fluidi;ed bed boiler in -ankine cycle and the combusted products are returned to the cultivation ponds as algae nutrients source 2$3. 9ccording to *ruton et al" 2@3, in France, annual green tides generate about @),))) tons of wet Ulva spp, 0or !,))) tons dry weight1 which have been considered to be utili;ed for local energy production. 7eaweed species suitable for biomass energy should display high productivity in terms of standing crop and biomass yield. The species should be easily cultivated and harvested. 9lso, chemical composition of seaweeds should be accounted since it determines the fuel 4uality and dictates the process of energy production 2"3. 7eaweeds that are considered as potential energy crops include 'acrocystis pyrifera, (aminaria, Sargassum and Ulva 2@,",*3. These seaweeds are said to have high productivity and biomass yield. 9mong the five species mentioned above, Sargassum and Ulva species are chosen in this study because of their local abundance and little economic value" Sargassum is a dominant genus in tropical and subtropical waters in terms of standing crop, percent cover and height. Ulva species are common in the intertidal ;ones of the /hilippines, but, at certain times, could over5 proliferate, producing blooms or Agreen tide< in some protected bays. Common Ulva species that proliferate in Cebu province are Ulva lactuca, Ulva fasciata and Ulva reticulata 2+3. In Mactan Island 0Cebu1, central /hilippines, at least two species constitute the Ulva population, either as free5living or

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attached form. Ulva lactuca mainly consists of free5living population while the species referred to as Ulva reticulata consists mainly of attached population 2+3 " Ulva species are fre4uently found in nutrient5 rich saline waters, attached to the bottom of the waters 2!3. )"+ ,he Calorific %alues =ood knowledge of the heating or calorific value of a fuel and its ash compositions is needed for control of ash5related conditions such as slagging, fouling, or erosion, management of environmental emissions, heat rate calculations, and modifying operating parameters 2#,&)3. The calorific value of a material is the amount of heat released by a material during combustion. It is affected by the ash and moisture contents of the biomass. The net calorific value or lower heating value is defined as the heat to be removed from the reaction products to obtain a final temperature e4ual to the initial temperature of the reactants, assuming that the reaction products remain in gaseous phase, i.e. that the heat of condensation of water is not available. :n the other hand, the reference state of the water for the gross calorific value 0higher heating value1 is li4uid state. The ash 0inorganic1 content of a fuel lowers down the calorific value and may cause maBor problems at high temperature combustion 0melting of ash and clogging of reactors1 2#,&)3. Ceber and Dygarlicke 2&)3 reported that ash5related problems, including slagging, agglomeration, corrosion, and erosion, can cause fre4uent unscheduled shutdowns, decreasing the availability and reliability of the energy source. The calorific value decreases with increasing moisture content. The presence of moisture in fuel lowers its effective heating value since a portion of the heat of combustion is utili;ed in evaporating the contained moisture, hence decreasing the calorific value. It is highly desirable, therefore, that the moisture content be kept as low as possible 2#3. The fixed carbon also affects the heating value of the fuel in such a way that the higher the fixed carbon, the higher the thermal value of fuel. In general, an increase in the ash content corresponds to a decrease in the fixed carbon content and hence a decrease in heating value 2&&3. Table & shows the heating values of commonly used biomass fuels.

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&able (. &y,ical c-aracteristics of different biomass fuels used commercially for ener#y #eneration &y,e Fruit 7tems2&3 :il5palm husks2*3 :il5palm fibers2*3 agasse2&3 Fibers2&3 Phaeophyta2%3 Chlorophyta2%3 -ice husks2&3 Mai;e Cobs2&3 Coffee husks2&3 Cocoa husks2&3 =roundnut shells2*3 Cood2&3 Coconut shell2&3 Cheat straw and husk2*3 7witch grass2*3 Charcoal2&3 Calorific Value .M/0$#1 $ +5! +5! +.+5! && #5&& !5&* &" &*5&$ &@ &*5&@ &@.+ !."5&+ &! &+5&# &!5%) %$5*% 2 moisture @* $$ $$ ")5@) ") 5 5 # &)5%) &) +5# *5&) &)5@) ! +5&$ !5&$ &5&) 2 as5 $ &) &.+5*.! 5 %$5"$ %"5") &# % ).@ +5&" "5&" ).%$5&.+ " !5# @ ).$5@

Eery few studies have been done to establish the calorific values of seaweeds, much less those of endemic seaweeds in the /hilippines. 9t the international level, Famare and Cing 2&%3 reported the calorific values of %! species in Gew Dealand. Their report showed that for the macroalgae species, the calorific value varies from species to species depending on the type of storage products that range from high5energy polysaccharide starch to mannitol and glycerol. The constituents that contribute to the calorific value of the seaweeds are carbohydrates, proteins and fats, which are all found to differ from species to species. It was reported that Chlorophyta 0green algae1, -hodophyta 0red algae1 and /haeophyta 0brown algae1 have different calorific values with Chlorophyta having the highest mean calorific content and the -hodophyta having the lowest as shown in Table &. In a similar study, Fittler and Murray 2&*3 reported that Chlorophyta had the highest average ash5free calorific content followed by -hodophyta and lastly /haeophyta. )"- ,he Calorific %alue Determination The calorific value can be determined using proximate analysis or adiabatic calorimetry 2&"3. ?owever, obtaining data from bomb calorimetry is usually tedious and expensive. For that reason several correlations are devised to predict the higher heating value from the proximate analysis data. /arikh et al" 2&$3 used "$) different types of biomass and presented the correlation, ??E . ).*$*@FC H ).&$$#EM I ).))+!97? 284uation &3

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where ??E is the higher heating value in M'(kg, FC is the fixed carbon content, EM is the volatile matter content and 97? is the ash content of the sample content in weight J on dry basis. Kemirbas 2&@3 calculated the calorific values 0higher heating values, ??E1 of &@ biomass samples experimentally from both ultimate and proximate analyses. The ??E 0M' kg L&1 of the biomass samples as a function of fixed carbon was calculated from the following e4uation, ??E 0M'(kg1 . ).&#@0FC1 H &".&&# 0-%. ).###+1 284uation %3

7heng et al" 2&+3 gave new correlation between the ??E and dry ash content of biomass 0in weight percent1 as follows, ??E 0M'(kg1 . &#.#&"I).%*%" 97? Famare and Cing 0%))&1 The maBor advantage of these correlations is that they allow the determination of ??E of fuels simply from their proximate analysis and thereby provide a useful tool for modelling of combustion processes. These can also be used in examining old(new data for probable errors when experimental results lie much outside the predicted results of ??E 2&$3. This study sought to explore the possibility of using locally available seaweeds as biomass fuel by pitting its heating values against those of the conventional biomass outlined in table &. The study also sought to establish relation between heating values and moisture contents of the seaweeds while being sun5dried and finally correlations between heating values and the proximate analyses were established for Ulva and Sargassum species. +. Materials and Met-ods +") Sampling 9lgal samples were taken from different areas around Mactan Island. The places chosen were dependent primarily on the abundance of seaweeds in one particular place. :rti; and Trono 2&!3 reported that +% species of Sargassum are found in the /hilippines. Table % gives the standing crop of Sargassum beds in Central Eisayas. 284uation *3

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&able +. Standin# cro, of dominant Sargassum spp. in Central Visayas 5(67 7ite Tongo, Mactan Is. Cordova, Mactan Is. Maribago, Mactan Is. Caubyan Is. KanaBon -eef ilangbilangan Is. :lango Is. 7tanding Crop 0kg wet weight per m% 1 %.$ *." %.+ ".# @.+ %.@ &.%! Kominant Sargassum species S" sili.uosum S" binderi S" polycystum , S" oligocystum S" polycystum S" polycystum S" polycystum, S" oligocystum S" polycystum, S" oligocystum and S" sili.uosum

In this study, Sargassum polycystum seaweeds were taken from the shores of Cordova while Ulva lactuca was taken from arangay uaya.

arangay

uagsong,

oth Sargassum oligocystum and Ulva

reticulata were taken from the shores of Maribago. The seaweeds were collected during low tides. :ne liter of seawater samples was also taken during the collection of the species to determine its K:, p?, temperature and salinity. The seaweeds were collected by thallus. Three thalli were collected for Sargassum polycystum, Sargassum oligocystum and Ulva lactuca. The thalli would serve as the samples of each species. There were three samples for each kind of species. 9nd since Ulva reticulata thrive in continuous mats, this species was obtained by composite sampling. The collection of seaweeds was done by hand. 7pecimens adhering to the seaweeds were removed using knife and the collected species were wrapped in a newspaper and placed in an ice bucket. Cater samples were analy;ed within %" hours after they were collected. p? was determined using the p? meter and the salinity was measured using the hand refractometer. The temperature of the seawater and its dissolved oxygen were measured using the K: meter. The seaweed samples were brought to the Marine macroalgae aided the determination of species. +"+ Preparation of Specimens for nalyses The seaweed samples were cleaned with water and the epiphytes were removed. 8xcess water from the samples was then removed by gently pressing the algae against tissue paper. 9ll the collected seaweed samples were sun dried. To determine relationship between calorific value and moisture content during sun5drying of seaweeds, one whole thallus of each species, Sargassum iology Kepartment for identification. The identification of the species was based on their external morphology, color and shape. /ictures of the

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polycystum and Ulva reticulata, was sampled for moisture content and calorific values analyses at different intervals of time for three days. 9 total of seven samples were taken from the whole thallus of each species during the sun5drying period and each sample had three replicates. 9fter all the seaweeds were sun5dried, they were stored and cut into small pieces for the proximate analyses and calorific value determination. The whole experiment was conducted in two trials, one month apart. +"- Pro&imate nalysis /roximate analysis is an indirect method of measuring the calorific value of a sample. It converts the component weights of proteins, fats and carbohydrates in the sample to their e4uivalent heating values. /roximate analysis re4uires the values of the ash content, moisture content, volatile combustible matter content, and the fixed carbon in order to determine the heating value of the sample. The /roximate analysis method used in this study was based on 97TM K*&+% 07tandard /ractice for /roximate 9nalysis of Coal and Coke1 but the temperatures were adBusted since proximate analysis of biomass is limited to @))MC only 2&#3. +"/ Calorific %alue Determination In adiabatic calorimetry, direct combustion of the samples is done in a temperature5controlled bomb. This Backet is maintained at the temperature of the bomb throughout the combustion process to eliminate the heat5leakage. The calorific value of the sample obtained from calorimetry is said to be more accurate than that obtained from proximate analysis 2&"3. The calorific value was determined using /arr &&)! :xygen net calorific value1. *. Results and 9iscussion omb Calorimeter based on I7: &#%!,&##$ 0Ketermination of gross calorific value by the bomb calorimetric method, and calculation of

-")" Calorific %alues of Different Sea$eed Species from Different Places 0'aribago, Cordova and *uaya1 9 preliminary run was done to investigate available seaweed species in Maribago, Cordova and uaya. Table * shows the seawater conditions when the seaweed samples were obtained.

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&able *. Seawater conditions of sam,lin# locations Parameter T 0oC1 K: 0g(ml1 7alinity 0J1 p? 'aribago *).! +.&+ %# +.## *uaya *) *.&" %@ !.*& Cordova *) *.&% *@ !.*"

In Maribago, the most abundant species were S" polycystum and U" reticulata" In Cordova, the most abundant specie was S" oligocystum" Figure & shows the calorific values of different seaweed species harvested.

;i#ure (. Calorific Values of 9ifferent Seaweed S,ecies from Mariba#o, Cordo<a and !uaya

From the figure above, it can be seen that the calorific values of Sargassum spp" range from !"#$.%& k'(kg to &%#"".") k'(kg while Ulva spp. have a mean calorific value of &*"++."& k'(kg on dry basis which is in agreement with values reported by Famare and Cing 2&%3. The results also show that the local species of Ulva and Sargassum collected in Mactan have comparable calorific values with those of the conventional biomass fuels like bagasse, rice husks and corn cobs as cited in Table %. -"+ " Calorific value as a function of moisture content during sun drying The most serious disadvantage of biomass fuel is that they often have high moisture content which readily inhibits combustion 2&#3. In general, a4uatic biomass contains !) to #)J water 2%)3. The best way to recover the lost energy because of high moisture content is through drying of biomass. In the study, samples of Sargassum polycystum and Ulva reticulata were sun5dried to minimi;e the moisture content. It was observed that when the moisture content was still higher than ")J, the calorific value of the seaweed

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samples could not be determined by bomb calorimetry since no temperature change is observed during ignition. Figures % and * below show the relation between moisture content of the seaweed and its calorific value for Sargassum polycystum and Ulva reticulata samples, respectively.

;i#ure +. Calorific Value of Sargassum polycystum <ersus ;i#ure *. Calorific Value of Ulva reticulata <ersus moisture content moisture content

In both figures, it can be clearly seen that at moisture content below ")J, the calorific values have negative linear correlations with moisture content consistently in the two experimental trials done. ?owever, Figure % shows that the two experimental trials produced different correlations despite involving the same species. :n the other hand, figure * shows that the two trials produced almost identical correlations. It is also seen that at moisture content &$J 0or below1, the calorific value of seaweeds is at par with those of the conventional biomass fuels. 7ince the two trials produced two different correlations, only correlation of Figure * is thus developed as, 284uation "3

-"- Correlation bet$een the calorific values of sea$eeds and pro&imate analysis data 9fter two to three days of sun5drying, the moisture content of the seaweeds lowered to &) to &$J by weight. 8ssentially all seaweed samples have negligible fixed carbon content 0N)J1 and have high volatile matter 0")5+$J1 and ash content 0&$5"$J1 on dry basis. The combustibles of a solid fuel are the volatile matter and the fixed carbon. 7ince the fixed carbon content is negligible, the volatile matter is the only contributor to the energy of seaweeds.

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9sh content is the remaining incombustible minerals of a fuel. Conse4uently, the calorific value decreases with increasing ash content. In general, fuels should have ash content less than $J 2#3. combustion of seaweeds as biofuels. Figure ", $ and @ are plots of calorific values against moisture contents, volatile matter contents, and ash contents, respectively, covering all the sampled species of Ulva and Sargassum. It can be seen in Figure " that the moisture content has a poor correlation with the calorific value, while volatile matter content and ash content each have good correlations with the calorific value 0- % . ).+*# and -% . ).+%*, respectively1. ut seaweeds in this study have been found to have high ash content which would then restrict the direct

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;i#ure 3. Calorific <alue <ersus moisture content

;i#ure 4. Calorific <alue <ersus <olatile matter content

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;i#ure 8. Calorific <alue <ersus as- content

y multiple linear regression analysis, moisture, volatile matter and ash contents were correlated with the calorific value. Constraints in the use of this correlation include &) to %)J moisture content, ") t) +$J volatile matter and &$ to "$J ash content.

284uation $3 To measure how well the correlation fits the data, coefficient of determination 0-%1 was computed. The -% computed was ).!). This means that !)J of the variation of the calorific values of the seaweed samples has been explained by the linear regression e4uation established here. 3. Conclusion and Recommendation 7eaweeds have high potential to be used as solid biofuel since it has comparable calorific values to the conventional biomass like bagasse, rice husks and corn cobs. ?owever, seaweeds had to be dried from about !+J to &$J moisture content in order to obtain calorific values close to those of the conventional biomass 0#))) I &%))) k'(kg1. In the case of Ulva reticulata species, there was a highly negative correlation between moisture content and calorific values. :n the bigger picture, 84uation $ can be used to predict calorific values of Ulva and Sargassum species. In the case of sun5drying of Sargassum species, more experiments should be conducted to establish a consistent correlation between moisture contents and calorific values. To improve -%, more species of Sargassum should be included. 4. References 2&3 ?oi, C. 0%))*1. /otential of biomass utili;ation for energy in asia pacific sharing of specific experience of /hilippine situation. Forest -easearch Institute. >epong, >uala Fumpur Malaysia. 2%3 -asmussen, M. and et" al. %))+. /rimary iomass /roduction from Marine 9lgae. 6niversity of cell 9arhus , Gational 8nvironmental -esearch InstituteO Memorandum for E85net, %))+. 2*3 Pokoyama, 7., 'onouchi, >., Imou, >. 0%))+1. 8nergy production from marine biomass, fuel power generation driven by methane produced from seaweed. 2orld cademy" $, &&*&5&&$&. 2"3 Chywoneth, K. 0%))%1. -eview of biomethane from marine biomass. 3uel. &),&)%$5&)*) 2$3 Pantovski, 8. 0%))!1. 7eaweed Ulva photosynthesis and ;ero emissions power generation. Proceedings of EC4S +005. *, &&&+5&&*).

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2@3 ruton, T., Fyons, ?., Ferat, P., 7tanley, M. 9nd -asmussen, M. 0%))@1. 9 review of the of marine algae as a source of biofuel in Ireland. Sustainable Energy 6reland" &*5%".

potential

2+3 Trono, =. 0&##+1. Field guide and atlas of the seaweed resources of the /hilippines. ookmark, Inc. %@"59 /ablo :campo 7r. 9ve. 2!3 ?ulsbergen, -. 0%))@1. /redicting Ulva growth in a saline Eolkelrak5Doomlake. Delft University of ,echnology report. !5&#. 2#3 Quaak, /., >noef, ?., 7tassen, ?. 0&###1. 8nergy from biomass 09 review of combustion and gasification techni4ues1. Gew Pork, 679. %5+. 2&)3 Ceber, =. 9nd Dygarlicke, C. 0%))&1. Control, %,+@$5++). 2&&3 6nesco. 0&#!!1. 8ngineering schools and endogenous technology development. /aris. 2&%3 Famare, M. and Cing, 7. 0%))&1. Calorific content of Gew Dealand marine macrophytes. 7e$ 8ealand 9ournal of 'arine and 3resh$ater :esearch" *$,**$5*"&. 2&*3 Fittler, M., Murray, 7. 0&#++1. 9nalyses of pathways of energy flow. 6n, Fittler, M. and Murray, 7. 08ds.1. Influence of domestic wastes on the structure and energetic of intertidal communities near Cilson Cove, 7an Clemente Island. University of California, Davis! California 2ater. "+5$@. 2&"3 Carefoot, T. 0&#!$1. Calorimetry. /ress 7yndicate of the 6niversity of Cambridge. In ?andbook of /hycological Methods, Macroalgae. Gew Pork, 679" "!)5"#) 2&$3 /arikh, '., Channiwala, 7., and =osal, =. 0%))"1. 9 correlation of calculating ??E from proximate analysis of solid fuels. Fuel.&).&)&! 2&@3 Kemirbas, 9. 0&##@1. Calculation of higher heating values of iomass fuels. Fuel, &),&)&@5&)%) 2&+3 7heng, C., and 9;evedo, '. 0%))"1. 8stimating the ??E of biomass fuels from basic analysis of data. Fuel. &).&)%). 2&!3 :rti;, 9., Trono, =. 0%)))1. =rowth and reproductive pattern of intertidal and subtidal Sargassum 07argassaceae, Fucales1 population in olinao, /angasinan. Science Diliman" &%,%,"$5$). 2&#3 ?enrich, -., Eodegel, =., >ocB, M. 0%))"1. Kefinition of standard a biomass. -8G8C. 0?enrich et" al, %))"1. 2%)3 ?ennenberg, >., Fritsche, 6., ?errera, -., 0%))#1. 94uatic biomass, sustainable bioenergy from algaeR :ko5Institut, Karmstadt, =ermany. arrier issues to the utili;ation of biomass. D Document

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