Partial Upgrading - Quitian2016

Subscriber access provided by UNIV OF CALIFORNIA SAN DIEGO LIBRARIES
Article
Partial upgrading of heavy crude oil by slurry-phase
hydrocracking with analytical grade and ore catalysts
Alexander Quitian, and Jorge Ancheyta
Energy Fuels, Just Accepted Manuscript DOI: 10.1021/acs.energyfuels.6b01648 Publication Date (Web): 25 Oct 2016
Downloaded from http://pubs.acs.org on October 31, 2016
Just Accepted
Just Accepted manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides Just Accepted as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. Just Accepted manuscripts
appear in full in PDF format accompanied by an HTML abstract. Just Accepted manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI). Just Accepted is an optional service offered
to authors. Therefore, the Just Accepted Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the Just
Accepted Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these Just Accepted manuscripts.
Energy & Fuels is published by the American Chemical Society. 1155 Sixteenth Street
N.W., Washington, DC 20036
Published by American Chemical Society. Copyright American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.
Page 1 of 33 Energy & Fuels
1
2
3
4 Partial upgrading of heavy crude oil by slurry-phase hydrocracking with analytical grade
5
6 and ore catalysts
7
8
9 Alexander Quitian,, Jorge Ancheyta*
10
11 Facultad de Qumica, Universidad Nacional Autnoma de Mxico, Ciudad Universitaria,
12
13
14
Coyoacn, Mexico D.F. C.P. 04510
15
16 Instituto Mexicano del Petrleo, Eje Central Lzaro Crdenas Norte 152 Col. San Bartolo
17
18 Atepehuacan, Mexico D.F. C.P 07730, Email: jancheyt@imp.mx
19
20
21
22 ABSTRACT
23
24
25
A heavy crude oil of 13 API and a viscosity of 6100 cSt at 37.8C was used to study the effect
26
27 of different hydrocracking catalysts at low severity conditions in a slurry-phase batch reactor.
28
29 The evaluated catalysts were Mo and Fe analytic grade oxides and ores (molybdenite, hematite
30
31
32 and magnetite) from different Mexican mine sites. The effect of the concentration of catalysts on
33
34 heavy oil upgrading was studied in the range of 0 to 13333 ppm of active metal (Mo or Fe). The
35
36 results showed that the required minimum concentration of catalyst to obtain upgraded crude oil
37
38
39 with suitable properties for transportation (API gravity> 16 and viscosity at 37.8 C <250 cSt) is
40
41 5000 ppm. At the evaluated operating conditions, coke formation is not observed and the
42
43
44
selectivity towards gases is low. Mo showed better hydrogenation capacity than Fe, which is
45
46 observed by an increase in the light fraction composition and reduction of the heavy vacuum
47
48 gasoil and vacuum residue. Depending on the concentration, type and active metal content of the
49
50
51 catalysts, vacuum residue conversion in the range of 37-49% was obtained.
52
53
54
55 Keywords: dispersed catalyst, ore, heavy crude oil, upgraded crude oil, hydrocracking
56
57
58
59
60
1
ACS Paragon Plus Environment
Energy & Fuels Page 2 of 33
1
2
3 1. INTRODUCTION
4
5
6 Heavy crude oils have low API gravity and high viscosity which make difficult their
7
8 transportation by pipeline. Handling high viscosity heavy crude oils involves high costs of
9
10
operation and capital investment in transportation facilities and pumping that together with the
11
12
13 low value of the heavy crude oils reduces the profitability of production processes. In some cases,
14
15 the required specifications for transportation of crude oils by pipeline depend on existing
16
17
18
infrastructure as well as on the agreement between the oil producer and the company that
19
20 provides the transportation service by pipeline. It is widely accepted that crude oils must have
21
22 API gravity higher than 16 and viscosity lower than 250 cSt at 37.8C for their feasible
23
24
25 transportation by pipeline1,2.
26
27 The most used commercial approaches to achieve the required flow properties of heavy crude oils
28
29 are heating and dilution. In the former, heavy oils are heated along the jacketed pipeline using
30
31
32 steam or flue gases. Various heating stations are needed along the pipeline in order to maintain
33
34 the required temperature. Heating not only has high requirements of energy but it can also
35
36
enhance sedimentation of water and solids present in crude oil that may cause plugging of piping
37
38
39 and damage of pumping systems.35
40
41 Dilution consists of mixing the heavy crude oil with lighter streams (light crude oils or diluents),
42
43
44 thus improving its flow properties. The advantage of using diluents such as light naphtha is that
45
46 they can be recovered by atmospheric distillation and their reusing is possible. However, heavy
47
48 oil may be incompatible with the diluent that can cause sedimentation of water, solids and even
49
50
51 asphaltenes thus provoking damage and blockages in the pumping and piping systems.68
52
53 Other more direct manners to achieve the required flow properties of heavy crude oils is by
54
55 transforming them into lighter hydrocarbons (upgraded crude oil) through thermal or catalytic
56
57
58 reactions. Such approaches, called partial upgrading processes, are classified as:
59
60
2
1
2
3 i. Carbon rejection that favors the thermal breakage of hydrocarbons with high molecular
4
5
6 weight and reduces the vacuum residue fraction of crude oils. The yield of upgraded crude
7
8 oils is low due to high formation of byproducts such as coke and gaseous hydrocarbons (C1-
9
10
C5). This type of processes is the most used because of its relatively low operating costs and
11
12
13 investment. Pyrolysis, thermal cracking and visbreaking belong to this category.911
14
15 ii. Hydrogen addition that favors the hydrogenation reactions of high molecular weight
16
17
18
molecules of heavy oil in the presence of catalysts and hydrogen donors. Also, the vacuum
19
20 residue fraction is reduced, and the formation of coke and volatile gases is inhibited which
21
22 increases the yield of the upgraded crude oil. Aquathermolysis and hydrocracking are the
23
24
25 most common hydrogen addition processes for upgrading of flow properties of crude oils. 12
26
15
27
28
29 Hydrocracking processes are commonly carried out at temperature of 360-480C, hydrogen
30
31
32 partial pressure of 3-15 MPa and reaction time of 1-6 hours for batch operation. Hydrogen
33
34 consumption is about 50-360 m3/m3 depending on the severity of the reaction. 16,17 According to
35
36
the type of catalyst, hydrocracking can be operated with:
37
38
39 a. Supported catalysts, consisting of transition metal sulfides that favor hydrogenation
40
41 reactions. They are supported on Al2O3 or SiO2 that promote the reactions of thermal
42
43
44 breakage. Such catalysts are used in commercial fixed-bed or ebullated-bed reactors.
45
46 b. Slurry-phase catalyst, wherein the catalyst precursors are added together with the feed as
47
48 powder-finely divided or as metal salts soluble in water or in oil. Catalyst precursors
49
50
51 become metal sulfides that are more stable and catalytically more active due to the
52
53 presence of hydrogen and hydrogen sulfide produced by the cracking and
54
55 hydrodesulfurization reactions at operating conditions. The catalyst precursors are
56
57
58 generally oxides, sulfides, salts or organometallic complexes of transition metals.
59
60
3
1
2
3 In general, hydrocracking reactions with supported catalysts occur at lower severity reaction
4
5
6 conditions than with slurry-phase catalysts due to the presence of acid sites in the supports. But in
7
8 both processes, the most used transition metals are in order of higher catalytic activity: Mo, W,
9
10
Ni, V, Co, Cr and Zn. 18,19
11
12
13 The coke formed during hydrocracking and the metals present in heavy crude oil cause rapid
14
15 deactivation of catalyst. For supported catalysts, deactivation is a critical issue that requires
16
17
18
continuous replacement of catalyst. In some cases, it is necessary to use more than two reactors to
19
20 maintain continuous operation.2022
21
22 With slurry-phase catalyst precursors, coke formation decreases as the particle size is closer to
23
24
25 the molecular size of the metal sulfides. Smaller particle size ensures greater activity, and
26
27 nanometric sizes can be obtained by using water and oil soluble precursors.23
28
29 Currently the low oil prices and the high costs of soluble catalysts do not make profitable their
30
31
32 commercial use. In order to reduce operating costs, some slurry-phase hydrocracking processes
33
34 use low cost precursors such as ores or "throw-away" material in the form of finely divided
35
36
powders, which contain high concentration of catalytically active transition metals (usually Fe,
37
38
39 Ni and V). The studied ores are mainly hematites and limonites.2426 Other inexpensive materials
40
41 include fly ash from the combustion of petroleum coke, red mud from aluminum production,
42
43
44 coke breeze preparation from metallurgical coke, fine coke from flexi-coking, etc.18
45
46 Slurry-phase hydrocracking of heavy crude oil is studied at low severity reaction conditions in
47
48 batch operation using ores as catalyst precursor, which were obtained from different Mexican
49
50
51 mines. The objective of this research is to explore the utilization of different ore catalysts to
52
53 upgrade the flow properties of a heavy crude oil that allow its pumping by pipeline (>16 API and
54
55 <250 cSt at 37.8C).
56
57
58
59
60
4
1
2
3 2. EXPERIMENTAL
4
5
6 2.1. Materials
7
8 The properties of the heavy crude oil used as feedstock are shown in Table 1. The ore catalysts
9
10
used were molybdenite, hematite A, hematite B and magnetite. These ores were recovered from
11
12
13 different Mexican mining sites located and exploited in the states of Sonora, Colima, Durango
14
15 and Chihuahua respectively.
16
17
18
For comparison purposes, analytical grade powders of molybdenum trioxide (MoO3) and ferric
19
20 oxide (Fe2O3) (Sigma Aldrich) are also used as catalysts, which compositions are shown in
21
22 Tables 2 and 3 respectively.
23
24
25 2.2. Preparation and characterization of ore catalysts
26
27 Rock samples of the different ores were crushed, pulverized and sieved to a size less than 5
28
29 microns. Subsequently, all samples used as catalyst powder were dried at 120 C for 2 hours
30
31
32 before being the experiments.
33
34 The composition of the dried powder ores was determined by X-ray fluorescence (XRF) and the
35
36
results are summarized in Table 4. XRF analyses were performed on a Siemens D500
37
38
39 diffractometer with Cu anode and graphite mono-chromed, using CuK radiation (=1.450589).
40
41 Diffraction sweeps were performed in the range of 2 angles between 0-5 and 10-70 with a
42
43
44 scan rate of 0.5 min-1. The crystalline phases were identified with reference to the standard data
45
46 of JCPDS powders using a specific software installed in the diffractometer for the peak
47
48 identification.
49
50
51 2.3. Hydrocracking of heavy crude oil
52
53 Reactions of slurry phase hydrocracking with the catalyst powders were conducted in batch
54
55 operation using a stirred Parr reactor of series model 4848, equipped with measuring and control
56
57
58 systems of pressure, temperature and stirring speed.
59
60
5
1
2
3 In previous work, the best operating conditions to achieve the desired values of API gravity and
4
5
6 viscosity using the same heavy oil, reaction system and powdered molybdenum trioxide in
7
8 analytical grade as catalyst were defined, which are initial pressure, temperature, and reaction
9
10
time of 3.92 MPa, 380C and 4 h respectively1. These conditions are used here to study the effect
11
12
13 of type and concentration of catalysts in the range of 0-13333 ppm.
14
15 The batch reactor was pressurized with hydrogen at room temperature. Subsequently, it is heated
16
17
18
to the reaction temperature (380C) at a heating rate of 5 C/min and then the initial pressure
19
20 (3.92 MPa) is reached at the same time. Afterwards stirring rate (800 rpm) is initiated and this
21
22 moment is considered as the beginning of the reaction.
23
24
25 At the end of the reaction time (4 h), the reactor was rapidly cooled to room temperature. After,
26
27 liquid and gaseous products were quantified. If there is formation of solids or sediments, they
28
29 were separated from the liquid by decantation, washed with toluene and dried at 110C and
30
31
32 finally their mass was quantified. Hydrogen consumption was calculated with the gas
33
34 composition, the weight of produced gas and the amount of hydrogen loaded to the reactor.
35
36
37
2.4. Product characterization
38
39 After each experiment, liquid, gas and solid (coke or insoluble in toluene) samples were taken,
40
41 measured and analyzed. Liquid samples were analyzed in terms of API gravity, viscosity,
42
43
44 simulated distillation and elemental analysis. Density and viscosity were determined in an Anton
45
46 Parr densimeter/viscometer model SVM3000. Simulated distillation was measured using an
47
48 Agilent 7890A gas chromatograph according to ASTM D7169 method. Elemental analyses
49
50
51 (carbon, hydrogen, sulfur, nitrogen and oxygen) were performed with a Pekin Elmer Model
52
53 Series II CHNS-O Analyzer 2400.
54
55 Gas samples were analyzed by gas chromatography using an Agilent Gas Chromatograph Model
56
57
58 6890 according to the UOP-539 standard for refinery gases.
59
60
6
1
2
3 The elemental analyses of coke were performed according to the ASTM D 3178, 3177 and 3179
4
5
6 methods for the determination of carbon and hydrogen, sulfur and nitrogen respectively.
7
8 The distribution of molecular weights of coke were determined by gel permeation
9
10
chromatography (GPC) in an Agilent HP 1100 Series HPLC System using a PL aquagel-OH
11
12
13 MIXED-H Column. The coke was diluted in a concentration of 1 g/lt using as eluent
14
15 tetrahydrofuran with a flow rate of 1 ml/min.
16
17
18
Nuclear magnetic resonance of 1H and 13
C was performed on a Bruker BioSpin GmbH
19
20 Spectrometer that was operated at 300 MHz for proton and 75 MHz for carbon.
21
22 Deuteriochloroform (CDCl3) was used to dissolve the coke. The calculation of structural
23
24
25 parameters was done with methods reported in the literature.27,28
26
27 The morphology and microstructures of coke were determined by X-ray diffraction using a
28
29
Siemens D500 diffractometer with nickel-filtered CuK radiation (=1.5418) at 35 kV and 35
30
31
32 mA with an angular scanning of 2 in the range between 0-80 and a scanning speed of
33
34 0.02/min. The interlayer spacing and microcrystalline parameters of coke were calculated using
35
36
37 the Braggs Law and other equations reported elsewhere for such materials.2931
38
39 Thermogravimetric analyzes (TGA) and differential thermogravimetric analyzes (DTA) of coke
40
41 were conducted in a TA Instrument's 2950 Thermogravimetric analyzer with a heating rate of 10
42
43
44 C/min from 20C to 1100C using nitrogen.
45
46 3. RESULTS AND DISCUSSION
47
48
The analytic grade oxides or ore catalysts inhibit the formation of coke as shown in Figure 1.
49
50
51 Coke is formed at low catalyst concentration (up to 9 wt%), and it is null above 5000 ppm.
52
53 Analytical grade oxides exhibited slightly lower tendency to form coke than ore catalysts. During
54
55
56
slurry-phase hydrocracking, free radicals are formed from thermal breakage of C-C bonds of high
57
58
59
60
7
1
2
3 molecular weight hydrocarbons. The catalyst accelerates hydrogenation rate of the formed
4
5
6 radicals, however, if the amount of catalyst is insufficient, the high complexity and poly-
7
8 aromaticity free radicals undergo condensation reactions that lead to coke formation. This coke is
9
10
deposited on the reactor walls and agitator as well as on the dispersed catalyst causing its
11
12
13 deactivation, however, for certain concentration of catalyst (> 5000 ppm in this study), then there
14
15 is not coke deposition.25,26,32
16
17
18
Elemental analyses of coke obtained with (2500 ppm molybdenite) and without catalyst are
19
20 shown in Table 5. They indicate that both cokes have almost the same chemical composition and
21
22 aromaticity (H/C ratio). The distribution of molecular weights of cokes obtained by GPC/SEC are
23
24
25 shown in Table 5. The calculated polydispersity index resulted to be low and identical
26
27 (PDI=1.25), which indicates that both cokes have compounds with common chemical structure.
28
29 The high average molecular weights and the low H/C ratios indicate a high degree of aromaticity
30
31
32 in the carbonaceous compounds.
33
34 The NMR spectra of the cokes are presented in Figure 2, and the corresponding structural
35
36
parameters are reported in Table 5. These results confirm that both cokes have similar chemical
37
38
39 structure, i.e., about 95-98 aromatic rings and 5 carbons by aliphatic chains. These similar
40
41 structures are the result of thermal hydrocracking and condensation of asphaltenes reactions and
42
43
44 indicate that ores do not catalyze reactions of thermal breakage but they only inhibit coke
45
46 formation.
47
48 Figure 3 and Table 5 show the results of X-ray diffraction, the calculated interlayer spacing and
49
50
51 microcrystalline parameters for cokes obtained with and without catalyst. The average staking
52
53 height of graphene layers Lc is a good indication of graphitizability due to the hydrocracking. The
54
55 feature of diffractions peaks (002) and (100) in both cokes has a typical turbostratic crystalline
56
57
58 structure in which the coke is made of graphite-like microcrystallites, bounded by cross linking
59
60
8
1
2
3 network, consisting of several graphite-like layers, stacked nearly parallel and equidistant with
4
5
6 each layer having a random orientation.
7
8 The TGA and DTA results are shown in Figure 4. The thermal behavior of both cokes is similar
9
10
and occurs in three stages, which are typical of coke obtained at low temperatures by thermal
11
12
13 cracking: 1) From room temperature to 400C there is a minimum loss of weight and thus no
14
15 release of light volatiles or thermal cracking reactions is observed; 2) between 400C and 600C
16
17
18
there is high loss of volatile, however, there is not highly evolved gas. Weight losses are mainly
19
20 due to intermolecular associations, destroy of weaker chemical bonds and rupture of alkyl chains
21
22 to generate gaseous molecules; and 3) above 600C, where more volatiles are produced
23
24
25 constantly until no more gases are released. In this point, the stronger bonds are broken, the
26
27 molecules of coke are fully destroyed and consequently gaseous molecules are obtained until a
28
29 heavier coke prevails as final product of coke pyrolysis.
30
31
32 Similar behavior than coke is exhibited by gases yield, which is inhibited as the concentration of
33
34 catalyst is increased (Figure 1). At concentrations greater than 5000 ppm, the amount of gas
35
36
formed remains constant at about 2 wt.%. Gas formation is mainly due to thermal breakage of C-
37
38
39 C bonds of paraffinic compounds present in the fraction of saturates and from the aliphatic chains
40
41 arising during thermal cracking of fractions of aromatics, resins and asphaltenes. The aliphatic
42
43
44 chains undergo decomposition reactions and hydrogen abstraction that lead to gas formation.
45
46 This type of reactions is inhibited by the presence of hydrogen and catalyst.33
47
48 The composition of gases (C1-C2, C3-C4, C5+) is quite similar with all the used catalysts (Table 6).
49
50
51 At high catalyst concentration, it is slightly lower. Hydrogen sulfide exhibits the opposite
52
53 behavior, which indicates that higher concentration of catalyst favors the selectivity towards the
54
55 hydrodesulfurization reactions and therefore increasing the production of H2S.
56
57
58
59
60
9
1
2
3 API gravity and viscosity of the upgraded crude oils present similar tendencies as can be
4
5
6 observed in Figures 5 and 6, respectively. Above 5000 ppm, constant values of these properties
7
8 are achieved. Analytical grade oxides increased more the API gravity and reduced more the
9
10
viscosity as compared with ores. In general, analytical MoO3 exhibited the best performance
11
12
13 among all the catalyst studied. Molybdenite was the best among the ore catalysts. Above 5000
14
15 ppm, the upgraded crude oils have suitable properties for their transportation by pipeline (<250
16
17
18
cSt at 37.8C).
19
20 The removal of sulfur is presented in Figure 7. The trends are the same than for the other
21
22 properties. However, it is important to highlight that the maximum level of hydrodesulfurization
23
24
25 with analytical grade oxides is between 13-16%, while for the ore catalysts is between 7-11%.
26
27 These values of HDS are considerably lower than those typically obtained with supported
28
29 catalysts. 20,3436
30
31
32 This fact could be of great importance when designing a commercial process, since the gas
33
34
35 product stream is typically sent to a sweeting unit to remove the hydrogen sulfide and then to a
36
37 purification unit to be able to recycle a high purity hydrogen stream. Having low level of HDS
38
39 and hence low production of H2S would indicate that both sweeting and purification units can be
40
41
42 either eliminated or designed to work for the new required efficiency, which will reduce the
43
44 investment and operation costs.
45
46
47 Hydrogen consumption is reported in Figure 8. With analytical grade oxides, higher hydrogen
48
49 consumptions are obtained than with ores, which agrees with the flow properties and selectivity
50
51
52 towards the different reactions discussed above. The consumption of hydrogen increases as the
53
54 concentration of catalyst also increases, which reaches a maximum value after 5000 ppm. For all
55
56 the catalyst, the consumed hydrogen is relatively low (100-160 ft3/bbl) which is due to the low
57
58
59
60
10
1
2
3 severity reaction conditions used in the experiments. The formation of free radicals depends only
4
5
6 on the nature of feed and temperature, since the dispersed catalysts have very low activity for the
7
8 thermal cracking reactions. There is also a low breaking of C-C bonds by thermal cracking,
9
10
therefore, using catalyst concentrations higher than 5000 ppm with a hydrogen excess do not
11
12
13 allow for an additional hydrogenation. In this research, the slurry-phase hydrocracking has been
14
15 mainly focused on reducing the viscosity at low pressure and temperature with ore catalysts. This
16
17
18
approach is new and there is only few information about hydrogen consumption at these
19
20 conditions. Matzamura et al.26 studied the slurry-phase hydrocracking of Brazilian Marlim
21
22 vacuum residue at 8 MPa, 440C and 4 h using limonite from Australia (56.6 wt% iron) and
23
24
25 Brazil (45.5 wt% iron) in concentrations of 3 wt%. They reported hydrogen consumptions of 960
26
27 and 1118 ft3/bbl respectively. Du et al.37 obtained a hydrogen consumption of 181 ft3/bbl in the
28
29 slurry-phase hydrocracking of a vacuum residue of Karamay crude oil (API gravity of 14.48 and
30
31
32 viscosity at 80C of 901.6 cSt) at 8 MPa, 400C and 1 h using 500 ppm of a dispersed oil soluble
33
34 molybdenum. It is then seen that the hydrogen consumption determined in this work is lower than
35
36
those reported in the literature, which is mainly due to the differences in reaction conditions.
37
38
39 All the previous results indicate that the enhancement of flow properties and reduction of sulfur
40
41
42 content of the crude oil through slurry-phase hydrocracking is greater as the content of active
43
44 metal (Mo or Fe) in the ore catalyst is higher. Therefore, higher amount of active metal in the
45
46
mineral catalyst allows for higher hydrogenation and hydrogenolysis, which can be also
47
48
49 corroborated by the higher hydrogen/carbon ratio of the upgraded oils compared with that of the
50
51 hydrocracking without catalyst (Table 7).
52
53
54
In summary, the flow properties, HDS and hydrogen consumption hardly change at catalyst
55
56 concentrations higher than 5000 ppm. This behavior is typical of hydrocracking processes using
57
58
59
60
11
1
2
3 catalyst in slurry phase without acid sites (unsupported) since they are limited by the formation of
4
5
6 free radicals and the amount of catalyst.38 Firstly, a homolytic breaking of chemical bonds (C-C,
7
8 C-S, C-N) occurs due to temperature in the presence of hydrogen (thermal hydrocracking) that
9
10
leads to the formation of free radicals. The hydrogen sulfide released during HDS converts metal
11
12
13 oxide (in this case analytic grade oxide or ore) into active metal sulfide, which catalyzes the
14
15 reactions of dissociation of hydrogen and hydrogenation of free radicals.32,39
16
17
18
At concentration of metal active lower than 5000 ppm, there is not enough amount of catalyst to
19
20 inhibit the condensation reactions of free radicals, which cause a rise in the formation of coke and
21
22 gas. By contrast, above 5000 ppm of active metal, there is a sufficient amount of catalyst to
23
24
25 hydrogenate the radicals formed by thermal breakage, accordingly, the properties of upgrade
26
27 crude oil and hydrogen consumption are similar because reaction temperature limits the
28
29 formation of free radicals.4042
30
31
32 For both analytical grade oxides and ores, Mo-based catalysts have better ability to hydrogenate
33
34 than Fe-based catalysts, which is a well-known fact reported for supported catalyst. The reasons
35
36
for this are not very well-known yet but it is attributed to the electron configuration of
37
38 4345
39 molybdenum and its lower binding energy with sulfur. These characteristics allow for
40
41 having greater number of vacant sites to interact with unpaired electrons of free radicals and with
42
43
44 hydrogen. Analytic grade catalysts (MoO3 and Fe2O3) have better performance than ore catalysts
45
46 due to their purity. When hydrodesulfurization reactions occur, the produced hydrogen sulfide
47
48 causes the sulfurization of the catalyst precursor, so that the metal oxides in the ores are
49
50
51 transformed into metal sulfides which are catalytically more stable. The produced metal sulfides
52
53 have an irregular crystal structure that facilities the hydrogenation reactions of formed free
54
55 radicals by thermal cracking.44,46 Ores and their sulfides species have a perfectly developed
56
57
58 lattices in their crystalline structure, vacancies of active metal and a random distribution of the
59
60
12
1
2
3 various non-active catalytically compounds. These features may prevent adsorption, dissociation
4
5
6 and subsequent transport of hydrogen to free radicals. 25,47,48
7
8 The compositions of upgraded crude oils determined by simulated distillation for different
9
10
catalysts using 5000 ppm of concentration of active metal are shown in Table 8. It is clearly seen
11
12
13 that the composition of light straight-run naphtha does not change while those of the other
14
15 fractions (except vacuum residue) increase as compared with that of the feed. At low severity
16
17
18
reaction conditions, fractions of kerosene and vacuum gasoils are mainly formed from the
19
20 hydrocracking of the vacuum residue fraction and the medium and heavy straight-run naphtha are
21
22 produced by the hydrocracking of middle fractions. The values of residue conversion are typical
23
24
25 of those obtained at low severity conditions (<50%).
26
27 CONCLUSIONS
28
29 The analytic grade oxides and ores catalysts have the ability to inhibit the gas and coke formation
30
31
32 caused by decomposition and condensation reactions, promote the hydrogenation and slightly
33
34 enhance the hydrogenolysis of the free radicals formed primarily by thermal cracking of C-C
35
36
bonds.
37
38
39 The ability of powdered ores and analytic grade oxides to upgrade flow properties increases
40
41 according to their active metal purity and decreases as the catalyst concentration is reduced at
42
43
44 values lower than 5000 ppm. The type and active metal content also affect the flow properties of
45
46 the upgraded oils. Catalysts rich in molybdenum allow for greater conversion to lighter fractions
47
48 and therefore an increase of the H/C ratio as compared with catalysts rich in iron. Higher content
49
50
51 of active metal in the catalysts also favors the hydrogenation and hydrogenolysis reactions
52
53 causing an increase of lighter fractions and H/C ratio.
54
55
56
57
58
59
60
13
1
2
3 The upgrading of flow properties in the slurry-phase hydrocracking at low severity reaction
4
5
6 conditions with the studied powdered catalysts is due to the conversion of residue fraction into
7
8 middle distillates fractions and then into light, medium and heavy straight-run naphtha.
9
10
11
12
13 ACKNOWLEDGEMENTS
14
15 The authors thank The Mexican Institute of Petroleum for the financial support. A. Quitian also
16
17
18
thanks Consejo Nacional de Ciencia y Tecnologa (CONACYT) for the PhD Scholarship.
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
14
1
2
3 REFERENCES
4
5
6 (1) Quitian, A.; Leyva, C.; Ramrez, S.; Ancheyta, J. Energy & Fuels 2015, 29 (1), 915.
7 (2) Muoz, J. A. D.; Ancheyta, J.; Castaeda, L. C. Energy & Fuels 2016, DOI:
8 10.1021/acs.energyfuels.6b01908.
9 (3) Saniere, A.; Hnaut, I.; Argillier, J. F. Sci. Technol. IFP 2004, 59 (5), 455466.
10
(4) Domnguez, J. . Ing. Qumica 2008, 465, 5465.
11
12 (5) Borden, K. Oil Gas Facil. 2015, 2 (5), 2226.
13 (6) Alomair, O. A.; Almusallam, A. S. Energy & Fuels 2013, 27 (12), 72677276.
14 (7) Argillier, J.-F.; Barre, L.; Brucy, F.; Dournaux, J.-L.; Henaut, I.; Bouchard, R. In SPE
15 International Thermal Operations and Heavy Oil Symposium; Society of Petroleum
16 Engineers, 2013.
17
18
(8) Roenko, E. V.; Kalinichenko, O. A.; Tertyshnaya, E. V.; Snezhko, L. A. Chem. Technol.
19 Fuels Oils 2014, 50 (3), 217224.
20 (9) Speight, J. G. Sci. Iran. 2012, 19 (3), 569573.
21 (10) Barrufet, M.; Lokhandwala, T. M. In International Petroleum Technology Conference;
22 International Petroleum Technology Conference, 2014.
23
(11) Muraza, O. J. Anal. Appl. Pyrolysis 2015, 114, 110.
24
25 (12) Maity, S. K.; Ancheyta, J.; Marroqun, G. Energy & Fuels 2010, 24 (5), 28092816.
26 (13) Wu, C.; Lei, G.; Yao, C.; Jia, X. In International Oil and Gas Conference and Exhibition
27 in China; Society of Petroleum Engineers, 2013.
28 (14) Wang, J.; Liu, L.; Zhang, L.; Li, Z. Energy & Fuels 2014, 28 (12), 74407447.
29 (15) Castaneda, L.; Muoz, J.; Ancheyta J. Catal. Today 2014, 220222, 248273.
30
31
(16) Ancheyta, J. Modeling of processes and reactors for upgrading of heavy petroleum; CRC
32 Press, Taylor and Francis Group: Boca de Raton, 2013.
33 (17) Ancheyta, J.; Speight, J. Hydroprocessing of heavy oils and residua; Taylor & Francis
34 Group: Boca Raton, 2007.
35 (18) Zhang, S.; Liu, D.; Deng, W.; Que, G. Energy and Fuels 2007, 21 (6), 27.
36
(19) Eijsbouts, S.; Mayo, S. W.; Fujita, K. Appl. Catal. A Gen. 2007, 322, 5866.
37
38 (20) Maity, S. K.; Blanco, E.; Ancheyta, J.; Alonso, F.; Fukuyama, H. Fuel 2012, 100, 1723.
39 (21) Furimsky, E. Catalysts for Upgrading Heavy Petroleum Feeds, First Edit.; 2010.
40 (22) Absi-Halabi, M.; Stanislaus, A.; Trimm, D. L. Appl. Catal. 1991, 72 (2), 193215.
41 (23) Bellussi, G.; Rispoli, G.; Landoni, A.; Millini, R.; Molinari, D.; Montanari, E.; Moscotti,
42 D.; Pollesel, P. J. Catal. 2013, 308, 189200.
43
44 (24) Nguyen-Huy, C.; Kweon, H.; Kim, H.; Kim, D. K.; Kim, D.-W.; Oh, S. H.; Shin, E. W.
45 Appl. Catal. A Gen. 2012, 447448, 186192.
46 (25) Matsumura, A.; Kondo, T.; Sato, S.; Saito, I.; Desouza, W. Fuel 2005, 84 (4), 411416.
47 (26) Matsumura, A.; Sato, S.; Kondo, T.; Saito, I.; Desouza, W. Fuel 2005, 84 (4), 417421.
48 (27) Picn-Hernndez, H.-J.; Centeno-Hurtado, A.; Pantoja-Agreda, E.-F. CT&F - Ciencia,
49
Tecnol. y Futur. 3 (4), 169183.
50
51 (28) Wang, G.; Eser, S. Energy & Fuels 2007, 21 (6), 35633572.
52 (29) Popovici, I. C.; Birghila, S.; Voicu, G.; Ionescu, V.; Ciupina, V.; Prodan, G. 2010, 12 (9),
53 19031908.
54 (30) Feret, F. R. Analyst 1998, 123 (4), 595600.
55 (31) Zhan, X.; Jia, J.; Zhou, Z.; Wang, F. Energy Convers. Manag. 2011, 52 (4), 18101814.
56
57 (32) Rezaei, H.; Ardakani, S. J.; Smith, K. J. Energy and Fuels 2012, 26 (5), 27682778.
58 (33) Kseoglu, R. .; Phillips, C. R. Fuel 1988, 67 (4), 552556.
59
60
15
1
2
3 (34) Furimsky, E. Appl. Catal. A Gen. 1998, 171 (2), 177206.
4
5
(35) Ramrez, S.; Martnez, J.; Ancheyta, J. Fuel 2013, 110, 8388.
6 (36) Botchwey, C.; Dalai, A. K.; Adjaye, J. Energy & Fuels 2003, 17 (5), 13721381.
7 (37) Du, H.; Liu, D.; Li, M.; Wu, P.; Yang, Y. Energy and Fuels 2015, 29 (2), 626633.
8 (38) Shuyi, Z.; Wenan, D.; Hui, L.; Dong, L.; Guohe, Q. Energy & Fuels 2008, 22 (6), 3583
9 3586.
10
(39) Panariti, N.; Del Bianco, a.; Del Piero, G.; Marchionna, M.; Carniti, P. Appl. Catal. A
11
12 Gen. 2000, 204 (2), 215222.
13 (40) Chenguang, L.; Guohe, Q. Wenjie, L.; Yajie, Z. Pet. Process. Petrochemicals 1993, 4.
14 (41) Kennepoh, D.; Sanford, E. Energy Fuels 1996, 10, 229234.
15 (42) Quitian, A.; Ancheyta, J. Energy & Fuels 2016, 30 (6), 44194437.
16 (43) Topsoe, H.; Clausen, B. S.; Massoth, F. E. Hydrotreating Catalysis Science and
17
18
Technology; Springer-Verlag: New York, 1996.
19 (44) Chianelli, R. R.; Siadati, M. H.; De la Rosa, M. P.; Berhault, G.; Wilcoxon, J. P.; Bearden,
20 R.; Abrams, B. L. Catal. Rev. 2006, 48 (1), 141.
21 (45) Chianelli, R. R.; Berhault, G.; Torres, B. Catal. Today 2009, 147 (34), 275286.
22 (46) Weisser, O.; Landa, S. Sulphide Catalysts, Their Properties and Applications; Publishing
23
House of Czechoslovak Academy of Sciences: Praga, 2013.
24
25 (47) Matsura, A.; Sato, S.; Kondo, T.; Saito, I.; Desouza, W. Fuel 2005, 84 (4), 417421.
26 (48) Nguyen-Huy, C.; Kim, H.; Kweon, H.; Kim, D. K.; Kim, D.-W.; Oh, S. H.; Shin, E. W.
27 Chem. Eng. Technol. 2013, 36 (8), 13651370.
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
16
1
2
3 Table 1. Properties of heavy crude oil
4
5 Property Method Value
6
7 Specific gravity @ 60/60F ASTM D1298 0.9812
8
9
10 API gravity ASTM D287 12.71
11
12 Viscosity, cSt ASTM D7042
13
14 25.0C 22791
15
16 37.8C 6110
17
18 54.4 C 1518
19
20 Insolubles in C7, wt% ASTM D3279 18.78
21
22
23 Simulated distillation, C ASTM D7169
24
25 IBP 67.8
26
27 10 vol% 222.0
28
29 25 vol% 343.3
30
31 50 vol% 501.2
32
33 75 vol% 605.8
34
35
36 90 vol% 679.8
37
38 FBP 739.4
39
40 CHNS/O
41
42 Elemental analysis, wt% Elemental
43
44 Analyzer
45
46 C 83.01
47
48
49 H 9.66
50
51 O 1.52
52
53 N 0.54
54
55 S 5.27
56
57
58
59
60
17
1
2
3 Table 2. Composition of molybdenum trioxide of analytic grade
4
5
6 Component Content (wt%)
7
8 MoO3 99.5
9
10
11 (AsO4)3 0.001
12
13 (SiO4)4- 0.001
14
15
16 Cl- 0.002
17
18 Pb 0.005
19
20
NH4+ 0.002
21
22
23 NO3- 0.003
24
25 (PO4)3- 0.000005
26
27
28 (SO4)2- 0.02
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
18
1
2
3 Table 3. Composition of ferric oxide of analytic grade
4
5
6 Elements Content (wt%)
7
8 Fe 71.3
9
10
11 O 28.6
12
13 Ca, C, P, Si, Mg, N, Al, Ti, Na, V, S, K, Cl, Mn,
14
15
16
Ce, Ba, Co, Zn, Cu, Sr, Y, Ni, Rb, B, Cd, Dy, <0.002
17
18 Sn, Tm
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
19
1
2
3 Table 4. Composition (wt%) of the ores catalysts
4
5
6 Element Molybdenite Magnetite Hematite A Hematite B
7 Mo 41.76 0.00 0.00 0.00
8 Fe 1.05 55.90 72.06 53.02
9 O 1.79 16.63 16.71 17.84
10
11
S 19.63 0.09 0.27 0.09
12 C 10.95 8.25 3.07 8.70
13 B 21.94 0.00 1.65 0.00
14 Cu 0.91 0.01 0.02 0.01
15 Si 0.73 2.32 0.19 2.29
16
Al 0.33 0.30 0.14 0.32
17
18 Ca 0.21 11.28 5.19 12.32
19 Zn 0.13 0.01 0.01 0.01
20 Mg 0.12 0.65 0.05 0.65
21 K 0.12 0.09 0.01 0.08
22 Rh 0.09 0.00 0.00 0.00
23
24
Na 0.09 0.13 0.1 0.13
25 Ag 0.02 0.00 0.00 0.00
26 Pb 0.02 0.00 0.00 0.00
27 Ti 0.01 0.20 0.01 0.20
28 W 0.01 0.00 0.00 0.00
29
Se 0.01 0.00 0.00 0.00
30
31 Ar 0.01 0.00 0.00 0.00
32 Mn 0.01 0.03 0.05 0.03
33 Ce 0.01 0.02 0.00 0.02
34 Pr 0.01 0.00 0.00 0.00
35 Nb 0.01 0.00 0.00 0.00
36
37
In 0.01 0.00 0.00 0.00
38 Nd 0.01 0.00 0.00 0.00
39 V 0.00 0.10 0.00 0.11
40 Y 0.00 0.01 0.00 0.01
41 Sn 0.00 0.00 0.36 0.00
42
Dy 0.00 0.00 0.03 0.00
43
44 Cr 0.00 0.00 0.02 0.00
45 Tm 0.00 0.00 0.02 0.00
46 Ni 0.00 0.01 0.02 0.01
47 CI 0.00 0.07 0.01 0.07
48 P 0.00 3.39 0.01 3.57
49
50 Sr 0.00 0.01 0.00 0.01
51 N 0.00 0.46 0.00 0.46
52 Ba 0.00 0.02 0.00 0.02
53 Co 0.00 0.02 0.00 0.02
54
55
56
57
58
59
60
20
1
2
3
4
5 Without With 2500 ppm
6
catalyst of molybdenite
7
8 Elemental Analysis 81.21 81.19
9 Carbon, wt% 81.21 81.19
10 Hydrogen, wt% 8.46 8.48
11 Oxygen, wt% 3.40 3.52
12 Nitrogen, wt% 1.02 1.01
13 Sulfur, wt% 5.91 5.80
14 H/C 1.241 1.245
15 Molecular Weight
16 Weight average molecular weight (Mw), g/mol 35,140 34,858
17 Number average molecular weight (MN), g/mol 44,074 43,596
18
Polydispersity Index (PDI) 1.25 1.25
19
20
Proton NMR
21 Fraction of aromatic hydrogen (Har) 0.11 0.11
22 Fraction of alpha aliphatic hydrogen (H) 0.18 0.18
23 Fraction of aliphatic hydrogen other than alpha (Hd) 0.71 0.71
24 Fraction of aliphatic hydrogen (Hal) 0.89 0.89
25 Fraction of aromatic carbon (Car) 0.33 0.33
26 Fraction of aliphatic carbon (Cal) 0.67 0.67
27 13
Carbon NMR
28 Numbers of carbons by aliphatic chain 4.94 4.94
29 Wt% of aromatic carbon 27.79 27.76
30 Wt% of unbridged aromatic carbon substituted by alkyl groups 11.41 11.40
31
Wt% of unbridged and no-substituted aromatic carbon 11.17 11.19
32
33
Wt% of unbridged aromatic carbon 22.58 22.59
34 Number of aromatic carbons 1020.65 1008.51
35 Number of unbridged aromatic carbons 829.26 820.78
36 Number of aromatic rings 96.70 94.86
37 % substitution of aromatic carbons in aromatic rings by
50.54 50.45
38 unbridged alkyl groups
39 Number of alkyl substituents on the aromatic carbons 419.10 414.12
40 Number of aliphatic carbons 2072.24 2047.57
41 Number of aliphatic hydrogens 3318.51 3290.28
42 Number of internal quaternary carbons and / or methylene
43 631.86 627.05
bridges and / or biaryl
44
Aromaticity factor 0.33 0.33
45
46 Interlayer spacing and microcrystalline parameters
47 d002, 3.48 3.46
48 d100, 2.14 2.14
X-Ray data
49 2002, deg. 25.6 25.7
50 2100, deg. 42.2 42.2
51 Lc, 14.69 16.95
52
Microcrystalline parameter
La, 31.74 36.62
53 Effective Dimension L, 22.65 26.13
54 Table 5. Properties of cokes
55
56
57
58
59
60
21
1
2
3
4
5
Table 6. Composition of gas product (mol%) as function of the concentration and type of catalyst
6
7 Concentration
Analytical Analytical Hematite Hematite
8 of catalyst Molybdenite Magnetite
MoO3 Fe2O3 A B
9 (ppm)
10 C1-C2 26.56 26.56 26.56 26.56 26.56 26.56
11 C3-C4 6.05 6.05 6.05 6.05 6.05 6.05
0
12
13 C5+ 0.11 0.11 0.11 0.11 0.11 0.11
14 H 2S 1.51 1.51 1.51 1.51 1.51 1.51
15 C1-C2 14.41 e14.82 13.92 13.51 14.21 14.09
16
C3-C4 2.26 2.44 2.17 2.97 2.92 2.11
17 3333
18 C5+ 1.18 0.79 0.92 0.89 0.61 0.77
19 H 2S 7.62 7.54 7.04 7.15 6.92 7.06
20
C1-C2 12.07 12.41 11.86 11.33 12.78 12.13
21
22 C3-C4 1.97 2.13 1.96 3.47 2.63 4.80
5000
23 C5+ 0.79 0.64 0.77 0.81 0.57 0.86
24
H 2S 7.91 8.91 7.79 8.83 9.28 7.84
25
26 C1-C2 11.37 10.90 11.15 12.06 11.58 10.33
27 C3-C4 2.01 2.08 2.12 2.77 2.22 3.89
28 6665
C5+ 0.71 0.66 0.63 0.47 0.53 0.72
29
30 H 2S 8.31 7.96 8.23 9.61 9.29 9.07
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
22
1
2
3 Table 8. Elemental analysis of upgraded oils as function of type of catalyst using 0 and 5000 ppm
4
5
6 of metal active.
7
8 Concentration
9 C H O N S
10 of catalyst Upgrade Oil H/C
11 (wt.%) (wt.%) (wt.%) (wt.%) (wt.%)
12 (ppm)
13
14
Without
0 81.84 11.35 1.82 0.52 4.47 1.654
15 catalyst
16
17 Analytical
18 5000 81.30 11.86 1.87 0.51 4.46 1.740
19 MoO3
20
21 Analytical
22
5000 81.22 11.74 1.90 0.53 4.61 1.724
Fe2O3
23
24 5000 Molybdenite 81.18 11.70 1.84 0.53 4.75 1.719
25
26 5000 Hematite A 81.41 11.48 1.82 0.55 4.74 1.682
27
28 5000 Hematite B 81.49 11.30 1.78 0.52 4.91 1.654
29
5000 Magnetite 81.34 11.57 1.86 0.43 4.80 1.697
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
23
1
2
3 Table 9. Composition of upgraded oils as function of type of catalyst using 5000 ppm of metal
4
5
6 active.
7
8 Analytical Analytical Hematite Hematite
9 Distillation fraction Feed Molybdenite Magnetite
MoO3 Fe2O3 A B
10
11 LSRN 0.10 0.10 0.10 0.10 0.10 0.10 0.10
12 MSRN 5.87 9.97 8.85 8.85 8.04 7.34 7.97
13 HSRN 2.33 3.96 3.94 3.70 4.05 3.94 3.52
14
JF 7.30 12.84 12.88 12.13 11.55 11.88 11.46
15
16 K 5.61 8.99 8.71 8.41 8.06 8.42 8.04
17 SRGO 3.73 6.73 6.52 6.38 6.19 6.39 6.20
18 LVGO 17.35 22.32 22.04 22.02 22.32 21.00 21.30
19
20 HVGO 17.30 14.04 14.79 14.97 15.12 14.89 15.76
21 VR 40.41 21.03 22.17 23.44 24.56 26.04 25.64
22 VRC, % - 48.98 46.23 43.15 40.44 36.83 37.82
23
24
25
26 LSRN: Light straight-run naphtha (<71C), MSRN: Medium straight-run naphtha (71-177C),
27
28 HSRN: Heavy straight-run naphtha (177-204C), JF: Jet fuel (204-274C), K: Kerosene (274-
29
30
31
316C), SRGO: Straight-run gasoil (316-343C), LVGO: Light vacuum gasoil (343-454C),
32
33 HVGO: Heavy vacuum gasoil (454-538C), VR: Vacuum residue (>538C), VRC: Vacuum
34
35 residue conversion.
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
24
1
2
3 FIGURE CAPTIONS
4
5
6 Figure 1. Coke and gas yields as function of type and concentration of catalyst. () Analytic
7
8 molybdenum trioxide (MoO3), () Analytic ferric oxide (Fe2O3), (*) Molybdenite, ()
9
10
Magnetite (--) Hematite A, () Hematite B.
11
12
13 Figure 2. Nuclear resonance magnetic of cokes without catalyst and with catalyst. (A) Proton
14
15 13
NMR of coke without catalyst, (B) Carbon NMR of coke without catalyst, (C)
16
17 13
18
Proton NMR of coke with 2500 ppm of molybdenite, (D) Carbon NMR of coke
19
20 with 2500 ppm of molybdenite.
21
22 Figure 3. XRD of cokes without catalyst and using 2500 ppm of molybdenite. (---) Coke with
23
24
25 2500 ppm of molybdenite, () Coke without catalyst.
26
27 Figure 4. TGA and DTA curves of cokes without catalyst and 2500 ppm of molybdenite.
28
29 Figure 5. API gravity of upgrading crude oils as function of type and concentration of catalyst.
30
31
32 () Analytic molybdenum trioxide (MoO3), () Analytic ferric oxide (Fe2O3), (*)
33
34 Molybdenite, () Magnetite (--) Hematite A, () Hematite B.
35
36
37
Figure 6. Viscosity at 37.8C of upgrading crude oils as function of type and concentration of
38
39 catalyst. () Analytic molybdenum trioxide (MoO3), () Analytic ferric oxide
40
41 (Fe2O3), (*) Molybdenite, () Magnetite (--) Hematite A, () Hematite B.
42
43
44 Figure 7. Hydrodesulfurization of upgrading crude oils as function of type and concentration of
45
46 catalyst. () Analytic molybdenum trioxide (MoO3), () Analytic ferric oxide
47
48 (Fe2O3), (*) Molybdenite, () Magnetite (--) Hematite A, () Hematite B.
49
50
51 Figure 8. Hydrogen consumption as function of type and concentration of ore catalyst. ( ) 0
52
53 ppm, ( ) 3333 ppm, ( ) 5000 ppm, ( ) 6665 ppm.
54
55
56
57
58
59
60
25
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52 Figure 1.
53
54
55
56
57
58
59
60
26
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15 C
16
A
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31 B D
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
Figure 2.
57
58
59
60
27
1
2
3
4
5
6
7
8
9
10 002
11
12
13
14
15
16
17
18
19
20
21 100
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53 Figure 3.
54
55
56
57
58
59
60
28
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55 Figure 4.
56
57
58
59
60
29
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57 Figure 5.
58
59
60
30
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 Figure 6.
59
60
31
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 Figure 7.
59
60
32
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58 Figure 8.
59
60
33

Partial Upgrading - Quitian2016

Caricato da

Informazioni sul documento

Titolo originale

Copyright

Formati disponibili

Condividi questo documento

Condividi o incorpora il documento

Opzioni di condivisione

Hai trovato utile questo documento?

Questo contenuto è inappropriato?

Copyright:

Formati disponibili

Partial Upgrading - Quitian2016

Caricato da

Copyright:

Formati disponibili

Subscriber access provided by UNIV OF CALIFORNIA SAN DIEGO LIBRARIES

Potrebbero piacerti anche