CN116328830B - Sulfurized hydroisomerization catalyst, and preparation method and application thereof - Google Patents
Sulfurized hydroisomerization catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 67
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 57
- 239000011733 molybdenum Substances 0.000 claims abstract description 57
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000003225 biodiesel Substances 0.000 claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 claims abstract description 23
- 238000004073 vulcanization Methods 0.000 claims abstract description 20
- 239000002028 Biomass Substances 0.000 claims abstract description 19
- 230000000694 effects Effects 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 5
- -1 molybdenum ions Chemical class 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 51
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 229910052717 sulfur Inorganic materials 0.000 claims description 28
- 239000011593 sulfur Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006317 isomerization reaction Methods 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 13
- 229940094933 n-dodecane Drugs 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 238000012360 testing method Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000002608 ionic liquid Substances 0.000 claims description 6
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 claims description 4
- IHXDOEFPCHIDKW-UHFFFAOYSA-N N1C=NC=C1.[Mo] Chemical compound N1C=NC=C1.[Mo] IHXDOEFPCHIDKW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 4
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000009833 condensation Methods 0.000 abstract description 3
- 230000005494 condensation Effects 0.000 abstract description 3
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 2
- 239000000194 fatty acid Substances 0.000 abstract description 2
- 229930195729 fatty acid Natural products 0.000 abstract description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 abstract description 2
- 150000004665 fatty acids Chemical class 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 239000010696 ester oil Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 239000003921 oil Substances 0.000 abstract 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 9
- 101150116295 CAT2 gene Proteins 0.000 description 6
- 101100392078 Caenorhabditis elegans cat-4 gene Proteins 0.000 description 6
- 101100326920 Caenorhabditis elegans ctl-1 gene Proteins 0.000 description 6
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 description 6
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 description 6
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 description 6
- 101100126846 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) katG gene Proteins 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000004519 grease Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- FLIACVVOZYBSBS-UHFFFAOYSA-N Methyl palmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC FLIACVVOZYBSBS-UHFFFAOYSA-N 0.000 description 4
- 101100005280 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-3 gene Proteins 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910015667 MoO4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000027455 binding Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/12—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation
- C11C3/126—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by hydrogenation using catalysts based principally on other metals or derivates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
- C11C3/14—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom by isomerisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
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Abstract
The invention discloses a sulfurized hydroisomerization catalyst, a preparation method and application thereof, wherein the catalyst is a sulfurized hydroisomerization composition obtained by physically mixing a molybdenum source and a molecular sieve as raw materials and in-situ sulfurizing, wherein the molar ratio of molybdenum ions to Al 2O3 in the molecular sieve is 1 (20-30). The in-situ vulcanization of the obtained vulcanized hydroisomerization catalyst has high hydrogenation activity of biomass oil and selectivity of long-chain isomerism hydrocarbon, and conventional fatty acid and fatty acid methyl ester oil products thereof can be subjected to hydrodeoxygenation isomerism under milder conditions. The catalyst has proper acidity, reduces cracking side reaction to the greatest extent, reduces the condensation point of biodiesel, and has good thermal stability.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a low-condensation-point biodiesel catalyst prepared by sulfurized hydroisomerization, a preparation method and application thereof.
Background
The exploitation and development of traditional fossil energy promotes the progress of human civilization, and simultaneously brings a series of environmental pollution problems. With the rapid development of civilization and socioeconomic performance of humans, the demand of energy for humans is more urgent. The energy crisis caused by non-renewable fossil resources has attracted considerable attention in countries around the world. Therefore, from the viewpoint of resource strategy and environmental protection, development of an environmentally friendly renewable energy source is desired.
The biodiesel has the advantages of good safety, high combustion efficiency, environmental friendliness, reproducibility and the like when being used as biomass energy, and is a potential substitute of fossil diesel. The development of biodiesel has also undergone the first generation biodiesel, the second generation biodiesel and the third generation biodiesel. The first generation biodiesel of fatty acid methyl ester is obtained by transesterification of fatty acid and methanol, the technology is relatively mature, and the biodiesel is widely applied worldwide. The main production methods include acid-base catalysis, enzyme catalysis and supercritical methods, but the first generation biodiesel has the defects of high oxygen content, poor low-temperature fluidity, low heat value and the like. In general, the first generation biodiesel cannot completely replace petroleum diesel, and can only be added and used with petroleum diesel. The second generation biodiesel refers to the production of saturated long-chain alkane with the chemical composition similar to petrochemical diesel through hydrodeoxygenation, decarboxylation, decarbonylation and other ways under the action of a catalyst. Compared with the first generation biodiesel, the biodiesel has the characteristics of high cetane number, low oxygen content, high stability and the like. The development of the second generation biodiesel gradually inclines to isoparaffin with low condensation point. The third generation biodiesel mainly adopts non-grease biomass and microbial grease, and the biodiesel is produced by means of extraction, separation, hydrofining and the like. Due to the difference of raw materials, the method realizes that the grain is not contended with people and the ground is not contended with grains, and has good development prospect. The hydrodeoxygenation and isomerization catalyst is needed in the third generation biodiesel production process, but the existing hydrodeoxygenation and isomerization catalyst for biomass oil has the problems of low activity, poor stability and the like, so that the production cost is high, and the hydrodeoxygenation and isomerization catalyst for biomass oil is not popularized on a large scale at present.
Disclosure of Invention
The invention aims to solve the problems of low activity, poor stability and the like of the conventional biomass oil hydrodeoxygenation and isomerization catalyst, and provides a low-condensation-point biodiesel catalyst prepared by sulfur state hydroisomerization and a preparation method thereof.
The invention adopts the following technical scheme:
a sulfurized hydroisomerization catalyst is used for preparing low-condensation-point biodiesel, and is a sulfurized hydroisomerization composition obtained by in-situ sulfurizing a molybdenum source and a molecular sieve, wherein the molar ratio of molybdenum ions to Al 2O3 in the molecular sieve is 1 (20-30).
The molybdenum source is one or more of oil-soluble molybdenum or non-oil-soluble molybdenum.
Preferably, the molybdenum source is oil-soluble molybdenum, and the oil-soluble molybdenum is one or more of molybdenum isooctanoate, molybdenum hexacarbonyl and imidazole molybdenum based ionic liquid.
The molecular sieve is one or more of SAPO-11 molecular sieve, ZSM-22 molecular sieve and ZSM-5 molecular sieve.
A method for preparing a sulfided hydroisomerization catalyst, comprising the steps of:
s1, synthesizing a series of molecular sieves under a hydrothermal condition;
S2, roasting the molecular sieve in a muffle furnace at 550-600 ℃ for 3-4 hours, and removing the template agent;
S3, sequentially adding n-dodecane solvent, a molecular sieve, a molybdenum source and sulfur powder into a suspension bed reaction kettle, screwing up the reaction kettle, and heating from room temperature to vulcanization temperature at a heating rate of 5-6 ℃/min, and carrying out in-situ vulcanization for 1-1.5h to obtain a vulcanized catalyst;
and S4, centrifugally washing the sulfided catalyst obtained in the step S3 for 4-6 times by using a mixed solution of ethanol and toluene, and then placing the catalyst into a vacuum drying oven at 75-80 ℃ for drying for 10-12 hours to obtain the required sulfided hydroisomerization catalyst.
In the step S3, the adding amount of the molecular sieve is 10-15wt.% of the n-dodecane solvent, the adding amount of the molybdenum source is 1200-1500ppm Mo, and the sulfur powder is added according to the atomic ratio of sulfur to molybdenum (10-12): 1.
The application of a sulfurized hydroisomerization catalyst in hydrodeoxygenation and isomerization reaction of biomass oil is characterized in that the catalyst is sulfurized in situ in a sulfur-containing environment and a hydrogen atmosphere, and the hydrodeoxygenation and isomerization activity test of the biomass oil are directly carried out after the catalyst is treated.
The catalyst is added in an amount of 8-10% of the weight of the biomass oil to be treated, and sulfur powder is added in a suspension bed reactor according to a sulfur-molybdenum atomic ratio (10-12) of 1 to maintain a sulfur-containing environment.
The hydrogen pressure is 2-10MPa, the heating rate is 5-6 ℃/min, the reaction temperature is 320-420 ℃, and the reaction time is 1-6h when the isomerization test of the hydrodeoxygenation agent is carried out.
The technical scheme of the invention has the following advantages:
A. The sulfur state hydroisomerization catalyst provided by the invention can realize the deoxidation of grease under the condition of lower Mo content, and can generate biodiesel with higher cetane number. The molecular sieve is introduced, so that the dispersivity of MoS 2 after in-situ vulcanization is improved, the stripe length is shorter, the number of stacked layers is smaller, more S vacancies are exposed, and the HDO activity of the catalyst is improved.
B. The in-situ vulcanized MoS 2 is used as a hydrogenation active phase, the molecular sieve is used as an acid center, and the metal-acid double-function catalyst is formed to catalyze grease to produce biodiesel. Wherein the alcohol or the linear alkane is dehydrogenated to generate alkene, rearranged at an acid site to generate isoalkene, and then hydrogenated to saturate to generate isoparaffin. The surface acidity of the molecular sieve can be changed by adjusting the Mo content, and unnecessary cracking side reactions are inhibited.
C. The catalyst provided by the invention has the advantages of simple preparation method, relatively low catalyst cost and wide adaptability to complex oil products with high oxygen content. The use effect shows that the invention has higher activity in hydrodeoxygenation and isomerization of biomass oil, less cracking side reaction and higher selectivity (15-20%) on long-chain isoparaffin.
Drawings
FIG. 1 is an XRD spectrum of the hydroisomerization catalyst in the sulfided state and the SAPO-11 molecular sieve obtained in examples 1-4.
Detailed Description
The following description of the present invention will be made clearly and fully, and it is apparent that the embodiments described are some, but not all, of the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a sulfurized hydroisomerization catalyst, which is used for preparing biodiesel with a low condensation point, wherein the catalyst is a sulfurized hydroisomerization composition obtained by physically mixing a molybdenum source and a molecular sieve as raw materials and in-situ sulfurizing the raw materials in a suspended bed reaction kettle, wherein the molar ratio of molybdenum ions to Al 2O3 in the molecular sieve is 1 (20-30). The molybdenum source is one or more of oil-soluble molybdenum or non-oil-soluble molybdenum in any proportion, preferably oil-soluble molybdenum, and the oil-soluble molybdenum can be one or more of molybdenum isooctanoate, molybdenum hexacarbonyl and imidazole molybdenum based ionic liquid in any proportion. The molecular sieve is one or more of SAPO-11 molecular sieve, ZSM-22 molecular sieve and ZSM-5 molecular sieve in any proportion.
The sulfur state hydroisomerization catalyst provided by the invention can realize the deoxidation of grease under the condition of lower Mo content, and can generate biodiesel with higher cetane number. The molecular sieve is introduced, so that the dispersivity of MoS 2 after in-situ vulcanization is improved, the stripe length is shorter, the number of stacked layers is smaller, more S vacancies are exposed, and the HDO activity of the catalyst is improved. In-situ sulfurized MoS 2 is used as hydrogenating active phase and molecular sieve is used as acid center to form metal-acid double-function catalyst for catalyzing grease to produce biological diesel oil. Wherein the alcohol or the linear alkane is dehydrogenated to generate alkene, rearranged at an acid site to generate isoalkene, and then hydrogenated to saturate to generate isoparaffin. The surface acidity of the molecular sieve can be changed by adjusting the Mo content, and unnecessary cracking side reactions are inhibited.
The invention also provides a preparation method of the sulfur state hydroisomerization catalyst, which comprises the following steps:
S1, synthesizing a series of molecular sieves under a hydrothermal condition, wherein the specific synthesis method is the conventional technology;
S2, roasting the molecular sieve in a muffle furnace at 550-600 ℃ for 3-4 hours, and removing the template agent;
S3, sequentially adding n-dodecane solvent, a molecular sieve, a molybdenum source and sulfur powder into a suspension bed reaction kettle, screwing up the reaction kettle, and heating from room temperature to vulcanization temperature at a heating rate of 5-6 ℃/min, and carrying out in-situ vulcanization for 1-1.5h to obtain a vulcanized catalyst; wherein the adding amount of the molecular sieve is 10-15wt.% of the n-dodecane solvent, the adding amount of the molybdenum source is 1200-1500ppm Mo, and the sulfur powder is added according to the sulfur-molybdenum atomic ratio (10-12): 1;
and S4, centrifugally washing the sulfided catalyst obtained in the step S3 for 4-6 times by using a mixed solution of ethanol and toluene, and then placing the catalyst into a vacuum drying oven at 75-80 ℃ for drying for 10-12 hours to obtain the required sulfided hydroisomerization catalyst.
The invention also provides application of the sulfurized hydroisomerization catalyst in hydrodeoxygenation and isomerization reaction of biomass oil, wherein the catalyst is sulfurized in situ in a sulfur-containing environment and a hydrogen atmosphere, and the hydrodeoxygenation and isomerization activity test of the biomass oil are directly carried out after the catalyst is treated. The catalyst is added in an amount of 8-10% of the weight of the biomass oil to be treated, and sulfur powder is added in a suspension bed reactor according to the atomic ratio of sulfur to molybdenum (10-12): 1 to maintain a sulfur-containing environment. The hydrogen pressure is 2-10MPa, the heating rate is 5-6 ℃/min, the reaction temperature is 320-420 ℃, and the reaction time is 1-6h when the isomerization test of the hydrodeoxygenation agent is carried out.
The catalyst provided by the invention has the advantages of simple preparation method, relatively low catalyst cost and wide adaptability to complex oil products with high oxygen content.
The present invention will be described in detail with reference to specific examples.
Example 1:
the embodiment provides a preparation method of a sulfur state hydrodeoxygenation and isomerization catalyst, which comprises the following steps:
S1, synthesizing an SAPO-11 molecular sieve catalyst under a hydrothermal condition;
s2, roasting the SAPO-11 molecular sieve catalyst in a muffle furnace at 600 ℃ for 3 hours, and removing the template agent;
S3, sequentially adding 30g of n-dodecane solvent, 3g of SAPO-11 molecular sieve, 1200ppm of molybdenum iso-octoate and sulfur powder into a suspension bed reaction kettle, adding the sulfur powder according to the atomic ratio of sulfur to molybdenum of 10:1, then screwing the reaction kettle, raising the temperature to 350 ℃ and performing in-situ vulcanization for 1h to obtain a vulcanized catalyst named Cat-1;
S4, centrifugally washing the Cat-1 obtained in the step S3 for 4-6 times by using the mixed solution of ethanol and toluene, and then placing the washed Cat-1 into a vacuum drying oven at 80 ℃ for drying for 12 hours to obtain the required sulfur-state hydroisomerization catalyst.
Example 2
The embodiment provides a preparation method of a sulfur state hydrodeoxygenation and isomerization catalyst, which comprises the following steps:
S1, synthesizing an SAPO-11 molecular sieve catalyst under a hydrothermal condition;
S2, roasting the SAPO-11 molecular sieve catalyst in a muffle furnace at 550 ℃ for 4 hours, and removing the template agent;
S3, sequentially adding 30g of n-dodecane solvent, 4.5g of SAPO-11 molecular sieve, 1500ppm of molybdenum hexacarbonyl of Mo and sulfur powder into a suspension bed reaction kettle, adding the sulfur powder according to the atomic ratio of sulfur to molybdenum of 12:1, then screwing the reaction kettle, raising the temperature to 420 ℃, and carrying out in-situ vulcanization for 1.5h to obtain a vulcanized catalyst, which is named as Cat-2;
And S4, centrifugally washing the Cat-2 obtained in the step S3 for 4-6 times by using the mixed solution of ethanol and toluene, and then placing the washed Cat-2 into a vacuum drying oven at 75 ℃ to dry for 10 hours, thus obtaining the required hydroisomerization catalyst in a vulcanized state.
Example 3
The embodiment provides a preparation method of a sulfur state hydrodeoxygenation and isomerization catalyst, which comprises the following steps:
S1, synthesizing an SAPO-11 molecular sieve catalyst under a hydrothermal condition;
s2, roasting the SAPO-11 molecular sieve catalyst in a muffle furnace at 600 ℃ for 3 hours, and removing the template agent;
S3, sequentially adding 30g of n-dodecane solvent, 3g of SAPO-11 molecular sieve, 1200ppm of ammonium molybdate and sulfur powder into a suspension bed reaction kettle, adding the sulfur powder according to the atomic ratio of sulfur to molybdenum of 10:1, then screwing up the reaction kettle, raising the temperature to 350 ℃, and carrying out in-situ vulcanization for 1h to obtain a vulcanized catalyst named Cat-3;
And S4, centrifugally washing the Cat-3 obtained in the step S3 for 4-6 times by using the mixed solution of ethanol and toluene, and then placing the washed Cat-3 into a vacuum drying oven at 80 ℃ for drying for 12 hours to obtain the required hydroisomerization catalyst in a vulcanized state.
Example 4
The embodiment provides a preparation method of a sulfur state hydrodeoxygenation and isomerization catalyst, which comprises the following steps:
the embodiment provides a preparation method of a sulfur state hydrodeoxygenation and isomerization catalyst, which comprises the following steps:
S1, synthesizing an SAPO-11 molecular sieve catalyst under a hydrothermal condition;
S2, roasting the SAPO-11 molecular sieve catalyst in a muffle furnace at 600 ℃ for 4 hours, and removing the template agent;
s3, sequentially adding 30g of n-dodecane solvent, 4.5g of SAPO-11 molecular sieve and 1400ppm of Mo imidazole type ionic liquid [ C 8mim]2MoO4, sulfur powder, wherein the sulfur powder is added according to the atomic ratio of sulfur to molybdenum of 11:1, then screwing up the reaction kettle, raising the temperature to 420 ℃ and carrying out in-situ vulcanization for 1h to obtain a vulcanized catalyst, and the vulcanized catalyst is named as Cat-4;
And S4, centrifugally washing the Cat-4 obtained in the step S3 for 4-6 times by using the mixed solution of ethanol and toluene, and then placing the washed Cat-4 into a vacuum drying oven at 80 ℃ for drying for 12 hours to obtain the required hydroisomerization catalyst in a vulcanized state.
Example 5
The embodiment provides a preparation method of a sulfur state hydrodeoxygenation and isomerization catalyst, which comprises the following steps:
the embodiment provides a preparation method of a sulfur state hydrodeoxygenation and isomerization catalyst, which comprises the following steps:
s1, synthesizing a ZSM-22 molecular sieve catalyst under a hydrothermal condition;
s2, roasting the ZSM-22 molecular sieve catalyst in a muffle furnace at 550 ℃ for 4 hours, and removing the template agent;
S3, sequentially adding 30g of n-dodecane solvent, 4.5g of ZSM-22 molecular sieve, 1500ppm of molybdenum iso-octoate of Mo and sulfur powder into a suspension bed reaction kettle, adding the sulfur powder according to the atomic ratio of sulfur to molybdenum of 12:1, then screwing up the reaction kettle, raising the temperature to 420 ℃, and carrying out in-situ vulcanization for 1.5 hours to obtain a vulcanized catalyst named Cat-5;
and S4, centrifugally washing the Cat-5 obtained in the step S3 for 4-6 times by using the mixed solution of ethanol and toluene, and then placing the washed Cat-5 into a vacuum drying oven at 75 ℃ to dry for 10 hours, thus obtaining the required hydroisomerization catalyst in a vulcanized state.
Example 6
The embodiment provides a preparation method of a sulfur state hydrodeoxygenation and isomerization catalyst, which comprises the following steps:
s1, synthesizing a ZSM-5 molecular sieve catalyst under a hydrothermal condition;
s2, roasting the ZSM-5 molecular sieve catalyst in a muffle furnace at 600 ℃ for 3 hours, and removing the template agent;
S3, sequentially adding 30g of n-dodecane solvent, 3g of ZSM-5 molecular sieve, 1200ppm of molybdenum hexacarbonyl and sulfur powder into a suspension bed reaction kettle, adding the sulfur powder according to the atomic ratio of sulfur to molybdenum of 10:1, then screwing up the reaction kettle, raising the temperature to 350 ℃ and carrying out in-situ vulcanization for 1h to obtain a vulcanized catalyst named Cat-6;
and S4, centrifugally washing the Cat-6 obtained in the step S3 for 4-6 times by using the mixed solution of ethanol and toluene, and then placing the washed Cat-6 into a vacuum drying oven at 80 ℃ for drying for 12 hours to obtain the required hydroisomerization catalyst in a vulcanized state.
FIG. 1 shows XRD patterns of the sulfided hydroisomerization catalysts and SAPO-11 molecular sieves obtained in examples 1-4. As can be seen from XRD spectra, cat-1, cat-2, cat-4 and SAPO-11 molecular sieve catalysts have similar crystal form structures. Wherein 2θ=7.9°, 9.4 °, 12.9 °, 15.5 °, 20.2 °, 21.0 °, 22.1 °, 23.2 ° are characteristic diffraction peaks of the SAPO-11 molecular sieve. Molybdenum isooctanoate, molybdenum hexacarbonyl and imidazole type ionic liquid [ C 8mim]2MoO4 ] used by Cat-1, cat-2 and Cat-4 belong to oil-soluble molybdenum, and after in-situ vulcanization in a reactor, no characteristic diffraction peak of MoS 2 is found, which indicates that the molybdenum isooctanoate, molybdenum hexacarbonyl and imidazole type ionic liquid are highly dispersed on the surface of the SAPO-11 molecular sieve. In addition, the diffraction peaks of 2θ=23.3° and 26.3 ° were assigned to the characteristic diffraction peaks of MoO 3, indicating that the non-oily molybdenum was not completely sulfided. The results of the binding activity test also show that Cat-3 has poor hydrogenation activity due to incomplete vulcanization.
Activity test of suspended bed biomass oil:
The sulfided hydroisomerization catalysts prepared in examples 1-4 were tested for catalyst activity in conjunction with the SAPO-11 molecular sieve as a comparison. The reaction equipment is a batch high-pressure reaction kettle, and the design volume of the device is 200mL. The specific operation is as follows: methyl palmitate is taken as a biomass oil raw material, the addition amount of the methyl palmitate is 30g, the addition amount of the sulfided hydroisomerization catalyst is 3g (10 wt% of the addition amount of the raw material), and the addition amount of the SAPO-11 molecular sieve in the comparative example is 3g. The addition amount of sublimed sulfur was 0.5g, the reaction gas was 99.99% hydrogen gas, and the initial hydrogen pressure was 8MPa. After leak detection, the temperature is raised to 380 ℃ at a speed of 5 ℃/min, the reaction time is 6h, and activity test is carried out. The measurement results are shown in Table 1.
TABLE 1 comparison of catalytic Properties of different catalysts
As can be seen from Table 1, the SAPO-11 molecular sieves used as comparative examples also had catalytic activity at 380 ℃, but the conversion was much lower and more palmitic acid was produced than in examples 1-4. In example 3, the hydrogenation activity was significantly different from that of Cat-1, cat-2 and Cat-4 due to the incomplete vulcanization of molybdenum. In the whole, the sulfur state hydroisomerization catalyst MoS 2/SAPO-11 has the dual-function characteristic of metal-acid, and has good effect on preparing second-generation low-condensation-point biodiesel by catalyzing biomass oil. Meanwhile, the effect on preparing the third-generation biodiesel is very remarkable.
The invention is applicable to the prior art where nothing is said.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While obvious variations or modifications are contemplated as falling within the scope of the present invention.
Claims (9)
1. A sulfurized hydroisomerization catalyst for preparing low-condensation-point biodiesel is characterized in that the catalyst is a sulfurized hydroisomerization composition obtained by in-situ sulfurizing a molybdenum source and a molecular sieve, wherein the molar ratio of molybdenum ions to Al 2O3 in the molecular sieve is 1 (20-30);
The sulfided hydroisomerization catalyst is prepared by the following steps:
s1, synthesizing a series of molecular sieves under a hydrothermal condition;
S2, roasting the molecular sieve in a muffle furnace at 550-600 ℃ for 3-4 hours, and removing the template agent;
S3, sequentially adding n-dodecane solvent, a molecular sieve, a molybdenum source and sulfur powder into a suspension bed reaction kettle, screwing up the reaction kettle, and heating from room temperature to vulcanization temperature at a heating rate of 5-6 ℃/min, and carrying out in-situ vulcanization for 1-1.5h to obtain a vulcanized catalyst;
and S4, centrifugally washing the sulfided catalyst obtained in the step S3 for 4-6 times by using a mixed solution of ethanol and toluene, and then placing the catalyst into a vacuum drying oven at 75-80 ℃ for drying for 10-12 hours to obtain the required sulfided hydroisomerization catalyst.
2. The sulfided hydroisomerization catalyst of claim 1, wherein the molybdenum source is one or more of oil soluble molybdenum or non-oil soluble molybdenum.
3. The sulfided hydroisomerization catalyst of claim 2, wherein the molybdenum source is oil soluble molybdenum; the oil-soluble molybdenum is one or more of molybdenum isooctanoate, molybdenum hexacarbonyl and imidazole molybdenum based ionic liquid.
4. The sulfided hydroisomerization catalyst of claim 1, wherein the molecular sieve is one or more of SAPO-11 molecular sieve, ZSM-22 molecular sieve, ZSM-5 molecular sieve.
5. A process for the preparation of a hydroisomerization catalyst in the sulfided state as claimed in any one of claims 1 to 4, characterized in that it comprises the steps of:
s1, synthesizing a series of molecular sieves under a hydrothermal condition;
S2, roasting the molecular sieve in a muffle furnace at 550-600 ℃ for 3-4 hours, and removing the template agent;
S3, sequentially adding n-dodecane solvent, a molecular sieve, a molybdenum source and sulfur powder into a suspension bed reaction kettle, screwing up the reaction kettle, and heating from room temperature to vulcanization temperature at a heating rate of 5-6 ℃/min, and carrying out in-situ vulcanization for 1-1.5h to obtain a vulcanized catalyst;
and S4, centrifugally washing the sulfided catalyst obtained in the step S3 for 4-6 times by using a mixed solution of ethanol and toluene, and then placing the catalyst into a vacuum drying oven at 75-80 ℃ for drying for 10-12 hours to obtain the required sulfided hydroisomerization catalyst.
6. The method for preparing a hydroisomerization catalyst in a sulfur state according to claim 5, wherein in the step S3, the molecular sieve is added in an amount of 10 to 15wt.% based on the amount of n-dodecane solvent, the molybdenum source is added in an amount of 1200 to 1500ppm Mo, and the sulfur powder is added in a sulfur-molybdenum atomic ratio (10 to 12): 1.
7. Use of the sulfided hydroisomerization catalyst according to any one of claims 1-4 in hydrodeoxygenation and isomerization reactions of biomass oil, characterized in that the catalyst is sulfided in situ in a sulfur-containing environment and in a hydrogen atmosphere, and the hydrodeoxygenation and isomerization activity test of biomass oil is directly performed after treatment.
8. The use according to claim 7, wherein the catalyst is added in an amount of 8-10% by weight of the treated biomass oil, and sulfur powder is added in a suspension bed reactor in a sulfur molybdenum atomic ratio (10-12) of 1 to maintain a sulfur-containing environment.
9. The use according to claim 7, wherein the hydrogen pressure is 2-10MPa, the heating rate is 5-6 ℃/min, the reaction temperature is 320-420 ℃, and the reaction time is 1-6h when the hydrodeoxygenation agent isomerization test is performed.
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