CN101899318A - Method for preparing diesel hydrocarbons from vegetable fat through catalytic hydrogenation and deoxygenation - Google Patents
Method for preparing diesel hydrocarbons from vegetable fat through catalytic hydrogenation and deoxygenation Download PDFInfo
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- CN101899318A CN101899318A CN2010102341981A CN201010234198A CN101899318A CN 101899318 A CN101899318 A CN 101899318A CN 2010102341981 A CN2010102341981 A CN 2010102341981A CN 201010234198 A CN201010234198 A CN 201010234198A CN 101899318 A CN101899318 A CN 101899318A
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- vegetable oil
- oil lipoprotein
- catalytic hydrodeoxygenation
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- diesel hydrocarbons
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- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000009903 catalytic hydrogenation reaction Methods 0.000 title abstract 3
- 238000006392 deoxygenation reaction Methods 0.000 title abstract 3
- 235000019871 vegetable fat Nutrition 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
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- 238000003756 stirring Methods 0.000 claims abstract description 9
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- 102000004895 Lipoproteins Human genes 0.000 claims description 38
- 108090001030 Lipoproteins Proteins 0.000 claims description 38
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- 230000003197 catalytic effect Effects 0.000 claims description 27
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 10
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
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- 239000004480 active ingredient Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 210000000582 semen Anatomy 0.000 claims description 6
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- 238000002360 preparation method Methods 0.000 claims description 5
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- 235000020238 sunflower seed Nutrition 0.000 claims description 5
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- ZJKABZNFELLAQQ-UHFFFAOYSA-N octane Chemical compound CCCCCCCC.CCCCCCCC ZJKABZNFELLAQQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract 1
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 230000001172 regenerating effect Effects 0.000 abstract 1
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000010773 plant oil Substances 0.000 description 7
- 229910003178 Mo2C Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 244000068988 Glycine max Species 0.000 description 2
- 235000010469 Glycine max Nutrition 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 2
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 125000005908 glyceryl ester group Chemical group 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 229960004232 linoleic acid Drugs 0.000 description 2
- 229960004488 linolenic acid Drugs 0.000 description 2
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 2
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical group OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 206010024229 Leprosy Diseases 0.000 description 1
- 235000019483 Peanut oil Nutrition 0.000 description 1
- 235000004443 Ricinus communis Nutrition 0.000 description 1
- 240000000528 Ricinus communis Species 0.000 description 1
- 244000057114 Sapium sebiferum Species 0.000 description 1
- 235000005128 Sapium sebiferum Nutrition 0.000 description 1
- 241001314440 Triphora trianthophoros Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006324 decarbonylation Effects 0.000 description 1
- 238000006606 decarbonylation reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- -1 ester compound Chemical class 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 229960002969 oleic acid Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000000312 peanut oil Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 229960004274 stearic acid Drugs 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Classifications
-
- 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
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for preparing diesel hydrocarbons from vegetable fat through catalytic hydrogenation and deoxygenation, is a method for preparing alkane with a high calorific value from vegetable fat through catalytic hydrogenation and deoxygenation, and adopts a one-pot method reaction process, comprising the following steps: adding a molybdenum carbide catalyst, vegetable fact and solvent in a reactor, filling hydrogen in the reactor, stirring and heating, reacting for 3-10h with the reaction pressure of 1-10MPa and the reaction temperature of 250-350 DEG C, stopping reaction, cooling to room temperature, filtering and separating the catalyst out to obtain the diesel hydrocarbons with alkane at a high calorific value. By adopting the technical scheme in the invention, the method has low production cost and high product combustion value, is favor of large-scale industrialized popularization and is a clean and regenerative diesel alternative fuel.
Description
Technical field
The present invention relates to a kind ofly generate the method for diesel hydrocarbons through the hydrogenation deoxidation process, more particularly, relate to a kind of method that the Vegetable oil lipoprotein catalytic hydrodeoxygenation is prepared diesel hydrocarbons based on non-noble metal-based catalysts based on the catalyst Vegetable oil lipoprotein
Background technology
Along with the sustained and rapid development of Chinese national economy, the demand of liquid fuel is increased rapidly, expect the year two thousand twenty China's oil supply breach and will reach 2.5 hundred million tons, the external interdependency of oil will reach 54% when the time comes.Developing the present situation of the liquid fuel of the alternative oil with sustainable source for the shortage of alleviation China's oil, and then guarantee that the energy security of China and the Sustainable development of national economy are extremely important, is the secular from now on great demand of China.Animal-plant oil is the material that a class is widespread in nature, for example: rapeseed oil, Oleum Cocois, plam oil, soybean oil, peanut oil, the crazy oil of Ma, Chinese tallow tree wet goods.Its main ingredient is the glyceryl ester of free fatty acids and saturated or unsaturated fatty acids, belongs to renewable resources.Contained free fatty acids mainly is the palmitinic acid that contains 16 carbon atoms in the animal-plant oil, contains stearic acid, oleic acid, the linoleic acid plus linolenic acid of 18 carbon atoms; Contained ester compound mainly is monoglyceride, triglyceride and the triglyceride level that is obtained by palmitinic acid, stearic acid, oleic acid, linolic acid or linolenic acid and glycerine generation esterification in the animal-plant oil.Although animal-plant oil output is abundant, glyceryl ester oxygen level height, viscosity are big, and free fatty acids has stronger corrodibility to engine, thus animal-plant oil can not be directly as the fuel of engine.
Diesel oil mainly is made up of the alkane that contains 10~22 carbon atoms, alkene, naphthenic hydrocarbon etc., and the combustion heat value height is the good fuel of heavy equipment.In view of animal-plant oil and the diesel oil common feature (all containing long carbochain part) on structure is formed, change the mode of animal-plant oil by hydrogenation deoxidation into the renewable diesel class hydrocarbon that alkane can obtain cleaning, promptly so-called s-generation biofuel.Compare with fossil oil, the liquid fuel of producing from energy crop has recyclability, is a kind of real " green energy resource ", and it not only can alleviate the oil undersupply, can also increase farmers' income, and preserves the ecological environment, and has the meaning of killing three birds with one stone.
The bio-oil that extracts from farm-forestry crops such as reproducible Semen Brassicae campestris, castor-oil plant, soybean, cotton, leprosy fruit is converted into attention (United States Patent (USP): US2009077867,2009 that oil engine available liquid fuel more and more is subjected to national governments and scholar; United States Patent (USP): US20100000908,2010; P.Simacek, et al, Fuel, 2009,88,456.).The catalyzer that is used for the oil hydrogenation deoxidation of report mainly is noble metal-based catalysts such as Pt, Pd at present.Therefore this class catalyzer is restricted in the heavy industrialization application process owing to it costs an arm and a leg, reserves are limited.Molybdenum carbide has the valency layer electronic structure of class precious metal, shows the catalytic activity similar with precious metal in many hydrogen-involved reactions.Because the molybdenum carbide synthesis material is easy to get and is cheap, the preparation field that its alternative catalysts as precious metals such as Pt, Pd is applied to renewable diesel class hydrocarbon has important theoretical and realistic meaning.
Summary of the invention
The objective of the invention is to solve problem set forth above, provide a kind of catalyzer easily synthetic and cheap; Product combustion heat value height, and be the reproducible diesel oil alternative fuel of cleaning; Solvent is cheap and easy to get, and consumption is few, and boiling point is low, and the Vegetable oil lipoprotein catalytic hydrodeoxygenation that is easy to recycle prepares the method for diesel hydrocarbons.
Technical scheme of the present invention is such:
A kind of Vegetable oil lipoprotein catalytic hydrodeoxygenation prepares the method for diesel hydrocarbons, is that Vegetable oil lipoprotein makes high heating value alkane through catalytic hydrodeoxygenation, adopts the preparation of one kettle way reaction process;
Method is as follows:
In reactor, add catalyzer, Vegetable oil lipoprotein and solvent, charge into hydrogen, open and stir and heating, reaction pressure is 1-10MPa, temperature of reaction is 250-350 ℃, react stopped reaction after 3-10 hour, to be cooled to room temperature, filter to isolate the diesel hydrocarbons that catalyzer can obtain containing high heating value alkane.
As preferably, described catalyzer is activated carbon supported molybdenum carbide catalyst, and the quality percentage composition of active ingredient molybdenum carbide is 5-30%.
As preferably, the quality percentage composition of active ingredient molybdenum carbide is 15~25%.
As preferably, described solvent can be normal hexane or normal heptane or octane or dodecane or n-Hexadecane.
As preferably, Vegetable oil lipoprotein catalytic hydrodeoxygenation reaction solvent for use is a normal hexane.
As preferably, used Vegetable oil lipoprotein can be sunflower seed oil or rapeseed oil or soybean oil or Semen Maydis oil or sweet oil.
As preferably, the weight ratio of catalyzer and Vegetable oil lipoprotein is 1: 2~1: 10; The weightmeasurement ratio of vegetables oil and solvent is 1g: 10mL~1g: 35mL.
As preferably, Vegetable oil lipoprotein catalytic hydrodeoxygenation reaction pressure is 2-6MPa.
As preferably, Vegetable oil lipoprotein catalytic hydrodeoxygenation temperature of reaction is 270-320 ℃.
Beneficial effect of the present invention is as follows:
1, uses molybdenum carbide material cheap and easy to get to replace expensive noble metal catalysts such as Pt, Pd, production cost is reduced significantly, help large-scale industrialization promotion.
2, compare with noble metal catalysts such as Pt, Pd, Vegetable oil lipoprotein carries out mainly generating non-decarbonylation product after the hydrogenation deoxidation on molybdenum carbide catalyst, and the grease carbochain does not partly have cracking, and is good to target product selectivity.Therefore product combustion heat value height is the reproducible diesel oil alternative fuel of cleaning.
3, compare with the preparation technology of biofuel, no glycerine generates in the Vegetable oil lipoprotein hydrogenation deoxidation process, and reaction need not neutralize excessive acid, alkaline catalysts after finishing, thereby has effectively avoided the increase of the production cost that aftertreatment brings.
4, solvent is cheap and easy to get, and consumption is few, and boiling point is low, is easy to recycle.
Embodiment
Technical scheme of the present invention is such:
A kind of Vegetable oil lipoprotein catalytic hydrodeoxygenation prepares the method for diesel hydrocarbons, is that Vegetable oil lipoprotein makes high heating value alkane through catalytic hydrodeoxygenation, adopts the preparation of one kettle way reaction process;
Method is as follows:
In reactor, add catalyzer, Vegetable oil lipoprotein and solvent, charge into hydrogen, open and stir and heating, reaction pressure is 1-10MPa, temperature of reaction is 250-350 ℃, react stopped reaction after 3-10 hour, to be cooled to room temperature, filter to isolate the diesel hydrocarbons that catalyzer can obtain containing high heating value alkane.
Described catalyzer is activated carbon supported molybdenum carbide catalyst, and the quality percentage composition of active ingredient molybdenum carbide is 5-30%.In order to reach better effect, the quality percentage composition of active ingredient molybdenum carbide can be 15~25%.
Described solvent can be normal hexane or normal heptane or octane or dodecane or n-Hexadecane.
In implementing, Vegetable oil lipoprotein catalytic hydrodeoxygenation reaction solvent for use is respectively normal hexane, normal heptane, octane, dodecane, n-Hexadecane.
Used Vegetable oil lipoprotein can be sunflower seed oil or rapeseed oil or soybean oil or Semen Maydis oil or sweet oil.
The weight ratio of catalyzer and Vegetable oil lipoprotein is 1: 2~1: 10; The weightmeasurement ratio of vegetables oil and solvent is 1g: 10mL~1g: 35mL.
In order to reach better effect, Vegetable oil lipoprotein catalytic hydrodeoxygenation reaction pressure is 2-6MPa.
In order to reach better effect, Vegetable oil lipoprotein catalytic hydrodeoxygenation temperature of reaction is 270-320 ℃.
Embodiment 1
0.2g Mo2C/AC catalyzer, 1.0g sunflower seed oil and 20mL normal hexane are added in the 100mL reactor, charge into hydrogen, initial hydrogen pressure 2.5MPa, open and stir and heating, 270 ℃ are reacted stopped reaction after 10 hours, to be cooled to room temperature, the filtering separation catalyzer obtains the diesel hydrocarbons of clear.With high performance liquid chromatography and gas-chromatography product is carried out detection by quantitative respectively, the transformation efficiency of raw material sunflower seed oil can reach 97% as can be known, and the ultimate production of diesel hydrocarbons is 0.61g.
Shown in the product table composed as follows:
Embodiment 2
0.4g Mo2C/AC catalyzer, 2.0g sweet oil and 30mL octane are added in the 100mL reactor, charge into hydrogen, initial hydrogen pressure 4.0MPa, open and stir and heating, 320 ℃ are reacted stopped reaction after 6 hours, to be cooled to room temperature, the filtering separation catalyzer obtains the diesel hydrocarbons of clear.With high performance liquid chromatography and gas-chromatography product is carried out detection by quantitative respectively, the transformation efficiency of raw material sweet oil can reach 100% as can be known, and the ultimate production of diesel hydrocarbons is 1.44g.
Shown in the product table composed as follows:
Embodiment 3
0.25g Mo2C/AC catalyzer, 1.5g Semen Maydis oil and 25mL normal heptane are added in the 100mL reactor, charge into hydrogen, initial hydrogen pressure 2.5MPa, open and stir and heating, 290 ℃ are reacted stopped reaction after 8 hours, to be cooled to room temperature, the filtering separation catalyzer obtains the diesel hydrocarbons of clear.With high performance liquid chromatography and gas-chromatography product is carried out detection by quantitative respectively, the transformation efficiency of raw material Semen Maydis oil can reach 100% as can be known, and the ultimate production of diesel hydrocarbons is 1.00g.
Shown in the product table composed as follows:
Embodiment 4
0.2g Mo2C/AC catalyzer, 1.5g rapeseed oil and 15mL dodecane are added 100
In the mL reactor, charge into hydrogen, initial hydrogen pressure 3.5MPa opens and stirs and heating, and 300 ℃ of reactions stopped reaction after 4 hours is to be cooled to room temperature, and the filtering separation catalyzer obtains the diesel hydrocarbons of clear.With high performance liquid chromatography and gas-chromatography product is carried out detection by quantitative respectively, the transformation efficiency of raw material rapeseed oil can reach 98% as can be known, and the ultimate production of diesel hydrocarbons is 0.94g.
Shown in the product table composed as follows:
Embodiment 5
0.3g Mo2C/AC catalyzer, 2.0g soybean oil and 20mL n-Hexadecane are added in the 100mL reactor, charge into hydrogen, initial hydrogen pressure 4.0MPa, open and stir and heating, 310 ℃ are reacted stopped reaction after 7 hours, to be cooled to room temperature, the filtering separation catalyzer obtains the diesel hydrocarbons of clear.With high performance liquid chromatography and gas-chromatography product is carried out detection by quantitative respectively, the transformation efficiency of raw soybeans oil can reach 99% as can be known, and the ultimate production of diesel hydrocarbons is 1.34g.
Shown in the product table composed as follows:
Above-described only is preferred implementation of the present invention; should be pointed out that for the heavy those of ordinary skill in present technique field, under the prerequisite that does not break away from core technology feature of the present invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. a Vegetable oil lipoprotein catalytic hydrodeoxygenation prepares the method for diesel hydrocarbons, is that Vegetable oil lipoprotein makes high heating value alkane through catalytic hydrodeoxygenation, it is characterized in that, adopts the preparation of one kettle way reaction process;
Method is as follows:
In reactor, add catalyzer, Vegetable oil lipoprotein and solvent, charge into hydrogen, open and stir and heating, reaction pressure is 1-10MPa, temperature of reaction is 250-350 ℃, react stopped reaction after 3-10 hour, to be cooled to room temperature, filter to isolate the diesel hydrocarbons that catalyzer can obtain containing high heating value alkane.
2. Vegetable oil lipoprotein catalytic hydrodeoxygenation according to claim 1 prepares the method for diesel hydrocarbons, it is characterized in that, described catalyzer is activated carbon supported molybdenum carbide catalyst, and the quality percentage composition of active ingredient molybdenum carbide is 5-30%.
3. Vegetable oil lipoprotein catalytic hydrodeoxygenation according to claim 1 prepares the method for diesel hydrocarbons, it is characterized in that, described solvent can be normal hexane or normal heptane or octane or dodecane or n-Hexadecane.
4. Vegetable oil lipoprotein catalytic hydrodeoxygenation according to claim 2 prepares the method for diesel hydrocarbons, it is characterized in that, the quality percentage composition of active ingredient molybdenum carbide is 15~25%.
5. Vegetable oil lipoprotein catalytic hydrodeoxygenation according to claim 1 prepares the method for diesel hydrocarbons, it is characterized in that, used Vegetable oil lipoprotein can be sunflower seed oil or rapeseed oil or soybean oil or Semen Maydis oil or sweet oil.
6. Vegetable oil lipoprotein catalytic hydrodeoxygenation according to claim 1 prepares the method for diesel hydrocarbons, it is characterized in that, the weight ratio of catalyzer and Vegetable oil lipoprotein is 1: 2~1: 10; The weightmeasurement ratio of vegetables oil and solvent is 1g: 10mL~1g: 35mL.
7. Vegetable oil lipoprotein catalytic hydrodeoxygenation according to claim 1 prepares the method for diesel hydrocarbons, it is characterized in that, Vegetable oil lipoprotein catalytic hydrodeoxygenation reaction pressure is 2-6MPa.
8. Vegetable oil lipoprotein catalytic hydrodeoxygenation according to claim 1 prepares the method for diesel hydrocarbons, it is characterized in that, Vegetable oil lipoprotein catalytic hydrodeoxygenation temperature of reaction is 270-320 ℃.
9. Vegetable oil lipoprotein catalytic hydrodeoxygenation according to claim 1 prepares the method for diesel hydrocarbons, it is characterized in that, Vegetable oil lipoprotein catalytic hydrodeoxygenation reaction solvent for use is a normal hexane.
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CN2010102341981A CN101899318A (en) | 2010-07-23 | 2010-07-23 | Method for preparing diesel hydrocarbons from vegetable fat through catalytic hydrogenation and deoxygenation |
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103827270A (en) * | 2011-09-23 | 2014-05-28 | 环球油品公司 | Methods for co-production of alkylbenzene and biofuel from natural oils using hydrocracking |
CN103827270B (en) * | 2011-09-23 | 2015-08-05 | 环球油品公司 | Hydrocracking is used to be prepared the method for alkylbenzene and biofuel altogether by natural oil |
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US9079814B2 (en) | 2013-06-10 | 2015-07-14 | Uop Llc | Linear alkylbenzenes from natural oils and methods of producing |
CN107930662A (en) * | 2017-10-31 | 2018-04-20 | 浙江大学 | One kind is used for oil hydrogenation deoxygenation catalyst and preparation method thereof |
CN108745398A (en) * | 2018-05-23 | 2018-11-06 | 中国林业科学研究院林产化学工业研究所 | A kind of Mo2C/NMC catalyst and preparation method thereof and the application in the reaction of oleic acid hydrogenation deoxidation |
CN113262789A (en) * | 2021-05-28 | 2021-08-17 | 厦门大学 | Ni/RM hydrodeoxygenation catalyst and preparation method and application thereof |
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