CN116651506A - Oil-soluble molybdenum-based catalyst, and preparation method and application thereof - Google Patents
Oil-soluble molybdenum-based catalyst, and preparation method and application thereof Download PDFInfo
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- CN116651506A CN116651506A CN202310304240.XA CN202310304240A CN116651506A CN 116651506 A CN116651506 A CN 116651506A CN 202310304240 A CN202310304240 A CN 202310304240A CN 116651506 A CN116651506 A CN 116651506A
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- oil
- molybdenum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 67
- 239000011733 molybdenum Substances 0.000 title claims abstract description 67
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 85
- 239000003921 oil Substances 0.000 claims abstract description 37
- 238000010992 reflux Methods 0.000 claims abstract description 27
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 239000000295 fuel oil Substances 0.000 claims abstract description 15
- 239000004519 grease Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000002699 waste material Substances 0.000 claims abstract description 15
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 12
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 44
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000001704 evaporation Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 5
- 239000010806 kitchen waste Substances 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- SLINHMUFWFWBMU-UHFFFAOYSA-N Triisopropanolamine Chemical compound CC(O)CN(CC(C)O)CC(C)O SLINHMUFWFWBMU-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims 2
- 150000003077 polyols Chemical class 0.000 claims 2
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000004939 coking Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 235000019198 oils Nutrition 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 238000009835 boiling Methods 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 235000021313 oleic acid Nutrition 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 235000012343 cottonseed oil Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000002385 cottonseed oil Substances 0.000 description 2
- -1 fatty acid salt Chemical class 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910005432 FeSx Inorganic materials 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- LHEFLUZWISWYSQ-CVBJKYQLSA-L cobalt(2+);(z)-octadec-9-enoate Chemical compound [Co+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LHEFLUZWISWYSQ-CVBJKYQLSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 1
- 125000005609 naphthenate group Chemical group 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- LVBIMKHYBUACBU-CVBJKYQLSA-L nickel(2+);(z)-octadec-9-enoate Chemical compound [Ni+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LVBIMKHYBUACBU-CVBJKYQLSA-L 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000002889 oleic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/24—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles
- C10G47/26—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions with moving solid particles suspended in the oil, e.g. slurries
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/64—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1033—Oil well production fluids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/06—Gasoil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses an oil-soluble molybdenum-based catalyst, a preparation method and application thereof, and belongs to the technical field of chemical catalysts. The oil-soluble molybdenum-based catalyst is prepared by mixing waste grease serving as a raw material with polyalcohol or polyalcohol amine and carrying out reflux reaction in the presence of a water carrying agent, an alkaline catalyst and molybdenum salt. In the invention, the waste grease has wide sources, low cost, simple and easy operation of the preparation process, and the oil-soluble molybdenum-based catalyst prepared by the invention has good solubility in heavy oil, can be well applied to the hydrocracking process of the inferior heavy oil slurry bed, and has high catalytic activity, high yield of the obtained light oil and low coking rate.
Description
Technical Field
The invention belongs to the technical field of chemical catalysts, and particularly relates to an oil-soluble molybdenum-based catalyst, a preparation method and application thereof.
Background
With the gradual decrease of global petroleum reserves and the increasingly inferior quality, how to convert heavy oil into light fuel or chemical raw material cleanly and efficiently is one of important subjects faced by human beings. The slurry bed hydrogenation process using the dispersed catalyst has the advantages of strong raw material adaptability, no blockage of a bed layer, high conversion rate and the like, and can clean and process and utilize inferior raw materials such as residual oil, coal tar, coal/heavy oil and the like. The dispersion catalyst has no diffusion limitation in the pores, the catalyst active site and reactant molecules are easier to approach, and the metal utilization rate is higher. However, in order to reduce the operation cost, it is necessary to strictly control the addition amount of the catalyst, and it is required that the catalyst has high dispersibility in the raw material to effectively activate hydrogen molecules and prevent polycondensation between macromolecular hydrocarbon radicals, to increase the yield of light components and to suppress the formation of coke.
The dispersion type catalyst can be classified into two types of water-solubility and oil-solubility. The precursor of the water-soluble catalyst is generally an inorganic salt of a metal such as Fe, ni, mo, etc., which is relatively inexpensive but difficult to disperse in the raw material, resulting in low catalytic activity. The precursor of the oil-soluble catalyst is mainly metal organic salt, and the metal organic salt can be dissolved or uniformly dispersed in residual oil, has small dosage and high activity, and is an ideal dispersion catalyst. The oil-soluble catalyst which is used more at present mainly comprises naphthenate, fatty acid salt, organic amine salt, carbonyl salt and the like, such as nickel naphthenate, iron naphthenate, nickel oleate, cobalt oleate, molybdenum hexacarbonyl and the like. The active phase of the dispersed catalyst being the metal sulphide after sulphide precursor, e.g. FeSx, niSx, moS 2 Etc. Due to MoS 2 The excellent hydrogenation coke inhibition activity is shown in the heavy oil slurry bed hydrogenation process, and the oil-soluble molybdenum-based catalyst is more widely applied in industry.
In the prior art, when preparing the oil-soluble catalyst, the key is to select a proper organic ligand, so that on one hand, the catalyst precursor is ensured to have good oil solubility, and on the other hand, the preparation cost is reduced as much as possible. At present, common organic ligands such as naphthenic acid, oleic acid, isooctanoic acid and the like can be used for preparing a catalyst precursor with good oil solubility, but the source of the used organic ligand raw material is limited, the price is high, the cost of the catalyst is high, and the catalyst becomes a key bottleneck influencing the popularization of slurry bed hydrogenation technology. Therefore, it is necessary to adopt widely available and low-priced organic ligands, reduce the preparation cost of the oil-soluble molybdenum-based catalyst, and further improve the technical economy of the slurry bed hydrogenation process.
Disclosure of Invention
The invention takes the waste grease as the raw material to prepare the oil-soluble molybdenum-based catalyst, which has high catalytic activity, wide sources of raw materials and low cost, and can effectively reduce the operation cost of the heavy oil slurry bed hydrocracking process.
The technical scheme of the invention is as follows:
a preparation method of an oil-soluble molybdenum-based catalyst comprises the following steps:
mixing waste grease, polyalcohol or polyalcohol amine, adding a water carrying agent, and carrying out reflux reaction under the stirring condition; then adding an alkaline catalyst, and continuing to carry out reflux reaction under the stirring condition; adding molybdenum salt, and continuing reflux reaction under stirring; and after the reaction is finished, filtering and washing the reaction product, and evaporating out the water carrying agent to obtain the oil-soluble molybdenum-based catalyst.
In the preparation method, the following steps are adopted:
the waste oil is selected from one or more of palmitous oil, palmitous rancidity oil, cottonseed acidification oil and kitchen waste oil. The polyalcohol is one or more selected from glycerol, propylene glycol or ethylene glycol. The polyalcohol amine is selected from one or more of trimethylolpropane, diethanolamine, triethanolamine or triisopropanolamine. The molar ratio of the waste grease to the polyalcohol or polyalcohol amine is selected from 1:2-1:6. The water carrying agent is selected from one or more of benzene, toluene or xylene. The water carrying agent accounts for 10-30% of the total reaction materials in mass percent. The alkaline catalyst is selected from one or two of sodium hydroxide and potassium hydroxide. The alkaline catalyst accounts for 0.5-5% of the total reaction mass. The molybdenum salt is one or more selected from molybdenum trioxide, ammonium molybdate or sodium molybdate. The molar ratio of the molybdenum metal in the molybdenum salt to the waste grease is selected from 1:1-3:1. The reflux reaction is boiling reflux, and the reaction time is 1-5 h.
The present invention provides an oil-soluble molybdenum-based catalyst prepared by the above method.
The invention provides application of the oil-soluble molybdenum-based catalyst in preparing light oil by a poor-quality heavy oil slurry bed hydrocracking process. The inferior heavy oil includes but is not limited to the following characteristics: high asphaltene content, high carbon residue content, high metal content, and high sulfur content.
A method for preparing light oil by using slurry bed hydrocracking technology comprises the following steps:
adding sulfur powder into the oil-soluble molybdenum-based catalyst according to the molar ratio of sulfur to molybdenum of 2:1-4:1, and uniformly stirring to obtain an active phase; adding the active phase into the inferior heavy oil raw material according to the proportion of 100-2000 mug/g, uniformly mixing, then mixing with fresh hydrogen and circulating hydrogen, then feeding into a heating furnace, heating, feeding into the slurry bed reactor from the bottom, reacting at the temperature of 400-440 ℃, the reaction pressure of 10-20 MPa and the volume space velocity of 0.2-1.5 h -1 And (3) carrying out hydrocracking reaction under the condition that the volume ratio of the hydrogen oil is 600-1200:1 to obtain light oil.
The beneficial effects of the invention are as follows:
the invention prepares the molybdenum-based catalyst by taking the waste grease as the raw material, and the raw material has wide sources and low cost; the preparation process is simple and easy to operate; the oil-soluble molybdenum-based catalyst prepared by the invention has good solubility in heavy oil, high catalytic activity, high yield of the obtained light oil and low coking rate.
Detailed Description
Other materials used in the present invention, such as those not specifically stated, are available through commercial sources. Other terms used herein, unless otherwise indicated, generally have meanings commonly understood by those of ordinary skill in the art. The invention will be described in further detail below in connection with specific embodiments and with reference to the data. The following examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
Example 1
Preparation of oil-soluble molybdenum-based catalyst:
1mol of palmitoylated oil (632 g) and 2mol of diethanolamine (210.2 g) were charged into a reaction vessel, toluene (84.2 g) accounting for 10% of the total reaction mass was added as a water-carrying agent, and the mixture was boiled under reflux with stirring for 1 hour. Then potassium hydroxide (4.2 g) accounting for 0.5 percent of the total reaction mass is added as an alkaline catalyst, and the boiling reflux reaction is continued for 3 hours under the condition of stirring. 3mol of molybdenum trioxide (432 g) were added and the boiling reflux reaction was continued with stirring for 4h. And after the reaction is finished, filtering and washing the product, and finally evaporating toluene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The content of molybdenum is 20.1% by ICP detection.
Example 2
1mol of palm rancidity oil (717 g) and 2mol of triethanolamine (210 g) are filled into a reaction kettle, xylene (278.1 g) accounting for 30 percent of the total reaction mass is added as a water carrying agent, boiling reflux reaction is carried out for 1h under the condition of stirring, then sodium hydroxide (46.4 g) accounting for 5 percent of the total reaction mass is added as an alkaline catalyst, and the boiling reflux reaction is continued for 1h under the condition of stirring. 1mol of sodium molybdate (205.9 g) was added thereto, and the boiling reflux reaction was continued for 2 hours with stirring. And after the reaction is finished, filtering and washing the product, and finally evaporating dimethylbenzene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The content of molybdenum is 8.0% by ICP detection.
Example 3
1mol of cottonseed oil (680 g) and 6mol of glycol (372.4 g) are put into a reaction kettle, benzene (105.2 g) accounting for 10 percent of the total reaction mass is added as a water carrying agent, the mixture is boiled and refluxed for 1h under the condition of stirring, then sodium hydroxide (10.5 g) accounting for 1 percent of the total reaction mass is added as an alkaline catalyst, and the mixture is continuously boiled and refluxed for 2h under the condition of stirring. 2mol of ammonium molybdate (392.0 g) was added and the boiling reflux reaction was continued for 3h with stirring. And after the reaction is finished, filtering and washing the product, and finally evaporating benzene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The content of molybdenum is 14.3% by ICP detection.
Example 4
1mol of kitchen waste grease (855 g) and 3mol of glycerin (276.3 g) are put into a reaction kettle, toluene (113.1 g) accounting for 10 percent of the total reaction mass is added as a water carrying agent, the mixture is boiled and refluxed for 1h under the condition of stirring, then potassium hydroxide (11.3 g) accounting for 1 percent of the total reaction mass is added as an alkaline catalyst, and the mixture is continuously boiled and refluxed for 2h under the condition of stirring. 2mol of molybdenum trioxide (287.9 g) were added and the boiling reflux reaction was continued with stirring for 3h. And after the reaction is finished, filtering and washing the product, and finally evaporating toluene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The molybdenum content was 13.7% as measured by ICP.
Example 5
1mol of palmitoylated oil (632 g) and 3mol of propylene glycol (228.3 g) are put into a reaction kettle, toluene (86.0 g) accounting for 10 percent of the total reaction mass is added as a water carrying agent, the mixture is boiled and refluxed for 1h under the condition of stirring, then potassium hydroxide (8.6 g) accounting for 1 percent of the total reaction mass is added as an alkaline catalyst, and the mixture is continuously boiled and refluxed for 2h under the condition of stirring. 2mol of molybdenum trioxide (287.9 g) were added and the boiling reflux reaction was continued with stirring for 3h. And after the reaction is finished, filtering and washing the product, and finally evaporating toluene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The content of molybdenum is 13.4% by ICP detection.
Example 6
1mol of palmitoylated oil (632 g) and 3mol of trimethylolpropane (411.5 g) are put into a reaction kettle, benzene (104.3 g) accounting for 10 percent of the total reaction mass is added as a water carrying agent, the mixture is boiled and refluxed for 1 hour under the condition of stirring, then sodium hydroxide (5.2 g) accounting for 0.5 percent of the total reaction mass is added as an alkaline catalyst, and the mixture is continuously boiled and refluxed for 3 hours under the condition of stirring. 2mol of molybdenum trioxide (287.9 g) were added and the boiling reflux reaction was continued with stirring for 4h. And after the reaction is finished, filtering and washing the product, and finally evaporating benzene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The content of molybdenum is 13.1% by ICP detection.
Example 7
1mol of palmitoylated oil (632 g) and 2mol of triisopropanolamine (382.5 g) are put into a reaction kettle, xylene (101.4 g) accounting for 10 percent of the total reaction mass is added as a water carrying agent, the mixture is boiled and refluxed for 1h under the condition of stirring, then potassium hydroxide (5.1 g) accounting for 0.5 percent of the total reaction mass is added as an alkaline catalyst, and the mixture is continuously boiled and refluxed for 3h under the condition of stirring. 2mol of molybdenum trioxide (287.9 g) were added and the boiling reflux reaction was continued with stirring for 4h. And after the reaction is finished, filtering and washing the product, and finally evaporating dimethylbenzene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The content of molybdenum is 13.8% by ICP detection.
Example 8
1mol of cottonseed oil (680 g) and 2mol of diethanolamine (210.2 g) are filled into a reaction kettle, toluene (89.0 g) accounting for 10 percent of the total reaction mass is added as a water carrying agent, the mixture is boiled and refluxed for 1 hour under the condition of stirring, then potassium hydroxide (8.9 g) accounting for 1 percent of the total reaction mass is added as an alkaline catalyst, and the mixture is continuously boiled and refluxed for 2 hours under the condition of stirring. 2mol of molybdenum trioxide (287.9 g) were added and the boiling reflux reaction was continued with stirring for 3h. And after the reaction is finished, filtering and washing the product, and finally evaporating toluene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The content of molybdenum is 15.6% by ICP detection.
Example 9
1mol of kitchen waste grease (855 g) and 2mol of diethanolamine (210.2 g) are filled into a reaction kettle, dimethylbenzene (106.5 g) accounting for 10 percent of the total reaction mass is added as a water carrying agent, boiling reflux reaction is carried out for 1h under the condition of stirring, then potassium hydroxide (10.7 g) accounting for 1 percent of the total reaction mass is added as an alkaline catalyst, and boiling reflux reaction is continued for 2h under the condition of stirring. 2mol of molybdenum trioxide (287.9 g) were added and the boiling reflux reaction was continued with stirring for 3h. And after the reaction is finished, filtering and washing the product, and finally evaporating dimethylbenzene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The content of molybdenum is 13.6% by ICP detection.
Example 10
1mol of palm rancidity oil (717 g) and 2mol of diethanolamine (210.2 g) are filled into a reaction kettle, xylene (92.7 g) accounting for 10 percent of the total reaction mass is added as a water carrying agent, boiling reflux reaction is carried out for 1h under the condition of stirring, then potassium hydroxide (9.3 g) accounting for 1 percent of the total reaction mass is added as an alkaline catalyst, and boiling reflux reaction is continued for 2h under the condition of stirring. 2mol of molybdenum trioxide (287.9 g) were added and the boiling reflux reaction was continued with stirring for 3h. And after the reaction is finished, filtering and washing the product, and finally evaporating dimethylbenzene to obtain the oil-soluble molybdenum-based catalyst. The catalyst can be dissolved in common organic solvents such as petroleum ether, normal hexane, toluene and the like. The content of molybdenum is 15.4% by ICP detection.
Slurry bed hydrocracking test
Taking the oil-soluble molybdenum-based catalyst prepared in the example 1, adding sulfur powder according to the molar ratio of sulfur to molybdenum of 2:1, stirring uniformly, and marking as a catalyst C1; taking the oil-soluble molybdenum-based catalyst prepared in the example 2, adding sulfur powder according to the molar ratio of sulfur to molybdenum of 4:1, stirring uniformly, and marking as a catalyst C2; taking the oil-soluble molybdenum-based catalyst prepared in the example 3, adding sulfur powder according to the molar ratio of sulfur to molybdenum of 3:1, stirring uniformly, and marking as a catalyst C3; taking the oil-soluble molybdenum-based catalyst prepared in the example 4, adding sulfur powder according to the molar ratio of sulfur to molybdenum of 3:1, stirring uniformly, and marking as a catalyst C4; taking the oil-soluble molybdenum-based catalyst prepared in the example 5, adding sulfur powder according to the molar ratio of sulfur to molybdenum of 3:1, stirring uniformly, and marking as a catalyst C5; taking the oil-soluble molybdenum-based catalyst prepared in the example 6, adding sulfur powder according to the molar ratio of sulfur to molybdenum of 3:1, stirring uniformly, and marking as a catalyst C6; molybdenum naphthenate is taken as a comparative oil-soluble molybdenum-based catalyst, sulfur powder is added according to the molar ratio of sulfur to molybdenum of 3:1, and the mixture is stirred uniformly and is marked as a catalyst C7.
Adding the catalyst into a poor heavy oil raw material (Ma Rui vacuum residuum) according to the proportion of 100-2000 mug/g, uniformly mixing, mixing with fresh hydrogen and circulating hydrogen, then feeding into a heating furnace, heating, feeding into a slurry bed reactor from the bottom, reacting at the temperature of 400-440 ℃, the reaction pressure of 10-20 MPa and the volume space velocity of 0.2-1.5 h -1 And carrying out hydrocracking reaction under the condition that the volume ratio of hydrogen to oil is 600-1200:1. Specific reaction conditions are shown in Table 2 below.
The properties of the poor heavy oil feedstock are shown in table 1:
TABLE 1 Properties of inferior heavy oil feedstock
The conditions and reaction results of the slurry bed hydrocracking reaction are shown in table 2:
TABLE 2 reaction conditions and reaction results for slurry bed hydrocracking Process
As can be seen from Table 2, the oil-soluble molybdenum-based catalyst prepared by the invention can achieve the effects of low coking rate and high light oil yield under various conditions. General law of different reaction conditions: the light oil yield is higher when the reaction temperature is high, and the coking rate is lower when the catalyst addition amount is high. Molybdenum naphthenate is an oil-soluble molybdenum-based catalyst with better performance at present, but is more expensive. The 7 th group of test results show that the oil-soluble molybdenum-based catalyst can achieve the technical effect similar to that of molybdenum naphthenate, and the adopted raw materials are waste grease, so that the production cost of the catalyst is reduced.
In summary, it is common in the prior art to use organic acids or organic amines as ligands for preparing oil soluble molybdenum-based catalysts, such as naphthenic acids, caprylic acids, oleic acids, and the like. The long-chain fatty acid such as oleic acid is generally obtained by oil hydrolysis and distillation separation, and the cost is lower than that of naphthenic acid, but the cost is still higher. In order to reduce the cost of the ligand, the invention breaks through to directly adopt the upstream raw material grease of the oleic acid as the ligand to synthesize the oil-soluble molybdenum-based catalyst, and the synthetic route of the invention is finally determined through experiments and comparisons of various synthetic methods. Particularly, the cost can be further reduced by adopting the waste grease, the utilization of the waste grease is realized, and the win-win purpose is achieved.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the oil-soluble molybdenum-based catalyst is characterized by comprising the following steps:
mixing waste grease, polyalcohol or polyalcohol amine, adding a water carrying agent, and carrying out reflux reaction under the stirring condition; then adding an alkaline catalyst, and continuing to carry out reflux reaction under the stirring condition; adding molybdenum salt, and continuing reflux reaction under stirring; and after the reaction is finished, filtering and washing the reaction product, and evaporating out the water carrying agent to obtain the oil-soluble molybdenum-based catalyst.
2. The method according to claim 1, wherein the waste oil is one or more selected from the group consisting of palmitous oil, palmitous rancidity oil, cottonseed-acidified oil and kitchen waste oil.
3. The preparation method according to claim 1, wherein the polyol is one or more selected from glycerol, propylene glycol or ethylene glycol; the polyalcohol amine is selected from one or more of trimethylolpropane, diethanolamine, triethanolamine or triisopropanolamine.
4. The preparation method according to claim 1, wherein the water-carrying agent is one or more selected from benzene, toluene and xylene.
5. The method of claim 1, wherein the basic catalyst is selected from one or both of sodium hydroxide and potassium hydroxide.
6. The method according to claim 1, wherein the molybdenum salt is one or more selected from molybdenum trioxide, ammonium molybdate and sodium molybdate.
7. The method of claim 1, wherein the molar ratio of the waste oil to the polyol or polyalcohol amine is selected from 1:2 to 1:6; the water carrying agent accounts for 10-30% of the total reaction material in mass fraction; the alkaline catalyst accounts for 0.5-5% of the total reaction mass; the molar ratio of the molybdenum metal in the molybdenum salt to the waste grease is selected from 1:1-3:1.
8. An oil soluble molybdenum-based catalyst prepared by the method of any of claims 1-7.
9. The use of the oil-soluble molybdenum-based catalyst of claim 8 in the preparation of light oil by a poor quality heavy oil slurry bed hydrocracking process.
10. A method for preparing light oil by using slurry bed hydrocracking process is characterized by comprising the following steps:
adding sulfur powder into the alloy according to the molar ratio of sulfur to molybdenum of 2:1-4:1In the oil-soluble molybdenum-based catalyst of claim 8, stirring uniformly to obtain an active phase; adding the active phase into the inferior heavy oil raw material according to the proportion of 100-2000 mug/g, uniformly mixing, then mixing with fresh hydrogen and circulating hydrogen, then feeding into a heating furnace, heating, feeding into the slurry bed reactor from the bottom, reacting at the temperature of 400-440 ℃, the reaction pressure of 10-20 MPa and the volume space velocity of 0.2-1.5 h -1 And (3) carrying out hydrocracking reaction under the condition that the volume ratio of the hydrogen oil is 600-1200:1 to obtain light oil.
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