CN113797938B - Catalyst for selective hydrodesulfurization and olefin reduction of gasoline, and preparation method and application thereof - Google Patents
Catalyst for selective hydrodesulfurization and olefin reduction of gasoline, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 117
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 238000001035 drying Methods 0.000 claims abstract description 29
- 238000011282 treatment Methods 0.000 claims abstract description 22
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 229910052717 sulfur Inorganic materials 0.000 claims description 22
- 239000011593 sulfur Substances 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 238000004073 vulcanization Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004523 catalytic cracking Methods 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 238000005470 impregnation Methods 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 21
- 238000003917 TEM image Methods 0.000 description 18
- 238000004821 distillation Methods 0.000 description 14
- 239000003921 oil Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 101100228853 Saccharolobus solfataricus (strain ATCC 35092 / DSM 1617 / JCM 11322 / P2) gds gene Proteins 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 235000012431 wafers Nutrition 0.000 description 7
- 229910017313 Mo—Co Inorganic materials 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 210000003278 egg shell Anatomy 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 3
- 241000219782 Sesbania Species 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- OBWXQDHWLMJOOD-UHFFFAOYSA-H cobalt(2+);dicarbonate;dihydroxide;hydrate Chemical compound O.[OH-].[OH-].[Co+2].[Co+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O OBWXQDHWLMJOOD-UHFFFAOYSA-H 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 238000009704 powder extrusion Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000009740 moulding (composite fabrication) Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a gasoline selective hydrodesulfurization and olefin reduction catalyst and a preparation method and application thereof. The catalyst comprises a carrier and an active metal component, wherein the carrier is an alumina-based carrier with graphene oxide coated on the surface. The method comprises the following steps: (1) Mixing graphene oxide and an alumina-based carrier, adding an alkaline solution for performing second microwave treatment after first microwave treatment, filtering, and drying to obtain the alumina-based carrier with the surface coated with graphene oxide; (2) And (3) loading the active metal component on the carrier obtained in the step (1), and drying to obtain the catalyst. The catalyst is used in hydrogenation technology for producing clean gasoline, and compared with the traditional hydrodesulfurization catalyst, the catalyst has higher hydrodesulfurization selectivity and less octane number loss.
Description
Technical Field
The invention relates to a selective hydrodesulfurization catalyst and a preparation method thereof, which are particularly suitable for producing low-sulfur and low-olefin gasoline products in a gasoline hydrogenation process.
Background
With the rapid increase of the Chinese economy, the holding amount of the household automobiles is continuously increased, and the holding amount of the household automobiles is increased from 2.05 hundred million to 2.26 hundred million from the end of 6 months in 2017 to the end of 2019, which also causes the Chinese gasoline demand to be in a continuously increasing state in recent years. Meanwhile, in order to reduce the emission of harmful substances in automobile exhaust, china formulates stricter and stricter clean gasoline standards. From 2019, china is divided into two stages of national VI clean gasoline standard, which is implemented in stages, and the national VI gasoline standard is implemented in A, B stages, wherein the national VIA standard requires that the sulfur content is no more than 10 mu g/g, the olefin content is no more than 18.0v%, and the olefin content in the national VIB standard is further limited to be below 15.0 v%. The Chinese gasoline standard has increasingly stringent requirements on sulfur and olefin content in gasoline. Therefore, how to produce the finished gasoline meeting the national VI clean gasoline standard is a difficult problem which is urgently needed to be solved by oil refineries.
China is a large country of catalytic cracking, more than 150 sets of catalytic cracking devices of different types are built and put into production, and the total processing capacity of the catalytic cracking devices reaches approximately 150Mt/a. The gasoline component produced by the catalytic cracking device accounts for about 80% of the total gasoline product. The sulfur content in the catalytic cracking gasoline is generally 200-1000 mu g/g, and the olefin content is generally 20.0-45.0 v%. The sulfur and olefin content in the catalytic cracking gasoline are high, and the reduction of the sulfur and olefin content in the catalytic cracking gasoline is a key to meeting the increasingly strict clean gasoline standard.
In the prior art, the prior art of desulfurizing catalytically cracked gasoline is mainly represented by Prime-G + selective hydrodesulfurization process and S zorb adsorption desulfurization process in France. The Prime-G + technology takes Mo-Co/Al 2O3 as a hydrodesulfurization catalyst, adopts the processes of full-fraction pre-hydrogenation, light and heavy gasoline fractionation and heavy fraction gasoline hydrodesulfurization, has larger octane number loss when producing clean gasoline with the sulfur content of no more than 10 mug/G, and can further increase the octane number loss of products due to the hydrogenation saturation of olefin when producing national VI standard gasoline with the olefin content of no more than 15.0v percent. The S zorb technology uses NiO-ZnO as an adsorbent, and adopts an adsorption-regeneration circulation process to treat the full-fraction catalytic cracking gasoline, and compared with the raw materials, the product has the advantages that the sulfur content is greatly reduced, the olefin is slightly reduced, the alkane is slightly increased, and the (RON+MON)/2 loss is less than 1.0 unit. However, the method can not greatly reduce the olefin content in the gasoline product, and can not solve the problem of olefin reduction for the catalytic cracking gasoline with higher olefin content.
CN103450935A discloses a process for producing ultra-low sulfur gasoline. The method adopts a step-by-step impregnation method to prepare a traditional selective hydrodesulfurization MoO 3-CoO/Al2O3 catalyst, and comprises the following steps: mixing pseudo-thin aluminum hydroxide powder, sesbania powder extrusion aid and nitric acid aqueous solution, rolling and mixing to obtain plastic powder, extruding strips, drying and roasting to prepare a catalyst carrier; impregnating and supporting phosphorus and potassium on a catalyst carrier, and drying and roasting to prepare a P 2O5-K2O/Al2O3 catalyst intermediate; and (3) after the catalyst intermediate is impregnated with supported molybdenum and cobalt, drying and roasting to prepare the high-activity MoO 3-CoO-P2O5-K2O/Al2O3 catalyst. The hydrodesulfurization catalyst has more octane number loss when the sulfur content meets the national V standard gasoline.
CN108452846a discloses a gasoline hydrofining catalyst and a preparation method thereof. The method comprises the steps of uniformly mixing alumina powder and a TS-1 molecular sieve, adding graphene, kneading, forming, drying and roasting to obtain a carrier, preparing an impregnating solution by using heteropolyacid containing active metal components, and drying and roasting to obtain the catalyst. The catalyst can improve the hydrodesulfurization activity, but does not involve the problems of olefin saturation and octane number loss.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalyst for selective hydrodesulfurization and olefin reduction of gasoline, and a preparation method and application thereof. The catalyst is used in the hydrogenation process of catalytically cracked gasoline, and can produce gasoline products with low sulfur and low olefin under the condition of less octane number loss.
The invention provides a catalyst for selective hydrodesulfurization and olefin reduction of gasoline, which comprises a carrier and an active metal component, wherein the carrier is an alumina-based carrier with graphene oxide coated on the surface.
In the catalyst, the carrier is an alumina-based carrier with graphene oxide coated on the surface, the content of the graphene oxide is 0.1-10.0 wt% based on the weight of the carrier, the content of the alumina-based carrier is 90.0-99.9 wt%, preferably, the content of the graphene oxide is 0.5-8.0 wt%, and the content of the alumina-based carrier is 92.0-99.5 wt%.
In the catalyst of the invention, the active metal components are a VIB group metal and a VIII group metal, wherein the VIB group metal is preferably W and/or Mo, and the VIII group metal is preferably Ni and/or Co. The active metal component is preferably Mo and Co. The content of the VIB group metal is 5.0-22.0 wt% based on the weight of the catalyst, the content of the VIII group metal is 1.0-9.0 wt% based on the oxide, preferably the content of the VIB group metal is 8.0-20.0 wt% based on the oxide, and the content of the VIII group metal is 2.0-7.0 wt% based on the oxide.
In the catalyst of the present invention, the alumina-based carrier is a carrier comprising alumina as a main component, and may contain, in addition to alumina, at least one additive such as titanium oxide, silicon oxide, magnesium oxide, and the like. The content of the additive is below 20.0wt% of the weight of the alumina-based carrier and can be 1.0 wt% to 15.0wt%.
In the catalyst, the graphene oxide is ribbon-shaped nano graphene oxide. The thickness of the graphene oxide is 3.0-10.0 nm, and the length of the graphene oxide is 30.0-200.0 nm.
The second aspect of the invention provides a method for preparing the catalyst for selective hydrodesulfurization and olefin reduction of gasoline, which comprises the following steps:
(1) Mixing graphene oxide and an alumina-based carrier, adding an alkaline solution for performing second microwave treatment after first microwave treatment, filtering, and drying to obtain the alumina-based carrier with the surface coated with graphene oxide;
(2) And (3) loading the active metal component on the carrier obtained in the step (1), and drying to obtain the catalyst.
In the method of the present invention, the conditions of the first microwave treatment in the step (1) are as follows: the microwave power is 500-900W and the treatment time is 0.5-3.0 h. The conditions of the second microwave treatment are as follows: the microwave power is 500-800W, and the treatment time is 1.0-4.0 h.
In the method, the thickness of the graphene oxide in the step (1) is 3.0-10.0 nm.
In the method of the invention, the alkaline solution in the step (1) can be at least one of potassium hydroxide, sodium hydroxide and the like, and the mass concentration of the alkaline solution is 5.0% -40.0%. The ratio of the alkaline solution to the total volume of the graphene oxide and the alumina-based carrier is 1.5: 1-2.5: 1.
In the method of the invention, the drying conditions in the step (1) are as follows: and drying at 100-200 ℃ for 4-8 hours.
In the method of the present invention, the active metal component of step (2) is supported on the support obtained in step (1) by a conventional method, preferably an impregnation method. The impregnation may be saturated impregnation or unsaturated impregnation, one-step impregnation or multi-step impregnation. The drying conditions in the step (2) are as follows: and drying for 4-8 hours at 100-200 ℃.
In the method of the invention, the roasting step is not carried out in the step (1) and the step (2), and the roasting step refers to a heat treatment step at the temperature of more than 200 ℃.
In the method of the present invention, the shape of the alumina-based carrier may be a conventional shape, such as a bar shape or a sphere shape, preferably a bar-shaped carrier, and the diameter thereof is generally 1.0 to 3.0mm, and the length thereof is 3.0 to 10.0mm. In the alumina-based carrier, al 2O3 is gamma-Al 2O3.
In a third aspect, the present invention provides a process for producing clean gasoline, wherein a gasoline feedstock is contacted with the above gasoline selective hydrodesulfurization and olefin reduction catalyst in the presence of hydrogen to react to obtain a gasoline product.
In the process of the present invention, the catalyst is presulfided before the reaction is carried out, and the presulfiding process may presulfide the catalyst in the presence of a sulfiding agent and hydrogen. The pre-vulcanization conditions were: the pressure is 1.0 MPa-4.5 MPa, the temperature is 200-400 ℃, and the volume ratio of the hydrogen agent is 100:1-500:1; preferred vulcanization conditions: the pressure is 1.5 MPa-3.0 MPa, the temperature is 260-330 ℃, and the volume ratio of the hydrogen agent is 200:1-300:1. The vulcanizing agent can be at least one of sulfides which can be decomposed into H 2 S, such as carbon disulfide (CS 2) and dimethyl disulfide (DMDS); the vulcanized oil is at least one of straight-run gasoline or hydrogenated naphtha, and the distillation range is generally 40-180 ℃.
In the method of the invention, the gasoline raw material is from heavy fraction pre-fractionated from catalytic cracking gasoline. In the gasoline raw material, the mass content of sulfur is 100-800 mug/g, and the volume content of olefin is 15.0-35.0%. The initial distillation point of the gasoline raw material is 65-90 ℃ and the final distillation point is 180-205 ℃.
The process of the present invention may employ a fixed bed process.
In the method of the invention, the reaction conditions are as follows: the reaction pressure is 1.0 MPa-4.5 MPa, the reaction temperature is 200-400 ℃, the liquid hourly space velocity is 1.0h -1~5.0h-1, and the hydrogen-oil volume ratio is 100:1-500:1; preferred reaction conditions: the reaction pressure is 1.5-3.0 MPa, the reaction temperature is 250-300 ℃, the liquid hourly space velocity is 2.0h -1~4.0h-1, and the hydrogen-oil volume ratio is 200:1-400:1.
The method can produce gasoline products meeting the national VI standard, wherein the sulfur content is no more than 10 mu g/g, and the olefin content is no more than 15.0v%.
Compared with the prior art, the catalyst has the following advantages:
(1) The catalyst is used in the selective hydrodesulfurization and olefin reduction process of gasoline raw materials, greatly reduces the sulfur content and moderately reduces the olefin content under the condition of less octane number loss, so as to meet the requirements of national VI and above standard gasoline products on minimum sulfur and octane number loss and the like.
(2) In the preparation method of the catalyst, the graphene oxide and the alumina-based carrier are firstly treated by microwaves and then treated by microwaves in the presence of alkaline solution, and the alumina-based carrier with the surface covered with the graphene oxide can be obtained without high-temperature roasting, and after the active metal component is loaded, the high-temperature roasting is not needed, so that the adjustment of the loading state of the graphene oxide on the alumina-based carrier is facilitated, and under the cooperation of the graphene oxide-based carrier and the active metal component, the active sites are in an eggshell structure and are intensively distributed on the outer surface of the catalyst in the vulcanization process, the improvement of the hydrodesulfurization selectivity is facilitated, the excessive hydrogenation of olefin is prevented, and the loss of octane number is reduced.
(3) The catalyst of the invention is used for treating heavy fraction gasoline raw materials with the sulfur content of 320 mug/g, the olefin volume content of 26.0vol% and the Research Octane Number (RON) of 90.0, the sulfur content of a desulfurization product can be reduced to 4.5 mug/g, the olefin content can reach 13.0vol%, and the Research Octane Number (RON) loss is 2.5 units.
Drawings
FIG. 1 is a TEM image of an alumina-based support coated with graphene oxide prepared in example 1 of the present invention;
FIG. 2 is a TEM image of the crystal morphology of the Co-Mo-S active phase on the catalyst prepared in example 1 of the present invention;
FIG. 3 is a TEM image of an alumina-based support coated with graphene oxide prepared in example 2 of the present invention;
FIG. 4 is a TEM image of the crystal morphology of the Co-Mo-S active phase on the catalyst prepared in example 2 of the present invention;
FIG. 5 is a TEM image of an alumina-based support coated with graphene oxide prepared in example 3 of the present invention;
FIG. 6 is a TEM image of the crystal morphology of the Co-Mo-S active phase on the catalyst prepared in example 3 of the present invention;
FIG. 7 is a TEM image of the crystal morphology of the Co-Mo-S active phase on a Mo-Co/Al 2O3 hydrodesulfurization catalyst prepared by the conventional method of comparative example 1;
FIG. 8 is a TEM image of the graphene oxide-coated alumina-based carrier prepared in comparative example 2;
FIG. 9 is a TEM image of the crystal morphology of the Co-Mo-S active phase on the catalyst prepared in comparative example 2.
Detailed Description
The method and effect of the present invention will be further described with reference to the accompanying drawings and examples, but the scope of the present invention is not limited thereto.
In the present invention, the specific surface area and pore volume are measured by low temperature liquid nitrogen adsorption BET method.
Example 1
The gasoline selective hydrodesulfurization and olefin reduction catalyst prepared in this example is designated GDS-1.
Preparing an alumina-based carrier: weighing 1000g of pseudo-thin aluminum hydroxide powder (the content of Al 2O3 is 78 wt%) and adding sesbania powder extrusion aid accounting for 5wt% of the Al 2O3 dry basis and 200mL of 10% nitric acid aqueous solution, mixing, rolling and mixing to obtain plastic powder, preparing a cylindrical strip with the diameter of 1.5mm by a strip extruder, drying at 120 ℃ for 8 hours and roasting at 520 ℃ for 5 hours to prepare an alumina-based carrier;
Preparing an alumina-based carrier with graphene oxide coated on the surface: weighing 0.4g of Graphene Oxide (GO) and 50g of alumina-based carrier, adding into a beaker, placing into a microwave device, performing 700W microwave treatment for 1.0h, then adding 94mL of KOH solution with mass concentration of 10% for continuously performing 600W microwave treatment for 2.0h, taking out and filtering, and drying at 120 ℃ for 8.0h to obtain the alumina-based carrier with the surface covered with graphene oxide, wherein a TEM image is shown in figure 1;
And (3) preparing a catalyst: taking quantitative molybdenum oxide and basic cobalt carbonate according to the MoO 3 content of 13.0wt% and the CoO content of 4.0wt% on the catalyst, adding deionized water to prepare 60mL of impregnating solution, heating to 50 ℃, adding 10mL of concentrated ammonia water (ammonia content is less than 32.0%), continuing heating to micro-boil, keeping airtight heating for about 2.0h until the solid is completely dissolved into Mo-Co solution, and cooling to room temperature. The Mo-Co solution was sprayed onto 50g of the above alumina-based support coated with graphene oxide on the surface. The MoO 3(13.0wt%)-CoO(4.0wt%)/GO-Al2O3 catalyst, designated GDS-1 catalyst, was prepared by drying at 120deg.C for 8.0 h.
The properties of the GDS-1 catalyst are shown in Table 1, and a TEM image of the Co-Mo-S active phase crystal morphology of the GDS-1 catalyst after presulfiding is shown in FIG. 2.
From FIG. 1, it can be seen that graphene oxide filaments uniformly cover the outer surface of the alumina-based carrier in a ribbon shape, the average thickness is 3.0-10.0 nm, and the length is 80.0-200.0 nm; as can be seen from FIG. 2, the Co-Mo-S wafers of the GDS-1 catalyst after being presulfided are uniformly distributed, and the crystal appearance is characterized by 2.0-4.0 layers and 3.0-8.0 nm in length. In particular, the active sites CoMoS are characterized by eggshells, and CoMoS wafers are intensively distributed on the outer surface of the catalyst.
Example 2
The gasoline selective hydrodesulfurization and olefin reduction catalyst prepared in this example is designated GDS-2.
Preparing an alumina-based carrier: the same as in example 1;
Preparing an alumina-based carrier with graphene oxide coated on the surface: weighing 1.0g of Graphene Oxide (GO) and 50g of Al 2O3 carrier, adding into a beaker, placing into a microwave device, performing 700W microwave treatment for 1.0h, then adding 125mL of KOH solution with the mass concentration of 20% to continue 600W microwave treatment for 4.0h, taking out and filtering, and drying at 140 ℃ for 8 hours to obtain an alumina-based carrier with the surface covered with graphene oxide, wherein a TEM image is shown in figure 3;
And (3) preparing a catalyst: according to the content of MoO 3 and CoO content of 12.0wt% and 3.5wt% on the catalyst, quantitative molybdenum oxide and basic cobalt carbonate are taken, deionized water is added, and 60mL of impregnating solution is prepared. Heating to 80deg.C, adding 20mL of concentrated ammonia water (ammonia content is not less than 32.0%), heating to slight boiling, sealing, heating for about 2.0 hr until the solid is completely dissolved into Mo-Co solution, and cooling to room temperature. Then, 50g of the graphene oxide-coated alumina-based support was sprayed thereon. Drying 8h at 140℃produced MoO 3(12.0wt%)-CoO(3.5wt%)/GO-Al2O3 catalyst, designated GDS-2 catalyst.
The properties of the GDS-2 catalyst are shown in Table 1, and a TEM image of the Co-Mo-S active phase morphology of the GDS-2 catalyst after presulfiding is shown in FIG. 4.
From FIG. 3, it can be seen that graphene oxide filaments uniformly cover the outer surface of the alumina-based carrier in a ribbon shape, the average thickness is 3.0-10.0 nm, and the length is 80.0-200.0 nm; as can be seen from FIG. 4, the Co-Mo-S wafers of the GDS-2 catalyst after being presulfided are uniformly distributed, and the crystal appearance is characterized by 2.0-4.0 layers and 3.0-8.0 nm in length. In particular, the active sites CoMoS are characterized by eggshells, and CoMoS wafers are intensively distributed on the outer surface of the catalyst.
Example 3
The gasoline selective hydrodesulfurization and olefin reduction catalyst prepared in this example is designated GDS-3.
Preparing an alumina-based carrier: the same as in example 1;
Preparing an alumina-based carrier with graphene oxide coated on the surface: weighing 3.0g of Graphene Oxide (GO) and 50g of Al 2O3 carrier, adding into a beaker, placing into a microwave device, performing 700W microwave treatment for 1.0h, then adding 150mL of KOH solution with the mass concentration of 20% to continue 600W microwave treatment for 4h, taking out, filtering, and drying at 140 ℃ for 8 hours to obtain an alumina-based carrier with the surface covered with graphene oxide, wherein a TEM image is shown in figure 5;
And (3) preparing a catalyst: the same as in example 2 was designated as GDS-3 catalyst.
The properties of the GDS-3 catalyst are shown in Table 1, and a TEM image of the Co-Mo-S active phase morphology of the GDS-3 catalyst after presulfiding is shown in FIG. 6.
From FIG. 5, it can be seen that graphene oxide filaments uniformly cover the outer surface of the alumina-based carrier in a ribbon shape, the average thickness is 3.0-10.0 nm, and the length is 80.0-200.0 nm; as can be seen from FIG. 6, the Co-Mo-S wafers of the GDS-3 catalyst after being presulfided are uniformly distributed, and the crystal appearance is characterized by 2.0-4.0 layers and 3.0-8.0 nm in length. In particular, the active sites CoMoS are characterized by eggshells, and CoMoS wafers are intensively distributed on the outer surface of the catalyst.
Comparative example 1
This comparative example used a CN103450935A step impregnation to prepare a conventional selective hydrodesulfurization MoO3(13.0wt%)-CoO (4.0wt%)-P2O5(1.5wt%)-K2O-(2.0wt%)/Al2O3 catalyst, designated as the E-1 catalyst.
Weighing 1000g of pseudo-thin aluminum hydroxide powder (the content of Al 2O3 is 78 wt%) and adding sesbania powder extrusion aid accounting for 5wt% of the Al 2O3 dry basis and 200mL of 10% nitric acid aqueous solution, mixing, rolling and mixing to obtain plastic powder, preparing a cylindrical strip with the diameter of 1.5mm by a strip extruder, drying at 120 ℃ for 8 hours and roasting at 500 ℃ for 5 hours to prepare a catalyst carrier;
Taking quantitative phosphoric acid and potassium nitrate according to the content of P 2O5 wt% and the content of K 2 O2.0 wt% on the catalyst, adding deionized water to prepare 120mL of impregnating solution, and then spraying the impregnating solution onto 160g of the catalyst carrier. Drying at 120 deg.c for 10 hr and roasting at 500 deg.c for 5 hr to prepare P 2O5(1.5wt%)-K2O-(2.0wt%)/Al2O3 catalyst intermediate.
According to the content of MoO 3 and CoO content of 13.0wt% and 4.0wt% on the catalyst, quantitative molybdenum oxide and basic cobalt carbonate are taken, deionized water is added to prepare 60mL of impregnating solution, and then the impregnating solution is sprayed on 80g of the catalyst intermediate. Drying at 120deg.C for 8 hr, and calcining at 490 deg.C for 6 hr to obtain high-activity MoO3(13.0wt%)-CoO(4.0wt%)-P2O5(1.5wt%)-K2O-(2.0wt%)/Al2O3 catalyst, which is named as E-1 catalyst.
The properties of the E-1 catalyst are shown in Table 1, and a TEM image of the crystal morphology of the Co-Mo-S active phase of the E-1 catalyst after being presulfided is shown in FIG. 7.
As can be seen from FIG. 7, the Co-Mo-S crystal morphology of the conventional hydrodesulfurization catalyst after presulfiding is characterized by 3.0-6.0 layers and 3.0-8.0 nm distribution in length.
Comparative example 2
This comparative example uses the gasoline selective hydrodesulfurization and olefin reduction catalyst prepared in example 2, as opposed to the GDS-2 catalyst preparation in that: the graphene is not subjected to alkali treatment when being loaded on the alumina carrier, and is subjected to high-temperature roasting after being dried.
Preparing an alumina-based carrier: the same as in example 1;
Preparation of an alumina-based carrier containing graphene oxide: weighing 1.0g of Graphene Oxide (GO) and 50g of Al 2O3 carrier, adding into a beaker, placing into a microwave device, performing 700W microwave treatment for 5.0h, taking out, filtering, drying at 140 ℃ for 8 hours, and roasting at 500 ℃ for 5 hours to obtain an alumina-based carrier containing graphene oxide, wherein a TEM image is shown in figure 8;
and (3) preparing a catalyst: the same as in example 2. Denoted as E-2 catalyst.
The properties of the E-2 catalyst are shown in Table 1, and a TEM image of the crystal morphology of the Co-Mo-S active phase of the E-2 catalyst after presulfiding is shown in FIG. 9.
As can be seen from fig. 8, on the outer surface of the alumina-based carrier, no ribbon-like graphene oxide is seen; as can be seen from FIG. 9, the Co-Mo-S wafer distribution of the E-2 catalyst after presulfiding is similar to that of the conventional hydrodesulfurization catalyst prepared in comparative example 1, and the crystal morphology is characterized by 3.0-5.0 layers and 3.0-8.0 nm distribution.
Example 4
This example examines the performance of the catalyst of example 1.
10ML of GDS-1 catalyst was loaded into a small fixed bed hydrogenation reactor. The catalyst is pre-vulcanized, the vulcanized oil is straight-run gasoline (distillation range 40-175 ℃), and the CS 2 mass concentration is 2.0%. The volume ratio of hydrogen to oil is 200 when the pressure of the vulcanization reaction is 2.0 MPa: 1. the liquid hourly space velocity is 2.0h -1, and the reaction temperature is 280 ℃ for 8h.
After the vulcanization is finished, other conditions are unchanged, and the raw material heavy gasoline is fed after the temperature is reduced to 270 ℃, and the properties of the raw material heavy gasoline are shown in table 2; after stable operation for 10 hours, sampling analysis was performed, and properties of the obtained gasoline product are shown in table 3.
Example 5
This example examines the performance of the catalyst of example 2.
10ML of GDS-2 catalyst was loaded into a small fixed bed hydrogenation reactor. The catalyst is pre-vulcanized, the vulcanized oil is straight-run gasoline (distillation range 40-175 ℃), and the CS 2 mass concentration is 2.0%. The volume ratio of hydrogen to oil is 200 when the pressure of the vulcanization reaction is 2.0 MPa: 1. the liquid hourly space velocity is 2.0h -1, and the reaction temperature is 315 ℃ for vulcanization for 5.0h.
After the vulcanization is finished, other conditions are unchanged, the temperature is reduced to 270 ℃ and the raw material gasoline is fed, and after the raw material gasoline is stably operated for 10 hours, sampling analysis is carried out, and the properties of the obtained gasoline product are shown in Table 3.
Example 6
This example examines the performance of the catalyst of example 3.
10ML of GDS-3 catalyst was loaded into a small fixed bed hydrogenation reactor. The catalyst is pre-vulcanized, the vulcanized oil is straight-run gasoline (distillation range 40-175 ℃), and the CS 2 mass concentration is 2.0%. The volume ratio of hydrogen to oil is 200 when the pressure of the vulcanization reaction is 2.0 MPa: 1. the liquid hourly space velocity is 2.0h -1, and the reaction temperature is 315 ℃ for vulcanization for 5.0h.
After the vulcanization is finished, other conditions are unchanged, the temperature is reduced to 270 ℃ and the raw material gasoline is fed, and after the raw material gasoline is stably operated for 10 hours, sampling analysis is carried out, and the properties of the obtained gasoline product are shown in Table 3.
Comparative example 3
This comparative example examines the performance of comparative example 1 in preparing a hydrodesulfurization catalyst.
10ML of the E-1 hydrodesulfurization catalyst of comparative example 1 was charged into a small fixed bed hydrogenation reactor. The catalyst is pre-vulcanized, the vulcanized oil is straight-run gasoline (distillation range 40-175 ℃), and the concentration of CS 2 is 2.0%. The vulcanizing reaction pressure is 2.0MPa, the hydrogen-oil volume ratio is 200:1, the liquid hourly space velocity is 2.0h -1, and the vulcanizing is carried out for 8.0h at the reaction temperature of 280 ℃.
After the vulcanization is finished, other conditions are unchanged, the temperature is reduced to 270 ℃ and the raw material gasoline is fed, and after the raw material gasoline is stably operated for 10 hours, sampling analysis is carried out, and the properties of the obtained gasoline product are shown in Table 3.
As can be seen from Table 3, when the heavy fraction gasoline raw material is hydrodesulfurized, the sulfur content of the product is not more than 10.0 mug/g (about 98.0% of desulfurization rate), and compared with the traditional Mo-Co/Al 2O3 catalyst of comparative example 1, the Research Octane Number (RON) of the gasoline product is less lost by 0.5-1.5 units when the catalyst of the invention is adopted, and the higher hydrodesulfurization selectivity is shown.
Comparative example 4
This comparative example examines the performance of comparative example 2 in preparing a hydrodesulfurization catalyst.
10ML of the E-2 hydrodesulfurization catalyst of comparative example 2 was charged into a small fixed bed hydrogenation reactor. The catalyst is pre-vulcanized, the vulcanized oil is straight-run gasoline (distillation range 40-175 ℃), and the concentration of CS 2 is 2.0%. The vulcanizing reaction pressure is 2.0MPa, the hydrogen-oil volume ratio is 200:1, the liquid hourly space velocity is 2.0h -1, and the vulcanizing is carried out at the reaction temperature of 315 ℃ for 5.0h.
After the vulcanization is finished, other conditions are unchanged, the temperature is reduced to 270 ℃ and the raw material gasoline is fed, and after the raw material gasoline is stably operated for 10 hours, sampling analysis is carried out, and the properties of the obtained gasoline product are shown in Table 3.
TABLE 1 catalyst Properties
| Item(s) | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 |
| Catalyst numbering | GDS-1 | GDS-2 | GDS-3 | E-1 | E-2 |
| Shape and shape | Cylindrical bar shape | Cylindrical bar shape | Cylindrical bar shape | Cylindrical bar shape | Cylindrical bar shape |
| Diameter/length, mm | 1.5(3.0~8.0) | 1.5(3.0~8.0) | 1.5(3.0~8.0) | 1.5(3.0~8.0) | 1.5(3.0~8.0) |
| Graphene content in the carrier, wt% | 0.8 | 2.0 | 6.0 | / | 2.0 |
| Pore volume, mL.g -1 | 0.45 | 0.48 | 0.47 | 0.40 | 0.48 |
| Specific surface area, m 2·g-1 | 330 | 340 | 348 | 170 | 330 |
| Bulk density, g.cm -3 | 0.78 | 0.76 | 0.75 | 0.80 | 0.76 |
| MoO3,wt% | 13.0 | 12.0 | 12.0 | 13.0 | 12.0 |
| CoO，wt% | 4.0 | 3.5 | 3.5 | 4.0 | 3.5 |
Table 2 heavy ends feedstock gasoline properties
| Item(s) | Heavy fraction raw material gasoline |
| Density, g/cm 3 | 0.7850 |
| Sulfur content [ mu ] g/g | 320 |
| Research octane number RON | 90.0 |
| Gasoline composition by FIA method | |
| Alkane content, v% | 39.5 |
| Olefin content, v% | 26.0 |
| Aromatic hydrocarbon content, v% | 34.5 |
| Atmospheric distillation range, DEG C | |
| Initial point of distillation | 74.4 |
| 10% | 90.0 |
| 50% | 129.0 |
| 90% | 172.0 |
| End point of distillation | 195.0 |
TABLE 3 desulfurized gasoline product Properties
| Item(s) | Heavy fraction feedstock | Example 4 | Example 5 | Example 6 | Comparative example 3 | Comparative example 4 |
| Catalyst numbering | / | GDS-1 | GDS-2 | GDS-3 | E-1 | E-2 |
| Density, g/cm 3 | 0.7850 | 0.784 | 0.785 | 0.784 | 0.784 | 0.784 |
| Sulfur content [ mu ] g/g | 320 | 8.0 | 4.5 | 6.5 | 9.5 | 9.0 |
| Research octane number RON | 90.0 | 87.5 | 86.5 | 86.8 | 86.0 | 86.2 |
| RON loss | / | 2.5 | 3.5 | 3.2 | 4.0 | 3.8 |
| Gasoline composition by FIA method | ||||||
| Alkane content, v% | 39.5 | 52.6 | 53.8 | 53.3 | 52.0 | 53.4 |
| Olefin content, v% | 26.0 | 13.0 | 12.0 | 12.5 | 14.0 | 12.5 |
| Aromatic hydrocarbon content, v% | 34.5 | 34.4 | 34.2 | 34.2 | 34.0 | 34.1 |
| Atmospheric distillation range, DEG C | ||||||
| Initial point of distillation | 74.4 | 74.2 | 74.1 | 74.3 | 74.0 | 74.0 |
| 10% | 90.0 | 90.0 | 89.8 | 90.1 | 89.8 | 89.0 |
| 50% | 129.0 | 129.0 | 128.9 | 130.0 | 128.8 | 128.9 |
| 90% | 172.0 | 172.2 | 172.1 | 172.5 | 172.1 | 172.2 |
| End point of distillation | 195.0 | 195.1 | 195.2 | 195.5 | 195.0 | 195.1 |
Claims (18)
1. A method for producing clean gasoline, comprising: the gasoline raw material is contacted with a gasoline selective hydrodesulfurization and olefin reduction catalyst in the presence of hydrogen to react, so as to obtain a gasoline product; in the gasoline product, the sulfur content is not more than 10 mug/g, and the olefin content is not more than 15.0v%; the catalyst comprises a carrier and an active metal component, wherein the carrier is an alumina-based carrier with graphene oxide coated on the surface; the graphene oxide is ribbon-shaped nano graphene oxide;
the preparation method of the catalyst comprises the following steps:
(1) Mixing graphene oxide and an alumina-based carrier, adding an alkaline solution for performing second microwave treatment after first microwave treatment, filtering, and drying to obtain the alumina-based carrier with the surface coated with graphene oxide;
(2) And (3) loading the active metal component on the carrier obtained in the step (1), and drying to obtain the catalyst.
2. The method of claim 1, wherein: based on the weight of the carrier, the content of the graphene oxide is 0.1 to 10.0 weight percent, and the content of the alumina-based carrier is 90.0 to 99.9 weight percent.
3. A production method according to claim 2, characterized in that: based on the weight of the carrier, the content of the graphene oxide is 0.5 to 8.0 weight percent, and the content of the alumina-based carrier is 92.0 to 99.5 weight percent.
4. The method of claim 1, wherein: the active metal component is VIB group metal and VIII group metal.
5. The method of claim 4, wherein: the VIB group metal is W and/or Mo, and the VIII group metal is Ni and/or Co.
6. The method of claim 4, wherein: the active metal component is Mo and Co.
7. The method of claim 4, wherein: the content of the VIB group metal in terms of oxide is 5.0-22.0 wt% based on the weight of the catalyst, and the content of the VIII group metal in terms of oxide is 1.0-9.0 wt%.
8. The method of claim 7, wherein: the content of the VIB group metal in terms of oxide is 8.0-20.0 wt% based on the weight of the catalyst, and the content of the VIII group metal in terms of oxide is 2.0-7.0 wt%.
9. The method of claim 1, wherein: the conditions of the first microwave treatment in the step (1) are as follows: the microwave power is 500-900W and the treatment time is 0.5-3.0 h; the conditions of the second microwave treatment are as follows: the microwave power is 500-800W and the treatment time is 1.0-4.0 h.
10. The method of claim 1, wherein: the alkaline solution in the step (1) is at least one of potassium hydroxide and sodium hydroxide, and the mass concentration of the alkaline solution is 5.0-40.0%; the ratio of the alkaline solution to the total volume of the graphene oxide and the alumina-based carrier is 1.5:1 to 2.5:1.
11. A method according to claim 1, characterized in that: the drying conditions in the step (1) are as follows: drying at 100-200 deg.c for 4-8 hr.
12. A method according to claim 1, characterized in that: the method for loading the active metal component in the step (2) on the carrier obtained in the step (1) is an impregnation method; the drying conditions in the step (2) are as follows: drying at 100-200 deg.c for 4-8 hr.
13. The method of claim 1, wherein: the gasoline raw material is from a heavy fraction pre-fractionated from catalytic cracking gasoline; in the gasoline raw material, the mass content of sulfur is 100-800 mug/g, and the volume content of olefin is 15.0-35.0%.
14. The method of claim 1, wherein: a fixed bed process is employed.
15. The method of claim 1, wherein: the catalyst needs to be presulfided before the reaction, and presulfiding is carried out on the catalyst in the presence of a vulcanizing agent and hydrogen by the presulfiding method under the following conditions: the pressure is 1.0 MPa-4.5 MPa, the temperature is 200-400 ℃, and the volume ratio of the hydrogen agent is 100:1-500:1; the vulcanized oil is at least one of straight-run gasoline or hydrogenated naphtha.
16. The method of claim 15, wherein: the pre-vulcanization conditions were: the pressure is 1.5 MPa-3.0 MPa, the temperature is 260-330 ℃, and the volume ratio of the hydrogen agent is 200:1-300:1.
17. The method of claim 1, wherein: the reaction conditions were as follows: the reaction pressure is 1.0 MPa-4.5 MPa, the reaction temperature is 200-400 ℃, the liquid hourly space velocity is 1.0h -1～5.0h-1, and the hydrogen-oil volume ratio is 100:1-500:1.
18. The method of claim 1, wherein: the reaction conditions were as follows: the reaction pressure is 1.5 MPa-3.0 MPa, the reaction temperature is 250-300 ℃, the liquid hourly space velocity is 2.0h -1～4.0h-1, and the hydrogen-oil volume ratio is 200:1-400:1.
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| 田纪伟.石墨烯氧化铝复合材料的制备与催化应用.万方数据知识服务平台.2013,正文部分第20-28、41-45页. * |
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