CN113801687A - Hydrogenation method for producing aviation kerosene - Google Patents
Hydrogenation method for producing aviation kerosene Download PDFInfo
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- CN113801687A CN113801687A CN202010532411.0A CN202010532411A CN113801687A CN 113801687 A CN113801687 A CN 113801687A CN 202010532411 A CN202010532411 A CN 202010532411A CN 113801687 A CN113801687 A CN 113801687A
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- aviation kerosene
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- alumina
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- 239000003350 kerosene Substances 0.000 title claims abstract description 49
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 99
- 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 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 5
- 238000005260 corrosion Methods 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 238000011282 treatment Methods 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 238000001035 drying Methods 0.000 description 18
- 239000003921 oil Substances 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
- 238000003917 TEM image Methods 0.000 description 14
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000003502 gasoline Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 12
- 229910052593 corundum Inorganic materials 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 7
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910017318 Mo—Ni Inorganic materials 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000012670 alkaline solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052961 molybdenite Inorganic materials 0.000 description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- 239000003795 chemical substances by application Substances 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
- 238000001914 filtration Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000009704 powder extrusion Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003278 egg shell Anatomy 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000295 fuel oil Substances 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
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Images
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
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- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- 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
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- Optics & Photonics (AREA)
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Abstract
The invention discloses a hydrogenation method for producing aviation kerosene. The method comprises the following steps: the method comprises the following steps of contacting and reacting a aviation kerosene raw material with a hydrodesulfurization catalyst in the presence of hydrogen to obtain an aviation kerosene product, wherein the hydrodesulfurization catalyst comprises an alumina-based carrier with the surface being coated with graphene oxide and active metal components Mo and Ni. The method can produce the aviation kerosene under mild conditions, has low cost and low energy consumption, can greatly improve the treatment capacity of the aviation kerosene, and increases the economic benefit.
Description
Technical Field
The invention belongs to the technical field of oil refining, and particularly relates to a hydrogenation method for producing aviation kerosene.
Background
With the rapid increase of Chinese economy into high quality increase, the problem of excess capacity of the current and future Chinese oil refining industry is highlighted, the increase of the demand of fuel oil, particularly gasoline and diesel oil, is greatly slowed, the demand of diesel oil is reduced from 2010, the diesel-gasoline ratio is reduced from 2.17 in 2010 to about 1.1 in 2020, the gasoline demand is expected to enter the plateau about 2025, and the aviation kerosene demand is expected to continuously increase along with the development of the aviation transportation industry.
The jet fuel fraction is mainly derived from straight-run components obtained by cutting directly from an atmospheric fractionation unit. At present, the problems of high sulfur content, high mercaptan sulfur content, corrosion, high acidity, darker color and the like of aviation kerosene fractions need to be solved by a hydrofining process.
CN1361229A discloses an aviation fuel selective mercaptan removal catalyst and a preparation method thereof. The catalyst comprises the following components: 60-100 parts of titanium dioxide, 0-40 parts of alumina, 7-20 parts of molybdenum oxide and 0.1-5 parts of cobalt oxide, and when the catalyst is used for aviation kerosene hydrodesulfurization, the mercaptan removal effect of the catalyst taking the alumina as the carrier is obviously inferior to that of the catalyst taking the titanium dioxide and the alumina as the carrier.
CN101089134A discloses a method for hydro-upgrading aviation kerosene fraction. Wherein, the hydro-upgrading reaction zone at least comprises a bulk phase catalyst, the bulk phase catalyst contains three metal components of Mo, W and Ni, and the catalyst exists in a composite oxide form of W, Ni before vulcanization: NixWyOz, z ═ x +3y, Mo exists in oxide form: MoO3(ii) a The ratio of x to y in the composite oxide NixWyOz is 1: 8-8: 1, composite oxide NixWyOz and oxide MoO3The weight ratio of (1): 10-10: 1, bulk phase catalyst mesoreductionOxide NixWyOz and oxide MoO3The total weight content of the components is 40-100%. From the test results, it can be known that the hydrodesulfurization needs to adopt more severe reaction conditions, such as higher reaction pressure and higher hydrogen-oil volume ratio (the reaction pressure is 5.0MPa, and the hydrogen-oil volume ratio is 1000: 1).
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 and molding, drying and roasting to obtain a carrier, preparing an impregnation solution by using heteropolyacid containing an active metal component, drying and roasting at 500 ℃ to obtain the catalyst. The catalyst can improve the hydrodesulfurization activity, but does not relate to the problem of aviation kerosene hydrotreatment.
With the continuous increase of aviation kerosene demand, the load of aviation kerosene hydrogenation units will increase day by day, and the development of a new generation of high-activity aviation kerosene hydrodesulfurization catalyst is one of effective methods for increasing the yield of aviation kerosene.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a hydrogenation method for producing aviation kerosene. The method can produce the aviation kerosene under mild conditions, has low cost and low energy consumption, can greatly improve the treatment capacity of the aviation kerosene, and increases the economic benefit.
The invention provides a hydrogenation method for producing aviation kerosene, which comprises the following steps: the method comprises the following steps of contacting and reacting a aviation kerosene raw material with a hydrodesulfurization catalyst in the presence of hydrogen to obtain an aviation kerosene product, wherein the hydrodesulfurization catalyst comprises an alumina-based carrier with the surface being coated with graphene oxide and active metal components Mo and Ni.
In the hydrodesulfurization catalyst, the alumina-based carrier with the surface coated with the graphene oxide is 0.1-6.0 wt% based on the weight of the carrier, the alumina-based carrier is 94.0-99.9 wt%, preferably, the graphene oxide is 0.3-4.0 wt%, and the alumina-based carrier is 96.0-99.7 wt%.
In the hydrodesulfurization catalyst, based on the weight of the catalyst, the content of Mo in oxide is 5.0wt% -22.0 wt%, the content of Ni in oxide is 1.0wt% -9.0 wt%, preferably, the content of Mo in oxide is 8.0wt% -20.0 wt%, and the content of Ni in oxide is 2.0wt% -7.0 wt%.
In the hydrodesulfurization catalyst of the present invention, the alumina-based carrier is a carrier containing alumina as a main component, and may contain an additive, such as at least one of titanium oxide, silicon oxide, magnesium oxide, and the like, in addition to alumina. The content of the additive accounts for less than 20.0wt% of the weight of the alumina-based carrier, and can be 1.0wt% to 15.0 wt%.
In the hydrodesulfurization catalyst, the graphene oxide is ribbon-shaped nano graphene oxide. The graphene oxide has a thickness of 3.0-10.0 nm and a length of 80.0-200.0 nm.
The preparation method of the hydrodesulfurization catalyst comprises the following steps:
(1) mixing graphene oxide and an alumina-based carrier, performing first microwave treatment, adding an alkaline solution for second microwave treatment, filtering, and drying to obtain the alumina-based carrier with the surface coated with the graphene oxide;
(2) and (2) loading an active metal component on the carrier obtained in the step (1), and drying to obtain the catalyst.
In the preparation method of the invention, the conditions of the first microwave treatment in the step (1) are as follows: the microwave power is 500-900W, and the processing 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 processing time is 1.0-4.0 h.
In the preparation method, the thickness of the graphene oxide in the step (1) is 3.0-10.0 nm.
In the preparation method, 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 preparation method of the invention, the drying conditions in the step (1) are as follows: drying for 4-8 h at 100-200 ℃.
In the preparation method of the present invention, the method of loading the active metal component described in step (2) on the carrier obtained in step (1) may be a conventional method, preferably an impregnation method. The impregnation can be carried out by a saturated impregnation method, an unsaturated impregnation method, a one-step impregnation method or a multi-step impregnation method. The drying conditions in the step (2) are as follows: drying for 4-8 h at 100-200 ℃.
In the preparation method, the step (1) and the step (2) are both free of roasting step, and the roasting step refers to a heat treatment step at the temperature of more than 200 ℃.
In the preparation method, the shape of the alumina-based carrier can be a conventional shape, such as a strip shape or a spherical shape, and is preferably a strip-shaped carrier, the diameter of which is generally 1.0-3.0 mm, and the length of which is 3.0-10.0 mm. In the alumina-based carrier, Al2O3Is gamma-Al2O3。
In the method, the catalyst needs to be presulfurized before reaction, and the presulfurization method can presulfurize the catalyst in the presence of a vulcanizing agent and hydrogen. The prevulcanization conditions are as follows: the pressure is 1.0-4.5 MPa, the temperature is 200-400 ℃, and the volume ratio of the hydrogen agent is 100: 1-500: 1; preferred vulcanization conditions are: the pressure is 1.5 MPa-3.0 MPa, the temperature is 260 ℃ to 330 ℃, and the volume ratio of the hydrogen agent is 200: 1-300: 1. The vulcanizing agent may be carbon disulfide (CS)2) Dimethyl disulfide (DMDS), etc. can be decomposed to H2At least one of S sulfides; the vulcanized oil is at least one of straight-run gasoline or hydrogenated naphtha, and the distillation range of the vulcanized oil is generally 40-180 ℃.
According to the method, in the aviation kerosene raw material, the sulfur content is 100-1200 mug/g, the mercaptan sulfur content is 50-180 mug/g, the initial boiling point is 120-150 ℃, and the final boiling point is 240-280 ℃.
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 1.0MPa to 3.0MPa, the reaction temperature is 180 ℃ to 300 ℃, and the liquid hourly volume space velocity is 4.0h-1~15.0h-1The volume ratio of hydrogen to oil is 100: 1-500: 1; preferred reaction conditions are: the reaction pressure is 1.5MPa to 2.0MPa, and the reaction temperature is 200 ℃ to 2 DEG CThe liquid hourly space velocity is 5.0h at 50 DEG C-1~12.0h-1The volume ratio of hydrogen to oil is 150: 1-300: 1.
The method can be used for producing the aviation kerosene product, wherein the sulfur content is not more than 10 mu g/g, and the silver sheet corrosion is grade 0.
Compared with the prior art, the method has the following advantages:
(1) the aviation kerosene produced by the method of the invention can be processed with large treatment capacity under mild conditions (low temperature, low pressure and low hydrogen-oil volume ratio), and the sulfur content of the obtained aviation kerosene product can be reduced to 10 mug/g, even below 5 mug/g.
(2) In the preparation method of the hydrodesulfurization catalyst, the graphene oxide and the alumina-based carrier are firstly treated by microwaves, then are treated by microwaves in the presence of an alkaline solution, and do not need high-temperature roasting, so that the alumina-based carrier coated with the graphene oxide on the surface can be obtained, and after the active metal components are loaded, the high-temperature roasting is not needed, so that the load state of the graphene oxide on the alumina-based carrier can be adjusted, and under the coordination action of the graphene oxide on the alumina-based carrier and the active metal components Mo and Ni, the active sites are in an eggshell structure and are intensively distributed on the outer surface of the catalyst in the vulcanization process, the hydrodesulfurization activity can be improved, and the hydrodesulfurization catalyst is particularly suitable for the aviation kerosene hydrodesulfurization process.
(3) When the hydrodesulfurization catalyst is adopted to treat the aviation kerosene with the sulfur content of 100-1200 mug/g and the mercaptan sulfur content of 50-180 mug/g, the sulfur content of the product is not more than 10.0 mug/g, which is compared with that of the traditional Mo-Ni/Al2O3Compared with the catalyst, the reaction temperature can be greatly reduced (such as from 220 ℃ to 200 ℃), or the volume space velocity can be greatly increased (such as from 5.0 h)-1Increased to 12.0h-1) Therefore, the aviation kerosene can be produced efficiently at low cost by adopting the catalyst of the invention.
Drawings
FIG. 1 shows comparative example 1, in which a hydrodesulfurization catalyst MoS was prepared by a conventional method2A crystal appearance TEM image;
FIG. 2 shows Al coated with graphene oxide prepared in example 12O3A TEM image of the support;
FIG. 3 shows a hydrodesulfurization catalyst MoS coated with graphene oxide prepared in example 12A crystal appearance TEM image;
FIG. 4 shows Al coated with graphene oxide prepared in example 22O3A TEM image of the support;
FIG. 5 shows the hydrodesulfurization catalyst MoS coated with graphene oxide prepared in example 22A crystal appearance TEM image;
FIG. 6 shows Al coated with graphene oxide prepared in comparative example 22O3A TEM image of the support;
FIG. 7 shows a hydrodesulfurization catalyst MoS coated with graphene oxide prepared in comparative example 22Crystal appearance TEM image.
Detailed Description
The method and effect of the present invention will be further described with reference to the drawings and examples, but the scope of the present invention is not limited thereby.
In the invention, the specific surface area and the pore volume are measured by adopting a low-temperature liquid nitrogen adsorption BET method.
Comparative example 1
The comparative example adopts the preparation of the traditional aviation kerosene hydrodesulfurization MoO3-NiO/Al2O3A catalyst.
Al2O3Preparing a carrier: 1000g of pseudo-thin aluminum hydroxide powder (Al) is weighed2O3Dry basis content of 78 wt%), Al was added2O3Mixing and rolling a sesbania powder extrusion aid with a dry basis of 5wt% and 200mL of a nitric acid aqueous solution with a mass concentration of 10% to form plastic powder, preparing a cylindrical strip with the diameter of 1.5mm by using a strip extruding machine, drying the cylindrical strip at 120 ℃ for 8 hours, and roasting the cylindrical strip at 500 ℃ for 5 hours to prepare a catalyst carrier;
MoO3-NiO/Al2O3catalyst: MoO on catalyst3The content of the catalyst carrier is 13.0wt% and the content of NiO is 4.0wt%, taking quantitative molybdenum oxide and nickel nitrate, adding deionized water to prepare 60mL of impregnation liquid, and then spraying the impregnation liquid onto 80g of the catalyst carrier. Drying at 120 deg.C for 8 hr, and calcining at 490 deg.C for 6 hr to obtain MoO3(13.0wt%)-NiO(4.0wt%)/Al2O3Catalyst, recordKR-1 catalyst.
The KR-1 catalyst properties are shown in Table 1; a TEM image of the crystal appearance of the Ni-Mo-S active phase of KR-1 catalyst after presulfiding is shown in FIG. 1.
As can be seen from FIG. 1, the crystal morphology of Ni-Mo-S of the traditional hydrodesulfurization catalyst after pre-vulcanization presents the characteristics of 5.0-10.0 layers and 10.0-15.0 nm of length distribution.
Example 1
The aviation kerosene hydrodesulfurization catalyst prepared in this example was designated KGS-1.
Al2O3Preparing a carrier: 1000g of pseudo-thin aluminum hydroxide powder (Al) is weighed2O3Dry basis content of 78 wt%), Al was added2O3Mixing and rolling a sesbania powder extrusion aid with a dry basis of 5wt% and 200mL of a nitric acid aqueous solution with a mass concentration of 10% to form plastic powder, preparing a cylindrical strip with the diameter of 1.5mm by using a strip extruding machine, drying the cylindrical strip at 120 ℃ for 8 hours, and roasting the cylindrical strip at 520 ℃ for 5 hours to prepare an alumina-based carrier;
al coated with graphene oxide2O3Preparation of the carrier: weighing 0.4g of Graphene Oxide (GO) and 50g of an aluminum oxide-based carrier, adding the graphene oxide and the aluminum oxide-based carrier into a beaker, placing the beaker into a microwave apparatus for 700W microwave treatment for 1.0h, then adding 94mL of KOH solution with the mass concentration of 10%, continuing 600W microwave treatment for 2.0h, taking out the solution for filtration, and drying the solution at 120 ℃ for 8.0h to obtain the aluminum oxide-based carrier with the surface coated with the graphene oxide, wherein a TEM image of the aluminum oxide-based carrier is shown in FIG. 2;
preparing a catalyst: MoO on catalyst3Taking quantitative molybdenum oxide and nickel nitrate, adding deionized water to prepare 60mL of impregnation liquid, heating to 50 ℃, adding 10mL of strong ammonia water (the ammonia content is not less than 32.0%), continuing heating to slightly boil, keeping the closed heating for about 2.0 hours until the solid is completely dissolved into Mo-Ni solution, and then cooling to room temperature. The Mo-Ni solution was sprayed onto 50g of the above-mentioned alumina-based carrier having a graphene oxide-coated surface. Drying at 120 deg.C for 8.0h to obtain MoO3(13.0wt%)-NiO(4.0wt%)/GO-Al2O3The catalyst is designated as KGS-1 catalyst.
The properties of the KGS-1 catalyst are shown in Table 1, the KGS-1 catalyst being presulfidedPost-conversion MoS2A TEM image of the crystal morphology of the active phase is shown in fig. 3.
As can be seen from FIG. 2, the 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. 3, the MoS of the KGS-1 catalyst after presulfiding2The distribution of the wafer is uniform, the crystal appearance presents 2.0-4.0 layers, and the length is 5.0-10.0 nm. In particular the active site MoS2Exhibits an eggshell-like character, MoS2The wafers are centrally distributed on the outer surface of the catalyst.
Example 2
The aviation kerosene hydrodesulfurization catalyst prepared in this example was designated KGS-2.
Preparing an alumina-based carrier: same as example 1;
preparing an alumina-based carrier with the surface coated with graphene oxide: weighing 1.0g of Graphene Oxide (GO) and 50gAl2O3Adding the carrier into a beaker, placing the beaker into a microwave apparatus for 700W microwave treatment for 1.0h, then adding 125mL of KOH solution with the mass concentration of 20% for continuing 600W microwave treatment for 4h, taking out and filtering the KOH solution, and drying the KOH solution at the temperature of 140 ℃ for 8h to prepare the alumina-based carrier with the surface coated with the graphene oxide, wherein a TEM image of the alumina-based carrier is shown in FIG. 4;
preparing a catalyst: MoO on catalyst3The content of the molybdenum oxide and the NiO is 12.0wt% and 3.5wt%, and a certain amount of molybdenum oxide and nickel nitrate are taken and added with deionized water to prepare 60mL of impregnation liquid. Heating to 80 deg.C, adding 20mL of concentrated ammonia water (ammonia content not less than 32.0%), boiling, sealing, heating for about 2.0 hr until the solid is completely dissolved to obtain Mo-Ni solution, and cooling to room temperature. Then, the solution was sprayed onto 50g of the above-mentioned alumina-based carrier having a surface coated with graphene oxide. Drying at 140 ℃ for 8h to prepare MoO3(12.0wt%)-NiO(3.5wt%)/GO-Al2O3The catalyst is designated as KGS-2 catalyst.
The properties of the KGS-2 catalyst are shown in Table 1; MoS of pre-vulcanized KGS-2 catalyst2A TEM image of the crystal morphology of the active phase is shown in fig. 5;
as can be seen from FIG. 4, the graphene oxide filaments are uniformly coated on 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 3.0-10.0 nm80.0-200.0 nm; as can be seen from FIG. 5, the MoS of the KGS-2 catalyst after presulfiding2The distribution of the wafer is uniform, the crystal appearance presents 2.0-4.0 layers, and the length is 5.0-10.0 nm. In particular the active site MoS2Exhibits an eggshell-like character, MoS2The wafers are centrally distributed on the outer surface of the catalyst.
Comparative example 2
This comparative example used the hydrodesulfurization catalyst prepared in example 2, which differs from the preparation of the KGS-2 catalyst in that: when the graphene supports the alumina carrier, alkali treatment is not carried out, and high-temperature roasting is carried out after drying.
Preparing an alumina-based carrier: same as example 1;
preparing an alumina-based carrier with the surface coated with graphene oxide: weighing 1.0g of Graphene Oxide (GO) and 50gAl2O3Adding the carrier into a beaker, placing the beaker into a microwave device for 700W microwave treatment for 5.0h, taking out the beaker, filtering the beaker, and drying the beaker at 140 ℃ for 8h to prepare an alumina-based carrier with the surface coated with graphene oxide; a TEM image thereof is shown in FIG. 6;
preparing a catalyst: MoO on catalyst3The content of the molybdenum oxide and the NiO is 12.0wt% and 3.5wt%, and a certain amount of molybdenum oxide and nickel nitrate are taken and added with deionized water to prepare 60mL of impregnation liquid. Heating to 80 deg.C, adding 20mL of concentrated ammonia water (ammonia content not less than 32.0%), boiling, sealing, heating for about 2.0 hr until the solid is completely dissolved to obtain Mo-Ni solution, and cooling to room temperature. Then, the solution was sprayed onto 50g of the above-mentioned alumina-based carrier having a surface coated with graphene oxide. Drying at 140 deg.C for 8h, and calcining at 500 deg.C for 6h to obtain MoO3(12.0wt%)-NiO(3.5wt%)/GO-Al2O3Catalyst, noted KR-2 catalyst.
The KR-2 catalyst properties are shown in Table 1; MoS of KR-2 catalyst after pre-vulcanization2A TEM image of the crystal morphology of the active phase is shown in fig. 7.
As can be seen from fig. 6, on the alumina-based support, the ribbon-like graphene oxide was not seen; as can be seen from FIG. 7, the KR-2 catalyst was MoS after pre-sulfiding2The crystal appearance of the wafer is 4.0-8.0 layers, and the length is 8.0-15.0 nm.
Comparative example 3
This comparative example examines the performance of the catalyst of comparative example 1.
10mL KR-1 catalyst was charged to a small fixed bed hydrogenation reactor. The catalyst is pre-vulcanized, the vulcanized oil is straight-run gasoline (distillation range 40-175 ℃), CS2The mass concentration is 2.0%. The pressure of the sulfuration reaction is 1.5MPa, the volume ratio of hydrogen to oil is 150:1, and the liquid hourly space velocity is 2.0h-1Vulcanizing at 315 ℃ for 6 h.
After the vulcanization is finished, the temperature is reduced to 220 ℃ without changing the other parts, the aviation kerosene raw material is replaced, and the volume airspeed is adjusted to be 5.0h-1After the gasoline runs for 10 hours stably, sampling and analyzing are carried out, and the properties of the obtained gasoline product are shown in a table 3.
Example 3
This example examines the performance of the catalyst of example 1.
10mL of KGS-1 catalyst was charged to a small fixed bed hydrogenation reactor. The catalyst is pre-vulcanized, the vulcanized oil is straight-run gasoline (distillation range 40-175 ℃), CS2The mass concentration is 2.0%. The pressure of the sulfuration reaction is 1.5MPa, the volume ratio of hydrogen to oil is 150:1, and the liquid hourly space velocity is 2.0h-1And sulfurizing at 315 deg.c for 6.0 hr.
After the vulcanization is finished, other conditions are unchanged, the temperature is reduced to 220 ℃, the aviation kerosene raw material is replaced, and the volume airspeed is adjusted to be 12.0h-1And after the stable operation is carried out for 10 hours, sampling and analyzing are carried out, and the properties of the obtained aviation kerosene product are shown in Table 3.
Example 4
This example examines the performance of the catalyst of example 2.
10mL of KGS-2 catalyst was charged to a small fixed bed hydrogenation reactor. The catalyst is pre-vulcanized, the vulcanized oil is straight-run gasoline (distillation range 40-175 ℃), CS2The mass concentration is 2.0%. The pressure of the sulfuration reaction is 1.5MPa, the volume ratio of hydrogen to oil is 150:1, and the liquid hourly space velocity is 2.0h-1And sulfurizing at 315 deg.c for 6.0 hr.
After the vulcanization is finished, other conditions are unchanged, the temperature is reduced to be below 200 ℃, the aviation kerosene raw material is replaced, and the volume airspeed is adjusted to be 5.0h-1And after the stable operation is carried out for 10 hours, sampling and analyzing are carried out, and the properties of the obtained aviation kerosene product are shown in Table 3.
Comparative example 4
This comparative example examines the performance of the catalyst of comparative example 2.
10mL of KR-2 catalyst was charged to a small fixed bed hydrogenation reactor. The catalyst is pre-vulcanized, the vulcanized oil is straight-run gasoline (distillation range 40-175 ℃), CS2The mass concentration is 2.0%. The pressure of the sulfuration reaction is 1.5MPa, the volume ratio of hydrogen to oil is 150:1, and the liquid hourly space velocity is 2.0h-1Vulcanizing at 315 ℃ for 6 h.
After the vulcanization is finished, the temperature is reduced to 220 ℃ without changing the other parts, the aviation kerosene raw material is replaced, and the volume airspeed is adjusted to be 5.0h-1After the gasoline runs for 10 hours stably, sampling and analyzing are carried out, and the properties of the obtained gasoline product are shown in a table 3.
As can be seen from Table 3, the sulfur content of the product during hydrodesulfurization of the aviation kerosene raw material is not more than 10.0 mu g/g, which is the same as that of the traditional Mo-Ni/Al of the comparative example 12O3Compared with the catalyst, the reaction temperature can be reduced by 20 ℃ by adopting the catalyst of the invention (from 220 ℃ to 200 ℃), or the volume space velocity can be reduced by 5.0h-1Increased to 12.0h-1Therefore, the catalyst of the invention is shown to have low-temperature and high-space velocity hydrodesulfurization performance.
TABLE 1 physicochemical Properties of the catalyst
| Item | Comparative example 1 | Example 1 | Example 2 | Comparative example 2 |
| Catalyst numbering | KR-1 | KGS-1 | KGS-2 | KR-2 |
| Shape of | 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) |
| Graphene content in the carrier, wt% | / | 0.8 | 2.0 | 2.0 |
| Pore volume, mL. g-1 | 0.42 | 0.46 | 0.49 | 0.47 |
| Specific surface area, m2·g-1 | 171 | 332 | 342 | 341 |
| Pile upDensity, g.cm-3 | 0.79 | 0.80 | 0.79 | 0.79 |
| MoO3，wt% | 13.0 | 13.0 | 12.0 | 12.0 |
| NiO，wt% | 4.0 | 4.0 | 3.5 | 3.5 |
TABLE 2 aviation kerosene feedstock Properties
| Item | Aviation kerosene feedstock |
| Density, g/cm3 | 0.7788 |
| Sulphur content, μ g/g | 1100 |
| Mercaptan sulfur content, μ g/g | 105 |
| Corrosion of silver flakes | Fail to be qualified |
| Saybolt color comparison | +22 |
| Distillation range under normal pressure, deg.C | 150~235 |
TABLE 3 aviation kerosene hydrodesulfurization product Properties
| Item | Aviation kerosene feedstock | Comparative example 3 | Example 3 | Example 4 | Comparative example 4 |
| Catalyst numbering | / | KR-1 | KGS-1 | KGS-2 | KR-2 |
| Density, g/cm3 | 0.7788 | 0.7788 | 0.7787 | 0.7786 | 0.7787 |
| Sulphur content, μ g/g | 1100 | 8.0 | 2.0 | 3.0 | 5.0 |
| Mercaptan sulfur content, μ g/g | 105 | 4.0 | <1.0 | <1.0 | 2.0 |
| Corrosion of silver flakes | / | Level 0 | Level 0 | Level 0 | Level 0 |
| Saybolt color comparison | +22 | +28 | +35 | +32 | +30 |
| Distillation range under normal pressure, deg.C | 150~235 | 150~235 | 150~235 | 150~235 | 150~235 |
Claims (10)
1. A hydrogenation process for producing aviation kerosene comprising: the method comprises the following steps of contacting and reacting a aviation kerosene raw material with a hydrodesulfurization catalyst in the presence of hydrogen to obtain an aviation kerosene product, wherein the hydrodesulfurization catalyst comprises an alumina-based carrier with the surface being coated with graphene oxide and active metal components Mo and Ni.
2. The method of claim 1, wherein: in the aviation kerosene raw material, the sulfur content is 100-1200 mug/g, the mercaptan sulfur content is 50-180 mug/g, the initial boiling point is 120-150 ℃, and the final boiling point is 240-280 ℃.
3. The method of claim 1, wherein: a fixed bed process is adopted, and the reaction conditions are as follows: the reaction pressure is 1.0MPa to 3.0MPa, the reaction temperature is 180 ℃ to 300 ℃, and the liquid hourly volume space velocity is 4.0h-1~15.0h-1The volume ratio of hydrogen to oil is 100: 1-500: 1.
4. A method according to claim 3, characterized by: the reaction conditions were as follows: the reaction pressure is 1.5MPa to 2.0MPa, the reaction temperature is 200 ℃ to 250 ℃, and the liquid hourly volume space velocity is 5.0h-1~12.0h-1The volume ratio of hydrogen to oil is 150: 1-300: 1.
5. The method of claim 1, wherein: the graphene oxide-coated alumina-based carrier comprises, by weight of the carrier, 0.1-6.0 wt% of graphene oxide and 94.0-99.9 wt% of alumina-based carrier.
6. The method of claim 1, wherein: the graphene oxide-coated alumina-based carrier comprises, by weight of the carrier, 0.3-4.0 wt% of graphene oxide and 96.0-99.7 wt% of alumina-based carrier.
7. The method of claim 1, 5 or 6, wherein: in the hydrodesulfurization catalyst, the weight of the catalyst is taken as a reference, the content of Mo in oxide is 5.0-22.0 wt%, and the content of Ni in oxide is 1.0-9.0 wt%.
8. The method of claim 1, 5 or 6, wherein: in the hydrodesulfurization catalyst, the weight of the catalyst is taken as a reference, the content of Mo in oxide is 8.0-20.0 wt%, and the content of Ni in oxide is 2.0-7.0 wt%.
9. The method of claim 1, wherein: in the hydrodesulfurization catalyst, the graphene oxide is ribbon-shaped nano graphene oxide; the graphene oxide has a thickness of 3.0-10.0 nm and a length of 80.0-200.0 nm.
10. The method of claim 1, wherein: the aviation kerosene product has the sulfur content not more than 10 mu g/g and silver sheet corrosion level 0.
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