CN106318452A - Aviation kerosene hydrofining process - Google Patents
Aviation kerosene hydrofining process Download PDFInfo
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- CN106318452A CN106318452A CN201610691355.9A CN201610691355A CN106318452A CN 106318452 A CN106318452 A CN 106318452A CN 201610691355 A CN201610691355 A CN 201610691355A CN 106318452 A CN106318452 A CN 106318452A
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- catalyst
- sba
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- fixed bed
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- 239000003350 kerosene Substances 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 229910020057 NbOPO4 Inorganic materials 0.000 claims abstract description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 tungsten nitride Chemical class 0.000 claims abstract description 12
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 5
- 238000005516 engineering process Methods 0.000 claims description 19
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 26
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 238000006477 desulfuration reaction Methods 0.000 abstract description 6
- 230000023556 desulfurization Effects 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract 1
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 150000004767 nitrides Chemical class 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 description 26
- 239000011593 sulfur Substances 0.000 description 26
- 230000000694 effects Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012467 final product Substances 0.000 description 13
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 10
- 239000010779 crude oil Substances 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- 235000016768 molybdenum Nutrition 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000002079 cooperative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000004939 coking Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 239000013335 mesoporous material Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 244000050510 Cunninghamia lanceolata Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an aviation kerosene hydrofining process. The aviation kerosene hydrofining process uses a fixed bed reactor filled with a hydrogen desulfurization and denitrification catalyst, the catalyst comprises a carrier and an active component, the carrier is a compound or a mixture of MSU-G, SBA-15 and HMS, the active component is a mixture of dimolybdate nitride MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide WC, the catalyst further comprises a catalytic additive which is a mixture of TiO2, CeO2, V2O5 and NbOPO4, the reaction conditions of the fixed bed reactor are as follows: the reaction temperature is 260-320 DEG C, the hydrogen partial pressure is 2.8-3.6 MPa, the hydrogen to oil volume ratio is 150-250, and the liquid hourly space velocity is 2.0-4.0 h<1>. According to the process, the total sulphur content of the aviation kerosene is controlled to be lower than 5 ppm, and meanwhile, the total nitrogen content of the aviation kerosene is controlled to be within 10 ppm.
Description
Technical field
The present invention relates to aerial kerosene hydrodesulfurization process for refining, be specifically related to a kind of boat using special catalyst to carry out
Empty kerosene hydrogenation desulfuration purification technique.
Background technology
Aerial kerosene is one of oil product.English name Jet fuel No.3, calls jet fuel.Main by difference
The hydrocarbon compound composition of fraction.Aerial kerosene is mainly used as the fuel of aero-turbine.
Along with transportation is increasingly stronger to Economic Stimulus effect, China's transportation cause development in recent years is swift and violent.
From the point of view of the consumption figure of State Statistics Bureau's statistics, China's jet fuel consumption figure the whole year in 2008 is 1279.9 ten thousand tons, with
The consumption figure of the same period in 2007 is compared and has been gone up 3.6%, and from the point of view of the import volume of customs statistics, China fires 2008 years jets
Expecting import altogether 647.8 ten thousand tons, increased by 23.5% on a year-on-year basis, monthly import volume reaches 540,000 tons.
In the world always according to the standard of JETA-1, the quality of jet fuel being come requirement, this also becomes jet combustion in the world
The standard criterion of material trade deal.Its total acid number of this standard-required (mgKOH/g) is not more than 0.015, and total sulfur content maximum must not
More than 0.30wt%, i.e. cannot be greater than 30ppm, corrosive nature is also required by aerial kerosene simultaneously.Analysis of experiments shows, impact
The main cause of boat coal silver slice corrosion is the elementary sulfur in active sulfide, and when its content reaches 2 μ g/g, boat coal silver slice corrosion is the most not
Qualified, silver slice corrosion can be promoted with elementary sulfur when mercaptan and disulphide etc. coexist.
Along with heaviness, the in poor quality of world's crude oil are deepened day by day, crude oil sulfur content is more and more higher, and the lightweight of high-quality is former
Oil is constantly reducing.The crude oil of refinery's processing in recent years mostly is imported crude oil, and relative density increases year by year, in several years of the beginning of this century
The average density of whole world refinery processing crude oil rises to about 0.8633.The problem that sulfur content is high is the most extremely serious, the current world
The yield of upper sour crude oil and sour crude accounts for more than the 75% of world's crude oil total output.20th century the mid-90 whole world refinery
The crude oil average sulfur content of processing is 0.9%, and the beginning of this century has increased to 1.6%.
For producing the cleaning jet fuel (aerial kerosene) of high-quality, desulfurization technology obtains huge attention.Current desulfurization
Technology, divides from the angle whether being hydrogenated with, is divided into hydrodesulfurization and non-hydrodesulfurization.Hydrodesulfurization technology is intrinsic excellent due to it
Gesture becomes the technology of processing high grade fuel oil the most ripe.Compared to conventional process for refining, kerosene hydrogenation
Technique decreases alkaline residue and hargil exhaust emission, and it is the most higher for the adaptability of raw material, and therefore hydrogenation technique is future development
Main way.
The hydrogenation technique of current jet fuel (aerial kerosene) is similar, and typical technique is as follows: virgin kerosene is certainly
Raw material tank field is sent into raw material surge tank, with kerosene raffinate heat exchange after feed pump boosts to about 3.0MPa, then mixes with hydrogen
Again with product heat exchange.Enter charging heating furnace after mixed hydrogen raw material and product heat exchange to be heated to reacting temperature required entrance
Hydrogenation reactor.Mixed hydrogen raw material carries out hydrogenation reaction under the effect of catalyst, enters after product and mixed hydrogen raw material heat exchange
High pressure hot separator is isolated major part and is generated oil, high-pressure separator top oil gas priority and recycle hydrogen, cold high pressure separator base oil
After heat exchange inject desalted water, then enter air cooler, water cooler be cooled to 40 DEG C enter cold high pressure separators isolate hydrogen.Cold anticyclone
It is combined into stripper with high pressure hot separator base oil after separator oil and high pressure hot separator gas heat exchange.
But existing hydrofining technology is all to arrange for former high-quality edible vegetable oil.For current high sulfur content
The virgin kerosene that crude oil production obtains, owing to its high sulfur content, its catalyst used and hydroconversion condition are all difficult to be suitable for, produces
The setting that meets the requirements be reduce sulfur content to below 10ppm, can not be suitable for.
A kind of jet fuel (aerial kerosene) hydrodesulfurization is provided, can be effectively by the aviation of high sulfur content
Sulfur content in kerosene controls at below 10ppm, with satisfied discharge and Corrosion standards, is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of aerial kerosene hydrodesulfurization process for refining, this technique can be by aerial kerosene
In total sulfur content be reduced to below 10ppm, with satisfied discharge and Corrosion standards.
For reaching this purpose, the present invention by the following technical solutions:
A kind of aerial kerosene hydrofining technology, described technique uses fixed bed reactors, loads in fixed bed reactors
Hydrogenation catalyst, described catalyst is had to include carrier and active component.
Described carrier is complex or the mixture of MSU-G, SBA-15 and HMS.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixing
Thing.
The reaction condition of described fixed bed reactors is: reaction temperature is 260-320 DEG C, and hydrogen dividing potential drop is 2.8-3.6MPa,
Hydrogen to oil volume ratio 150-250, volume space velocity 2.0-4.0h-1。
An object of the present invention is that, it is provided that the compound of a kind of 3 kinds of different mesopore molecular sieves works in coordination with effect to show
Should be with special catalytic performance, described cooperative effect shows that desulfuration purification aspect, special catalytic performance are then to show right
On the service life of catalyst and the raising of catalysis activity.
In catalyst field, according to the definition of IUPAC (IUPAC), the aperture title less than 2nm
For micropore；The aperture referred to as macropore more than 50nm；Aperture the most mesoporous (or claiming mesopore) between 2 to 50nm.Mesoporous material
Being a kind of aperture new material with huge specific surface area and three-dimensional open-framework between micropore and macropore, it has
The excellent specific property that other porous material does not has: there is the pore passage structure of high-sequential；The single distribution in aperture, and aperture size
Can change at relative broad range；Mesoporous various shapes, hole wall composition and character controllable；Height can be obtained by optimum synthesis condition
Heat stability and hydrothermal stability.
But in present applications ' the tail must be taken, described mesoporous material, when for catalytic field, is all single use, such as MCM system
Row, such as MCM-22, MCM-36, MCM-41, MCM-48, MCM-49, MCM56, such as MSU series, such as MSU-1, MSU-2, MSU-
4, MSU-X, MSU-G, MSU-S, MSU-J etc., and SBA series, such as SBA-1, SBA-2, SBA-3, SBA-6, SBA-7, SBA-
8, SBA-11, SBA-15, SBA-16 etc., and other mesoporous series etc..
Two kinds of carriers of a few studies literature research compound, such as Y/SBA-15, Y/SAPO-5 etc., majority is to be situated between
Hole-mesoporous-microporous composite molecular sieve and micropore-mesoporous-microporous composite molecular sieve are main.Use the compound with performance of 3 kinds of different mesopore molecular sieves
Go out cooperative effect and the research of special catalytic performance, have not yet to see report.
The catalyst carrier of the present invention is complex or the mixture of MSU-G, SBA-15 and HMS.Described complex or mixed
In compound, the weight ratio of MSU-G, SBA-15 and HMS is 1:(0.8-1.2): (0.4-0.7), preferably 1:(1-1.15):
(0.5-0.7)。
MSU-G, SBA-15 and HMS mesopore molecular sieve that the present invention uses is all the existing molecular sieve of catalytic field, and it is
Through obtaining widely studied and application at catalytic field.
MSU-G is a kind of to have vesicle structure shape particle shape and the mesopore molecular sieve of layered framework structure, and it has height
Degree skeleton crosslinking and relatively thick skeleton wall and there is superpower heat stability and hydrothermal stability, its skeleton hole is with vertical
Being cross-linked with each other in layer and the hole being parallel to layer, diffusion path is the shortest because its vesicle shell is thick.The vesicle shape particle of MSU-G molecular sieve
Form facilitates reagent to enter the catalytic center of layered framework, and its catalysis activity is the highest.
SBA-15 belongs to the one of mesopore molecular sieve, has two-dimentional six square tube pore structures, has P3mm space group.At XRD
In diffracting spectrum, main peak is near about 1 °, for (10) crystal face peak.Secondary strong peak is followed successively by (11) peak and (20) peak.Other peaks are relatively
Weak, it is difficult to observe.Additionally, the silicon dioxide on SBA-15 skeleton is generally amorphous state, observe not in Radix Rumicis XRD diffraction
To obvious diffraction maximum.SBA-15 has a bigger aperture (maximum up to 30nm), thicker hole wall (wall thickness is up to 6.4nm), because of
And there is preferable hydrothermal stability.
Hexagonal mesoporous silicon HMS has long-range order and the most unordered hexagonal mesoporous duct of short distance, and its hole wall compares HCM41S
Type mesoporous material is thicker, thus hydrothermal stability is more preferable, and short distance is the most unordered simultaneously organizational structure and aperture modulation scope are more
Greatly, make HMS material have higher molecular transport efficiency and absorption property, be suitable in the activity as bulky molecular catalysis reaction
The heart.
The present invention, from each mesoporous material, carries out compound pairing, screens through widely, filter out MSU-G, SBA-15
With the compound of HMS or mixing.Inventor finds, in numerous complex/mixture, and only MSU-G, SBA-15 and HMS tri-
Compound or the mixing of person, could realize the collaborative lifting of hydrofinishing effect, and enables to catalysis activity and do not reduce for a long time, makes
Can be greatly increased with the life-span.In other words, the only specific compound or mixing of MSU-G, SBA-15 and HMS three of the present invention,
Solve collaborative and two technical problems in service life the most simultaneously.Other coordinate, or do not possess synergism, or use the longevity
Order shorter.
Described complex, can use being simply mixed of MSU-G, SBA-15 and HMS three, it would however also be possible to employ be combined two-by-two
After mixing, such as MSU-G/SBA-15 complex, the mixing of MSU-G/HMS and SBA-15/HMS complex.Described being combined can
To use known electrostatic matching method, ion exchange, two step crystallization methods etc. to be prepared.These mesopore molecular sieves are combined with it
The preparation method of thing is the known method of catalyst field, and the present invention no longer repeats with regard to it.
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28-
0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
In the range of Gai, sulfur content in aerial kerosene can be realized and control at below 10ppm and denitrification ability notable.It is to say, this
Four kinds of active components of invention are only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just possess association
Same effect.Outside this molar ratio range, or omit or replace any one component, all can not realize cooperative effect.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-
0.5): (0.35-0.45): (0.8-1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0),
Preferably 1:0.48:0.42:0.95.
The total content of described active component is the 1%-15% of vehicle weight, preferably 3-12%, further preferred 5-10%.
Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%,
7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%,
14%, 14.5% etc..
An object of the present invention also resides in the promoter providing described catalyst.Catalyst of the present invention also contains
Having catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its
For regulating the character of carrier, weaken interaction strong between metal and carrier, improve the surface texture of catalyst, improve metal
Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps
Agent application with the carrier of the present invention with active component time, for high-sulfur component, it promotes the effect of catalytic desulfurization/refined
?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounding,
Find eventually to use TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy
Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improve its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that TiO2、CeO2、V2O5With
NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention uses2、CeO2、V2O5And NbOPO4
Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching
To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting
During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water
Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass
System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5,
Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it
Difference, its beds coking is relatively rapid, thus causes catalyst duct to block, and beds pressure drop rise is relatively
Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal
Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop
Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce catalysis
Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention.
Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase
To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid,
Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention
Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine
The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 280-300 DEG C, and hydrogen dividing potential drop is 3.0-
3.4MPa, hydrogen to oil volume ratio 180-220, volume space velocity 2.0-4.0h-1。
Preferably, described technological process includes, virgin kerosene, after filter, surge tank, is pumped into heat exchanger by feed pump
With product boat coal heat exchange, after heat exchange, it is mixed to form hydrogen oil mixture with recycle hydrogen and new hydrogen, again laggard with product heat exchange
Enter heating furnace, be heated to reaction temperature and enter hydrofining reactor (fixed bed reactors), hydrogen oil mixture in the reactor
Under catalyst action, the reaction such as carry out that hydrodesulfurization, denitrogenation, deoxidation, alkene is saturated and aromatic hydrocarbons is saturated, product is through changing
Heat, more water cooled to predetermined temperature, enter high-pressure separator, high-pressure separator top gas phase returns recycle hydrogen as recycle hydrogen and delays
Rushing tank, oil phase enters low pressure separator, and the generation oil drawn bottom low pressure separator enters stripper after product heat exchange,
Tower top oil gas enters separatory tank after air cooling, water-cooled and obtains Petroleum, and stripping tower bottom obtains aerial kerosene.
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrofining technology of the present invention is by choosing specific catalyst, and described catalyst is by choosing special ratios
MSU-G, SBA-15 and HMS complex/mixture is as carrier, and chooses the nitridation two molybdenum MO of special ratios2N, tungsten nitride
W2N, molybdenum carbide Mo2C and tungsten carbide wc are as active component, and described catalyst is possibly together with catalyst aid, and described catalyst aid is
TiO2、CeO2、V2O5And NbOPO4Mixture so that this catalyst produce cooperative effect, the hydrodesulfurization energy to aerial kerosene
Control at total sulfur content less than 5ppm, the total nitrogen content in aerial kerosene is controlled within 10ppm simultaneously.
Detailed description of the invention
The hydrofining technology of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is the mixture of MSU-G, SBA-15 and HMS, and mixed proportion is 1:
1.1:0.5.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is carrier
The 10% of quality, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Becoming, beds is set to 3 layers, and reaction bed temperature UGU808 type temp controlled meter is measured, and raw material aerial kerosene is by north
The double plunger micro pump of capital satellite manufactory manufacture carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-by gas cylinder
11A/ZM mass-flow gas meter coutroi velocity, loaded catalyst is 2kg.Reacted product is laggard through the cooling of water-bath room temperature
Row gas-liquid separation.
Raw materials used for virgin kerosene, its total sulfur content 267ppm, basic n content is 299ppm.
Controlling reaction condition is: temperature 300 DEG C, hydrogen dividing potential drop 3.2MPa, hydrogen to oil volume ratio 200, volume space velocity 2h-1。
Testing final product, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 7ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is MSU-G/SBA-15 complex, MSU-G/HMS and SBA-15/
The mixing of HMS complex, wherein the ratio of MSU-G, SBA-15 and HMS is same as in Example 1.Described active component nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The total content of C and tungsten carbide wc is the 10% of carrier quality, and its mol ratio is 1:0.6:
0.45):1.2。
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 4ppm, and total alkaline nitrogen content is reduced to 5ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with MSU-G, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 38ppm, and total alkaline nitrogen content is reduced to 31ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with SBA-15, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 31ppm, and total alkaline nitrogen content is reduced to 25ppm.
Comparative example 3
The carrier of embodiment 1 is replaced with HMS, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 42ppm, and total alkaline nitrogen content is reduced to 39ppm.
Comparative example 4
Carrier in embodiment 1 is replaced with MSU-G/SBA-15 complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 39ppm, and total alkaline nitrogen content is reduced to 47ppm.
Comparative example 5
Carrier in embodiment 1 is replaced with SBA-15/HMS complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 38ppm, and total alkaline nitrogen content is reduced to 45ppm.
Comparative example 6
Carrier in embodiment 1 is replaced with MSU-G/HMS complex, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 30ppm, and total alkaline nitrogen content is reduced to 34ppm.
Embodiment 1 shows with comparative example 1-6, and the present invention uses MSU-G, SBA-15 and HMS complex of special ratios/mixed
Compound is as carrier, when replacing with single carrier or complex carrier two-by-two, does not all reach the technique effect of the present invention, therefore originally
MSU-G, SBA-15 and HMS complex/mixture of the special ratios of invention has as between carrier and other components of catalyst
Standby cooperative effect, described hydrofining technology creates unforeseeable technique effect.
Comparative example 7
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 32ppm, and total alkaline nitrogen content is reduced to 48ppm.
Comparative example 8
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 34ppm, and total alkaline nitrogen content is reduced to 42ppm.
Above-described embodiment and comparative example 7-8 explanation, several active component of catalyst of the hydrofining technology of the present invention it
Between there is specific contact, be omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that it produces
Give birth to cooperative effect.
Embodiment 3
Containing catalyst aid TiO in catalyst2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 1% and
3%, remaining is same as in Example 1.
Testing final product, after it uses 3 months, beds pressure drop is not any change, and uses compared to same
The beds pressure drop of time embodiment 1 reduces 12%.
Comparative example 9
Compared to embodiment 3, by NbOPO therein4Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 3.7%.
Comparative example 10
Compared to embodiment 3, by CeO therein2Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 4.3%.
Embodiment 3 shows with comparative example 9-10, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted
When one of them or several component, all can not reach the minimizing coking when present invention adds catalyst aid thus stop catalyst bed
The technique effect that lamination falling-rising is high.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst,
And other catalyst aid effects are not as this specific catalyst aid.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in
Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art
Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool
Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (7)
1. an aerial kerosene hydrofining technology, described technique uses fixed bed reactors, is filled with in fixed bed reactors
Hydrogenation catalyst, described catalyst includes carrier and active component, it is characterised in that
Described carrier is complex or the mixture of MSU-G, SBA-15 and HMS, and described active component is nitridation two molybdenum MO2N, nitrogen
Change tungsten W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described catalyst is possibly together with catalyst aid, and described catalyst aid is
TiO2、CeO2、V2O5And NbOPO4Mixture；
The reaction condition of described fixed bed reactors is: reaction temperature is 260-320 DEG C, and hydrogen dividing potential drop is 2.8-3.6MPa, hydrogen oil
Volume ratio 150-250, volume space velocity 2.0-4.0h-1。
2. hydrofining technology as claimed in claim 1, it is characterised in that the weight ratio of MSU-G, SBA-15 and HMS is 1:
(0.8-1.2): (0.4-0.7), preferably 1:(1-1.15): (0.5-0.7).
3. hydrofining technology as claimed in claim 1, it is characterised in that the total content of described active component is vehicle weight
3-12%, preferably 5-10%.
4. hydrofining technology as claimed in claim 1, it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide
Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5): (0.35-0.45): (0.8-1.0), more preferably 1:
(0.45-0.48): (0.4-0.45): (0.9-1.0), most preferably 1:0.48:0.42:0.95.
5. hydrofining technology as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is:
Reaction temperature is 280-300 DEG C, and hydrogen dividing potential drop is 3.0-3.4MPa, hydrogen to oil volume ratio 180-220, volume space velocity 2.0-4.0h-1。
6. hydrofining technology as claimed in claim 1, it is characterised in that described fixed bed reactors include 1-5 catalysis
Agent bed, preferably includes 2-3 beds.
7. hydrofining technology as claimed in claim 1, it is characterised in that TiO2、CeO2、V2O5And NbOPO4Respective content
It is respectively the 1-7%, preferably 2-4% of carrier quality.
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Application publication date: 20170111 |