CN106244213A - A kind of aerial kerosene hydrofining technology - Google Patents
A kind of aerial kerosene hydrofining technology Download PDFInfo
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- CN106244213A CN106244213A CN201610691359.7A CN201610691359A CN106244213A CN 106244213 A CN106244213 A CN 106244213A CN 201610691359 A CN201610691359 A CN 201610691359A CN 106244213 A CN106244213 A CN 106244213A
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- catalyst
- sapo
- fixed bed
- bed reactors
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- 239000003350 kerosene Substances 0.000 title claims abstract description 30
- 238000005516 engineering process Methods 0.000 title claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 22
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- -1 tungsten nitride Chemical class 0.000 claims abstract description 13
- 229910020057 NbOPO4 Inorganic materials 0.000 claims abstract description 12
- 239000000203 mixture Substances 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 7
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 3
- 238000010348 incorporation Methods 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 28
- 239000011593 sulfur Substances 0.000 abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 238000006477 desulfuration reaction Methods 0.000 abstract description 5
- 230000023556 desulfurization Effects 0.000 abstract description 4
- 241000269350 Anura Species 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 22
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 239000010779 crude oil Substances 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- 235000016768 molybdenum Nutrition 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 230000002079 cooperative effect Effects 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
- 230000007547 defect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000007670 refining 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
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 238000001802 infusion 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
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000002199 base oil Substances 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010457 zeolite Substances 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
- 229910002796 Si–Al Inorganic materials 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
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000005341 cation exchange Methods 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
- 239000013078 crystal Substances 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
- 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
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 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
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 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
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- 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
- B01J21/066—Zirconium or hafnium; 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
- 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
- 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
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- C10G2300/70—Catalyst aspects
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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of aerial kerosene hydrofining technology, described technique uses fixed bed reactors, is filled with hydrogenation desulfurization and denitrogenation catalyst in fixed bed reactors, and described catalyst includes carrier and active component;Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+SAPO 5;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 Cr2O3、ZrO2、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 to oil volume ratio 150 250, volume space velocity 2.0 4.0h‑1.Aerial kerosene total sulfur content can be controlled, less than 5ppm, to control the total nitrogen content in aerial kerosene within 10ppm by this technique simultaneously.
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 incorporation hetero atom Co in synthetic bone shelf structure2+SAPO-5.Described active component is nitridation two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.Described catalyst possibly together with catalyst aid, described in urge
Change auxiliary agent is Cr2O3、ZrO2、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 to oil volume ratio 150-250, volume space velocity 2.0-4.0h-1。
SAPO-5 molecular sieve is the one in SAPO (SAPO) Series Molecules sieve, and its channel system is by six sides couple
The twelve-ring that the four-membered ring of title property and hexatomic ring are constituted is constituted, and has large aperture structure, and its aperture is 0.8nm.SAPO-5
Acidic zeolite is gentle, and has faint controllability, also has cation exchange capacity (CEC).In a way, its materialization
Character not only has the characteristic of aluminophosphate molecular sieve, and also is similar to the characteristic of Si-Al zeolite.Owing to it has novel
Crystal structure, good heat stability and hydrothermal stability, in meta-xylene isomerization and normal hexane catalytic pyrolysis etc. react
Tool is widely used.But it is used for hydrofinishing rather than hydrocracking field, rarely seen document is reported.
The present invention through in numerous silicoaluminophosphamolecular molecular sieves, such as SAPO-11, SAPO-17, SAPO-20, SAPO-31,
SAPO-34, SAPO-44, SAPO-46, SAPO-47 etc., carry out contrast test selection one by one, finds that only SAPO-5 can reach
The goal of the invention of the present invention, other mesoporous materials have such-and-such defect, exist when being applied in the present invention and are difficult to gram
The technical difficulty of clothes, therefore the present invention selects to turn the SAPO-5 modification being used for being hydrocracked to do for hydrorefined carrier base
Plinth.
Inventor finds through research, for affecting the silica alumina ratio of silicoaluminophosphamolecular molecular sieves performance, phosphorus aluminum ratio, in the present invention
In, after being modified, the change of silica alumina ratio and phosphorus aluminum ratio is less to hydrofinishing influential effect, and therefore the present invention is no longer to sial
It is defined than with phosphorus aluminum ratio.For ease of the explanation present invention, typically it is defined to mol ratio and is respectively less than 1.
Owing to existing SAPO-5 molecular sieve catalytic temperature is high, and being easily caused raw material hydrocracking, therefore, the present invention is to it
Being modified, to increase its catalysis activity, reduce catalytic temperature and make it be applicable to catalytic refining, minimizing is hydrocracked.This
The bright approach to the modification of SAPO-5 mesopore molecular sieve is: introduce to the total silicon SAPO-5 mesopore molecular sieve duct inner surface of finished product
Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of SAPO-5, thus improves on the whole
Catalysis activity, absorption and the Thermodynamically stable performance etc. of SAPO-5 mesopore molecular sieve.
Although the method being modified SAPO-5 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges
Agent can only use doping Cu2+SAPO-5 could realize sulfur content as carrier and control and the balance of loss of octane number, invention
People has attempted adulterating in SAPO-5: Ca2+、Fe3+、Zn2+、Ti2+、Ga3+And alkali metal etc. produces anionic surface center
Ion, finds all to realize described effect.Although described mechanism is current and unclear, but this has no effect on the reality of the present invention
Executing, inventor is according to well-known theory and it is experimentally confirmed that there is cooperative effect between itself and the active component of the present invention.
Described Co2+Doping in SAPO-5 must control within specific content range, and its doping is with weight
Meter, for the 0.56%-0.75% of SAPO-5 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%,
0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%,
0.74 etc..
Inventor finds, outside this range, can cause drastically reducing of aerial kerosene desulfurized effect.More pleasurable
It is to work as Co2+When doping in SAPO-5 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when draw with
Co2+Doping is transverse axis, and during curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content can control extremely low
Within the scope of, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier S APO-5 weight, preferably 3-12%, further preferably
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..
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 three of the purpose of the present invention are to provide the promoter of described catalyst.Catalyst of the present invention possibly together with
Catalyst aid, described catalyst aid is Cr2O3、ZrO2、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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) the catalyst facilitation to the present invention
Substantially, its hydrothermal stability can be significantly improved, and improve its anti-coking deactivation, thus improve its service life.
Described Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that Cr2O3、ZrO2、
CeO2、V2O5And NbOPO4Each respective content reaches effective dose.Preferably, the Cr that the present invention uses2O3、ZrO2、
CeO2、V2O5And NbOPO4Respective 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 mixing hetero atom Co2+
SAPO-5 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
As active component, described catalyst is possibly together with catalyst aid, and described catalyst aid is Cr2O3、ZrO2、CeO2、V2O5With
NbOPO4Mixture so that this catalyst produce cooperative effect, the hydrodesulfurization to aerial kerosene can 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 doping Co2+SAPO-5, Co2+Doping in SAPO-5
Control at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, 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 8ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+SAPO-5, Co2+Doping in SAPO-5
Control at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, 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 2ppm, and total alkaline nitrogen content is reduced to 7ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, total sulfur content is reduced to 33ppm, and total alkaline nitrogen content is reduced to 41ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated SAPO-5, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 30ppm, and total alkaline nitrogen content is reduced to 39ppm.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 27ppm, and total alkaline nitrogen content is reduced to 42ppm.
Comparative example 4
By the Co in embodiment 12+Doping in SAPO-5 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 38ppm, and total alkaline nitrogen content is reduced to 44ppm.
Comparative example 5
By the Co in embodiment 12+Doping in SAPO-5 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 36ppm, and total alkaline nitrogen content is reduced to 48ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion
SAPO-5 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+During doping difference, all reach
Less than the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping SAPO-5 carrier and catalyst other
Possessing cooperative effect between component, described hydrofining technology creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 41ppm, and total alkaline nitrogen content is reduced to 49ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 42ppm, and total alkaline nitrogen content is reduced to 46ppm.
Above-described embodiment and comparative example 6-7 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 Cr in catalyst2O3、ZrO2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 2%,
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 16.2%.
Comparative example 8
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 9
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 2.4%.
Embodiment 3 shows with comparative example 8-9, 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 incorporation hetero atom Co in synthetic bone shelf structure2+SAPO-5, described active component for nitridation two molybdenum MO2N、
Tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc, described catalyst possibly together with catalyst aid, described catalyst aid
For Cr2O3、ZrO2、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 hetero atom Co2+Doping be SAPO-5 weight
0.63%-0.72%.
3. hydrofining technology as claimed in claim 1, it is characterised in that the total content of described active component is carrier
The 3-12% of SAPO-5 weight, 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 Cr2O3、ZrO2、CeO2、V2O5And NbOPO4Each
Content be respectively the 1-7%, preferably 2-4% of carrier quality.
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