CN106479561A - A kind of diesel hydrogenation for removal sulphur denitrification process - Google Patents
A kind of diesel hydrogenation for removal sulphur denitrification process Download PDFInfo
- Publication number
- CN106479561A CN106479561A CN201610689481.0A CN201610689481A CN106479561A CN 106479561 A CN106479561 A CN 106479561A CN 201610689481 A CN201610689481 A CN 201610689481A CN 106479561 A CN106479561 A CN 106479561A
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- China
- Prior art keywords
- catalyst
- fixed bed
- sapo
- bed reactors
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- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 17
- 239000005864 Sulphur Substances 0.000 title claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 80
- 239000002283 diesel fuel Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 25
- 230000023556 desulfurization Effects 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 tungsten nitride Chemical class 0.000 claims abstract description 13
- 229910020057 NbOPO4 Inorganic materials 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 239000010937 tungsten Substances 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 7
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000009432 framing Methods 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 abstract description 32
- 229910052717 sulfur Inorganic materials 0.000 abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 12
- 241000269350 Anura Species 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 30
- 238000012360 testing method Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012467 final product Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 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
- 235000016768 molybdenum Nutrition 0.000 description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 238000004939 coking Methods 0.000 description 5
- 230000002079 cooperative effect Effects 0.000 description 5
- 239000007789 gas Substances 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 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
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle 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
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003225 biodiesel Substances 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
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000003502 gasoline Substances 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
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-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
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 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
- 238000007639 printing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011435 rock Substances 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
- 239000000126 substance Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
-
- B01J35/19—
-
- 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
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a kind of diesel hydrogenation for removal sulphur denitrification process, described technique includes carrier and active component using the fixed bed reactors being filled with hydrogenation desulfurization and denitrogenation catalyst, described catalyst；Described carrier is to mix hetero atom Cu in synthesis framing 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 contains catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture；The reaction condition of described fixed bed reactors：320 360 DEG C of reaction temperature, reaction pressure 6 8MPa, hydrogen to oil volume ratio 300 600, volume space velocity 1.0 2.5h‑1.Diesel oil total sulfur content can be controlled less than 5ppm by this technique, and the total nitrogen content in diesel oil is controlled within 10ppm.
Description
Technical field
The present invention relates to diesel hydrogenation for removal sulphur denitrification process is and in particular to a kind of taken off using the hydrogenation that special catalyst is carried out
Sulfur denitrification process.
Background technology
Enter 21st century, the demand of fuel oil and use increase substantially, and sulfur-containing compound therein is brought
Problem of environmental pollution, more cause the concern of people.The oxysulfide that sulfide in fuel oil produces through engine combustion
(SOx) it is discharged in the air, produce acid rain and the pollution of fumes of sulphuric acid type etc., cause atmospheric pollution.
Sulfur is that nature is present in one of gasoline harmful substance, and Beijing rate in 1 day January in 2008 first carries out phase
When in the capital IV cleaning diesel oil standard (sulfur content≤50mg/g) of the Europe IV standard, on May 5th, 2016, the Committee of Development and Reform, the Ministry of Finance, ring
Department of guarantor portion etc. seven issues with regard to printing and distributing《Accelerate product oil quality upgrading programme of work》Notify, scheme clearly expand automobile-used vapour,
Diesel oil state five standard execution scope.Expand whole eastern region from original Jing-jin-ji region, the Yangtze River Delta, Pearl River Delta region key cities to
11 provinces and cities (Beijing, Tianjin, Hebei, Liaoning, Shanghai, Jiangsu, Zhejiang, Fujian, Shandong, Guangdong and Hainan).In October, 2015
Before 31 days, eastern region is protected possesses manufacturing country five standard motor petrol (oil of blend component containing ethanol petrol), automobile-used bavin for enterprise
The ability of oil.From 1 day January in 2016, the motor petrol (ethanol vapor containing E10 meeting state five standard is supplied in eastern region comprehensively
Oil), derv fuel (biodiesel containing B5).The Europe V diesel oil that total sulfur content is not more than 10ppm was carried out in Europe in 2009
Standard.So, produce ultra-low sulfur diesel oil have become as domestic oil refining enterprises institute must faced by realistic problem.
At present, the method producing ultra-low sulfur diesel oil mainly includes hydrofinishing, oxidation sweetening, selective absorption, life
Thing desulfurization etc..But most effective, the most economical sulfur method that hydrodesulfurization (HDS) technology is well recognized as.Research finds, in diesel oil
The organic sulfur compound being most difficult to remove is 4 and (or) 4, the oil-source rock correlation that 6 alkyl replace, this kind of sulfide due to
There is the sterically hindered of alkyl when adsorbing on catalyst activity position, hinder reactant molecule connecing on adsorption activity position
Nearly property, so that its hydrodesulfurization activity is low；Theoretical research also finds, Ni, Co, Mo are mutually layers with the hydrogenation activity of W sulfide
The MoS of shape stacking2And WS2Nanoparticle, MoS2The appropriate stacking of nanoparticle contributes to reactant molecule on adsorption activity position
Accessibility and highly active II class activity phase formation.
External diesel hydrogenation for removal sulphur technology commonly uses double base or multicomponent catalyst at present, belongs to middle pressure depth and ultra-deep
One section or two-stage desulfurization process, this process moreover it is possible to reduce nitrogen and polycyclic aromatic hydrocarbon, improves Cetane number in addition to desulfurization.It can
The raw material ratio of processing is wide, can process straight run oil, also can process cracking fraction oil.Product sulfur content is：Using depth
Hydrodesulfurization, less than 500 μ g/g；Using one section of ultra-deep hydrodesulfuration, less than 30 μ g/g.If acceptable using two sections of technology
Reduce polycyclic aromatic hydrocarbon and improve Cetane number.
Triumphant King Company of Japan develops STARS hydrogenation catalyst technology, on this basis two kinds of catalyst of industrialization, that is,
KF-757 Ultra-deep Desulfurization of Diesel Fuels catalyst and the KF-848 refining catalytic with high desulfurization, denitrogenation, Tuo Fang and hydrogenation activity
Agent, is applicable not only to hydro-refining unit, and is applied to the raw material prerefining being hydrocracked, FCC feedstock weighted BMO spaces etc..
For high-pressure diesel hydrogenation plant, its diesel oil sulfur content can be removed to 50ppm or lower, to reduce refined diesel oil density and
Depth takes off virtue fabulous effect.
Rope company of Top of Denmark catalyst newly developed has TK-554 (deep desulfuration), TK-574 (ultra-deep desulfurization), TK-
573 (deep desulfurations), TK-907 (aromatic hydrocarbons saturation and raising Cetane number) and TK-908 (aromatic hydrocarbons saturation and raising Cetane number)
Deng.Wherein TK-574 high activity cobaltmolybdate catalyst is ultra-deep desulfurization catalyst, than TK-544 deep desulfurization catalyst opposite bank
Long-pending activity improves 30%～40%, adopts TK-544 catalyst, can make product on the diesel device producing sulfur content 500 μ g/g
Product sulfur content is down to 350 μ g/g.
American Association catalyst Co. AS-AT desulfurization removing nitric Porous deproteinized bone three function catalyst newly developed, deep for diesel oil
Degree desulfurization take off virtue device second reactor (first reactor desulfurization takes off to below 50 μ g/g), can make total aromatic hydrocarbons take off to 10% with
Under, sulfur takes off to below 10 μ g/g.Typical operation conditions are：316 DEG C of reaction temperature, pressure 6.18MPa, liquid hourly space velocity (LHSV) is less than 2h-1,
Hydrogen-oil ratio 712.
Currently commonly used both at home and abroad poor ignition quality fuel modification means are hydrofinishing and hydro-upgrading.Hydrofinishing can be bright
Aobvious color and the stability improving product, but it is limited to be limited Cetane number increase rate by thermodynamics of reactions, therefore passes through to add
Hydrogen refines far from meeting the requirement to product Cetane number for the enterprise.Improve cetane number of inferior diesel oil, desulfurization for oil plant
The demand of denitrogenation Porous deproteinized bone, American Standard Inc. be proposed MHUG hydro-upgrading technology and DN3110 Hydrobon catalyst,
Z5723 gas reversion catalyst, and obtained first time commercial Application in 2000.The DN3110 hydrofinishing catalysis of Standard Co., Ltd
Agent, Z5723 gas reversion catalyst are the one kind adopting CENTINEL technology and the production of actiCAT pre-curing technology with aluminium oxide
For the nickel molybdenum pre-sulfide catalyst of carrier, CENTINEL key problem in technology is than general catalyst in terms of active metal dispersion
More preferably it is easier to convert metal oxides are metal sulfide.And actiCAT part pre-curing technology, it is in catalyst
Sulfur-loaded in production, is opening utilization of hour catalyst self-contained sulfur to realize the sulfuration of catalyst it is not necessary to catalyst
It is dried it is not necessary to additionally inject vulcanizing agent, and soak time is shorter, so will make that device is quick, easily and safely drive.
How a kind of diesel hydrogenation for removal sulphur technique is therefore provided, can effectively by the sulfur content in diesel oil control 10ppm with
Under, to meet state five standard, can effectively remove the nitride in diesel oil simultaneously, be the difficult problem that this area faces.
Content of the invention
It is an object of the invention to proposing a kind of diesel hydrogenation for removal sulphur denitrification process, this technique can will be total in diesel oil
Sulfur content is reduced to below 10ppm, to meet diesel oil state five standard.Meanwhile, this technique adopt catalyst also make diesel oil
The removing of middle nitride is than more significant.
For reaching this purpose, the present invention employs the following technical solutions：
A kind of diesel hydrogenation for removal sulphur denitrification process, described technique adopts fixed bed reactors, loads in fixed bed reactors
There is hydrogenation catalyst, described catalyst includes carrier and active component.
Described carrier is to mix hetero atom Cu in synthesis framing 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 also contains catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixing
Thing.
The reaction condition of described fixed bed reactors is：Reaction temperature is 320-360 DEG C, reaction pressure 6-8MPa, hydrogen oil
Volume ratio 300-600, volume space velocity 1.0-2.5h-1.
SAPO-5 molecular sieve is one of 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 is constituted with hexatomic ring is constituted, and has macropore gauge 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
Property not only has the characteristic of aluminophosphate molecular sieve, and also the characteristic similar to Si-Al zeolite.Due to its have new
Crystal structure, good heat stability and hydrothermal stability, in the reaction such as meta-xylene isomerization and normal hexane catalytic pyrolysiss
Tool is widely used.But it is used for hydrofinishing rather than hydrocracking field, rarely seen document report.
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, find only have 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, the therefore present invention select to do modified for the SAPO-5 being used for being hydrocracked turning for hydrorefined carrier base
Plinth.
Inventor finds through research, for the silica alumina ratio of impact silicoaluminophosphamolecular molecular sieves performance, phosphorus aluminum ratio, in the present invention
In, modified after, 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 present invention is described, typically it is defined to mol ratio and is respectively less than 1.
Because existing SAPO-5 molecular sieve catalytic temperature is high, and it is easily caused raw material hydrocracking, therefore, the present invention is to it
It is modified, to increase its catalysis activity, reduce catalytic temperature and make it be applied to catalytic refining, minimizing is hydrocracked.This
The bright approach modified to SAPO-5 mesopore molecular sieve be：Introduce to the total silicon SAPO-5 mesopore molecular sieve duct inner surface of finished product
Cu2+, this approach can be by ion exchange by Cu2+It is supported on the inner surface of SAPO-5, thus improving on the whole
The catalysis activity of SAPO-5 mesopore molecular sieve, absorption and Thermodynamically stable performance etc..
Although the method that SAPO-5 mesopore molecular sieve is modified or approach are a lot, inventor finds, the present invention urges
Agent can only be using doping Cu2+SAPO-5 just enable sulfur content as carrier and control and the balance of loss of octane number, invention
People has attempted doping in SAPO-5：Ca2+、Fe3+、Zn2+、Ti2+、Ga3+And alkali metal etc. produces anionic surface center
Ion, finds not enabling described effect.Although described mechanism is not known at present, this has no effect on the reality of the present invention
Apply, according to well-known theory and it is experimentally confirmed that it has cooperative effect and the active component of the present invention between to inventor.
Described Cu2+Must control within specific content range in the doping in SAPO-5, its doping is with weight
Meter, be 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%th, 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 lead to drastically reducing of diesel oil denitrogenation and desulfurized effect.More pleasurable
, work as Cu2+When the doping in SAPO-5 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, works as drafting
With Cu2+When doping is transverse axis, curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content can control in pole
Within the scope of low, the desulfurized effect that it produces, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is 1%-15%, the preferably 3-12% of carrier S APO-5 weight, further preferably
5-10%.For example, described content can for 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%th, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%th, 14%, 14.5% etc..
In the present invention, being particularly limited to active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor finds, 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
Should in the range of, can realize that in diesel oil, sulfur content controls in below 10ppm and denitrification ability is notable.That is, the present invention
Four kinds of active components only mol ratio be 1:(0.4-0.6):(0.28-0.45):(0.8-1.2), when, just possesses collaborative effect
Should.Outside this molar ratio range, or omit or replace any one component, do not enable 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 third object of the present invention is to provide the promoter of described catalyst.Catalyst of the present invention also contains
There is catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, there is a catalyst aid of maturation, such as P, F and B etc., its
For adjusting the property of carrier, weaken strong interaction 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 in application with the carrier of the present invention with active component when, for high sulphur 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, compounds,
Find eventually to adopt 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 improving its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no the ratio of fixation that is to say, that TiO2、CeO2、V2O5With
NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention adopts2、CeO2、V2O5And NbOPO4
Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although not having specific proportion requirement between catalyst aid of the present invention, each auxiliary agent allows for reaching
To the requirement of effective dose, the content of catalyst aid effect, the 1-7% of such as carrier quality can be played.The present invention is selecting
During find, omitting or replacing one or more of described auxiliary agent, the technique effect all not reaching the present invention (improves water
Heat stability, reduces coking and improves service life) close that is to say, that there is specific cooperation between the catalyst aid of the present invention
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 leading to catalyst duct to block, beds pressure drop rise is relatively
Hurry up.The present invention also once attempted introducing other phosphate, although this attempt introducing phosphate anion, but equally existed hydro-thermal
Stability is relatively slightly worse, and its beds coking is relatively rapid, thus leading to catalyst duct to block, beds pressure drop
Rise relatively fast.
Although present invention introduces catalyst aid has so many advantage, the present invention should be noted that, introduces 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.
Do not introduce the catalyst aid particularly niobium phosphate of the present invention,, compared to the scheme introducing catalyst aid, its defect is only phase for it
To.I.e. this defect be with respect to introduce catalyst aid after defect, its with respect to other prior arts outside the present invention,
Institute mentioned by the present invention is advantageous or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention
Indispensable technological means, it is optimization further to technical solution of the present invention, solves new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods of routine, people in the art
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 340-350 DEG C, reaction pressure 6.5-
7.5MPa, hydrogen to oil volume ratio 400-600, volume space velocity 1.5-2.0h-1.
Preferably, described technological process includes, after diesel oil is mixed with hydrogen, through optional heat exchanger heat exchange more heated
Enter fixed bed reactors after stove heat and carry out hydrogenation desulfurization and denitrogenation, product separates through gas-liquid separation tower.Optionally, gas phase
Return and mix with diesel oil and hydrogen, liquid phase can further be refined, such as amine washes, strip and fractional distillation etc..
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrogenation desulfurization and denitrogenation technique of the present invention is passed through to choose specific catalyst, and described catalyst passes through to mix hetero atom
Cu2+SAPO-5 as carrier, and the nitridation two molybdenum MO choosing special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and carbonization
Tungsten WC also contains catalyst aid as active component, described catalyst, and described catalyst aid is TiO2、CeO2、V2O5With
NbOPO4Mixture；Make this catalyst produce cooperative effect, the hydrodesulfurization of diesel oil can be controlled and be less than in total sulfur content
5ppm, controls within 10ppm to the total nitrogen content in diesel oil simultaneously.
Specific embodiment
The present invention is illustrated to the hydrogenation desulfurization and denitrogenation technique of the present invention by following embodiments.
Embodiment 1
Catalyst is prepared by infusion process, carrier is doping Cu2+SAPO-5, Cu2+Doping in SAPO-5
Control 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 be carrier quality 10%, its mol ratio be 1:0.4:0.3:0.8.
Described Catalyst packing is entered fixed bed reactors, the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Become, beds are set to 3 layers, reaction bed temperature is measured with UGU808 type temp controlled meter, and raw material diesel oil is by Bei Jingwei
The double plunger micro pump continuous conveying that star maker manufactures, hydrogen is supplied by gas cylinder and uses Beijing Sevenstar-HC D07-11A/
ZM gas mass flow gauge coutroi velocity, loaded catalyst is 2kg.Reacted product cools down laggard circulation of qi promoting through water-bath room temperature
Liquid separates.
Raw materials used for straight-run diesel oil, its total sulfur content 788 μ g/g, basic n content is 499.8 μ g/g.
Control reaction condition be：350 DEG C of temperature, reaction pressure 7.0MPa, hydrogen to oil volume ratio 500, volume space velocity 2h-1.
Test final product, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 10ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is doping Cu2+SAPO-5, Cu2+Doping in SAPO-5
Control 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 be carrier quality 10%, its mol ratio be 1:0.6:0.45):1.2.
Remaining condition is same as Example 1.
Test final product, total sulfur content is reduced to 4ppm, and total alkaline nitrogen content is reduced to 9ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Test final product, total sulfur content is reduced to 24ppm, and total alkaline nitrogen content is reduced to 45ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated SAPO-5, remaining condition is constant.
Test final product, total sulfur content is reduced to 21ppm, and total alkaline nitrogen content is reduced to 32ppm.
Comparative example 3
Cu by embodiment 12+Replace with Zn2+, remaining condition is constant.
Test final product, total sulfur content is reduced to 33ppm, and total alkaline nitrogen content is reduced to 43ppm.
Comparative example 4
By the Cu in embodiment 12+Doping in SAPO-5 controls the 0.5% of carrier quality, and remaining condition is constant.
Test final product, total sulfur content is reduced to 36ppm, and total alkaline nitrogen content is reduced to 49ppm.
Comparative example 5
By the Cu in embodiment 12+Doping in SAPO-5 controls the 0.8% of carrier quality, and remaining condition is not
Become.
Test final product, total sulfur content is reduced to 33ppm, and total alkaline nitrogen content is reduced to 42ppm.
Embodiment 1 and comparative example 1-5 show, certain content scope and certain loads metal ions that the application adopts
SAPO-5 carrier, when replacing with other known carriers of this area, or carrier is identical but Cu2+When doping is different, all reach
Less than the technique effect of the present invention, the therefore Cu of the certain content scope of the present invention2+Doping SAPO-5 carrier and catalyst other
Possesses cooperative effect, described hydrogenation desulfurization and denitrogenation technique creates unforeseeable technique effect between component.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Test final product, total sulfur content is reduced to 41ppm, and total alkaline nitrogen content is reduced to 49ppm.
Comparative example 7
Omit the WC in embodiment 1, remaining condition is constant.
Test final product, total sulfur content is reduced to 36ppm, and total alkaline nitrogen content is reduced to 47ppm.
Above-described embodiment and the explanation of comparative example 6-7, several activearm of catalyst of the hydrodesulfurization of the present invention divides it
Between exist 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 its product
Give birth to cooperative effect.
Embodiment 3
Catalyst aid TiO is contained in catalyst2、CeO2、V2O5And NbOPO4, its content respectively 1%, 1.5%, 1% and
3%, remaining is same as Example 1.
Test final product, after it uses 3 months, beds pressure drop is not any change, use compared to same
The beds pressure drop of time embodiment 1 reduces 18%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time
The beds pressure drop applying example 1 only reduces 7%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omit, remaining condition is identical.
Test final product, after it uses 3 months, beds pressure drop raises, real compared to same use time
The beds pressure drop applying example 1 only reduces 4%.
Embodiment 3 and comparative example 8-9 show, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted
One of or several groups of timesharing, all can not reach the present invention and add minimizing coking during catalyst aid thus stoping catalyst bed
The high technique effect of lamination falling-rising.That is, it demonstrates the service life that the catalyst aid of the present invention can improve described catalyst,
And other catalyst aid effects are not so good 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, that is, do not 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, the equivalence replacement to each raw material of product of the present invention 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 (8)
1. a kind of diesel hydrogenation for removal sulphur denitrification process is it is characterised in that described technique adopts fixed bed reactors, fixed bed reaction
It is filled with hydrogenation desulfurization and denitrogenation catalyst, described catalyst includes carrier and active component in device；
Described carrier is to mix hetero atom Cu in synthesis framing 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 also contains catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture；
The reaction condition of described fixed bed reactors is：Reaction temperature is 320-360 DEG C, reaction pressure 6-8MPa, hydrogen oil volume
Ratio 300-600, volume space velocity 1.0-2.5h-1.
2. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1 is it is characterised in that hetero atom Cu2+Doping be SAPO-5
The 0.63%-0.72% of weight.
3. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1 is 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. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1 is it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, carbonization
Molybdenum 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. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1 is it is characterised in that the reaction condition of described fixed bed reactors
For：Reaction temperature is 340-350 DEG C, reaction pressure 6.5-7.5MPa, hydrogen to oil volume ratio 400-600, volume space velocity 1.5-2.0h-1It is preferred that the reaction condition of described fixed bed reactors is：350 DEG C of temperature, reaction pressure 7.0MPa, hydrogen to oil volume ratio 500,
Volume space velocity 2h-1.
6. it is characterised in that described technological process includes, diesel oil is mixed hydrodesulfurization as claimed in claim 1 with hydrogen
After conjunction, through optional heat exchanger heat exchange, then after heated stove heat, entrance fixed bed reactors carry out hydrodesulfurization, product
Separate through gas-liquid separation tower.
7. hydrodesulfurization as claimed in claim 1 is it is characterised in that described fixed bed reactors include 1-5 catalysis
Agent bed, preferably includes 2-3 beds.
8. hydrodesulfurization as claimed in claim 1 is 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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