CN106350103A - Diesel oil hydrogenation, desulfurization and denitrification process - Google Patents
Diesel oil hydrogenation, desulfurization and denitrification process Download PDFInfo
- Publication number
- CN106350103A CN106350103A CN201610698396.0A CN201610698396A CN106350103A CN 106350103 A CN106350103 A CN 106350103A CN 201610698396 A CN201610698396 A CN 201610698396A CN 106350103 A CN106350103 A CN 106350103A
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- CN
- China
- Prior art keywords
- catalyst
- fixed bed
- mcm
- carrier
- desulfurization
- Prior art date
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- Pending
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 29
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 27
- 230000023556 desulfurization Effects 0.000 title claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 230000008569 process Effects 0.000 title claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 239000010937 tungsten Substances 0.000 claims description 11
- -1 tungsten nitride Chemical class 0.000 claims description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 229910039444 MoC Inorganic materials 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000009432 framing Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 abstract description 33
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 abstract 2
- 229910003178 Mo2C Inorganic materials 0.000 abstract 1
- 229910020057 NbOPO4 Inorganic materials 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 31
- 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
- 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
- 239000002994 raw material Substances 0.000 description 6
- 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
- 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
- 239000002808 molecular sieve Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000013335 mesoporous material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 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
- 239000002105 nanoparticle Substances 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
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 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
- 230000009849 deactivation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 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
- 238000003475 lamination Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 230000007246 mechanism Effects 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
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-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
- 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
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 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
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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/042—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing iron group metals, noble metals or copper
- B01J29/044—Iron group metals or copper
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a diesel oil hydrogenation, desulfurization and denitrification process, which adopts a fixed bed reactor; a hydrogenation, desulfurization and denitrification catalyst is added in the fixed bed reactor; the catalyst comprises a carrier and an active component; the carrier is MCM-41 doped with heteroatoms Cu<2+> in a synthetic skeleton structure; the active component is a mixture of MO2N, W2N, Mo2C and WC; the catalyst also contains a catalytic promoter; the catalytic promoter is a mixture of Cr2O3, ZrO2, CeO2, V2O5 and NbOPO4; the reaction conditions of the fixed bed reactor are characterized in that the reaction temperature is 320 to 360 DEG C, the reaction pressure is 6 to 8MPa, the hydrogen-oil volume ratio is 300 to 600, and the volume space velocity is 1.0 to 2.5h<1>. According to the process, the total sulfur content of diesel oil can be controlled to be lower than 5ppm, and meanwhile, the total nitrogen content in the diesel oil is controlled to be 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 capital cleaning diesel oil standard (sulfur content≤50mg/g) accurate in Europe superscript, on May 5th, 2016, the Committee of Development and Reform, the Ministry of Finance, ring
Department of guarantor portion etc. seven issues and " accelerates product oil quality upgrading programme of work " with regard to printing and distributing and 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 of difficult removing 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 accessible on adsorption activity position
Property, so that its hydrodesulfurization activity is low；Theoretical research also finds, ni, co, mo are mutually stratiforms with the hydrogenation activity of w sulfide
The mos of stacking2And ws2Nanoparticle, mos2The appropriate stacking of nanoparticle contributes to reactant molecule on adsorption activity position
Accessibility and the formation of highly active class activity phase.
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: adopts 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 raw material 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, and 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 using centinel technology and acticat？One kind that pre-curing technology produces is to aoxidize
Aluminum is the nickel molybdenum pre-sulfide catalyst of carrier, and centinel key problem in technology is than general catalysis in terms of active metal dispersion
Agent more preferably it is easier to convert metal oxides are metal sulfide.And acticat？Part pre-curing technology, is in catalysis
Agent produce in sulfur-loaded, opening the self-contained sulfur of utilization of hour catalyst to realize the sulfuration of catalyst it is not necessary to catalyst
Drying it is not necessary to additionally inject vulcanizing agent, and soak time is shorter, so will make that device is quick, easily and safely open
Car.
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 be by the total sulfur in diesel oil
Content is reduced to below 10ppm, to meet diesel oil state five standard.Meanwhile, this technique adopt catalyst also make in diesel oil
The removing of 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+Mcm-41.
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 cr2o3、zro2、ceo2、v2o5And nbopo4's
Mixture.
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.
Mcm-41 is ordered into mesoporous material, and its duct is in six side's ordered arrangement, uniform in size, and aperture size can be with during synthesis
Directed agents and the difference of synthetic parts is added to change between 1.5～10nm, lattice parameter about 4.5nm, specific pore volume about 1ml/g,
Mcm-41 uniform pore diameter, has higher specific surface area (1000m2/ g) and big adsorption capacity (0.7ml/g), be conducive to organic
The free diffusing of molecule.The present invention through in numerous mesoporous materials, such as mcm-22, mcm-36, mcm-48, mcm-49,
Mcm56, carries out contrast test selection, finds the goal of the invention only having mcm-41 can reach the present invention, other mesoporous materials are all
There is such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, the therefore present invention selects to use
Mcm-41 is as carrier basis.
Pure silicon mcm-41 acidity itself is very weak, is directly used as catalyst activity relatively low.Therefore, the present invention changes to it
Property, to increase its catalysis activity.The present invention approach modified to mcm-41 mesopore molecular sieve is: is situated between to the total silicon mcm-41 of finished product
Porous molecular sieve inner surfaces of pores introduces cu2+, this approach can be by ion exchange by cu2+It is supported on the inner surface of mcm-41,
Thus improving the catalysis activity of mcm-41 mesopore molecular sieve, absorption and Thermodynamically stable performance etc. on the whole.
Although the method that mcm-41 mesopore molecular sieve is modified or approach are a lot, inventor finds, the present invention urges
Agent can only be using doping cu2+Mcm-41 just enable sulfur content control and denitrification effect as carrier, inventor attempts
Mcm-41 adulterates: al3+、fe3+、zn2+、ga3+In the ion producing anionic surface center, discovery does not enable described
Effect.Although described mechanism is not known at present, this has no effect on the enforcement of the present invention, and inventor is according to well-known theory and reality
Checking is real, and it has cooperative effect and the active component of the present invention between.
Described cu2+Must control within specific content range in the doping in mcm-41, its doping is with weight
Meter, be the 0.56%-0.75% of mcm-41 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 mcm-41 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 mcm-41 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), only control nitridation two molybdenum mo2N, 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 be 1:(0.4-0.6 only in mol ratio): (0.28-0.45): when (0.8-1.2), just possess 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
Catalyst aid, described catalyst aid is cr2o3、zro2、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 cr2o3、zro2、ceo2、v2o5And nbopo4The catalyst facilitation to the present invention for the mixture of (niobium phosphate)
Substantially, its hydrothermal stability can be significantly improved, and improve its anti-coking deactivation, thus improving its service life.
Described cr2o3、zro2、ceo2、v2o5And nbopo4Between there is no the ratio of fixation that is to say, that cr2o3、zro2、
ceo2、v2o5And nbopo4Each respective content reaches effective dose.Preferably, the cr that the present invention adopts2o3、zro2、
ceo2、v2o5And nbopo4Respective 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+Mcm-41 as carrier, and the nitridation two molybdenum mo choosing special ratios2N, tungsten nitride w2N, molybdenum carbide mo2C and carbonization
Tungsten wc can control low in total sulfur content as active component so that this catalyst produces cooperative effect to the hydrodesulfurization of diesel oil
In 5ppm, the total nitrogen content in diesel oil is controlled within 10ppm 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+Mcm-41, cu2+Doping in mcm-41
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 is: 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 8ppm.
Embodiment 2
Catalyst is prepared by infusion process, carrier is doping cu2+Mcm-41, cu2+Doping in mcm-41
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 26ppm, and total alkaline nitrogen content is reduced to 45ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated mcm-41, remaining condition is constant.
Test final product, total sulfur content is reduced to 23ppm, and total alkaline nitrogen content is reduced to 28ppm.
Comparative example 3
Cu by embodiment 12+Replace with zn2+, remaining condition is constant.
Test final product, total sulfur content is reduced to 31ppm, and total alkaline nitrogen content is reduced to 36ppm.
Comparative example 4
By the cu in embodiment 12+Doping in mcm-41 controls the 0.5% of carrier quality, and remaining condition is constant.
Test final product, total sulfur content is reduced to 27ppm, and total alkaline nitrogen content is reduced to 38ppm.
Comparative example 5
By the cu in embodiment 12+Doping in mcm-41 controls the 0.8% of carrier quality, and remaining condition is constant.
Test final product, total sulfur content is reduced to 33ppm, and total alkaline nitrogen content is reduced to 35ppm.
Embodiment 1 and comparative example 1-5 show, certain content scope and certain loads metal ions that the application adopts
Mcm-41 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 mcm-41 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 43ppm, and total alkaline nitrogen content is reduced to 41ppm.
Comparative example 7
Omit the wc in embodiment 1, remaining condition is constant.
Test final product, total sulfur content is reduced to 39ppm, and total alkaline nitrogen content is reduced to 46ppm.
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 cr is contained in catalyst2o3、zro2、ceo2、v2o5And nbopo4, its content be respectively 2%, 3.5%,
2.7%th, 2.4% and 3%, remaining is same as Example 1.
Test final product, total sulfur content is reduced to 2ppm, and total alkaline nitrogen content is reduced to 7ppm, it uses 3 months
Afterwards, beds pressure drop is not any change, and reduces compared to the beds pressure drop of same use time embodiment 1
13%.
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 4.2%.
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 3.9%.
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+Mcm-41；
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 cr2o3、zro2、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.
2. hydrogenation desulfurization and denitrogenation technique as claimed in claim 1 is it is characterised in that hetero atom cu2+Doping be mcm-41
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 mcm-41 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 cr2o3、zro2、ceo2、v2o5And nbopo4Each
Content be respectively carrier quality 1-7%, preferably 2-4%.
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