CN106244195A - Coalite tar hydrofining technology in one - Google Patents
Coalite tar hydrofining technology in one Download PDFInfo
- Publication number
- CN106244195A CN106244195A CN201610689087.7A CN201610689087A CN106244195A CN 106244195 A CN106244195 A CN 106244195A CN 201610689087 A CN201610689087 A CN 201610689087A CN 106244195 A CN106244195 A CN 106244195A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- fixed bed
- kit
- bed reactors
- hydrofining technology
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000005516 engineering process Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 14
- -1 tungsten nitride Chemical class 0.000 claims abstract description 13
- 229910020057 NbOPO4 Inorganic materials 0.000 claims abstract description 12
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 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 7
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 3
- 238000010348 incorporation Methods 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 22
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 16
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000023556 desulfurization Effects 0.000 abstract description 3
- 239000003921 oil Substances 0.000 description 31
- 239000011269 tar Substances 0.000 description 26
- 239000011280 coal tar Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 19
- 230000008569 process Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
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- 239000007789 gas Substances 0.000 description 12
- 239000003502 gasoline Substances 0.000 description 11
- 239000002283 diesel fuel 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
- 239000003245 coal Substances 0.000 description 8
- 239000000295 fuel oil Substances 0.000 description 8
- 239000002808 molecular sieve Substances 0.000 description 8
- 235000016768 molybdenum Nutrition 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000004939 coking Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- 230000002079 cooperative effect Effects 0.000 description 5
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- 238000005260 corrosion Methods 0.000 description 5
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- 238000002156 mixing Methods 0.000 description 5
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
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- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 4
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- 238000001802 infusion Methods 0.000 description 4
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- 238000010992 reflux Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000004508 fractional distillation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000011287 low-temperature tar Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 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
- 239000010955 niobium Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 235000019640 taste Nutrition 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
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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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses coalite tar hydrofining technology in one, described technique uses fixed bed reactors, is filled with hydrogenation desulfurization and denitrogenation catalyst in fixed bed reactors, and described catalyst includes carrier and active component；Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT 1；Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc；Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture；The reaction condition of described fixed bed reactors is: reaction temperature is 300 420 DEG C, and hydrogen dividing potential drop is 13 15MPa, hydrogen to oil volume ratio 800 1200, volume space velocity 0.3 0.8h‑1.Total sulfur content in middle coalite tar can be reduced to below 5ppm by this technique, and reduces the cracking of aromatic hydrocarbons.
Description
Technical field
The present invention relates to coalite tar hydrodesulfurization process for refining in one, be specifically related to a kind of employing special catalyst
Coalite tar hydrodesulfurization process for refining in the one carried out.
Background technology
Coal tar is one of product in the raw gas that coking industry pyrolysis of coal generates, and its yield accounts for the 3% of shove charge coal
～4% at normal temperatures and pressures its product be black viscous liquid.Coal tar is the primary raw material of coal chemical industry, and its composition reaches
Ten thousand kinds, mainly contain the aromatic hydrocarbons such as benzene,toluene,xylene, naphthalene, anthracene, and aromatic series oxygenatedchemicals is (such as phenols chemical combination such as phenol
Thing), the gas chromatography such as nitrogenous, sulfur heterocyclic ring compound, can use the method for fractional distillation that coal tar is divided into different boiling
The fraction of scope.According to the difference of coal hot procedure, obtained coal tar be typically divided into high temperature tar (900 DEG C～
1000 DEG C), middle temperature tar (650 DEG C～900 DEG C) and low temperature tar (450 DEG C～650 DEG C).
China is big coal country, has abundant tar resource, and coal tar is as producing semi-coke, coke and coal gasification
Side-product, produces about 15,000,000 tons per year at present, and in addition to part high temperature coal-tar is used for extracting chemical products, most coal tar do not obtain
To reasonably utilizing, in major part, coalite tar and a small amount of high temperature coal-tar are carried out extensive burning as fuel.Because of coal tar
Containing circulus compounds such as substantial amounts of aromatic series in oil, it is more difficult to fully burn, coal tar phosphorus content is high simultaneously, hydrogen content
Low, it is easier to during burning generate white carbon black, causes incomplete combustion and produce substantial amounts of flue dust.Further, since in coal tar sulfur and
The content of nitrogen is higher, does not the most carry out desulfurization removing nitric process before burning, so giving off substantial amounts of SO when burningxAnd NOx, make
Becoming serious environmental pollution, the trend of the environmental protection energy advocated energetically with Present Global runs in the opposite direction.If by this part
Coal tar makes the fuel oil of abrasive (gasoline and diesel oil) by catalytic hydrogenation, can not only improve the exploitation value of coal tar
Value, greatly reduces environmental pollution, it is also possible to every year for the newly-increased gross national product more than 300 hundred million yuan of country.
The composition of middle coalite tar and character are different from high temperature coal-tar, containing more oxygen-containing in middle coalite tar
Compound and chain hydrocarbon, wherein phenol and derivant mass content thereof are up to 10%～30%, alkane shape hydrocarbon about 20%, heavy oil simultaneously
The content of (tar asphalt) is relatively fewer, is relatively suitable for using hydrogen addition technology to produce clean fuel oil.Middle coalite tar is (following
" coal tar " i.e. " middle coalite tar ") from the appearance, it is black thick liquid, density is slightly less than 1000kg/m3, viscosity
Greatly, having special abnormal smells from the patient, it mainly comprises is aromatic compound, and great majority are the condensed nucleus aromatic chemical combination of more than two rings
Thing.
Entering 21 century, China's coking industry develops rapidly, produces substantial amounts of high temperature coal-tar and production semi-coke is produced
A large amount of in coalite tar.Some research units are begun one's study and by catalytic hydrogenation, coal tar are made the fuel oil of cleaning
(such as gasoline and diesel oil).China Coal Research Institute and Sinopec Qilu Branch Company are once by coal gasification
Tar and high temperature coal-tar are through removing moisture, mechanical admixture and Colophonium pretreatment, then carry out hydrofinishing and the heavy of the degree of depth
Oil distillate be hydrocracked pilot plant test.
And the clean fuel oil of research report prepare to(for) middle coalite tar catalytic hydrogenation is less, abroad to coal tar
Mostly the research of catalytic hydrogenation is, with the hydrogenation reaction of some in coal tar or a compounds as model, to study it and be hydrogenated with
Complex chemical reaction included in journey, has research including to the hydrocracking reaction of naphthalene, carbolineum and phenanthrene etc..
But existing coal tar hydrogenating process include removing tar contains sulfur, nitrogen, the hetero atom such as oxygen, make unsaturation
Compound is hydrocracked the process generating light aromatic hydrocarbons by hydrogenation reaction enhanced stability and heavy component.This technical process meeting
Make the aromatic hydrocarbons cracking of substantial amounts of high economic worth, affect product income.
Coalite tar process for refining in the most how providing, can effectively control the sulfur content in middle coalite tar
Below 5ppm, and reduce the cracking of aromatic hydrocarbons, is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose coalite tar hydrodesulfurization process for refining in one, this technique can by low
Total sulfur content in temperature coal tar is reduced to below 5ppm, and reduces the cracking of aromatic hydrocarbons, to meet following process standard.
For reaching this purpose, the present invention by the following technical solutions:
Coalite tar hydrofining technology in one, described technique uses fixed bed reactors, in fixed bed reactors
Being filled with hydrogenation catalyst, described catalyst includes carrier and active component.
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT-1.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixing
Thing.
The reaction condition of described fixed bed reactors is: reaction temperature is 300-420 DEG C, and hydrogen dividing potential drop is 13-15MPa, hydrogen
Oil volume is than 800-1200, volume space velocity 0.3-0.8h-1。
KIT-1 molecular sieve has one-dimensional channels and crosses each other to form three-dimensional disordered structure, and this structure is conducive to catalysis, absorption
During material transmission.Pure silicon mesopore molecular sieve KIT-1 has heat stability more more preferable than MCM-241, HMS and hydrothermally stable
Property.The present invention through in numerous mesoporous materials, such as KIT-1, KIT-6, MCM-22, MCM-36, MCM-48, MCM-49,
MCM56 etc., carry out contrast test selection, find that only KIT-1 can reach the goal of the invention of the present invention, and other mesoporous materials are all
Having such-and-such defect, there is the technical difficulty being difficult to overcome when being applied in the present invention, therefore the present invention selects to use
KIT-1 is as carrier basis.
Although pure silicon KIT-1 mesopore molecular sieve hydro-thermal performance is outstanding, but inventor's research is later discovered that, it adds
Hetero atom or surface are after chemical modification, and its hydrothermal stability obtains bigger raising.Therefore, it is modified by the present invention, with
Increase its catalysis activity.The approach that KIT-1 mesopore molecular sieve is modified is by the present invention: in KIT-1 building-up process, adds Co2+
Saline solution, before KIT-1 framework of molecular sieve structure is formed, by isomorphous substitution by Co2+Replace part backbone element thus embedding
Enter in the skeleton of molecular sieve, improve catalysis activity, absorption and the thermodynamic stability of KIT-1 mesopore molecular sieve on the whole
Can etc..
Although the method being modified KIT-1 mesopore molecular sieve or approach are a lot, inventor finds, the catalysis of the present invention
Agent can only use doping Co2+KIT-1 could realize sulfur content as carrier and control and the balance of loss of octane number, inventor tastes
Try to adulterate in KIT-1: Al3+、Fe3+、Zn2+、Ga3+In the ion at generation anionic surface center, find all to realize institute
State effect.Exchanged Cu by ion with another modified approach of inventor2+It is supported on KIT-1 inner surfaces of pores to compare, the present invention
Isomorphous substitution approach more stable.Although described mechanism is current and unclear, but this has no effect on the enforcement of the present invention, invention
People is according to well-known theory and it is experimentally confirmed that there is cooperative effect between itself and the active component of the present invention.
Described Co2+Doping in KIT-1 must control within specific content range, and its doping is with weight
Meter, for the 0.56%-0.75% of KIT-1 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%,
0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%,
0.74 etc..
Inventor finds, outside this range, can cause drastically reducing of middle coalite tar desulfurized effect.More make us glad
Happiness, works as Co2+When doping in KIT-1 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when painting
System is with Co2+Doping is transverse axis, and during curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content can control
Within the scope of extremely low, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier KIT-1 weight, preferably 3-12%, further preferred 5-
10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28-
0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
In the range of Gai, in can realizing, in coalite tar, sulfur content controls at below 10ppm and denitrification ability notable.Namely
Saying, four kinds of active components of the present invention are only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just tool
Standby cooperative effect.Outside this molar ratio range, or omit or replace any one component, all can not realize collaborative effect
Should.
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.
An object of the present invention also resides in the promoter providing described catalyst.Catalyst of the present invention also contains
Having catalyst aid, described catalyst aid is TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate).
Although in hydrofinishing particularly hydrodesulfurization field, had maturation catalyst aid, such as P, F and B etc., its
For regulating the character of carrier, weaken interaction strong between metal and carrier, improve the surface texture of catalyst, improve metal
Reducibility, promote active component to be reduced to lower valency, to improve the catalytic performance of catalyst.But above-mentioned P, F and B catalysis helps
Agent application with the carrier of the present invention with active component time, for high-sulfur component, it promotes the effect of catalytic desulfurization/refined
?.
The present invention passes through in numerous conventional cocatalyst component, and carries out in amount of activated component selecting, compounding,
Find eventually to use TiO2、CeO2、V2O5And NbOPO4The mixture of (niobium phosphate) is obvious to the catalyst facilitation of the present invention, energy
Significantly improve its hydrothermal stability, and improve its anti-coking deactivation, thus improve its service life.
Described TiO2、CeO2、V2O5And NbOPO4Between there is no fixing ratio, say, that TiO2、CeO2、V2O5With
NbOPO4Each respective content reaches effective dose.Preferably, the TiO that the present invention uses2、CeO2、V2O5And NbOPO4
Respective content is the 1-7% of (respectively) carrier quality, preferably 2-4%.
Although there is no specific proportion requirement between catalyst aid of the present invention, but each auxiliary agent allowing for reaching
To the requirement of effective dose, the 1-7% of the content of catalyst aid effect, such as carrier quality i.e. can be played.The present invention is selecting
During find, omit or replace one or more in described auxiliary agent, all do not reach the present invention technique effect (improve water
Heat stability, reduces coking and improves service life), say, that exist between the catalyst aid of the present invention and specifically coordinate pass
System.
It is true that the present invention once attempted the niobium phosphate NbOPO in catalyst aid4Replace with five oxidation two girl Nb2O5,
Have found that while in auxiliary agent and have also been introduced Nb, but its technique effect is significantly lower than niobium phosphate NbOPO4, not only hydrothermal stability is slightly for it
Difference, its beds coking is relatively rapid, thus causes catalyst duct to block, and beds pressure drop rise is relatively
Hurry up.The present invention the most once attempted introducing other phosphate, although but this trial introduces phosphate anion, but equally exist hydro-thermal
Stability is the most slightly worse, and its beds coking is relatively rapid, thus causes catalyst duct to block, beds pressure drop
Rise relatively fast.
Although present invention introduces catalyst aid have so many advantage, but the present invention should be noted that, introduce catalysis
Auxiliary agent is only one of preferred version, even if not introducing this catalyst aid, nor affects on the enforcement of main inventive purpose of the present invention.
Not introducing the catalyst aid particularly niobium phosphate of the present invention, it is compared to the scheme of introducing catalyst aid, and its defect is only phase
To.This defect i.e. is that it is relative to other prior aries outside the present invention relative to the defect introduced after catalyst aid,
Mentioned by the present invention had superiority or new features yet suffer from.This catalyst aid is not to solve technical problem underlying of the present invention
Indispensable technological means, its simply further optimization to technical solution of the present invention, solve new technical problem.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine
The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.The typical but non-limiting example of the present invention
As follows:
Sodium silicate, cetyl trimethylammonium bromide (CTAB), sodium ethylene diamine tetracetate (EDTA) and distilled water are massaged
You mix the ratio than 1:0.25:1:60, load with in teflon-lined autoclave pressure, after stirring under 373K
Constant temperature 24h, the pH of re-adjustments mixture are 10.5, after constant temperature 4 times, take out product, with distilled water cyclic washing to filtrate
PH=7, then under 373K, constant temperature overnight, obtains the KIT-1 with surfactant.KIT-1 with surfactant is existed
Roasting 1.5h under 523K, then roasting 6h in air atmosphere under 813K, obtains KIT-1 powder body.By this powder body 0.1mol/L
Salpeter solution carry out pickling (control solid-to-liquid ratio is 1:10), under room temperature stir 0.5h, filter, be washed with distilled water to filtrate
Dry under pH=7,373K and obtain matrix KIT-1 molecular sieve.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 350-370 DEG C, and hydrogen dividing potential drop is 13.0-
15.0MPa, hydrogen to oil volume ratio 800-1000, volume space velocity 0.4-0.6h-1。
Preferably, described technological process includes, device mainly includes raw material prefractionation part (dehydration and back-end crop), reacting part
Divide and fractionating section.
1, raw material prefractionation part
The raw oil come from tank field removes the solid particle more than 25 μm through raw oil filter, changes with prefractionation tower top vapour
After heat heats up, heat up with the backflow heat exchange of prefractionator stage casing, then with prefractionator at the bottom of heavy oil heat exchange heat up, after through pre-point
Evaporate tower charging heating furnace and be heated to 180 DEG C of entrance raw oil prefractionator (dehydration), after tower top vapour is condensed, enter prefractionator
Top return tank is also separated into gasoline and oil-polluted water, and a part of gasoline is made overhead reflux and used, and hydrogenation unit made by a part of gasoline
Raw material uses；The tops of prefractionator (dehydration) is discharged by the bottom of tower, then through heat exchange and heating furnace heat reach 360 DEG C laggard
Enter prefractionator (back-end crop), prefractionator (back-end crop) end heavy oil, go out device as Colophonium, and other make to add after distillating fraction mixing
Hydrogen unit raw material uses.
2, reactive moieties
Hydrogenation raw oil surge tank, raw oil surge tank fuel gas sealing gland is entered through pretreated coal tar.From
Raw oil surge tank come raw oil hydrogenated feed pump supercharging after, under flow-control with mix hydrogen mix, reacted outflow
After thing/reaction feed heat exchanger heat exchange, the most reacted charging heating furnace is heated to reacting temperature required, enters hydro-upgrading anti-
Answer device, between reactor, be provided with note quenching hydrogen facility.
The reacted effluent of autoreactor reaction effluent out/reaction feed heat exchanger, reaction effluent/low point of oil
Heat exchanger, reaction effluent/reaction feed heat exchanger successively with reaction feed, low point of oil, reaction feed heat exchange, the most reacted
Effluent air cooler and water cooler are cooled to 45 DEG C, enter high-pressure separator.In order to prevent the ammonium salt in reaction effluent low
Temperature position separates out, and is noted by flushing water by water injecting pump in the pipeline of reaction effluent air cooler upstream side.
Reaction effluent after cooling carries out oil, gas and water three phase separation in high-pressure separator.High score gas (recycle hydrogen) warp
After circulating hydrogen compressor entrance separatory tank separatory, enter circulating hydrogen compressor boosting, then divide two-way: a road is entered as quenching hydrogen
Reactor；One tunnel mixes with the new hydrogen from make-up hydrogen compressor, and mixing hydrogen mixes as reaction feed with raw oil.Sulfur-bearing, contain
Ammonia sewage is expelled to acidic water stripping device bottom high-pressure separator and processes.High score oil phase regulates through decompression under Liquid level
Valve enters low pressure separator, and its flash gas drains into factory's fuel gas pipe network.
Low point of oil through refined diesel oil/low point of oil heat exchanger and reaction effluent/low point oil heat exchanger respectively with refined diesel oil,
Fractionating column is entered after reaction effluent heat exchange.Enter tower temperature reaction effluent/low point of oil heat exchanger bypass regulation to control.
New hydrogen enters make-up hydrogen compressor through make-up hydrogen compressor entrance separatory tank after separatory, with recycle hydrogen after two-stage is boosted
Mixing.
3, fractionating section
The low point of oil come from reactive moieties changes through refined diesel oil/low point of oil heat exchanger, reaction effluent/low point of oil heat exchanger
Heat enters fractionating column to about 275 DEG C.Setting reboiler furnace at the bottom of tower, tower top oil gas is cooled to 40 through tower top air cooler and water cooler
DEG C, enter fractional distillation return tank of top of the tower and carry out gas, oil, water three phase separation.The gas flashed off drains into fuel gas pipe network.Sulfur-bearing contains ammonia
Sewage is carrying device together with high score sewage.Oil phase be fractionated into overhead reflux pump boosting rear portion as overhead reflux, one
It is allocated as removing stabilizer for raw gasoline.
The raw gasoline come from fractional distillation return tank of top of the tower enters gasoline after stable gasoline (refined Petroleum)/raw gasoline heat exchange
Stabilizer.Making to stablize reboiler thermal source with refined diesel oil at the bottom of stabilizer, stabilizer tower top oil gas is through stablizing the condensation of tower top water cooler
Being cooled to 40 DEG C, entrance is stablized return tank of top of the tower and is carried out gas, oil, water three phase separation.The gas flashed off drains into fuel gas pipe network.
Sulfur-bearing carrying device together with high score sewage in ammonia sewage.Oil phase returns mostly as tower top after stablizing the boosting of overhead reflux pump
Stream, fraction enters as light oil and goes out device in slops.At the bottom of tower, stable gasoline goes to tank field as Petroleum.
In order to suppress hydrogen sulfide to tower top pipeline and the corrosion of cold exchange device, use at fractionating column and stabilizer tower top pipeline
Inject corrosion inhibiter measure.Corrosion inhibiter enters tower top pipeline from corrosion inhibiter tank through corrosion inhibiter infusion.
Refined diesel oil at the bottom of fractionation column after refined diesel oil pump supercharging with low point of oily heat exchange to about 100 DEG C, subsequently into
Diesel oil air cooler goes out device and goes to tank field as high-grade fuel oil after being cooled to 50 DEG C.
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrofining technology of the present invention is by choosing specific catalyst, and described catalyst is by mixing hetero atom Co2+
KIT-1 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
As active component, described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4's
Mixture so that this catalyst produces cooperative effect, and the hydrodesulfurization of centering coalite tar can control to be less than at total sulfur content
5ppm, the aromatic hydrocarbons in centering coalite tar will not produce cracking simultaneously.
Detailed description of the invention
The hydrofining technology of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Co2+KIT-1, Co2+Doping control in KIT-1
System is at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is the 10% of carrier quality, and its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Becoming, beds is set to 3 layers, and reaction bed temperature UGU808 type temp controlled meter is measured, coalite tar in raw material
The double plunger micro pump manufactured by Beijing Satellite Manufacturing Factory carries continuously, and hydrogen is supplied by gas cylinder and uses Beijing Sevenstar-HC
D07-11A/ZM mass-flow gas meter coutroi velocity, loaded catalyst is 2kg.Reacted product cools down through water-bath room temperature
Laggard row gas-liquid separation.
Raw materials used for coalite tar in Kazakhstan, its sulfur content is up to 2400ppm.
Controlling reaction condition is: temperature 360 DEG C, hydrogen dividing potential drop 14.0MPa, hydrogen to oil volume ratio 900, volume space velocity 0.5h-1。
Testing final product, total sulfur content is reduced to 2ppm, and aromatic hydrocarbons loss rate is less than 2%.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Co2+KIT-1, Co2+Doping control in KIT-1
System is at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is the 10% of carrier quality, and its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 3ppm, and aromatic hydrocarbons loss rate is less than 2%.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, total sulfur content is reduced to 37ppm, and aromatic hydrocarbons loss rate is more than 5%.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated KIT-1, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 42ppm, and aromatic hydrocarbons loss rate is more than 5%.
Comparative example 3
Co by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 45ppm, and aromatic hydrocarbons loss rate is more than 5%.
Comparative example 4
By the Co in embodiment 12+Doping in KIT-1 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 41ppm, and aromatic hydrocarbons loss rate is more than 5%.
Comparative example 5
By the Co in embodiment 12+Doping in KIT-1 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 42ppm, and aromatic hydrocarbons loss rate is more than 5%.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion
KIT-1 carrier, when replacing with other known carriers of this area, or carrier is identical but Co2+During doping difference, all reach not
To the technique effect of the present invention, the therefore Co of the certain content scope of the present invention2+Doping KIT-1 carrier and other components of catalyst
Between possess cooperative effect, described hydrofining technology creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 52ppm, and aromatic hydrocarbons loss rate is more than 5%.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 53ppm, and aromatic hydrocarbons loss rate is more than 5%.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrofining technology of the present invention it
Between there is specific contact, be omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that it produces
Give birth to cooperative effect.
Embodiment 3
Containing catalyst aid TiO in catalyst2、CeO2、V2O5And NbOPO4, its content is respectively 1%, 1.5%, 1% and
3%, remaining is same as in Example 1.
Testing final product, after it uses 3 months, beds pressure drop is not any change, and uses compared to same
The beds pressure drop of time embodiment 1 reduces 12%.
Comparative example 8
Compared to embodiment 3, by NbOPO therein4Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 3.9%.
Comparative example 9
Compared to embodiment 3, by CeO therein2Omitting, remaining condition is identical.
Testing final product, after it uses 3 months, beds pressure drop raises, and uses the time real compared to same
The beds pressure drop executing example 1 only reduces 4.4%.
Embodiment 3 shows with comparative example 8-9, there is conspiracy relation between the catalyst aid of the present invention, when being omitted or substituted
When one of them or several component, all can not reach the minimizing coking when present invention adds catalyst aid thus stop catalyst bed
The technique effect that lamination falling-rising is high.That is, its catalyst aid demonstrating the present invention can improve the service life of described catalyst,
And other catalyst aid effects are not as this specific catalyst aid.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in
Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art
Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool
Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (7)
1. a coalite tar hydrofining technology in, described technique uses fixed bed reactors, fills in fixed bed reactors
Being filled with hydrogenation catalyst, described catalyst includes carrier and active component, it is characterised in that
Described carrier is incorporation hetero atom Co in synthetic bone shelf structure2+KIT-1,
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc,
Described catalyst is possibly together with catalyst aid, and described catalyst aid is TiO2、CeO2、V2O5And NbOPO4Mixture,
The reaction condition of described fixed bed reactors is: reaction temperature is 300-420 DEG C, and hydrogen dividing potential drop is 13-15MPa, hydrogen oil body
Long-pending ratio 800-1200, volume space velocity 0.3-0.8h-1。
2. hydrofining technology as claimed in claim 1, it is characterised in that hetero atom Co2+Doping be KIT-1 weight
0.63%-0.72%.
3. hydrofining technology as claimed in claim 1, it is characterised in that the total content of described active component is carrier KIT-
The 3-12% of 1 weight, preferably 5-10%.
4. hydrofining technology as claimed in claim 1, it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide
Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5): (0.35-0.45): (0.8-1.0), more preferably 1:
(0.45-0.48): (0.4-0.45): (0.9-1.0), most preferably 1:0.48:0.42:0.95.
5. hydrofining technology as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is:
Reaction temperature is 350-370 DEG C, and hydrogen dividing potential drop is 13.0-15.0MPa, hydrogen to oil volume ratio 800-1000, volume space velocity 0.4-0.6h-1。
6. hydrofining technology as claimed in claim 1, it is characterised in that described fixed bed reactors include 1-5 catalysis
Agent bed, preferably includes 2-3 beds.
7. hydrofining technology as claimed in claim 1, it is characterised in that TiO2、CeO2、V2O5And NbOPO4Respective content
It is respectively the 1-7%, preferably 2-4% of carrier quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786887A (en) * | 2018-06-20 | 2018-11-13 | 上海电力学院 | A kind of catalyst and preparation method for photocatalytic water splitting hydrogen manufacturing |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262969A (en) * | 2000-03-02 | 2000-08-16 | 南开大学 | Catalyst using TiO2 as carrier to load metal nitride Mo2N |
| CN1470327A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Metal nitride catalyst preparing method and catalyst |
| CN1895777A (en) * | 2005-07-14 | 2007-01-17 | 北京化工大学 | Porous molecular-sieve catalyst for assembling carbide and its preparation |
| WO2013149014A1 (en) * | 2012-03-29 | 2013-10-03 | Wayne State University | Bimetal catalysts |
| CN105251527A (en) * | 2015-11-11 | 2016-01-20 | 中国石油大学(北京) | Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier |
-
2016
- 2016-08-18 CN CN201610689087.7A patent/CN106244195A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1262969A (en) * | 2000-03-02 | 2000-08-16 | 南开大学 | Catalyst using TiO2 as carrier to load metal nitride Mo2N |
| CN1470327A (en) * | 2002-07-24 | 2004-01-28 | 北京石油化工学院 | Metal nitride catalyst preparing method and catalyst |
| CN1895777A (en) * | 2005-07-14 | 2007-01-17 | 北京化工大学 | Porous molecular-sieve catalyst for assembling carbide and its preparation |
| WO2013149014A1 (en) * | 2012-03-29 | 2013-10-03 | Wayne State University | Bimetal catalysts |
| CN105251527A (en) * | 2015-11-11 | 2016-01-20 | 中国石油大学(北京) | Composite molecular sieve and hydrodesulfurization catalyst prepared with composite molecular sieve as carrier |
Non-Patent Citations (14)
| Title |
|---|
| F．维拉尼: "《稀土技术及其应用》", 31 July 1986, 烃加工出版社 * |
| 中国石油化工集团公司人事部等: "《加氢裂化装置操作工》", 30 September 2008, 中国石化出版社 * |
| 何鸣元等: "《石油炼制和基本有机化学品合成的绿色化学》", 31 January 2006, 中国石化出版社 * |
| 姜琳琳: "《全馏分FCC汽油加氢改质中改性MCM-41催化性能研究》", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 崔克清等: "《化工工艺及安全》", 31 May 2004, 化学工业出版社 * |
| 张文成: "《改性MCM-41 分子筛的制备及加氢催化性能研究》", 《第十一届全国青年催化学术会议论文集（下）》 * |
| 李静海等: "《展望21世纪的化学工程》", 31 October 2004, 化学工业出版社 * |
| 林世雄: "《石油炼制工程（第三版）》", 31 July 2000, 化学工业出版社 * |
| 王基铭: "《石油炼制辞典》", 30 September 2013, 中国石化出版社 * |
| 王海彦，等: "《石油加工工艺学》", 31 January 2014, 中国石化出版社 * |
| 王福安等: "《绿色过程工程引论》", 31 October 2002, 化学工业出版社 * |
| 王雷，等: "《炼油工艺学》", 31 August 2011, 中国石化出版社 * |
| 邝生鲁: "《现代精细化工高新技术与产品合成工艺》", 31 December 1997, 科学技术文献出版社 * |
| 阎子峰: "《纳米催化技术》", 31 May 2003, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108786887A (en) * | 2018-06-20 | 2018-11-13 | 上海电力学院 | A kind of catalyst and preparation method for photocatalytic water splitting hydrogen manufacturing |
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