CN114433206B - Catalyst carrier, hydrogenation catalyst and heavy distillate oil hydrogenation modification method - Google Patents
Catalyst carrier, hydrogenation catalyst and heavy distillate oil hydrogenation modification method Download PDFInfo
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- CN114433206B CN114433206B CN202011197863.4A CN202011197863A CN114433206B CN 114433206 B CN114433206 B CN 114433206B CN 202011197863 A CN202011197863 A CN 202011197863A CN 114433206 B CN114433206 B CN 114433206B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 122
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 49
- 238000002715 modification method Methods 0.000 title abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 202
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000002808 molecular sieve Substances 0.000 claims abstract description 23
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000002902 bimodal effect Effects 0.000 claims abstract description 11
- 230000001186 cumulative effect Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 32
- 239000011812 mixed powder Substances 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 14
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 14
- 241000219782 Sesbania Species 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 238000004898 kneading Methods 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011959 amorphous silica alumina Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims 1
- -1 polypropylene Polymers 0.000 claims 1
- 229920001155 polypropylene Polymers 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 238000005336 cracking Methods 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 17
- 241000196324 Embryophyta Species 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 8
- 238000004517 catalytic hydrocracking Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910000480 nickel oxide Inorganic materials 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 8
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 8
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910001930 tungsten oxide Inorganic materials 0.000 description 8
- 239000005995 Aluminium silicate Substances 0.000 description 7
- 235000012211 aluminium silicate Nutrition 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000003225 biodiesel Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000004438 BET method Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- RHCSKNNOAZULRK-APZFVMQVSA-N 2,2-dideuterio-2-(3,4,5-trimethoxyphenyl)ethanamine Chemical compound NCC([2H])([2H])C1=CC(OC)=C(OC)C(OC)=C1 RHCSKNNOAZULRK-APZFVMQVSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- PGJHGXFYDZHMAV-UHFFFAOYSA-K azanium;cerium(3+);disulfate Chemical compound [NH4+].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O PGJHGXFYDZHMAV-UHFFFAOYSA-K 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- UAMZXLIURMNTHD-UHFFFAOYSA-N dialuminum;magnesium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mg+2].[Al+3].[Al+3] UAMZXLIURMNTHD-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000004069 differentiation Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury 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
- 150000002739 metals Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/308—Gravity, density, e.g. API
-
- 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
- C10G2400/08—Jet fuel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a carrier, a hydrogenation catalyst and a heavy distillate oil hydrogenation modification method, wherein the hydrogenation catalyst comprises a carrier and an active metal component; the carrier has a bimodal pore structure and contains 3-30wt% of beta type molecular sieve; in the bimodal pore structure, the pore diameter of a large pore which can be several pores is in the range of 600-1200 nm, the pore diameter of a small pore which can be several pores is in the range of 4-9 nm, and the ratio of the pore diameter of the large pore which can be several pores to the pore diameter of the small pore which can be several pores is 120-200; the ratio of the pore volume of the large pore to the pore volume of the small pore is 2-4, the pore volume of the large pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the large pore, and the pore volume of the small pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the small pore. The hydrogenation catalyst has moderate cracking activity, and is especially suitable for hydrotreating and hydro-upgrading of oil products with heavier fraction distribution than conventional VGO.
Description
Technical Field
The invention relates to the field of catalysts or carriers, in particular to a catalyst carrier, a hydrogenation catalyst and a heavy distillate oil hydrogenation modification method.
Background
Along with the increasing heavy and inferior crude oil, the conversion of heavy distillate oil becomes a difficult problem of oil refining catalysts and technologies. The hydrocracking technology is one of the classical means for hydroconversion of heavy distillate oil and has the characteristics of high product quality, long service period, flexible operation and the like. However, when the catalyst is used for processing heavy fractions, particularly heavy fractions with a dry point of more than 600 ℃, the catalyst performance is often unstable, and the service period is long.
The hydrocracking catalyst is a bifunctional catalyst having both cracking activity and hydrogenation activity, i.e., containing both an acidic component and a hydrogenation active component, the acidity of which is mainly provided by the refractory inorganic oxide and/or various zeolites constituting the support; the hydrogenation-active component is generally selected from the group consisting of metals of groups VIB and VIII of the periodic table of the elements, metal oxides and/or metal sulfides. In order to meet the different requirements of hydrocracking products, the acidic components and hydrogenation active components in the catalyst need to be adaptively modulated.
The acidic components can be classified into molecular sieves and amorphous silica alumina according to the degree of crystallization. Molecular sieves are used in catalysts that require more acid centers and are highly reactive. Compared with molecular sieves, the preparation method of the amorphous silica-alumina is simple, has low cost, larger pore diameter, larger silica-alumina ratio adjustment range and lower acid density, and is particularly suitable for treating macromolecular raw materials such as heavy oil, residual oil and the like; are commonly used in catalysts requiring lower acid densities, such as high middle distillate selectivity hydrocracking catalysts and hydroisomerization catalysts. Amorphous silica alumina is an acidic support for many industrial amorphous catalysts and is also an important component of many molecular sieve catalysts, but a common disadvantage of amorphous silica alumina materials is the relatively low cracking activity.
The hydrogenation component of the hydrocracking catalyst generally selects non-noble metal as the hydrogenation component, the hydrogenation activity of the non-noble metal is lower than that of the noble metal, the requirement cannot be met, and how to improve the hydrogenation performance of the catalyst becomes a problem to be solved by the partial hydrocracking catalyst.
The non-noble metal component is adopted as the hydrogenation component, the microscopic nature of the hydrogenation component has great influence on the performance of the catalyst, and a plurality of patents exist in the preparation of the catalyst at home and abroad. By selecting different metal components, the hydrogenation performance of the catalyst can be improved, for example, the metal component is selected from Ni-W components, the hydrogenation activity of which can be higher than that of Ni-Mo and Co-Mo type catalysts (contact catalysis, industrial catalyst principle preparation and application, J.F. Leba et al, li Xuanwen, huang Zhiyuan translation, oil industry Press, beijing, 1984, p 207).
For processing heavy fractions such as residuum, hydrogenation catalysts generally have bimodal pore structures, with typical pore locations ranging from 5 to 20nm or from 10 to 30nm, from 100 to 300nm, and from 300 to 500nm. Because of the larger molecular size of residuum molecules, the catalyst generally does not contain acidic components, which would otherwise severely impact catalyst life.
Chinese patent CN108654700a provides a trimodal pore distribution hydrodemetallization catalyst and a method for preparing the same. The invention controls the pore volume with the pore diameter smaller than 50nm to account for 30-50% of the total pore volume, the pore volume with the pore diameter of 50-100nm to account for 10-30% of the total pore volume, and the pore volume with the pore diameter larger than 100nm to account for 30-50% of the total pore volume. Compared with the prior art, the three-peak-pore-distribution hydrodemetallization catalyst prepared by the method is more suitable for heavy oil hydrodemetallization and deasphalting catalysts such as residual oil and the like.
Chinese patent CN106031880B provides a multi-stage pore hydrocracking catalyst and its application, wherein the pore volume of pores with a pore diameter smaller than 2nm is controlled to be 1.5% -75% of the total pore volume of the catalyst, the pore volume of pores with a pore diameter of 2-100 nm is controlled to be 20% -85% of the total pore volume of the catalyst, and the pore volume of pores with a pore diameter larger than 100nm is controlled to be 2.5% -65% of the total pore volume of the catalyst. The invention is said to provide catalysts having higher hydrocracking activity than catalysts provided by the prior art.
Chinese patent CN103551178A provides a supported ammonium cerium sulfate double mesoporous biodiesel catalyst and a preparation method thereof, and provides double mesoporous silicon, wherein the aperture of a small mesoporous is 3-5nm, the aperture of a large mesoporous is 10-15nm, when the catalyst is used for synthesizing biodiesel by taking methanol and oleic acid as raw materials, the biodiesel yield is higher than 90%, the biodiesel yield is reduced by not more than 3% after the catalyst is repeatedly used for 5 times, the repeated use performance is good, and the catalyst is easy to separate.
Most of these patents are used for residuum hydrogenation or as a carrier for a protective agent, divided into two or more pore size channels. The method is used for processing oil products which are heavier than the conventional VGO, but lighter than residual oil, and have too many macropores and less necessity. Thus, there is a need for a suitable hydrogenation catalyst to process heavy wax oil components that are heavier than VGO.
Disclosure of Invention
The invention aims to provide a method suitable for hydrotreating high-yield low-freezing diesel oil.
In order to achieve the above object, a first aspect of the present invention provides a carrier for preparing a hydrogenation catalyst, the carrier having a bimodal pore structure and containing 3 to 30wt% of a beta-type molecular sieve; in the bimodal pore structure, the pore diameter of a macropore which can be several pores is in the range of 600-1200 nm, the pore diameter of a micropore which can be several pores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropore which can be several pores to the pore diameter of the micropore which can be several pores is 120-200; the ratio of the pore volume of the large pore to the pore volume of the small pore is 2-4, the pore volume of the large pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the large pore, and the pore volume of the small pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the small pore.
In a second aspect, the present invention provides a process for producing a carrier for a hydrogenation catalyst, the process comprising:
s1, mixing pseudo-boehmite, amorphous silicon-aluminum oxide, beta-type molecular sieve, carboxymethyl cellulose and sesbania powder to obtain mixed powder;
s2, mixing the mixed powder with water, kneading and extruding to obtain an extruded strip;
s3, carrying out first drying and first roasting on the extruded strip.
In a third aspect the present invention provides a hydrogenation catalyst comprising the support and an active metal component as described above.
In a fourth aspect, the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:
SS1, impregnating the carrier by using an aqueous solution containing a hydrogenation active component compound to obtain an impregnated carrier;
SS2, subjecting the impregnated support to a second drying and a second calcination.
In a fifth aspect, the present invention provides a method for hydro-upgrading heavy distillate, comprising contacting heavy distillate and hydrogen with the hydrogenation catalyst under hydrogenation conditions.
Through the technical scheme, the hydrogenation catalyst provided by the invention comprises the carrier and the active metal component, wherein the carrier has a bimodal pore structure, and the hydrogenation catalyst has medium cracking activity and is particularly suitable for hydrotreating and hydro-upgrading of oil products with heavier fraction distribution than conventional VGO.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In a first aspect the present invention provides a support for use in the preparation of a hydrogenation catalyst, the support having a bimodal pore structure and comprising from 3 to 30wt% of a beta-type molecular sieve; in the bimodal pore structure, the pore diameter of a macropore which can be several pores is in the range of 600-1200 nm, the pore diameter of a micropore which can be several pores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropore which can be several pores to the pore diameter of the micropore which can be several pores is 120-200; the ratio of the pore volume of the large pore to the pore volume of the small pore is 2-4, the pore volume of the large pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the large pore, and the pore volume of the small pore is the cumulative pore volume of pores with the pore diameter within the range of 50-150% of the pore diameter of the few pores of the small pore.
Wherein, the bimodal pore in the invention refers to the existence of two obvious peaks on a pore distribution curve of mercury intrusion or BET, wherein the position of the fixed point of the peak becomes accessible pore diameter. The peaks mentioned in the present invention may have a symmetrical distribution or an asymmetrical distribution, and the present invention does not limit the peak type.
Kong Rongbi in the invention is the ratio of pore volume to pore volume, the units are mL/g, and the ratio is a dimensionless value. The coverage of 50% up and down of the pore diameter means that the pore volume in the range of the pore diameter is accumulated in the whole coverage of 5-15 nm of a given accessible pore diameter, such as an accessible pore diameter of 10 nm. Macropores in the present invention refer to the pores of the support or catalyst, most or most of which are above 3.0nm, or greater than 5.0nm, but it is not excluded that some of the pores fall below 5.0 nm. The most probable pore diameter in the present invention means a pore diameter corresponding to the maximum value of dV/dr in a distribution curve of the derivative of specific pore volume to pore diameter (i.e., dV/dr) with pore diameter obtained when measuring the pore structure of a sample by the BET method.
According to the first aspect of the present invention, in the carrier, the several pore diameters of the large pores may be in the range of 700 to 1050nm, and the several pore diameters of the small pores may be in the range of 5 to 9 nm; the pore volume of the macropores can account for 15-20% of the total pore volume of the carrier.
The hole concentration in the present invention means: when the pore structure of the sample is measured by the BET method, the obtained distribution curve of the differentiation of the specific pore volume to the pore diameter along with the pore diameter has the most probable dV/dr value corresponding to the pore diameter. The larger this value, the higher the pore size concentration of the porous support. According to the present invention, when there are a plurality of peaks in the distribution curve of dV/dr with pore diameter, the ratio of the peak height of each peak to the half-width of the peak should satisfy the above-mentioned requirement. As a preferred embodiment of the present invention, the pore concentration value of the small pores is not less than 0.5, preferably not less than 0.75.
According to a first aspect of the invention, the support may comprise a non-amorphous mesoporous acidic material and a beta molecular sieve; the non-amorphous mesoporous acidic material may be well known to those skilled in the art and may include, for example, a two-component oxide comprising at least one of alumina-silica, alumina-titania, alumina-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, and titania-zirconia; preferably, the non-amorphous mesoporous acidic material is selected from at least one of silicon aluminum composite oxide, titanium aluminum composite oxide, and titanium silicon composite oxide. As a preferred embodiment, the non-amorphous mesoporous acidic material may be a silicon aluminum composite oxide.
In a second aspect, the present invention provides a process for preparing a support for a hydrogenation catalyst, the process comprising:
s1, mixing pseudo-boehmite, amorphous silicon-aluminum oxide, beta-type molecular sieve, carboxymethyl cellulose and sesbania powder to obtain mixed powder;
s2, mixing the mixed powder with water, kneading and extruding to obtain an extruded strip;
s3, carrying out first drying and first roasting on the extruded strip.
According to a second aspect of the present invention, in step S1, the weight ratio of the pseudo boehmite, the amorphous silica-alumina oxide, the beta-type molecular sieve, the carboxymethyl cellulose, and the sesbania powder may be: 10-55:15-85:3-35:1.0-5.0:2-4;
in step S2, the amount of water used may be 80-140mL per 100g of the mixed powder.
According to a second aspect of the invention, the pseudoboehmite may be characterized in that it comprises: siO (SiO) 2 The content of (C) is less than 0.1wt%, fe 2 O 3 Less than 0.01wt%, na 2 The content of O is less than 0.15wt%, the content of water is less than 3wt%, and the ignition loss is 32-38 wt%; the pore volume of the pseudo-boehmite is 0.60-1.1mL/g, and the specific surface is 220-310m 2 /g; the amorphous silicon aluminum oxide may be characterized as comprising: siO (SiO) 2 The content of (C) is 15-55wt%, al 2 O 3 The content of (2) is 45-85wt%, and the bulk density is 250-450 g/L; the sodium content of the 2% aqueous solution of carboxymethyl cellulose is less than 2.0% by weight.
According to a second aspect of the present invention, in step S2, the mixing conditions may include: the temperature is 10-40 ℃ and the time is 1-10 minutes; in step S3, the first drying condition may include: the temperature is 100-130 ℃ and the time is 3-20 hours; the conditions of the first firing include: the temperature is 400-600 ℃, the time is 2-10 hours, and the air flow is 20-50L/h.
In a third aspect the present invention provides a hydrogenation catalyst comprising the support and an active metal component as described above.
According to a third aspect of the invention, the active metal component may be selected from the group consisting of group VIII and/or group VIB metal elements; preferably, the group VIII metal element may be cobalt and/or nickel, and the group VIB metal element may be molybdenum and/or tungsten.
According to the third aspect of the invention, the group VIB metal content may be 20-30 wt.% and the group VIII metal content may be 1.5-8.5 wt.% based on the total catalyst and calculated as oxides.
In a fourth aspect, the present invention provides a method for preparing a hydrogenation catalyst, the method comprising:
SS1, impregnating the carrier by using an aqueous solution containing a hydrogenation active component compound to obtain an impregnated carrier;
SS2, subjecting the impregnated support to a second drying and a second calcination.
According to a fourth aspect of the present invention, the hydrogenation-active component compound may comprise a group VIII metal-containing compound and/or a group VIB metal-containing compound; preferably, the group VIII metal-containing compound may be at least one of nitrate, acetate, carbonate, chloride, and complex of nickel and cobalt; the group VIB metal-containing compound can include at least one of molybdic acid, paramolybdic acid, molybdate, para-molybdate, tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate, and ethyl metatungstic acid.
According to a fourth aspect of the present invention, in step SS1, the conditions of the impregnation may include: the soaking temperature is 5-150 ℃ and the soaking time is 0.5-12 hours; in step SS2, the conditions of the first drying process may include: the drying temperature is 80-350deg.C, preferably 100-300deg.C; the drying time is 0.5 to 24 hours, preferably 1 to 12 hours; the conditions of the second firing may include: the roasting temperature is 360-700 ℃, preferably 400-650 ℃; the calcination time is 0.2 to 12 hours, preferably 1 to 10 hours.
In a fifth aspect, the present invention provides a method for hydro-upgrading a heavy distillate, wherein the heavy distillate and hydrogen are contacted with the hydrogenation catalyst under hydrogenation conditions.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way. In the examples and comparative examples of the present invention, the dry basis was determined by calcining the sample at 600℃for 4 hours.
Example 1
31.0g of SD (from ziquone catalyst plant, manufactured by Shandong aluminum plant, dry basis 64.5%), 94.10g of silicon-aluminum material Siral40 (from catalyst Kaolin division, manufactured by SASOL, silicon oxide content 40.3%, dry basis 79.7%), 5.55g of beta-molecular sieve beta-A (from catalyst Kaolin Co., silicon-aluminum ratio 25.8), 2g of carboxymethyl cellulose A (M450, inlet split charging) and 5g of sesbania powder are taken and mixed to obtain mixed powder. Mixing 125mL deionized water with the mixed powder, repeatedly kneading for 3 times by a small-sized extruding machine, and adoptingThe extruded strips are obtained by drying the extruded strips at 120 ℃ for 6 hours, the dried strips are taken and put into a roasting furnace, the dried strips are treated at 550 ℃ for 3 hours, the air flow is kept at 30L/h, the temperature is reduced to room temperature, and the dried strips are taken out and marked as carrier AC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the content of tungsten oxide in the catalyst being 23 weight percent and the content of nickel oxide being 5.5 weight percent, and impregnating the prepared carrier AC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 440℃for 3 hours, and the air flow rate was maintained at not less than 27.5 cubic meters/(kg carrier. Hr) during calcination, to thereby obtain a catalyst AS.
Example 2
SD (from the zipcocene catalyst plant, shandong aluminum plant, dry 64.5%) was taken at 46.5g of silica alumina material siral40 (obtained from catalyst Kaolin Co., SASOL production, silica content 40.3%, dry basis 79.7%) 69.01g, beta-molecular sieve beta-B (obtained from catalyst Kaolin Co., ltd., silica alumina ratio 56.3) 16.09g, carboxymethyl cellulose B (Shandong Heda Co., ltd.) 2.5g, sesbania powder 5g, and mixed to obtain a mixed powder. Mixing 92mL deionized water with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adoptingThe extruded strips are obtained by a trilobal orifice plate, dried at 115 ℃ for 6 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 2.5 hours at 600 ℃, the air flow is kept at 35L/h, and the dried strips are taken out after being cooled to room temperature and marked as carrier BC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the tungsten oxide content of 25 weight percent and the nickel oxide content of 7 weight percent in the catalyst, and impregnating the prepared carrier BC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 450℃for 3 hours, and the air flow rate was maintained at not less than 35 cubic meters/(kg carrier. Hr) during calcination, to thereby obtain a catalyst BS.
Example 3
20.3g of CL-B (from catalyst Kaolin Co., ltd., dry basis 74%) and SA-1 (from zipcocene catalyst Co., silica content 28.8%, dry basis 81.1%) were taken, 92.48g of beta-type molecular sieve beta-C (from catalyst Kaolin Co., ltd., silica-alumina ratio 91.6), 10.52g of carboxymethyl cellulose A (M451, inlet split charging) 3g and sesbania powder 5g were taken and mixed to obtain a mixed powder. Mixing 125mL deionized water with the mixed powder, repeatedly kneading for 3 times by a small-sized extruding machine, and adoptingThe extruded strips are obtained by a trilobal orifice plate, dried at 125 ℃ for 5 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 3 hours at 580 ℃, the air flow is kept at 40L/h, and the dried strips are taken out after being cooled to room temperature and marked as carrier CC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the tungsten oxide content of 26 weight percent and the nickel oxide content of 4 weight percent in the catalyst, and impregnating the prepared carrier CC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, and then calcined at 430℃for 3 hours, with the air flow rate kept at not less than 20 cubic meters/(kg carrier. Hr) during the calcination, to thereby obtain the catalyst CS.
Example 4
54.1g of CL-B (from catalyst Kaolin Co., ltd., dry basis: 74%) 43.59g of silica-alumina material SA-2 (from zipcocene catalyst Co., silica content: 32.6%, dry basis: 80.3%), 25.96g of beta-molecular sieve beta-D (from catalyst Kaolin Co., ltd., silica-alumina ratio: 119.0), 3.5g of carboxymethyl cellulose B (Shandong Heda Co., ltd.) and 5g of sesbania powder were mixed to obtain a mixed powder. Mixing 58mL of deionized water with the mixed powder, repeatedly kneading for 3 times by a small-sized extruding machine, and adoptingThe extruded strips are obtained by drying the extruded strips at 130 ℃ for 4 hours, the dried strips are taken and put into a roasting furnace, the dried strips are treated at 560 ℃ for 3 hours, the air flow is kept at 35L/h, the temperature is reduced to room temperature, and the dried strips are taken out and marked as carrier DC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (both from a long-term catalyst factory) according to the tungsten oxide content of 24 wt% and the nickel oxide content of 5wt% in the catalyst, and impregnating the prepared carrier DC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 440℃for 3 hours, and the air flow rate was maintained at not less than 25 cubic meters/(kg carrier. Hour) during calcination, to thereby obtain catalyst DS.
Example 5
33.1g of USA (from the ziquone catalyst plant, 75.5% on dry basis), 69.97g of silicon aluminum material SA-3 (from the ziquone catalyst plant, 39.7% on silica, 78.6% on dry basis), 21.60g of beta-molecular sieve beta-E (from the catalyst Kaolin Co., ltd., silicon-aluminum ratio 38.7), 4g of carboxymethyl cellulose A (M452, inlet split charging)5g of sesbania powder, and mixing to obtain mixed powder. Mixing 92mL deionized water with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adoptingThe extruded strips are obtained by a trilobal orifice plate, dried at 105 ℃ for 10 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 2 hours at 620 ℃, the air flow is kept at 45L/h, and the dried strips are taken out after being cooled to room temperature and marked as a carrier EC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are all taken from a kaolin catalyst factory) according to the tungsten oxide content of 25.5 weight percent and the nickel oxide content of 3.5 weight percent in the catalyst, and impregnating the prepared carrier EC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 425℃for 3 hours, and the air flow rate was maintained at not less than 17.5 cubic meters/(kg carrier. Hr) during calcination, to thereby obtain a catalyst ES.
Example 6
46.4g of USA (from the ziquone catalyst plant, 75.5% on dry basis), 59.19g of silicon-aluminum material SA-1 (from the ziquone catalyst plant, 28.8% on silica content, 81.1% on dry basis), 18.87g of beta-type molecular sieve beta-A (from the catalyst Kaolin Co., ltd., silicon-aluminum ratio of 25.8), 4.5g of carboxymethyl cellulose B (Shandong Heda Co., ltd.) and 5g of sesbania powder were mixed to obtain mixed powder. Mixing 80mL deionized water with the mixed powder, repeatedly kneading for 3 times by a small-sized strip extruder, and adoptingThe extruded strips are obtained by a trilobal orifice plate, dried at 110 ℃ for 8 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 3 hours at 590 ℃, the air flow is kept at 40L/h, and the dried strips are taken out after being cooled to room temperature and marked as carrier FC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the tungsten oxide content of 27 weight percent and the nickel oxide content of 3 weight percent in the catalyst, and impregnating the prepared carrier FC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 5 hours, and then calcined at 420℃for 3 hours, with the air flow rate kept at not less than 15 cubic meters/(kg carrier. Hr) during the calcination, to thereby obtain the catalyst FS.
Example 7
66.7g of USA-2 (from the ziquone catalyst plant, dry basis 75%) and 24.91g of silicon-aluminum material SA-2 (from the ziquone catalyst plant, silicon oxide content 32.6% and dry basis 80.3%), 32.19g of beta-type molecular sieve beta-B (from catalyst longline Co., ltd., silicon-aluminum ratio 56.3), 5g of carboxymethyl cellulose A (M453, import split charging) and 5g of sesbania powder are taken and mixed to obtain mixed powder. Mixing 33mL deionized water with the mixed powder, repeatedly kneading for 3 times by using a small-sized strip extruder, and adoptingThe extruded strips are obtained by a trilobal orifice plate, dried at 120 ℃ for 7 hours to obtain dried strips, the dried strips are taken and put into a roasting furnace to be treated for 2 hours at 610 ℃, the air flow is kept at 45L/h, and the dried strips are taken out after being cooled to room temperature and marked as a carrier GC.
Based on 100g of carrier, mixed aqueous solution of nickel nitrate and ammonium metatungstate (all from a long-term catalyst factory) is prepared according to the content of tungsten oxide in the catalyst of 24.5 weight percent and the content of nickel oxide of 4.5 weight percent, and a pore saturation method is adopted for impregnating the prepared carrier GC. The impregnated carrier was dried at 115℃for 5 hours, followed by calcination at 430℃for 3 hours, and the air flow rate was maintained at not less than 22.5 cubic meters/(kg carrier. Hr) during calcination, to thereby obtain the catalyst GS.
Comparative example 1
46.5g of SD (from the ziquone catalyst plant, produced by Shandong aluminum plant, dry basis 64.5%) and 69.97g of silicon aluminum material SA-3 (from the ziquone catalyst plant, silicon oxide content 39.7% and dry basis 78.6%) were taken, 18.69g of beta-type molecular sieve beta-D (from catalyst longline Co., ltd., silicon-aluminum ratio 119.0), 5g of sesbania powder were taken and mixed to obtain mixed powder. Mixing 70mL deionized water with the mixed powder, repeatedly kneading for 3 times by a small-sized extruding machine, and adoptingIs obtained by a trilobal orifice plateAnd (3) drying the extruded strip at 115 ℃ for 6 hours to obtain a dry strip, putting the dry strip into a roasting furnace, treating for 3 hours at 550 ℃, keeping the air flow at 40L/h, cooling to room temperature, taking out, and marking as a carrier XC.
Based on 100g of carrier, preparing a mixed aqueous solution of nickel nitrate and ammonium metatungstate (which are taken from a kaolin catalyst factory) according to the tungsten oxide content of 22.5 weight percent and the nickel oxide content of 4 weight percent in the catalyst, and impregnating the prepared carrier XC by adopting a pore saturation method. The impregnated carrier was dried at 115℃for 6 hours, followed by calcination at 440℃for 3 hours, and the air flow rate was maintained at not less than 20 cubic meters/(kg carrier. Hour) during calcination, to thereby obtain catalyst XS.
Test example 1
Model number commercially available from Quantachrome IncThe specific surface area and pore volume of the porous supports prepared in examples 1 to 7 and comparative example 1 were measured by BET method according to the method specified in RIPP 151-90 on a six-station fully automatic specific surface area and pore size distribution measuring apparatus of 6B, and the specific results are shown in Table 1.
TABLE 1
Test example 2
The once-through process is adopted, and the HVGO is adopted as raw oil. Density (20 ℃ C.) 0.9631g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the Sulfur content 17000. Mu.g/g; nitrogen content 3500 mug/g; hydrogen content 10.80%; ni+V<2 μg/g; 3.20% of carbon residue; asphaltenes<0.1%; the distillation range ASTM D-1160, IBP163 ℃; FBP 687 ℃.
Crushing the catalyst into particles with the diameter of 0.5-1.0 mm, loading 150 ml of the catalyst into a 200 ml fixed bed reactor, and before oil passing, firstly placing the catalyst in hydrogenVulcanizing for 28 hours under the conditions of partial pressure of 5.0MPa and temperature of 300 ℃, then introducing raw oil at the hydrogen partial pressure of 5.0MPa and the temperature of 350 ℃, wherein the hydrogen-oil ratio is 1500 volumes/volumes, and the liquid hourly space velocity is 5 hours -1 And sampled after 12 hours and 1000 hours of reaction. The yield of aviation kerosene and the content of isomerised hydrocarbons in the hydrogenated oil were determined and the specific results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the catalyst provided by the invention has lower product density and higher hydrogen content in the product by adopting a one-pass process to process heavy oil products. Compared with the comparative example, namely the conventional catalyst preparation method, the catalyst provided by the invention has higher maintenance activity and lower loss rate under a long period (after 240 hours).
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (17)
1. A support for use in the preparation of a hydrogenation catalyst, characterized in that:
the carrier contains a non-amorphous mesoporous acid material and a beta-type molecular sieve;
the carrier has a bimodal pore structure and contains 3-30wt% of beta type molecular sieve;
in the bimodal pore structure, the pore diameter of a macropore which can be few pores is in the range of 600-1200 nm, the pore diameter of a micropore which can be few pores is in the range of 4-9 nm, and the ratio of the pore diameter of the macropore which can be few pores to the pore diameter of the micropore which can be few pores is 120-200;
the ratio of the pore volume of the large pore to the pore volume of the small pore is 2-4, the pore volume of the large pore is the cumulative pore volume of pores with the pore diameter within 50-150% of the pore diameter of the small pore, and the pore volume of the small pore is the cumulative pore volume of pores with the pore diameter within 50-150% of the pore diameter of the small pore; the pore volume of the macropores accounts for 15-20% of the total pore volume of the carrier;
the hole concentration value of the small holes is not lower than 0.5;
the non-amorphous mesoporous acid material is silicon-aluminum composite oxide.
2. The carrier according to claim 1, wherein in the carrier, the macropore has a pore diameter of about 700 to 1050nm, and the macropore has a pore diameter of about 5 to 9 nm.
3. The carrier of claim 1, wherein the pores have a pore concentration value of not less than 0.75.
4. A method for producing the carrier for hydrogenation catalyst according to any one of claims 1 to 3, characterized by comprising:
s1, mixing pseudo-boehmite, amorphous silicon-aluminum oxide, beta-type molecular sieve, carboxymethyl cellulose and sesbania powder to obtain mixed powder;
s2, mixing the mixed powder with water, kneading and extruding to obtain an extruded strip;
s3, carrying out first drying and first roasting on the extruded strip.
5. The preparation method according to claim 4, wherein in step S1, the weight ratio of the pseudo-boehmite, the amorphous silica-alumina oxide, the beta-type molecular sieve, the carboxymethyl cellulose and the sesbania powder is 10 to 55:15-85:3-35:1.0-5.0:2-4;
in the step S2, the water is used in an amount of 80-140mL for every 100g of the mixed powder.
6. The process according to claim 4 or 5, wherein,
SiO in the pseudo-boehmite 2 The content of (C) is less than 0.1wt%, fe 2 O 3 Less than 0.01wt%, na 2 The content of O is less than 0.15wt%, the content of water is less than 3wt%, and the ignition loss is 32-38 wt%; the pore volume of the pseudo-boehmite is 0.60-1.1mL/g, and the specific surface is 220-310m 2 /g;
SiO in the amorphous silicon aluminum oxide 2 The content of (C) is 15-55wt%, al 2 O 3 The content of the modified polypropylene is 45-85wt% and the bulk density is 250-450 g/L;
the sodium content of the 2% aqueous solution of carboxymethyl cellulose is less than 2.0% by weight.
7. The production method according to claim 4 or 5, wherein, in step S2, the conditions of mixing include: the temperature is 10-40 ℃ and the time is 1-10 minutes;
in step S3, the first drying conditions include: the temperature is 100-130 ℃ and the time is 3-20 hours; the conditions of the first firing include: the temperature is 400-600 ℃, the time is 2-10 hours, and the air flow is 20-50L/h.
8. A hydrogenation catalyst comprising the support of any one of claims 1 to 3 and an active metal component.
9. The hydrogenation catalyst of claim 8, wherein the active metal component is selected from the group consisting of group VIII and/or group VIB metal elements.
10. The hydrogenation catalyst according to claim 9, wherein the group VIII metal element is cobalt and/or nickel and the group VIB metal element is molybdenum and/or tungsten.
11. The hydrogenation catalyst according to claim 10, wherein the group VIB metal content is 20-30 wt.% and the group VIII metal content is 1.5-8.5 wt.% based on the total catalyst and on oxide basis.
12. A method for preparing a hydrogenation catalyst, comprising:
SS1, impregnating the support according to any one of claims 1 to 3 with an aqueous solution containing a hydrogenation-active component compound to obtain an impregnated support;
SS2, subjecting the impregnated support to a second drying and a second calcination.
13. The process according to claim 12, wherein the hydrogenation-active component compound comprises a group VIII metal-containing compound and/or a group VIB metal-containing compound.
14. The production method according to claim 13, wherein the group VIII metal-containing compound is at least one of nitrate, acetate, carbonate, chloride, and complex of nickel and cobalt; the group VIB metal-containing compound comprises at least one of molybdic acid, paramolybdic acid, molybdate, para-molybdate, tungstic acid, metatungstic acid, ethyl metatungstic acid, tungstate, metatungstate, and ethyl metatungstic acid.
15. The process according to claim 14, wherein,
in step SS1, the conditions of the impregnation include: the soaking temperature is 5-150 ℃ and the soaking time is 0.5-12 hours;
in step SS2, the conditions of the second drying process include: the drying temperature is 80-350 ℃; the drying time is 0.5-24 hours; the conditions of the second firing include: the roasting temperature is 360-700 ℃; the roasting time is 0.2-12 hours.
16. The production method according to claim 15, wherein the conditions of the second drying treatment include: the drying temperature is 100-300 ℃; the drying time is 1-12 hours; the conditions of the second firing include: the roasting temperature is 400-650 ℃; the roasting time is 1-10 hours.
17. A process for the hydro-upgrading of a heavy distillate, characterized in that the heavy distillate and hydrogen are contacted with a hydrogenation catalyst according to any one of claims 8-11 under hydrogenation conditions.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1216316A (en) * | 1998-06-22 | 1999-05-12 | 中国石化扬子石油化工公司 | Hydrogenation protecting catalyst and its preparation |
CN103028442A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Porous support, preparation method and application thereof, catalyst, and hydrocracking method |
CN106391103A (en) * | 2015-07-28 | 2017-02-15 | 中国石油化工股份有限公司 | Multi-level pore hydrocracking catalyst containing silicon-aluminum, and applications thereof |
CN110773182A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Hydrogenation activity protection catalyst and preparation and application thereof |
CN110773187A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
MX2008006050A (en) * | 2008-05-09 | 2009-11-09 | Mexicano Inst Petrol | Moderate-acidity catalyst for hydroprocessing of heavy crude and waste, and synthesis method therefor. |
-
2020
- 2020-10-30 CN CN202011197863.4A patent/CN114433206B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1216316A (en) * | 1998-06-22 | 1999-05-12 | 中国石化扬子石油化工公司 | Hydrogenation protecting catalyst and its preparation |
CN103028442A (en) * | 2011-09-30 | 2013-04-10 | 中国石油化工股份有限公司 | Porous support, preparation method and application thereof, catalyst, and hydrocracking method |
CN106391103A (en) * | 2015-07-28 | 2017-02-15 | 中国石油化工股份有限公司 | Multi-level pore hydrocracking catalyst containing silicon-aluminum, and applications thereof |
CN110773182A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Hydrogenation activity protection catalyst and preparation and application thereof |
CN110773187A (en) * | 2018-07-31 | 2020-02-11 | 中国石油化工股份有限公司 | Heavy oil hydrogenation deasphaltened catalyst and preparation and application thereof |
Non-Patent Citations (1)
Title |
---|
重油加氢催化剂孔结构改善的研究进展;秦川;;广州化工(第02期);第18-20页 * |
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