CN111889133A - Preparation method of vulcanization type hydrocracking catalyst - Google Patents
Preparation method of vulcanization type hydrocracking catalyst Download PDFInfo
- Publication number
- CN111889133A CN111889133A CN202010781436.4A CN202010781436A CN111889133A CN 111889133 A CN111889133 A CN 111889133A CN 202010781436 A CN202010781436 A CN 202010781436A CN 111889133 A CN111889133 A CN 111889133A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- hydrocracking catalyst
- acid
- group
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000004073 vulcanization Methods 0.000 title claims abstract description 12
- 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 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 239000012298 atmosphere Substances 0.000 claims abstract description 20
- 238000001291 vacuum drying Methods 0.000 claims abstract description 17
- 125000000524 functional group Chemical group 0.000 claims abstract description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 11
- 239000011593 sulfur Substances 0.000 claims abstract description 11
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims description 19
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 19
- 239000010457 zeolite Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 14
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 150000007522 mineralic acids Chemical class 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 3
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 3
- 150000003657 tungsten Chemical class 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims description 2
- 125000003368 amide group Chemical group 0.000 claims description 2
- -1 amino, sulfydryl Chemical group 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 229910021472 group 8 element Inorganic materials 0.000 claims 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000007787 solid Substances 0.000 description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 16
- 239000002245 particle Substances 0.000 description 16
- 239000011148 porous material Substances 0.000 description 14
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 13
- 235000019441 ethanol Nutrition 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000011068 loading method Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 6
- 229910021417 amorphous silicon Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000005486 sulfidation Methods 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000010724 circulating oil Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- XUIMIQQOPSSXEZ-NJFSPNSNSA-N silicon-30 atom Chemical compound [30Si] XUIMIQQOPSSXEZ-NJFSPNSNSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds 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
-
- 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
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalyst materials, and particularly relates to a preparation method of a vulcanization type hydrocracking catalyst. The preparation method comprises the steps of preparing a catalyst carrier by using a mixed molecular sieve, modifying a new functional group on the surface of the prepared carrier through a chemical bond, impregnating a VIB group element-containing compound, a VIII group element-containing compound and a sulfur-containing nonmetal compound solution, and roasting in a vacuum drying inert atmosphere to prepare the vulcanized hydrocracking catalyst, wherein pre-vulcanization treatment is not needed before use. The hydrocracking catalyst obtained by the invention has higher hydrocracking activity and diesel selectivity.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, and particularly relates to a preparation method of a vulcanization type hydrocracking catalyst.
Background
The hydrocracking process is an oil refining process that converts high boiling feedstocks into low boiling naphtha and diesel fractions. Compared with catalytic cracking, the method has the advantages of high raw material adaptability, high yield of diesel oil fraction and good quality. With the increasing demand of society for clean transportation fuel oil, the hydrocracking process becomes one of the core processes of modern refineries. The hydrocracking catalyst is the core of the overall hydrocracking process, which typically includes a bifunctional center: the first one is an acid center provided by a carrier, which basically determines the activity of the catalyst, and during the development of hydrocracking catalysts, materials such as halogenated (chlorine or fluorine) alumina, amorphous silica-alumina and molecular sieves have been used as acid components, and since the last 70 th century, with the development of molecular sieve preparation technology, silica-alumina molecular sieves gradually become the main component of the acid center in hydrocracking catalysts due to their definite structures and adjustable acidity. The second is a metal center which plays a hydrogenation/dehydrogenation role in the reaction process, provides a reaction raw material for the acid center, and timely saturates the acid center product to prevent deep cracking. The metal center is generally composed of a group VIB metal or a group VIB and VIIIB binary metal system, providing true hydrogenation/dehydrogenation activity in the form of sulfides. The acidic center is tightly bound to the hydrogenation/dehydrogenation center, and the coordination of the two is the key to the successful operation of the hydrocracking catalyst.
In order to meet the increasing demand of society for clean transportation fuel oil, high boiling point raw materials are fully utilized in the hydrocracking process to produce more naphtha and diesel oil products, and the production of low-value gaseous products (C1-C4) is reduced. Meanwhile, in order to reduce the operating cost of the production, the industrial production is expected to use a catalyst with higher activity to reduce the reaction temperature. Specifically, it is desirable to improve both the acid-center and metal-center properties of the catalyst during catalyst design: the performance of the acid sites can be enhanced by increasing the acid strength of the acidic material (e.g., molecular sieve) or its amount used; the metal core performance is limited by the effective specific surface area provided by the carrier and the characteristics of the metal itself, and cannot be improved simply by increasing the amount used. Therefore, how to improve the performance of the metal center has been a hot spot of research in this field.
The performance of the acid center can be improved by increasing the acid strength or the use amount of the molecular sieve, and the invention improves the performance of the acid center by mixing two molecular sieves. The limitation of the properties of the metal core is due to the fact that the surface of inorganic oxides such as alumina has a large number of hydroxyl groups, and the types of the hydroxyl groups can be classified into five types according to the coordination environment of the aluminum atoms (reference: Catal Rev. Sci. Eng. 17(1), 31-70, 1978). The formation of Al-O-M chemical bonds by condensation of these hydroxyl groups is the key reason for the stronger interaction between the group VIB metal and the alumina support. The invention carries out surface modification on the inorganic oxide carrier, replaces all or part of strong hydroxyl on the surface of the inorganic oxide carrier with other functional groups, and leads the inorganic oxide carrier and VI B metal to form weak interaction, even to directly participate in the vulcanization process of VI B metal oxide, thereby essentially changing the interaction between the transition metal and the surface of the inorganic carrier, being beneficial to fully presulfurizing the transition metal oxide, and further playing the best hydrogenation/dehydrogenation performance in hydrocracking reaction.
The active metal of the hydrocracking catalyst is mostly dispersed on the carrier in an oxidation state, and can perform reactions such as hydrodesulfurization, nitrogen, hydrodearomatization, hydrocracking and the like. Research shows that the activity, selectivity and stability of the catalyst without pre-sulfurization are lower than those of the catalyst in the sulfurization state, and the service life is shorter. The presulfurization of the catalyst in the hydrogenation process is one of the important links of the application of the catalyst. The catalyst in an oxidation state is presulfurized to convert active metal components into a vulcanization state, so that the activity of the hydrogenation catalyst can be exerted to the maximum extent, and the presulfurization mode of the catalyst can be divided into in-situ presulfurization and out-of-situ vulcanization according to different places where the sulfidization reaction is carried out.
However, no matter the in-situ presulfurization technology or the out-of-situ presulfurization technology is adopted, the catalyst must undergo the process of converting the active metal into the oxidation state and then converting the oxidation state into the sulfidization state before the catalyst is actually applied, and the process is complex and has a plurality of influencing factors. In addition, the final completion of the catalyst sulfidation through multiple steps is likely to cause the insufficient sulfidation of the portion of the active metal which can only form strong interaction with the catalyst carrier, thereby affecting the catalyst performance.
Disclosure of Invention
The invention aims to provide a preparation method of a vulcanization type hydrocracking catalyst, which can greatly shorten the start-up time, avoid the safety risk, improve the stability of the catalyst, and has higher hydrocracking activity and diesel selectivity by using the hydrocracking catalyst prepared by using a mixed molecular sieve without pre-vulcanization treatment before use.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a vulcanization type hydrocracking catalyst comprises the following steps:
(1) fully mixing pseudo-boehmite, amorphous silicon-aluminum, USY molecular sieve and beta zeolite according to a certain proportion, adding a certain amount of acid solution, kneading for 2-60 minutes, and then extruding and molding; drying the obtained molded body at 100-200 ℃ for 2-24 h, and roasting at 400-750 ℃ for 2-8 h to prepare the catalyst carrier;
(2) adding a modifying reagent with the weight of 0.5-20% of that of the catalyst carrier obtained in the step (1), reacting at 5-40 ℃ for 1-24h, heating to 40-100 ℃, and reacting for 1-12h, so as to connect new functional groups on the surface of the inorganic carrier through chemical bonds, thereby obtaining the surface-modified inorganic carrier;
(3) and (3) dispersing a VIB group element-containing compound, a VIII group element-containing compound and a sulfur-containing nonmetal compound in a solvent, impregnating the catalyst carrier obtained in the step (2) for 1-12h, then carrying out vacuum drying at 50-100 ℃ for 6-48 h, and roasting at 200-350 ℃ for 2-24 h in an inert atmosphere to obtain the hydrocracking catalyst.
The weight ratio of the pseudoboehmite, the amorphous silicon-aluminum, the USY molecular sieve and the beta zeolite used in the step (1) is (20-80): (20-60): (1-20): (0.05-4).
The adding amount of the acid solution used in the step (1) is 0.5-10% of the total weight of the pseudo-boehmite, the amorphous silicon-aluminum and the molecular sieve, and the concentration of the acid solution is not more than 10 wt%; the acid solution comprises inorganic acid or organic acid, wherein the inorganic acid comprises any one of sulfuric acid, hydrochloric acid and nitric acid, and the organic acid comprises any one of formic acid, acetic acid and citric acid;
preferably, the acid solution is a nitric acid solution, and the concentration of the acid solution is 0.5wt% to 5wt%, preferably 1wt% to 3 wt%.
The USY molecular sieve in the step (1) has the following properties: the specific surface area is 500-800 m2(ii) a total pore volume of 0.40 to 0.65 cm3Per g, wherein the mesoporous volume is 0.05-0.35 cm3The molar ratio of Si to Al is 10-30.
The beta zeolite in the step (1) is specifically: the molar ratio of Si/Al is 0-30, the specific surface area is 360-2Per g, pore volume of 0.32-0.50 cm3A beta zeolite having an SF6 adsorption capacity of at least 28 wt.%.
The weight ratio of the USY molecular sieve to the beta zeolite in the step (1) is (5-20): 1.
the amorphous silicon-aluminum obtained in the step (1) has the following properties after being roasted for 6 hours at 530 ℃ in an air atmosphere: the specific surface area is 350-600 m2(ii)/g; the pore volume is 0.6-1.8 cm3A concentration of 1.0 to 1.4 cm3(ii)/g; in terms of weight fraction, SiO2The content is 20-80%.
The aluminum oxide obtained by roasting the pseudo-boehmite in the step (1) for 6 hours at 530 ℃ in the air atmosphere has the following properties: the specific surface area is 150-400 m2Per g, preferably 200 to 350 m2(ii)/g; the pore volume is 0.3-0.8 cm3Per g, preferably 0.40 to 0.65 cm3(ii)/g; the content of Na element is less than or equal to 0.1 percent in weight fraction.
The size and shape of the formed body in the step (1) are preferably similar to those of a traditional hydrocracking commercial catalyst, and the formed body is more preferably prepared into an extrudate with a diameter of 1.5-3.5 nm and a length of 3-12 nm and a circular or clover section.
The modifying reagent in the step (2) contains two or more functional groups, wherein one functional group needs to be capable of reacting with the surface of the inorganic carrier and is selected from any one of hydroxyl, carboxyl, amino, acid anhydride, halogen substituent (such as-Cl, -Br, -I and the like), siloxyl, phosphate, metaphosphate or phosphite, and the preferred functional group is siloxyl; the other functional group is required to be capable of reacting with an oxide or salt containing a group VIB metal element or a group VIIB metal element, and is selected from any one of hydroxyl, carboxyl, amino, sulfydryl, amido or halogen substituent, and the preferred functional group is sulfydryl.
The compound containing the VIII group element in the step (3) is preferably a nickel salt, and the nickel salt comprises one or more of nickel nitrate, nickel acetate and basic nickel carbonate.
Preferably, the group VIB element-containing compound in step (3) is a sulfur-containing tungsten salt, and the sulfur-containing tungsten salt includes, but is not limited to, one or more of ammonium trithiotungstate, ammonium tetrathiotungstate, ammonium dodecathiotungstate and ammonium tridecylthiotungstate.
The sulfur-containing nonmetal compound in the step (3) includes but is not limited to one or more of ammonium sulfide, thiourea and ammonium thiosulfate.
The solvent described in the step (3) is not particularly limited as long as impregnation loading can be achieved, and these solvents may be dissolved or dissolved by adjusting pH, may be those capable of forming a colloid or forming a colloid by adjusting pH, may be a single solvent, or may be mixed solvents.
In the step (3), the mass ratio of the VIB group element-containing compound, the VIII group element-containing compound and the sulfur-containing nonmetal compound is (1-600): (1-50): (0.3-500).
And (3) roasting at 0-5MPa, wherein the roasting comprises one or more of nitrogen, argon and helium.
The invention has the following remarkable advantages: the invention modifies functional groups on the surface of the inorganic carrier through chemical bonds, and simultaneously, the low amount of beta zeolite relative to Y zeolite is beneficial to reducing the formation of undesirable heavy polynuclear aromatic byproducts which can reduce the stability, improving the stability of the catalyst and simultaneously leading the obtained catalyst to have higher diesel oil yield. And the catalyst does not need to be vulcanized or activated in the process of start-up, so that the start-up time can be greatly shortened, the safety risk can be avoided, and the catalyst has a good application prospect.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
The USY molecular sieve used has the following properties: specific surface area of 600 m2(ii)/g, total pore volume 0.48 cm3Per g, wherein the mesoporous volume is 0.15 cm3The molar ratio Si/Al is 22.
The amorphous silicon-aluminum is roasted for 6 hours at 530 ℃ in air atmosphere, and the specific surface area is 382 m2G, pore volume 1.22 cm3/g，SiO2The content is 35%.
The pseudo-boehmite is roasted for 6 h at 530 ℃ to obtain alumina with the specific surface of 235 m2Per g, pore volume of 0.63 cm3The content of Na element is less than 0.08 percent.
The beta zeolite used has the following properties: the Si/Al molar ratio is 25, and the specific surface area is 470 m2Per g, pore volume of 0.39cm3G, SF6 adsorption capacity of 30 wt% beta zeolite.
Example 1:
weighing 200 g of pseudo-boehmite (dry basis, all raw materials are not particularly specified below, all the weight is dry basis weight), 170 g of amorphous silicon aluminum, 25 g of USY molecular sieve and 5g of beta zeolite, fully mixing the three solid powders, adding a prepared dilute nitric acid solution, kneading for 15 minutes, extruding strips through a 3.0mm pore plate, drying at 140 ℃ for 12 hours, and roasting at 560 ℃ in an air atmosphere for 4 hours to obtain the catalyst carrier S1.
Example 2:
5.6g of 3-aminopropyltriethoxysilane was weighed into 100mL of 95% ethanol solution, and stirred at room temperature for 20min to be sufficiently dissolved. Then, 40g of the support S1 prepared in example 1 was added to the above solution, the reaction vessel was purged with nitrogen gas and kept under a slight positive pressure of nitrogen atmosphere, and the mixture was left at room temperature for reaction for 12 hours, then heated to 60 ℃ and reacted for 4 hours. After the reaction, the excess ethanol solution was poured out, the obtained solid particles were washed with anhydrous ethanol at room temperature for 3 times, then predried in an air atmosphere at room temperature for 4 hours, and then put into a vacuum drying oven to be fully dried at 70 ℃ to obtain a surface-modified carrier Z1.
Example 3:
adding 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate into 26 mL of deionized water, stirring until the ammonium tetrathiotungstate, the nickel nitrate and the ammonium thiosulfate are completely dissolved to obtain a mixed aqueous solution, then impregnating and loading 40.0 g of catalyst carrier Z1, then carrying out vacuum drying at 60 ℃ for 12h, and roasting at 315 ℃ in a nitrogen atmosphere for 3 h to obtain the hydrocracking catalyst C1.
Example 4:
weighing 200 g of pseudo-boehmite (dry basis, all raw materials are not particularly specified below, all the weight is dry basis weight), 170 g of amorphous silicon aluminum, 26.25 g of USY molecular sieve and 3.75g of beta zeolite, fully mixing the three solid powders, adding a prepared dilute nitric acid solution, kneading for 15 minutes, extruding strips through a 3.0mm pore plate, drying at 140 ℃ for 12 hours, and roasting at 560 ℃ in air atmosphere for 4 hours to obtain a catalyst carrier S2; then, 5.6g of 3-aminopropyltriethoxysilane was weighed into 100mL of 95% ethanol solution, and stirred at room temperature for 20min to be sufficiently dissolved. Then 40g of the prepared carrier S2 was added to the above solution, the reaction vessel was purged with nitrogen and kept under a slight positive pressure of nitrogen atmosphere, left to react at room temperature for 12 hours, then heated to 60 ℃ and reacted for 4 hours. After the reaction is finished, pouring out excessive ethanol solution, washing the obtained solid particles for 3 times at room temperature by using absolute ethyl alcohol, then pre-drying the solid particles for 4 hours at room temperature in an air atmosphere, and then fully drying the solid particles in a vacuum drying oven at 70 ℃ to obtain a surface-modified carrier Z2; and finally, adding 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate into 26 mL of deionized water, stirring until the ammonium tetrathiotungstate, the nickel nitrate and the ammonium thiosulfate are completely dissolved to obtain a mixed aqueous solution, then impregnating and loading 40.0 g of catalyst carrier Z2, then carrying out vacuum drying at 60 ℃ for 12h, and roasting at 315 ℃ in a nitrogen atmosphere for 3 h to obtain the hydrocracking catalyst C2.
Example 5:
weighing 200 g of pseudo-boehmite (dry basis, all raw materials are not particularly specified below, all the weight is dry basis weight), 170 g of amorphous silicon aluminum, 26.67 g of USY molecular sieve and 3.33g of beta zeolite, fully mixing the three solid powders, adding a prepared dilute nitric acid solution, kneading for 15 minutes, extruding strips through a 3.0mm pore plate, drying at 140 ℃ for 12 hours, and roasting at 560 ℃ in air atmosphere for 4 hours to obtain a catalyst carrier S3; then, 5.6g of 3-aminopropyltriethoxysilane was weighed into 100mL of 95% ethanol solution, and stirred at room temperature for 20min to be sufficiently dissolved. Then 40g of the prepared carrier S3 was added to the above solution, the reaction vessel was purged with nitrogen and kept under a slight positive pressure of nitrogen atmosphere, left to react at room temperature for 12 hours, then heated to 60 ℃ and reacted for 4 hours. After the reaction is finished, pouring out excessive ethanol solution, washing the obtained solid particles for 3 times at room temperature by using absolute ethyl alcohol, then pre-drying the solid particles for 4 hours at room temperature in an air atmosphere, and then fully drying the solid particles in a vacuum drying oven at 70 ℃ to obtain a surface-modified carrier Z3; and finally, adding 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate into 26 mL of deionized water, stirring until the ammonium tetrathiotungstate, the nickel nitrate and the ammonium thiosulfate are completely dissolved to obtain a mixed aqueous solution, then impregnating and loading 40.0 g of catalyst carrier Z3, then carrying out vacuum drying at 60 ℃ for 12h, and roasting at 315 ℃ in a nitrogen atmosphere for 3 h to obtain the hydrocracking catalyst C3.
Example 6:
weighing 200 g of pseudo-boehmite (dry basis, all raw materials are not particularly specified below, all the weight is dry basis weight), 170 g of amorphous silicon aluminum, 27.27 g of USY molecular sieve and 2.73g of beta zeolite, fully mixing the three solid powders, adding a prepared dilute nitric acid solution, kneading for 15 minutes, extruding strips through a 3.0mm pore plate, drying at 140 ℃ for 12 hours, and roasting at 560 ℃ in air atmosphere for 4 hours to obtain a catalyst carrier S4; then, 5.6g of 3-aminopropyltriethoxysilane was weighed into 100mL of 95% ethanol solution, and stirred at room temperature for 20min to be sufficiently dissolved. Then 40g of the prepared carrier S4 was added to the above solution, the reaction vessel was purged with nitrogen and kept under a slight positive pressure of nitrogen atmosphere, left to react at room temperature for 12 hours, then heated to 60 ℃ and reacted for 4 hours. After the reaction is finished, pouring out excessive ethanol solution, washing the obtained solid particles for 3 times at room temperature by using absolute ethyl alcohol, then pre-drying the solid particles for 4 hours at room temperature in an air atmosphere, and then fully drying the solid particles in a vacuum drying oven at 70 ℃ to obtain a surface-modified carrier Z4; and finally, adding 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate into 26 mL of deionized water, stirring until the ammonium tetrathiotungstate, the nickel nitrate and the ammonium thiosulfate are completely dissolved to obtain a mixed aqueous solution, then impregnating and loading 40.0 g of catalyst carrier Z4, then carrying out vacuum drying at 60 ℃ for 12h, and roasting at 315 ℃ in a nitrogen atmosphere for 3 h to obtain the hydrocracking catalyst C4.
Example 7:
weighing 200 g of pseudo-boehmite (dry basis, all raw materials are not particularly specified below, all the weight is dry basis weight), 170 g of amorphous silicon aluminum, 28.12 g of USY molecular sieve and 1.88g of beta zeolite, fully mixing the three solid powders, adding a prepared dilute nitric acid solution, kneading for 15 minutes, extruding strips through a 3.0mm pore plate, drying at 140 ℃ for 12 hours, and roasting at 560 ℃ in air atmosphere for 4 hours to obtain a catalyst carrier S5; then, 5.6g of 3-aminopropyltriethoxysilane was weighed into 100mL of 95% ethanol solution, and stirred at room temperature for 20min to be sufficiently dissolved. Then 40g of the prepared carrier S5 was added to the above solution, the reaction vessel was purged with nitrogen and kept under a slight positive pressure of nitrogen atmosphere, left to react at room temperature for 12 hours, then heated to 60 ℃ and reacted for 4 hours. After the reaction is finished, pouring out excessive ethanol solution, washing the obtained solid particles for 3 times at room temperature by using absolute ethyl alcohol, then pre-drying the solid particles for 4 hours at room temperature in an air atmosphere, and then fully drying the solid particles in a vacuum drying oven at 70 ℃ to obtain a surface-modified carrier Z5; and finally, adding 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate into 26 mL of deionized water, stirring until the ammonium tetrathiotungstate, the nickel nitrate and the ammonium thiosulfate are completely dissolved to obtain a mixed aqueous solution, then impregnating and loading 40.0 g of catalyst carrier Z5, then carrying out vacuum drying at 60 ℃ for 12h, and roasting at 315 ℃ in a nitrogen atmosphere for 3 h to obtain the hydrocracking catalyst C5.
Comparative example 1:
weighing 200 g of pseudo-boehmite (dry basis, all raw materials are not particularly specified below, all the weight is dry basis weight), 170 g of amorphous silicon aluminum and 30 g of USY molecular sieve, fully mixing the three solid powders, adding a pre-prepared dilute nitric acid solution, kneading for 15 minutes, extruding strips through a 3.0mm pore plate, drying at 140 ℃ for 12 hours, and roasting at 560 ℃ in air atmosphere for 4 hours to obtain a catalyst carrier S0; then, 5.6g of 3-aminopropyltriethoxysilane was weighed into 100mL of 95% ethanol solution, and stirred at room temperature for 20min to be sufficiently dissolved. Then 40g of the prepared carrier S0 was added to the above solution, the reaction vessel was purged with nitrogen and kept under a slight positive pressure of nitrogen atmosphere, left to react at room temperature for 12 hours, then heated to 60 ℃ and reacted for 4 hours. After the reaction is finished, pouring out excessive ethanol solution, washing the obtained solid particles for 3 times at room temperature by using absolute ethyl alcohol, then pre-drying the solid particles for 4 hours at room temperature in an air atmosphere, and then fully drying the solid particles in a vacuum drying oven at 70 ℃ to obtain a surface-modified carrier Z0; and finally, adding 19.1 g of ammonium tetrathiotungstate, 7.8 g of nickel nitrate and 7.8 g of ammonium thiosulfate into 26 mL of deionized water, stirring until the ammonium tetrathiotungstate, the nickel nitrate and the ammonium thiosulfate are completely dissolved to obtain a mixed aqueous solution, then impregnating and loading 40.0 g of catalyst carrier Z0, then carrying out vacuum drying at 60 ℃ for 12h, and roasting at 315 ℃ in a nitrogen atmosphere for 3 h to obtain the hydrocracking catalyst C0.
Application example 1: wax oil hydrocracking reaction
The hydrocracking reaction conditions are as follows: the hydrogen pressure is 15.2 MPa, the hydrogen-oil volume ratio is 700:1, and the airspeed is 4.0 h-1. The modified catalysts C0-C5 were used as received. The hydrocracking circulating oil is adopted as a reaction raw material, the density is 0.855 g/ml, the nitrogen content is 1.1 ppmw, the sulfur content is 19 ppmw, and the distillation range distribution is as shown in the following table 1.
TABLE 1
The hydrocracking reaction device adopts a once-through hydrogenation process, and the device mainly comprises a gas feeding part, a liquid feeding part, a hydrogenation reaction part, a gas-liquid separation part, a product collection part and the like. A single reactor is filled with hydrocracking catalyst and heated by 5-section electric furnace. The reaction effluent enters a high-pressure separator and a low-pressure separation tank for gas-liquid separation. High-concentration hydrogen-rich gas is separated by a liquid separating tank, and ammonium salt is crystallized and settled by adopting jacket water cooling and corresponding technical measures, so that downstream pipelines and equipment are prevented from being blocked. The low pressure tail gas after the pressure control valve is metered with a gas flow meter and consists of on-line chromatographic analysis. The liquid product is analyzed off-line for distillation range. The catalyst test results are shown in table 2 below.
Table 2 catalyst test results
Catalyst test results show that catalyst C0, prepared by adding a different USY: the activity of catalysts C1-C5 prepared after the amount of beta zeolite with the mass ratio of beta is increased, the product selectivity is obviously changed, the naphtha selectivity of the catalysts C1-C2 is increased by about 1-3 percentage points, and the diesel oil selectivity of the catalysts C4-C5 is increased by 1-2 percentage points, which shows that by adding different USY: the amount of beta zeolite in the beta mass ratio helps to reduce the formation of undesirable heavy polynuclear aromatic byproducts that may reduce stability, helps to increase catalyst stability, and does help to increase catalyst addition/dehydrogenation performance.
Claims (10)
1. A preparation method of a vulcanization type hydrocracking catalyst is characterized by comprising the following steps: the method comprises the following steps:
(1) fully mixing pseudo-boehmite, amorphous silicon-aluminum, USY molecular sieve and beta zeolite according to a certain proportion, adding a certain amount of acid solution, kneading for 2-60 minutes, and then extruding and molding; drying and roasting the obtained formed body to prepare a catalyst carrier;
(2) adding a modifying reagent into the catalyst carrier obtained in the step (1), reacting at 5-40 ℃ for 1-24h, heating to 40-100 ℃, and reacting for 1-12h, so that a new functional group is connected to the surface of the carrier through a chemical bond to obtain a surface modified catalyst carrier;
(3) and (3) dispersing a VIB group element-containing compound, a VIII group element-containing compound and a sulfur-containing nonmetal compound in a solvent, impregnating the catalyst carrier obtained in the step (2) for 1-12 hours, then carrying out vacuum drying, and roasting in an inert atmosphere to obtain the hydrocracking catalyst.
2. The process of claim 1 for the preparation of a sulfided hydrocracking catalyst, wherein: the weight ratio of the pseudo-boehmite, the amorphous silicon-aluminum, the USY molecular sieve and the beta zeolite used in the step (1) is (20-80): (20-60): (1-20): (0.05-4).
3. The process of claim 1 for the preparation of a sulfided hydrocracking catalyst, wherein: the adding amount of the acid solution used in the step (1) is 0.5-10% of the total weight of the pseudo-boehmite, the amorphous silicon-aluminum, the USY molecular sieve and the beta zeolite, and the concentration of the acid solution is not more than 10 wt%; the acid solution comprises inorganic acid or organic acid, wherein the inorganic acid comprises any one of sulfuric acid, hydrochloric acid and nitric acid, and the organic acid comprises any one of formic acid, acetic acid and citric acid.
4. The process of claim 1 for the preparation of a sulfided hydrocracking catalyst, wherein: the drying and roasting in the step (1) are specifically drying at 100-200 ℃ for 2-24 h, and roasting at 400-750 ℃ for 2-8 h.
5. The process of claim 1 for the preparation of a sulfided hydrocracking catalyst, wherein: the modifying reagent in the step (2) contains two or more functional groups, wherein one functional group can react with the surface of the inorganic carrier and is selected from any one of hydroxyl, carboxyl, amino, acid anhydride, halogen substituent, siloxy, phosphate group, metaphosphate group or phosphite group; the other functional group can react with oxide or salt containing VIB group metal element or VIIB group metal element, and is selected from any one of hydroxyl, carboxyl, amino, sulfydryl, amido or halogen substituent.
6. The process of claim 1 for the preparation of a sulfided hydrocracking catalyst, wherein: the adding amount of the modifying reagent in the step (2) is 0.5-20% of the weight of the catalyst carrier obtained in the step (1).
7. The process of claim 1 for the preparation of a sulfided hydrocracking catalyst, wherein: the group VIII element-containing compound of step (3) includes, but is not limited to, nickel salts; the group VIB element-containing compound comprises a sulfur-containing tungsten salt; the sulfur-containing nonmetal compound comprises one or more of ammonium sulfide, thiourea and ammonium thiosulfate.
8. The process of claim 1 for the preparation of a sulfided hydrocracking catalyst, wherein: in the step (3), the mass ratio of the VIB group element-containing compound, the VIII group element-containing compound and the sulfur-containing nonmetal compound is (1-600): (1-50): (0.3-500).
9. The process of claim 1 for the preparation of a sulfided hydrocracking catalyst, wherein: and (3) the inert atmosphere comprises one or more of nitrogen, argon and helium, and the pressure is 0-5 MPa.
10. The process of claim 1 for the preparation of a sulfided hydrocracking catalyst, wherein: the vacuum drying in the step (3) comprises the following steps: vacuum drying at 50-100 ℃ for 6-48 h, and roasting at 200-350 ℃ for 2-24 h in an inert atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010781436.4A CN111889133A (en) | 2020-08-06 | 2020-08-06 | Preparation method of vulcanization type hydrocracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010781436.4A CN111889133A (en) | 2020-08-06 | 2020-08-06 | Preparation method of vulcanization type hydrocracking catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111889133A true CN111889133A (en) | 2020-11-06 |
Family
ID=73247089
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010781436.4A Pending CN111889133A (en) | 2020-08-06 | 2020-08-06 | Preparation method of vulcanization type hydrocracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111889133A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070102322A1 (en) * | 2005-11-04 | 2007-05-10 | Li Wang | Hydrocracking catalyst containing beta and Y zeolites, and process for its use to make jet fuel or distillate |
| CN103372458A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Molecular-sieve-containing hydrotreating catalyst, and preparation and application thereof |
| US20170043330A1 (en) * | 2015-08-11 | 2017-02-16 | Chevron U.S.A. Inc. | Noble metal zeolite catalyst for second-stage hydrocracking to make middle distillate |
| CN108055832A (en) * | 2015-08-11 | 2018-05-18 | 雪佛龙美国公司 | The midbarrel hydrocracking catalyst of β zeolites containing USY zeolite and with Low acid and big crystal domain size |
| CN108714434A (en) * | 2018-06-04 | 2018-10-30 | 中国中化股份有限公司 | A kind of light oil type hydrogen cracking catalyst and preparation method thereof |
| CN108722473A (en) * | 2018-06-04 | 2018-11-02 | 中国中化股份有限公司 | A kind of preparation method of hydrocracking catalyst |
-
2020
- 2020-08-06 CN CN202010781436.4A patent/CN111889133A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070102322A1 (en) * | 2005-11-04 | 2007-05-10 | Li Wang | Hydrocracking catalyst containing beta and Y zeolites, and process for its use to make jet fuel or distillate |
| CN103372458A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Molecular-sieve-containing hydrotreating catalyst, and preparation and application thereof |
| US20170043330A1 (en) * | 2015-08-11 | 2017-02-16 | Chevron U.S.A. Inc. | Noble metal zeolite catalyst for second-stage hydrocracking to make middle distillate |
| CN108055832A (en) * | 2015-08-11 | 2018-05-18 | 雪佛龙美国公司 | The midbarrel hydrocracking catalyst of β zeolites containing USY zeolite and with Low acid and big crystal domain size |
| CN108714434A (en) * | 2018-06-04 | 2018-10-30 | 中国中化股份有限公司 | A kind of light oil type hydrogen cracking catalyst and preparation method thereof |
| CN108722473A (en) * | 2018-06-04 | 2018-11-02 | 中国中化股份有限公司 | A kind of preparation method of hydrocracking catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7169354B2 (en) | Modified Y-type molecular sieve and production method, hydrocracking catalyst and production method, and hydrocracking method for hydrocarbon oil | |
| JP6236399B2 (en) | Catalyst comprising at least one zeolite NU-86, at least one zeolite USY, and a porous mineral matrix, and a hydrocarbon feedstock hydroconversion process using the catalyst | |
| CN108714434B (en) | Light oil type hydrocracking catalyst and preparation method thereof | |
| CN108722473B (en) | Preparation method of hydrocracking catalyst | |
| CN103285909B (en) | A kind of hydrocracking catalyst containing mesoporous-microporomolecular molecular sieve and preparation method thereof | |
| RU2607908C1 (en) | Method of preparing catalyst for hydrocracking hydrocarbon material | |
| CN111760585A (en) | Preparation method of vulcanization type hydrocracking catalyst | |
| CN108262065A (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| CN108816273A (en) | A kind of preparation method of the hydrocracking catalyst of high light oil selectivity | |
| CN111889133A (en) | Preparation method of vulcanization type hydrocracking catalyst | |
| CN112275310A (en) | Heavy aromatic hydrocarbon lightening catalyst based on VIB and VIII group composite metal elements and preparation method and application thereof | |
| CN1234814C (en) | Hydrogenation of distilled oil | |
| CN107774296B (en) | Preparation method of hydrocracking catalyst | |
| CN108262067A (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| CN112295607B (en) | Processing method for light conversion of heavy aromatics and heavy aromatics selective hydrogenation catalyst | |
| RU2610869C2 (en) | Hydroprocessing catalyst and methods of making and using such catalyst | |
| RU2794727C1 (en) | Method for preparing catalyst for hydrocracking of hydrocarbon feeds | |
| WO2021113348A1 (en) | Hierarchical zeolite y and nano-sized zeolite beta composite | |
| CN114746176A (en) | Platinum-encapsulated zeolite hydrocracking catalyst and method for preparing platinum-encapsulated zeolite hydrocracking catalyst | |
| RU2786516C1 (en) | Method for hydrocracking of hydrocarbon raw materials | |
| RU2788742C1 (en) | Hydrocracking catalyst of hydrocarbons | |
| RU2763723C1 (en) | Method for preparation of diesel fuel hydrotreating catalyst | |
| CN1246425C (en) | Method of producing jet fuel from coking distillate | |
| RU2763889C1 (en) | Diesel fuel hydrotreating catalyst | |
| CN116060117B (en) | Catalytic diesel hydrocracking catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201106 |