CN112221535A - Medium oil type hydrocracking catalyst and preparation method thereof - Google Patents
Medium oil type hydrocracking catalyst and preparation method thereof Download PDFInfo
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- CN112221535A CN112221535A CN202011162134.5A CN202011162134A CN112221535A CN 112221535 A CN112221535 A CN 112221535A CN 202011162134 A CN202011162134 A CN 202011162134A CN 112221535 A CN112221535 A CN 112221535A
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- molecular sieve
- hydrocracking catalyst
- roasting
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- drying
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 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 101
- 239000002808 molecular sieve Substances 0.000 claims abstract description 100
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011148 porous material Substances 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 10
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 239000002563 ionic surfactant Substances 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 5
- 229910052906 cristobalite Inorganic materials 0.000 claims description 5
- 238000010335 hydrothermal treatment Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052682 stishovite Inorganic materials 0.000 claims description 5
- 229910052905 tridymite Inorganic materials 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 229910021472 group 8 element Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000012263 liquid product Substances 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 239000003921 oil Substances 0.000 description 19
- 239000000843 powder Substances 0.000 description 17
- 238000005336 cracking Methods 0.000 description 15
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 5
- 239000011959 amorphous silica alumina Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 229910009112 xH2O Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 VIB group metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—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
- 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
- B01J29/084—Y-type faujasite
-
- B01J35/612—
-
- B01J35/647—
-
- 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
-
- 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
- B01J2229/14—After treatment, characterised by the effect to be obtained to alter the inside of the molecular sieve channels
-
- 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
- B01J2229/38—Base treatment
-
- 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
-
- 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
- B01J29/7892—MTT-type, e.g. ZSM-23, KZ-1, ISI-4 or EU-13
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Abstract
The invention discloses a medium oil type hydrocracking catalyst and a preparation method thereof, wherein the hydrocracking catalyst is prepared by mixing a modified Y molecular sieve, a beta molecular sieve and an SSZ-32 molecular sieve, so that the problems of low selectivity of middle distillate oil and low yield of liquid products of the existing catalyst are solved, and the output benefit of a medium oil type hydrocracking process is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a medium oil type hydrocracking catalyst and a preparation method thereof.
Background
The hydrocracking process is an oil refining process for converting high-boiling raw material into low-boiling naphtha, kerosene and diesel oil. Compared with catalytic cracking, the method has the advantages of high raw material adaptability, high yield of middle distillate and good quality. With the decline of the high-sulfur fuel oil market and the increasing demand of society for clean transportation fuel oil, the hydrocracking process becomes the core process of modern refineries.
Hydrocracking catalysts are typically bifunctional catalysts, generally comprising a bifunctional center: the first is a metal center, generally consists of VIB group metals or VIB and VIII group binary metal systems, has the hydrogenation/dehydrogenation function, and can also saturate aromatic hydrocarbon; the second is an acid center with cracking function, provided by amorphous silica-alumina or molecular sieve (most commonly Y molecular sieve), for cracking long-chain macromolecules.
When the hydrocracking catalyst prepared by the conventional Y molecular sieve is used in a hydrocracking process, middle distillate oil molecules, particularly kerosene fractions, are easy to undergo deep cracking reaction in microporous pore channels of the molecular sieve to generate C1-C4 gaseous light hydrocarbons with low value, so that the selectivity of the middle distillate oil in the product is low, and the yield of liquid products is low. Therefore, there is a need to develop new hydrocracking catalysts with higher selectivity for middle distillates, in particular diesel distillates.
The pore channel structure of the hydrocracking catalyst is reformed to form more mesoporous pore channels, so that the primary cracking product can be rapidly diffused from the microporous pore channels, the probability of deep cracking reaction is reduced, the generation of low-value C1-C4 gaseous hydrocarbons is reduced, and the selectivity of middle distillate oil and the yield of liquid products are improved. Since the cracking reaction usually occurs in the microporous pore channels of the molecular sieve, forming mesoporous pores on the Y molecular sieve is the best way to modify the pore channel structure of the catalyst. Usually, a chemical method, such as strong acid, strong base or complexing agent, is used to remove silicon or aluminum on the framework of the Y molecular sieve part, and then high temperature heat treatment is carried out to form mesopores on the molecular sieve. The existing ultrastable Y molecular sieve used for a hydrocracking catalyst is generally subjected to dealuminization treatment to adjust the strength and concentration of acid centers, and further strong chemical treatment is easy to cause further reduction of the number of the acid centers and influence the activity of the catalyst; meanwhile, the further desiliconization of the molecular sieve framework or the reduction of the crystallinity is easily caused by aluminum, so that the thermal stability of the molecular sieve is reduced, and the catalyst is quickly inactivated in the operation process.
The beta molecular sieve is a medium-pore and high-silicon zeolite with a three-dimensional twelve-membered ring pore structure, the pore channel of the beta molecular sieve is between the ZSM-5 type molecular sieve and the Y type molecular sieve, and the beta molecular sieve has high catalytic activity of hydrocracking and hydroisomerization and the adsorption capacity for straight paraffin, and has good sulfur and nitrogen poisoning resistance and high heat stability. When the beta molecular sieve is used for a hydrocracking catalyst, the beta molecular sieve has better middle distillate selectivity and lower condensation point of a diesel oil product, and the octane number of gasoline can be improved by the combined use of the beta molecular sieve and the USY molecular sieve.
The SSZ-32 molecular sieve is a molecular sieve with one-dimensional ten-membered ring straight pore channel structure, has high hydroisomerization catalytic activity, and can be used for dewaxing paraffin raw materials when being combined with hydrogenation components (such as Pt, Pd, Ni and the like). The straight pore channel structure is beneficial to the rapid diffusion of the primary cracking product from the pore channel, reduces the probability of deep cracking reaction, and improves the selectivity of middle distillate oil and the yield of liquid products. SSZ-32 molecular sieves are not suitable for use with high silicon, small crystal SSZ-32 molecular sieves, which can reduce their cracking activity due to the inherent small crystals that alter the argon adsorption ratio.
Disclosure of Invention
Aiming at the problems of low selectivity of the prior hydrocracking catalyst to middle distillate and low yield of liquid products, the invention provides a novel hydrocracking catalyst and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
one of the objects of the present invention is to provide a medium oil type hydrocracking catalyst, which comprises the following components:
(a) a metal of group VIII element or an oxide thereof;
(b) a metal of group VIB element or an oxide thereof;
(c) amorphous silicon aluminum;
(d) alumina;
(e) and (3) modifying the Y molecular sieve.
(f) A beta molecular sieve;
(g) SSZ-32 molecular sieve;
in the technical scheme, the component (a) is 0.1-35 parts by weight, preferably 15-25 parts by weight.
In the technical scheme, the component (b) is 0.1-10 parts by weight, preferably 4-8 parts by weight.
In the above technical scheme, the component (c) is 1 to 60 parts by weight, preferably 20 to 40 parts by weight.
In the above technical scheme, the component (d) is 1 to 80 parts by weight, preferably 20 to 50 parts by weight.
In the technical scheme, the component (e) is 0.1-30 parts by weight, preferably 1-10 parts by weight.
In the technical scheme, the component (f) is 0.05-6 parts by weight, preferably 0.1-6 parts by weight.
In the technical scheme, the component (g) is 0.01-5 parts by weight, preferably 0.1-2 parts by weight.
In the above technical solution, the group VIII element is selected from at least one of Co or Ni.
In the above technical solution, the group VIB element is selected from at least one of Mo or W.
In the technical scheme, the mass ratio of the modified Y molecular sieve, the beta molecular sieve and the SSZ-32 molecular sieve is (5-20): (1-5): 1.
in the technical scheme, the amorphous silicon-aluminum is obtained by roasting at 500 ℃ for 4 hours in the air atmosphere in advance; the specific surface area is 200-600 m2A pore volume of 0.5 to 1.5 cm/g3Preferably 1.1 to 1.5 cm/g3(ii)/g; in percent by weight, SiO2The content is 20-80%.
In the technical scheme, the alumina is obtained by roasting pseudo-boehmite in an air atmosphere; the specific surface area is 150-400 m2Per g, poreThe volume is 0.3-0.8 cm3The Na element content is less than or equal to 0.2 percent in percentage by weight.
In the technical scheme, the modified Y molecular sieve is prepared by adding the Y molecular sieve and an ionic surfactant into ammonia water, fully stirring at room temperature, placing the mixture into a high-pressure reaction kettle for hydrothermal treatment, and then filtering and drying the mixture.
Wherein the Y molecular sieve is a hydrogen type molecular sieve, and the specific surface area of the Y molecular sieve is 400-900 m2Preferably 500 to 800 m/g2(ii)/g; the total pore volume is 0.30-0.80 cm3Per g, wherein the mesoporous volume is less than 0.15 cm3A Si/Al molar ratio of 5 to 30, and a unit cell size of 24.25 to 24.45
。
The mass ratio of the used Y molecular sieve to the ionic surfactant is 1: (0.1 to 3); the ionic surfactant is a cationic surfactant, preferably an ammonium salt or amine salt type cationic surfactant, and more preferably at least one of cetyltrimethylammonium chloride (CTAC) and cetyltrimethylammonium bromide (CTAB).
The mass ratio of the used Y molecular sieve to ammonia water is 1: (1-500); ammonia monohydrate (NH) in the ammonia water in percentage by weight4OH) content of 0.5 to 5%.
The temperature of the hydrothermal treatment is 100-200 ℃, and the time is 1-48 h; the drying temperature is 80-200 ℃, and the drying time is 1-24 hours.
In the above technical scheme, the beta molecular sieve is a hydrogen type molecular sieve, the Si/Al molar ratio is 0-30, and the specific surface area is 360-590 m2Per g, pore volume of 0.32-0.50 cm3A beta molecular sieve having an SF6 adsorption capacity of at least 28 wt.%.
In the technical scheme, the external surface area of the hydrogen type molecular sieve of the SSZ-32 molecular sieve is 40-60 m2G, argon adsorption ratio of 0.35-0.45, SiO2/Al2O3The molar ratio is 20-40, and the crystal size is 150-200 nm;
it is another object of the present invention to provide a method for preparing the hydrocracking catalyst, which comprises the steps of:
(1) uniformly mixing pseudo-boehmite, amorphous silicon-aluminum, a modified Y molecular sieve, a beta molecular sieve and an SSZ-32 molecular sieve, adding an acid solution, fully kneading, forming, drying, heating to a roasting target temperature in a nitrogen atmosphere, and then switching to an air atmosphere for roasting to obtain a catalyst carrier;
(2) and (2) dispersing a VIB group element-containing compound and a VIII group element-containing compound in a solvent, impregnating the catalyst carrier obtained in the step (1), and then drying and roasting to obtain the medium oil type hydrocracking catalyst.
In the above technical solution, the acid solution in step (1) may be inorganic acid such as sulfuric acid, hydrochloric acid, and nitric acid, or organic acid such as formic acid, acetic acid, and citric acid; the concentration of the acid solution is 0.5wt% to 5wt%, preferably 1wt% to 3 wt%.
In the technical scheme, the size and shape of the formed product in the step (1) are preferably similar to those of a traditional hydrocracking commercial catalyst, and the product 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.
In the technical scheme, the drying temperature in the step (1) is 80-200 ℃, and the drying time is 2-24 hours; the heating rate under the nitrogen atmosphere is 1-20 ℃/min, the target temperature is 400-650 ℃, and the roasting time under the air atmosphere is 3-12 h.
In the above technical scheme, the group VIB element-containing compound and the group VIII element-containing compound in step (2) are not particularly limited, and may be reasonably selected by those skilled in the art.
In the above technical solution, the solvent used in step (2) is not particularly limited as long as the impregnation loading operation can be achieved, and the solvent may be directly dissolved, or dissolved by adjusting pH, or may be those capable of forming a colloid or forming a colloid by adjusting pH, and may be a single solvent or a mixed solvent.
In the technical scheme, the drying temperature in the step (2) is 80-200 ℃, and the drying time is 2-24 hours; the roasting temperature is 400-600 ℃, and the roasting time is 2-12 h.
The invention has the advantages that:
the invention modifies the Y molecular sieve under the mild hydrothermal condition, and can be directly used for preparing the catalyst only by simple filtration and separation and without high-temperature heat treatment. Therefore, the improvement of the pore channel structure of the molecular sieve can be realized under the condition of not damaging the framework structure of the molecular sieve, more mesoporous channels are formed in the prepared hydrocracking catalyst, the rapid diffusion of a primary cracking product from the microporous channels is facilitated, the probability of deep cracking reaction is reduced, the generation of low-value C1-C4 gaseous hydrocarbons is reduced, and the selectivity of middle distillate oil and the yield of liquid products are improved.
Compared with the existing hydrocracking catalyst, the medium oil type hydrocracking catalyst prepared by mixing the modified Y molecular sieve, the beta molecular sieve and the SSZ-32 molecular sieve can improve the selectivity of the medium distillate oil on the basis of improving the activity of the catalyst, and the yield of liquid products is improved accordingly. The output benefit can be obviously improved for producing the medium oil type hydrocracking unit.
The SSZ-32 molecular sieve has the capability of hydrogenation and isomerization, the saturation of alkane can be improved by adding a small amount of the SSZ-32 molecular sieve into the catalyst, meanwhile, the ten-membered ring straight pore channel structure of the SSZ-32 molecular sieve is beneficial to the rapid diffusion of a primary cracking product from the pore channel, the probability of deep cracking reaction is reduced, the conversion rate and the selectivity of the SSZ-32 molecular sieve to middle distillate can be greatly improved at the reaction temperature of more than 300 ℃, and simultaneously, the isomerization capability and the selection can be reduced. The addition of the SSZ-32 molecular sieve can greatly improve the hydrocracking capability of the beta molecular sieve on straight paraffin, and when the beta molecular sieve is used for a hydrocracking catalyst, the beta molecular sieve has better middle distillate selectivity and lower diesel product condensation point. The modified Y molecular sieve can form more mesoporous structures, and the probability of deep cracking reaction is reduced, so that the deep cracking reaction can be reduced by the combined use of the Y molecular sieve, the beta molecular sieve and the SSZ-32 molecular sieve, and the generation of low-value C1-C4 gaseous hydrocarbon can be reduced, so that the selectivity of middle distillate oil and the yield of liquid products are improved.
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 amorphous silicon-aluminum is roasted for 4 hours at 500 ℃ in advance in the air atmosphere; the specific surface area is 200-600 m2A pore volume of 0.5 to 1.5 cm/g3(ii)/g; in percent by weight, SiO2The content is 20-80%.
135.0 g of Y molecular sieve powder and 180.0g of CTAC were added to 3150 g of ammonia (NH 4OH content: 2 wt%) and stirred well at room temperature for 60 minutes, and then placed in a high-pressure reaction vessel, subjected to hydrothermal treatment at 180 ℃ for 20 hours, then filtered and dried at 140 ℃ for 30 hours to obtain modified Y molecular sieve powder.
TABLE 1 pore volume comparison of Y molecular sieves
As can be seen from Table 1, compared with the Y molecular sieve, the mesoporous volume of the modified Y molecular sieve is increased, and particularly, the increase of pores of 2-10 nm is most obvious.
Comparative example 1
Uniformly mixing 80.0g of modified Y molecular sieve powder, 80.0g of amorphous silica-alumina powder and 96.0 g of pseudo-boehmite powder, then adding 1.5wt% of nitric acid solution, fully kneading, extruding into cloverleaf-shaped particles with the length of 3-10 mm and the diameter of 2 mm, drying for 10 hours at 140 ℃, then heating to 560 ℃ in nitrogen atmosphere, and then switching to air atmosphere for roasting for 6 hours to obtain the catalyst carrier S-0. Nickel nitrate (Ni (NO)) providing sufficient nickel oxide (NiO)3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) is dispersed in deionized water, then used for dipping the obtained catalyst carrier S-0, then dried for 10 hours at the temperature of 120 ℃, and finally roasted for 6 hours at the temperature of 550 ℃ to obtain the catalyst C-0.
Example 1
Uniformly mixing 66.67g of modified Y molecular sieve powder, 13.33g of beta molecular sieve, 80.0g of amorphous silicon aluminum powder and 96.0 g of pseudo-boehmite powder, then adding 1.5wt% of nitric acid solution, fully kneading, extruding into cloverleaf-shaped particles with the length of 3-10 mm and the diameter of 2 mm, drying for 10 hours at 140 ℃, then heating to 560 ℃ in nitrogen atmosphere, and then switching to air atmosphere for roasting for 6 hours to obtain the catalyst carrier S-1. Nickel nitrate (Ni (NO)) providing sufficient nickel oxide (NiO)3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) is dispersed in deionized water, then used for dipping the obtained catalyst carrier S-1, and then dried for 10 hours at the temperature of 120 ℃, and finally roasted for 6 hours at the temperature of 550 ℃ to obtain the catalyst C-1.
Example 2
63.16g of modified Y molecular sieve powder, 12.63g of beta molecular sieve, 4.21g of SSZ-32 molecular sieve, 80.0g of amorphous silica-alumina powder and 96.0 g of pseudo-boehmite powder are uniformly mixed, then 1.5wt% of nitric acid solution is added, after full kneading, clover-shaped particles with the length of 3-10 mm and the diameter of 2 mm are extruded, dried for 10 hours at the temperature of 140 ℃, heated to 560 ℃ under the nitrogen atmosphere, and then switched to the air atmosphere for roasting for 6 hours, thus obtaining the catalyst carrier S-2. Nickel nitrate (Ni (NO)) providing sufficient nickel oxide (NiO)3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) is dispersed in deionized water, then used for dipping the obtained catalyst carrier S-2, and then dried for 10 hours at the temperature of 120 ℃, and finally roasted for 6 hours at the temperature of 550 ℃ to obtain the catalyst C-2.
Example 3
Uniformly mixing 64g of modified Y molecular sieve powder, 12.8g of beta molecular sieve, 3.2g of SSZ-32 molecular sieve, 80.0g of amorphous silica-alumina powder and 96.0 g of pseudo-boehmite powder, then adding 1.5wt% of nitric acid solution, fully kneading and extruding into 3-10 mDrying cloverleaf particles with the length of m and the diameter of 2 mm at 140 ℃ for 10 hours, heating to 560 ℃ in nitrogen atmosphere, and then switching to air atmosphere for roasting for 6 hours to obtain the catalyst carrier S-3. Nickel nitrate (Ni (NO)) providing sufficient nickel oxide (NiO)3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) is dispersed in deionized water, then used for dipping the obtained catalyst carrier S-3, and then dried for 10 hours at the temperature of 120 ℃, and finally roasted for 6 hours at the temperature of 550 ℃ to obtain the catalyst C-3.
Example 4
Uniformly mixing 75g of modified Y molecular sieve powder, 5g of SSZ-32 molecular sieve, 80.0g of amorphous silica-alumina powder and 96.0 g of pseudo-boehmite powder, then adding 1.5wt% of nitric acid solution, fully kneading, extruding into cloverleaf particles with the length of 3-10 mm and the diameter of 2 mm, drying for 10 hours at 140 ℃, then heating to 560 ℃ under nitrogen atmosphere, and then switching to air atmosphere for roasting for 6 hours to obtain the catalyst carrier S-4. Nickel nitrate (Ni (NO)) providing sufficient nickel oxide (NiO)3)2·6H2O) and sufficient tungsten trioxide (WO)3) Ammonium metatungstate ((NH)4)10W12O41·xH2O) is dispersed in deionized water, then used for dipping the obtained catalyst carrier S-4, then dried for 10 hours at the temperature of 120 ℃, and finally roasted for 6 hours at the temperature of 550 ℃ to obtain the catalyst C-4.
Evaluation of catalyst Performance
The catalyst performance was evaluated using a 50 mL small hydrogenation evaluation apparatus with one pass. H of 5% by volume was used before evaluation2S and 95% H2The catalyst is presulfurized by the formed mixed gas. The raw material used for evaluating the performance of the catalyst is hydrocracking cycle oil, and the properties and reaction process conditions thereof are shown in tables 2 and 3. The reaction temperature was adjusted as needed to ensure that the conversion was maintained at 68% by mass over 100 hours. The results of comparing the reaction properties of the respective catalysts are shown in Table 4.
TABLE 2 Properties of the feed oils
TABLE 3 reaction Process conditions
TABLE 4 catalyst evaluation results
As can be seen from Table 4, the activity of catalysts C-2 and C-3 is slightly better than that of C-0 and C-4 at the same conversion rate, but there is not much difference, but the selectivity of diesel fraction in middle distillate oil is improved to a certain extent (by 0-1 percentage point) compared with that of C-0, C-1 and C-4, the liquid yield of the comparative example and the example can be basically kept equivalent, and the liquid yield of the C-3 catalyst is slightly higher than that of other catalysts. The conversion rate of diesel oil fraction in the middle distillate oil is improved by about 1 percent, and the method is a remarkable process for ten thousand ton-class oil refining.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (10)
1. A hydrocracking catalyst characterized by: comprises the following components:
(a) a metal of group VIII element or an oxide thereof;
(b) a metal of group VIB element or an oxide thereof;
(c) amorphous silicon aluminum;
(d) alumina;
(e) modifying a Y molecular sieve;
(f) a beta molecular sieve;
(g) SSZ-32 molecular sieve;
the modified Y molecular sieve is prepared by adding the Y molecular sieve and an ionic surfactant into ammonia water, fully stirring at room temperature, placing in a high-pressure reaction kettle for hydrothermal treatment, and then filtering and drying.
2. The hydrocracking catalyst according to claim 1, characterized in that: the adhesive comprises, by weight, 0.1-35 parts of a component (a), 0.1-10 parts of a component (b), 1-60 parts of a component (c), 1-80 parts of a component (d), 0.1-30 parts of a component (e), 0.05-6 parts of a component (f) and 0.01-5 parts of a component (g).
3. The hydrocracking catalyst according to claim 1, characterized in that: the mass ratio of the modified Y molecular sieve to the beta molecular sieve to the SSZ-32 molecular sieve is (5-20): (1-5): 1.
4. the hydrocracking catalyst according to claim 1, characterized in that: the VIII group element is at least one selected from Co or Ni, and the VIB group element is at least one selected from Mo or W.
5. The hydrocracking catalyst according to claim 1, characterized in that: the amorphous silicon-aluminum is roasted for 4 hours at 500 ℃ in advance in the air atmosphere before use; the specific surface area is 200-600 m2A pore volume of 0.5 to 1.5 cm/g3In% by weight, SiO2The content is 20-80%.
6. The hydrocracking catalyst according to claim 1, characterized in that: the alumina is obtained by roasting pseudo-boehmite in air atmosphere; the specific surface area is 150-400 m2A pore volume of 0.3 to 0.8 cm3The Na element content is less than or equal to 0.2 percent in percentage by weight.
7. The hydrocracking catalyst according to claim 1, characterized in that: the Y molecular sieve used for preparing the modified Y molecular sieve is a hydrogen type molecular sieve, and the specific surface area of the Y molecular sieve is 400-900 m2(ii) a total pore volume of 0.30 to 0.80 cm3Per g, wherein the mesoporous volume is less than 0.15 cm3A Si/Al molar ratio of 5 to 30, and a unit cell size of 24.25 to 24.45
；
The mass ratio of the used Y molecular sieve to the ionic surfactant is 1: 0.1 to 3; wherein the ionic surfactant is a cationic surfactant;
the mass ratio of the used Y molecular sieve to ammonia water is 1: 1 to 500; the content of the ammonia monohydrate in the ammonia water is 0.5-5% by weight percentage;
the temperature of the hydrothermal treatment is 100-200 ℃, and the time is 1-48 h;
the drying temperature is 80-200 ℃, and the drying time is 1-24 hours.
8. The hydrocracking catalyst according to claim 1, characterized in that: the beta molecular sieve has a Si/Al molar ratio of 0-30, a specific surface area of 360-2Per g, pore volume of 0.32-0.50 cm3A beta zeolite having an SF6 adsorption capacity of at least 28 wt%.
9. The hydrocracking catalyst according to claim 1, characterized in that: the external surface area of the SSZ-32 molecular sieve is 40-60 m2G, argon adsorption ratio of 0.35-0.45, SiO2/Al2O3The molar ratio is 20-40, and the crystal size is 150-200 nm.
10. A process for preparing a hydrocracking catalyst according to claim 1, characterized by: the method comprises the following steps:
(1) uniformly mixing pseudo-boehmite, amorphous silicon-aluminum, a modified Y molecular sieve, a beta molecular sieve and an SSZ-32 molecular sieve, adding an acid solution, fully kneading, forming, drying, heating to a roasting target temperature in a nitrogen atmosphere, and then switching to an air atmosphere for roasting to obtain a catalyst carrier;
(2) dispersing a compound containing VIB group elements and a compound containing VIII group elements in a solvent, impregnating the catalyst carrier obtained in the step (1), and then drying and roasting to obtain the hydrocracking catalyst;
the drying temperature in the step (1) is 80-200 ℃, and the drying time is 2-24 hours; the heating rate under the nitrogen atmosphere is 1-20 ℃/min, the target temperature is 400-650 ℃, and the roasting time under the air atmosphere is 3-12 h;
the drying temperature in the step (2) is 80-200 ℃, and the drying time is 2-24 hours; the roasting temperature is 400-600 ℃, and the roasting time is 2-12 h.
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