CN115582142B - Cyclo-cycloalkane isomerism catalyst, and preparation method and application thereof - Google Patents
Cyclo-cycloalkane isomerism catalyst, and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 28
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 150000004767 nitrides Chemical class 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 239000002808 molecular sieve Substances 0.000 claims description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 14
- 239000002283 diesel fuel Substances 0.000 claims description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 8
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000006317 isomerization reaction Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 5
- 239000010724 circulating oil Substances 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 238000005987 sulfurization reaction Methods 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 8
- 150000001336 alkenes Chemical class 0.000 abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 10
- 238000004073 vulcanization Methods 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- -1 alkane compound Chemical class 0.000 description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 4
- 229910000480 nickel oxide Inorganic materials 0.000 description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N benzocyclopentane Natural products C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 101100503316 Artemisia spiciformis FDS-1 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012854 evaluation process Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002468 indanes Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000006467 substitution reaction Methods 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/705—Passivation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a naphthene ring isomerism catalyst, a preparation method and application thereof. The preparation method adopts organic nitride as a passivating agent to passivate the hydroisomerization catalyst in situ. The invention obviously improves the hydroisomerization effect of the naphthene ring in the catalytic cracking diesel, has the advantages of effectively enhancing the carbon deposit resistance, improving the liquid yield and the like, is particularly suitable for hydroisomerization reaction of the naphthene ring in poor catalytic cracking diesel, and is beneficial to the maximized conversion production of low-molecular olefins and aromatic hydrocarbons in the catalytic cracking process.
Description
Technical Field
The invention relates to the technical field of petrochemical industry, in particular to a naphthene ring isomerism catalyst and a preparation method and application thereof.
Background
In recent years, with the continuous upgrading of clean oil quality standards, the continuous reduction of diesel market demands and the continuous growth of the markets of low-olefin high-octane gasoline components such as polyester base aromatic hydrocarbon (BTX), alkylate, MTBE and the like, the problems of shortage of BTX, C4 alkylation and MTBE raw materials are highlighted. On one hand, the poor-quality catalytic diesel needs to be converted with high efficiency so as to reduce the diesel-gasoline ratio of a refinery and improve the economic benefit; on the other hand, the problem of shortage of low-olefin high-octane gasoline components such as BTX, alkylate, MTBE and the like in the market raw materials needs to be solved. Aiming at the clear characteristics of high content of polycyclic aromatic hydrocarbon in the catalytic cracking circulating oil, how to effectively convert and utilize the polycyclic aromatic hydrocarbon in the catalytic cracking circulating oil to become an effective way for the development and synergy of enterprises.
The combined technology of catalytic cracking diesel oil hydrotreatment and catalytic cracking can obtain clean gasoline with high octane number and by-product liquefied gas rich in olefin, and has low hydrogen consumption, higher liquid yield and lower dry gas yield. However, the selectivity of the catalytic cracking catalyst is not ideal, the directional conversion of the naphthenic aromatic hydrocarbon cannot be accurately controlled, the six-membered cyclohexane ring (cyclohexane ring) connected with the aromatic ring is extremely easy to generate hydrogen transfer dehydrogenation reaction, and the polycyclic aromatic hydrocarbon is reversely generated, so that ineffective circulation is caused. Therefore, a naphthene ring isomerization catalyst is developed, the existing six-membered ring alkane compound which exists stably after hydrogenation is activated, and the six-membered ring alkane compound is isomerized into an unstable five-membered ring, so that the cracking activity of the six-membered ring alkane compound is improved.
At present, the existence of strong acid sites on the surface of a molecular sieve in a hydroisomerization catalyst carrier leads to high initial activity of the catalyst, strong cracking capability, reduced liquid yield, increased carbon deposition on the surface of the catalyst and influence on long-period stable operation of the catalyst.
Therefore, the naphthenic ring isomerization catalyst is provided, so that the hydroisomerization effect of the catalytic cracking diesel is remarkably improved, meanwhile, the preparation cost of the catalyst and the running cost of a device are effectively reduced, the efficient conversion of poor-quality catalytic cracking diesel is realized, and the maximized production of low-molecular olefins and aromatic hydrocarbons is a problem to be solved by those skilled in the art.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing a naphthene ring isomerism catalyst, so as to at least partially solve the problem of low conversion rate of low molecular olefins and aromatics in the prior art.
In order to solve the problems, the invention provides the following technical scheme:
a process for preparing the catalyst used for hydroisomerizing naphthene ring features that the organic nitride is used as passivating agent to passivate the hydroisomerizing catalyst in situ.
Further, the method comprises the steps of: preparing an impregnating solution, wherein the impregnating solution comprises an active component, an auxiliary component and the passivating agent; impregnating, namely impregnating the hydroisomerization catalyst carrier by adopting an isovolumetric impregnation method, wherein the impregnation temperature is 10-100 ℃ and the impregnation time is 0.5-3 hours; drying, wherein the drying temperature is 70-120 ℃ and the drying time is 1-4 hours; and (3) heating, namely heating in an oxygen-free atmosphere at a heating temperature of 100-400 ℃ for 1-4 hours.
Further, the molar ratio of the nitrogen content of the organic nitride to the active component is: n/metal molar ratio=0.1 to 0.5/1.
Further, the active component is one or more of oxides of Mo, W or Co and Ni of VIIB family or precursors thereof, and the content of the active component in the catalyst is 5-30 weight percent based on the oxide.
Further, the auxiliary agent component is P, and the content of P in the catalyst is 0.5-3 weight percent based on the simple substance; the catalyst carrier is molecular sieve and alumina, the content of the molecular sieve is 20-70 weight percent, and the alumina is 30-80 weight percent based on the carrier; the molecular sieve is one or more of Y, ZSM-5 and beta.
Further, the organic nitride is one or more of triethanolamine, diethylenetriamine, polyacrylamide and dimethylformamide.
The invention also provides a naphthene ring isomerism catalyst which is prepared by the method.
In addition, the invention also provides a hydroisomerization method of the catalytic cracking cycle oil, which uses the naphthene ring isomerization catalyst.
Further, the hydroisomerization method is used for straight run diesel oil, straight run wax oil, coker wax oil, catalytic cracking diesel oil or catalytic cracking cycle oil; the catalyst is vulcanized in a hydrogenation reactor before hydroisomerization reaction, the vulcanization temperature is 200-400 ℃, and the vulcanization time is 1-8 hours; the temperature of the hydroisomerization reaction is 330-400 ℃, the hydrogen pressure is 4-10 MPa, and the liquid hourly space velocity is 0.5-1.5 h -1 The volume ratio of the hydrogen to the catalytic cracking circulating oil is 500-1500 Nm 3 /m 3 。
Further, the vulcanization treatment is to raise the temperature to 100-200 ℃ in the hydrogen atmosphere, carry out vulcanization dehydration on the catalyst for 1-3 hours, raise the temperature to 200-400 ℃ at the temperature raising speed of 1-4 ℃ and treat for 2-4 hours.
In one or more specific embodiments, the invention has the following beneficial technical effects:
the preparation method of the naphthene ring isomerism catalyst provided by the invention adopts an aqueous solution containing organic nitride as a passivating agent to prepare an impregnating solution, adopts a Co-impregnating method to load one or more of VIB Mo, W or VIIIB Co and Ni onto a catalyst carrier, and realizes the selective passivation of a strong acid site in a molecular sieve composite carrier while finishing the loading of a catalyst metal oxide precursor by treating the hydroisomerization catalyst at a high temperature in an oxygen-free atmosphere. The catalyst prepared by passivation has strong carbon deposition resistance, high naphthene ring isomerization activity and selectivity, can stably run for a long period, is particularly suitable for hydroisomerization reaction of naphthene rings in poor-quality catalytic cracking diesel, and is beneficial to the maximized conversion production of low-molecular olefins and aromatic hydrocarbons in the catalytic cracking process.
Detailed Description
Embodiments of the present invention are described in detail below.
It should be noted that, without conflict, the following embodiments and features in the embodiments may be combined with each other; and, based on the embodiments in this disclosure, all other embodiments that may be made by one of ordinary skill in the art without inventive effort are within the scope of the present disclosure.
It is noted that various aspects of the embodiments are described below within the scope of the following claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the present disclosure, one skilled in the art will appreciate that one aspect described herein may be implemented independently of any other aspect, and that two or more of these aspects may be combined in various ways. For example, an apparatus may be implemented and/or a method practiced using any number of the aspects set forth herein. In addition, such apparatus may be implemented and/or such methods practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
The preparation method of the naphthene ring isomerism catalyst provided by the invention adopts organic nitride as a passivating agent to passivate the hydroisomerization catalyst in situ.
In a specific technical process, the preparation method of the invention can comprise the following steps: preparing an impregnating solution, wherein the impregnating solution comprises an active component, an auxiliary component and the passivating agent; an impregnation step, namely, impregnating the hydroisomerization catalyst carrier by adopting an isovolumetric impregnation method, wherein the impregnation temperature is between room temperature and 100 ℃ (for example, between 10 and 100 ℃), and the impregnation time is between 0.5 and 3 hours; a drying step, wherein the drying temperature is 70-120 ℃ and the drying time is 1-4 hours; and a heating treatment step, namely heating treatment is carried out in an oxygen-free atmosphere, the heating temperature is 100-400 ℃, and the heating time is 1-4 hours.
The organic nitride can be one or more of triethanolamine, diethylenetriamine, polyacrylamide and dimethylformamide, and the molar ratio of the nitrogen content of the organic nitride to the active component is preferably: n/metal molar ratio=0.1 to 0.5/1.
The active component can be one or more of oxides of Mo, W or Co and Ni of VIIB family or precursors thereof, and the content of the active component in the catalyst is preferably 5-30 weight percent based on the oxide. The auxiliary component can be P, and the content of P in the catalyst is preferably 0.5-3 weight percent based on the simple substance. The catalyst carrier can be selected from molecular sieve and alumina, the content of the molecular sieve is preferably 20-70 weight percent, the content of the alumina is preferably 30-80 weight percent based on the carrier, and the type of the molecular sieve can be one or more of Y, ZSM-5 and beta.
The invention also provides a naphthene ring isomerism catalyst prepared by the method.
In addition, the invention also provides a method for hydroisomerizing catalytic cracking cycle oil by using the naphthene ring isomerism catalyst. The hydroisomerization method can be applied to straight run diesel oil, straight run wax oil, coker wax oil, catalytic cracking diesel oil or catalytic cracking cycle oil. Before the reaction, the catalyst may be sulfurized in a hydrogenation reactor at 200-400 deg.c for 1-8 hr. The temperature of hydroisomerization reaction is preferably 330-400 ℃, the hydrogen pressure is preferably 4-10 MPa, and the liquid hourly space velocity is preferably 0.5-1.5 h -1 The volume ratio of hydrogen to the catalytic cracking cycle oil is preferably 500 to 1500Nm 3 /m 3 。
Further, the above-mentioned vulcanization treatment may be performed in two steps: firstly, heating to 100-200 ℃ in hydrogen atmosphere, vulcanizing and dehydrating the catalyst for 1-3 hours, heating to 200-400 ℃ at a heating speed of 1-4 ℃ and treating for 2-4 hours.
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
Weighing a certain amount of Y molecular sieve and pseudo-boehmite, adding sesbania powder, grinding uniformly, acidifying with 3wt% nitric acid aqueous solution, fully kneading into gel, extruding into cylindrical strips with the diameter of 1.6mm on a strip extruder, drying in a baking oven at 120 ℃ for 3 hours, roasting in a muffle furnace at 550 ℃ for 3 hours, and obtaining the catalyst carrier S1 by a conventional kneading molding preparation method, wherein the Y molecular sieve content is 70 wt% and the alumina content is 30 wt%.
200 g of the catalyst carrier S1 is weighed, and a solution containing a certain amount of molybdenum, nickel, phosphorus and triethanolamine is impregnated on the carrier by adopting an isovolumetric impregnation method, wherein the nitrogen content of the triethanolamine is N/metal (Mo and Ni) mole ratio=0.2/1. Drying in an oven at 80 ℃ for 3 hours, and heating in a tube furnace in the presence of nitrogen at a treatment temperature of 300 ℃ for 2 hours to obtain a passivated hydroisomerization catalyst SC1, wherein the composition is as follows: 15% of molybdenum oxide, 4% of nickel oxide and 2% of phosphorus oxide.
Example 2
A certain amount of beta molecular sieve and pseudo-boehmite are weighed, sesbania powder is added, grinding is carried out uniformly, 3wt% nitric acid aqueous solution is used for acidification, after full kneading into gel, cylindrical strips with the diameter of 1.6mm are extruded on a strip extruder, and are dried in an oven at 120 ℃ for 3 hours, and are baked in a muffle furnace at 550 ℃ for 3 hours, so that the catalyst carrier S2 is obtained, wherein the beta molecular sieve content is 70 wt% and the alumina content is 30 wt%.
The catalyst carrier S2 was weighed 200 g and a solution containing a certain amount of molybdenum, nickel, phosphorus, triethanolamine was impregnated on the carrier by an isovolumetric impregnation method, wherein the nitrogen content of the triethanolamine was N/metal (Mo, ni) molar ratio=0.2/1. Drying in an oven at 80 ℃ for 3 hours, and heating in a tube furnace in the presence of nitrogen at a treatment temperature of 300 ℃ for 2 hours to obtain a passivated hydroisomerization catalyst SC2, wherein the composition is as follows: 15% of molybdenum oxide, 4% of nickel oxide and 2% of phosphorus oxide.
Example 3
The catalyst carrier S2 was weighed 200 g and a solution containing a certain amount of molybdenum, nickel, phosphorus and dimethylformamide was impregnated on the carrier by an isovolumetric impregnation method, wherein the nitrogen content of dimethylformamide was N/metal (Mo, ni) molar ratio=0.3/1. Drying in an oven at 100 ℃ for 3 hours, and heating in a tube furnace in the presence of nitrogen at a treatment temperature of 350 ℃ for 2 hours to obtain a passivated hydroisomerization catalyst SC3, wherein the composition is as follows: 20% of molybdenum oxide, 5% of nickel oxide and 2% of phosphorus oxide.
Comparative example 1:
weighing 200 g of the catalyst carrier S2, impregnating a solution containing a certain amount of molybdenum, nickel and phosphorus on the carrier by adopting an isovolumetric impregnation method, drying in an oven at 120 ℃ for 3 hours, and roasting in a muffle furnace at 500 ℃ for 2 hours to obtain a hydroisomerization catalyst OC1, wherein the composition is as follows: 15% of molybdenum oxide, 4% of nickel oxide and 2% of phosphorus oxide.
The physicochemical properties of the four catalysts are shown in table 1:
TABLE 1 physicochemical Properties of the catalysts of examples 1-3 and comparative example 1
| Catalyst | Specific surface area, square meter/g | Pore volume, cm 3 /g | Strength, N/cm |
| SC1 | 315 | 0.32 | 189 |
| SC2 | 321 | 0.33 | 193 |
| SC3 | 305 | 0.32 | 194 |
| OC1 | 300 | 0.32 | 196 |
The four catalysts were evaluated for performance using the hydrofined catalytic cracking diesel, and the raw material properties are shown in table 2. The hydrofining reaction conditions are as follows: the temperature is 340 ℃, the hydrogen pressure is 6MPa, and the liquid hourly space velocity is 1.5h -1 The hydrogen-oil ratio is 500/1 (V/V), and the catalyst is FDS-1 catalyst developed by national heavy oil national emphasis laboratory of China university (China east).
TABLE 2 catalytic cracking diesel oil Primary Properties
The hydroisomerization performance of the catalytic cracking diesel oil of the catalysts prepared in examples 1 to 3 and comparative example was evaluated, and the specific evaluation procedure is as follows: the catalyst loadings were 78 grams (100 ml) using a high pressure fixed bed pilot plant. The catalyst needs to be presulfided before performance evaluation, and the vulcanized oil is straight-run diesel oil containing 2 weight percent of dimethyl disulfide, and the vulcanization conditions are as follows: the temperature is 320 ℃, the hydrogen pressure is 6MPa, the liquid hourly space velocity is 1.5h < -1 >, the hydrogen-oil ratio is 500/1 (V/V), and the vulcanizing time is 8 hours. After the vulcanization is finished, introducing the hydrocracked diesel, wherein the reaction evaluation conditions are as follows: the temperature is 360 ℃, the hydrogen pressure is 6MPa, the liquid hourly space velocity is 1.5h < -1 >, the hydrogen-oil ratio is 500/1 (V/V), and the sample analysis is carried out after the sample is stabilized for 12 hours.
The reaction evaluation results are shown in Table 3:
table 3 results of reaction evaluation of four catalysts
As can be seen from the results of Table 3, the passivated catalytic cracking diesel naphthene hydroisomerization catalyst prepared by the process of the present invention has a higher naphthene hydroisomerization performance than conventional in-situ sulfided catalysts, the yield of indane hydrocarbons for the SC2 catalyst is about 20.75 wt.%, while the yield of indane hydrocarbons for the conventional in-situ sulfided catalyst OC1 is only 12.58 wt.%. This shows that the deactivation process effectively inhibits the ring-opening cracking activity of the catalyst and significantly improves the isomerization activity and selectivity of the catalyst. In addition, the catalyst (SC 1) containing the Y molecular sieve has higher hydrocracking performance, and the yield of indane hydrocarbon is obviously lower than that of the catalyst prepared by the beta molecular sieve.
The reaction conditions were adjusted using the catalyst of example 2, and the results of the reaction evaluation are shown in Table 3. The specific evaluation process is as follows: the catalyst needs to be presulfided before performance evaluation, and the vulcanized oil is straight-run diesel oil containing 2 weight percent of dimethyl disulfide, and the vulcanization conditions are as follows: the temperature is 320 ℃, the hydrogen pressure is 10MPa, the liquid hourly space velocity is 1.5h < -1 >, the hydrogen-oil ratio is 500/1 (V/V), and the vulcanizing time is 8 hours. After the vulcanization is finished, introducing the hydrocracked diesel, wherein the reaction evaluation conditions are as follows: the temperature is 380 ℃, the hydrogen pressure is 10MPa, the liquid hourly space velocity is 1.5h < -1 >, the hydrogen-oil ratio is 800/1 (V/V), and the sample analysis is carried out after the sample is stabilized for 12 hours.
As can be seen from the results of Table 3, the indanes and tetrahydronaphthalene hydrocarbons content is significantly smaller and the total saturated hydrocarbon content is increased with increasing reaction temperature, indicating an enhanced ring opening performance of the catalyst. However, the naphthene ring isomerization performance of the catalyst is still higher than that of the conventional in-reactor sulfided catalyst (OC 1).
Therefore, the method adopts the aqueous solution containing the organic nitride as the passivating agent to prepare the co-impregnating solution, realizes the selective passivation of the strong acid site in the molecular sieve composite carrier while finishing the loading of the catalyst metal oxide precursor, improves the hydroisomerization activity and selectivity of the naphthene ring of the catalyst, is particularly suitable for hydroisomerization reaction of the naphthene ring in poor-quality catalytic cracking diesel, and is beneficial to the maximized conversion production of low-molecular olefin and aromatic hydrocarbon in the catalytic cracking process.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the scope of the present invention should be included in the present invention. Therefore, the protection scope of the invention is subject to the protection scope of the claims.
Claims (3)
1. The hydroisomerization method of the catalytic cracking cycle oil is characterized in that a naphthene ring isomerism catalyst is used, and the preparation method of the naphthene ring isomerism catalyst adopts organic nitride as a passivating agent to passivate the hydroisomerization catalyst in situ;
the method specifically comprises the following steps:
preparing an impregnating solution, wherein the impregnating solution comprises an active component, an auxiliary component and the passivating agent;
impregnating the hydroisomerization catalyst carrier by adopting an isovolumetric impregnation method, wherein the impregnation temperature is 10-100 ℃ and the impregnation time is 0.5-3 hours;
drying, wherein the drying temperature is 70-120 ℃ and the drying time is 1-4 hours;
heating, namely heating under an oxygen-free atmosphere at a heating temperature of 100-400 ℃ for 1-4 hours;
the active component is one or more of oxides of Mo, W or Co and Ni in the VIB group or the VIII group, and the content of the active component in the catalyst is 5-30 weight percent based on the oxide;
the auxiliary agent comprises the components of P, wherein the content of P in the catalyst is 0.5-3 weight percent based on the simple substance;
the catalyst carrier is a molecular sieve and alumina, the content of the molecular sieve is 20-70 weight percent, and the alumina is 30-80 weight percent based on the carrier;
the molecular sieve is one or more of Y, ZSM-5 and beta;
the organic nitride is one or more of triethanolamine, diethylenetriamine, polyacrylamide and dimethylformamide.
2. Hydroisomerization process according to claim 1, characterized in that the molar ratio of nitrogen content of the organic nitride to active component is: n/metal molar ratio=0.1 to 0.5/1.
3. Hydroisomerization process according to claim 1 or 2, characterized in that:
the hydroisomerization method is used for catalytically cracking diesel oil or catalytically cracking cycle oil;
before hydroisomerization reaction, carrying out sulfuration treatment on the naphthene ring isomerization catalyst in a hydrogenation reactor, wherein the sulfuration treatment temperature is 200-400 ℃, and the sulfuration treatment time is 1-8 hours;
the temperature of the hydroisomerization reaction is 330-400 ℃, the hydrogen pressure is 4-10 MPa, and the liquid hourly space velocity is 0.5-1.5 h -1 The volume ratio of the hydrogen to the catalytic cracking circulating oil is 500-1500 Nm 3 /m 3 。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566963A (en) * | 2012-08-09 | 2014-02-12 | 尤雷卡特股份公司 | Process for passivation by a nitrogen-containing compound of a zeolitic catalyst, in particular a hydrocracking catalyst |
| CN107185597A (en) * | 2017-05-02 | 2017-09-22 | 中国石油大学(华东) | Vulcanization type gasoline hydrogenation modifying catalyst and preparation method thereof |
| CN108262062A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of catalyst for cracking heavy oil of fecund isomeric olefine and preparation method thereof |
| CN110437875A (en) * | 2019-08-31 | 2019-11-12 | 中海油天津化工研究设计院有限公司 | A kind of catalytic cracking diesel oil hydroisomerizing-deep catalytic cracking technology |
| CN113881457A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Method for treating distillate oil rich in aromatic hydrocarbon |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FI102767B1 (en) * | 1997-05-29 | 1999-02-15 | Neste Oy | Process for the production of high quality diesel fuel |
| US8329610B2 (en) * | 2006-07-21 | 2012-12-11 | China Petroleum & Chemical Corporation | Hydrogenation catalyst composition, process for preparing the same and use thereof |
-
2022
- 2022-10-12 CN CN202211247456.9A patent/CN115582142B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103566963A (en) * | 2012-08-09 | 2014-02-12 | 尤雷卡特股份公司 | Process for passivation by a nitrogen-containing compound of a zeolitic catalyst, in particular a hydrocracking catalyst |
| CN108262062A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of catalyst for cracking heavy oil of fecund isomeric olefine and preparation method thereof |
| CN107185597A (en) * | 2017-05-02 | 2017-09-22 | 中国石油大学(华东) | Vulcanization type gasoline hydrogenation modifying catalyst and preparation method thereof |
| CN110437875A (en) * | 2019-08-31 | 2019-11-12 | 中海油天津化工研究设计院有限公司 | A kind of catalytic cracking diesel oil hydroisomerizing-deep catalytic cracking technology |
| CN113881457A (en) * | 2020-07-02 | 2022-01-04 | 中国石油化工股份有限公司 | Method for treating distillate oil rich in aromatic hydrocarbon |
Non-Patent Citations (4)
| Title |
|---|
| Beta和Y型分子筛催化四氢萘裂化规律的对比;陈妍等;《石油学报（石油加工）》;第31卷(第3期);650-656 * |
| 催化裂化柴油及其加氢产物中芳烃类型与分子结构的表征;王乃鑫等;《石油学报（石油加工）》;第37卷(第5期);1158-1166 * |
| 劣质柴油加氢改质催化剂及工艺研究;段同俊;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第11期);27-33 * |
| 环烷芳烃在不同类型分子筛上的催化裂化反应性能研究;刘鑫鑫;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》(第9期);1-11 * |
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