CN115582142A - Naphthenic ring isomerization catalyst and preparation method and application thereof - Google Patents
Naphthenic ring isomerization catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 33
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000002283 diesel fuel Substances 0.000 claims abstract description 10
- 150000004767 nitrides Chemical class 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000002161 passivation Methods 0.000 claims abstract description 6
- 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 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000004073 vulcanization Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000004480 active ingredient Substances 0.000 claims 1
- 150000001924 cycloalkanes Chemical class 0.000 claims 1
- 229950004864 olamine Drugs 0.000 claims 1
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000005470 impregnation Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 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
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 3
- LHAXNSZBNLVYIP-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;2-(2-hydroxyethylamino)ethanol Chemical compound OCCNCCO.OCCOCCO LHAXNSZBNLVYIP-UHFFFAOYSA-N 0.000 description 2
- 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
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N benzocyclopentane Natural products C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000012854 evaluation process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- -1 indane hydrocarbon Chemical class 0.000 description 2
- 239000012702 metal oxide precursor Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009412 basement excavation Methods 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
- 238000004939 coking Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002468 indanes Chemical class 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000005329 tetralinyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- 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 naphthenic ring isomerization catalyst, a preparation method and application thereof. The preparation method adopts organic nitride as a passivating agent to carry out in-situ passivation on the hydroisomerization catalyst. The method has the advantages of obviously improving the hydroisomerization effect of the naphthenic rings in the catalytic cracking diesel oil, effectively enhancing the carbon deposition resistance, improving the liquid yield and the like, is particularly suitable for the hydroisomerization reaction of the naphthenic rings in the poor-quality catalytic cracking diesel oil, and is favorable for the maximum 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 naphthenic ring isomerization catalyst and a preparation method and application thereof.
Background
In recent years, with the continuous upgrading of the quality standard of clean oil products, the continuous reduction of the demand of diesel market and the continuous growth of the market of aromatic hydrocarbon (BTX) as a polyester raw material and low-olefin high-octane gasoline components such as alkylate and MTBE, the problem of shortage of BTX, C4 alkylation and MTBE raw material supply is highlighted. On one hand, the poor catalytic diesel needs to be efficiently converted so as to reduce the diesel-gasoline ratio of the 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 oil and MTBE in the market is urgently needed to be solved. Aiming at the bright characteristic of high content of polycyclic aromatic hydrocarbon in catalytic cracking cycle oil, how to effectively convert and utilize the polycyclic aromatic hydrocarbon in the catalytic cracking cycle oil becomes an effective way for potential excavation and synergy of refining enterprises.
The combined technology of catalytic cracking diesel oil hydrotreating-catalytic cracking can obtain high octane value clean gasoline and byproduct liquefied gas rich in olefin, and has low hydrogen consumption, high liquid yield and low 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, and the six-membered naphthenic ring (cyclohexane ring) connected with the aromatic ring is easy to undergo hydrogen transfer dehydrogenation reaction to reversely generate the polycyclic aromatic hydrocarbon, so that ineffective circulation is caused. Therefore, a naphthene ring isomerization catalyst is developed to activate the existing six-membered naphthene ring compounds which exist stably after hydrogenation and isomerize them into unstable five-membered rings, thereby contributing to the improvement of cracking activity thereof.
At present, due to the existence of strong acid sites on the surface of a molecular sieve in a hydroisomerization catalyst carrier, the initial activity of the catalyst is too high, the cracking capability is strong, the liquid yield is reduced, carbon deposition on the surface of the catalyst is increased, and the long-period stable operation of the catalyst is influenced.
Therefore, providing a naphthenic ring isomerization catalyst can significantly improve the hydroisomerization effect of catalytic cracking diesel, effectively reduce the catalyst preparation and device operation costs, realize the high-efficiency conversion of poor-quality catalytic cracking diesel, and maximize the production of low-molecular olefins and aromatics, which 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 isomerization 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 above problems, the present invention provides the following technical solutions:
a process for preparing the catalyst used to prepare naphthenic ring includes such steps as passivating the catalyst by organic nitride 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; dipping, dipping the hydroisomerization catalyst carrier by an isovolumetric dipping method, wherein the dipping temperature is 10-100 ℃, and the dipping time is 0.5-3 hours; drying at 70-120 deg.c for 1-4 hr; and (3) heating treatment, namely heating treatment in an oxygen-free atmosphere at the heating temperature of 100-400 ℃ for 1-4 hours.
Further, the mole ratio of the nitrogen content of the organic nitride to the active component is as follows: n/metal molar ratio =0.1 to 0.5/1.
Furthermore, the active component is one or more of oxides of Mo and W in VIB group or Co and Ni in VIIIB group or precursors thereof, and the content of the oxides in the catalyst is 5-30 weight percent.
Furthermore, the auxiliary agent component is P, and the content of P in the catalyst is 0.5 to 3 weight percent in terms of simple substance; the catalyst carrier is a molecular sieve and alumina, and the catalyst carrier is used as a reference, wherein the content of the molecular sieve is 20-70 weight percent, and the content of the alumina is 30-80 weight percent; the type of the molecular sieve is one or more of Y, ZSM-5 and beta.
Further, the organic nitride is one or more of triethanolamine, diethylene glycol diethanolamine, polyacrylamide and dimethylformamide.
The invention also provides a naphthenic ring isomerization catalyst prepared by the method.
In addition, the invention also provides a hydroisomerization method of catalytic cracking cycle oil, which uses the naphthenic 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; before the hydroisomerization reaction, carrying out vulcanization treatment on the catalyst in a hydrogenation reactor, wherein the vulcanization treatment temperature is 200-400 ℃, and the vulcanization 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 cycle oil is 500-1500 Nm 3 /m 3 。
Further, the sulfurization treatment is to heat up to 100-200 ℃ under hydrogen atmosphere, sulfurize and dehydrate the catalyst for 1-3 hours, then heat up to 200-400 ℃ at a heating rate of 1-4 ℃ and treat for 2-4 hours.
In one or more embodiments, the present invention has the following beneficial technical effects:
the preparation method of the naphthenic ring isomerization catalyst adopts an aqueous solution containing organic nitride as a passivating agent to prepare an impregnation liquid, adopts a Co-impregnation method to load one or more of Mo, W or VIII Co and Ni of VIB family on a catalyst carrier, and carries out high-temperature treatment on the hydroisomerization catalyst in an oxygen-free atmosphere, thereby realizing selective passivation of a strong acid site in a molecular sieve composite carrier while completing the loading of a catalyst metal oxide precursor. 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 the hydroisomerization reaction of naphthene rings in inferior catalytic cracking diesel oil, and is beneficial to the maximum conversion production of low molecular olefins and aromatic hydrocarbons in the catalytic cracking process.
Detailed Description
The following describes embodiments of the present invention in detail.
It should be noted that, in the case of no conflict, the features in the following embodiments and examples may be combined with each other; moreover, all other embodiments that can be derived by one of ordinary skill in the art from the embodiments disclosed herein without making any creative effort fall within the scope of the present disclosure.
It is noted that various aspects of the embodiments are described below within the scope of the appended 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 disclosure, one skilled in the art should appreciate that one aspect described herein may be implemented independently of any other aspects 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. Additionally, such an apparatus may be implemented and/or such a method may be practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
The preparation method of the naphthenic ring isomerization catalyst provided by the invention adopts organic nitride as a passivating agent to carry out in-situ passivation on the hydroisomerization catalyst.
In a specific process, the preparation method of the invention may 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, wherein the heating temperature is 100-400 ℃, and the heating time is 1-4 hours.
The organic nitride can be one or more of triethanolamine, diethylene glycol diethanolamine, polyacrylamide and dimethylformamide, and the molar ratio of the nitrogen content of the organic nitride to the active component is preferably as follows: n/metal molar ratio =0.1 to 0.5/1.
The active component can be one or more of oxides of Mo and W in VIB group or Co and Ni in VIIIB group or precursors thereof, and the content of the active component in the catalyst is preferably 5 to 30 weight percent in terms of the oxides. The assistant component can be P, and the content of P in the catalyst is preferably 0.5 to 3 weight percent in terms of 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 and 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 naphthenic ring isomerization catalyst prepared by the method.
In addition, the invention also provides a method for hydroisomerizing catalytic cracking cycle oil by using the naphthenic ring isomerization catalyst. The hydroisomerization method can be applied to straight-run diesel oil, straight-run wax oil, coking wax oil, catalytic cracking diesel oil or catalytic cracking cycle oil. Before the reaction, the catalyst can be vulcanized in a hydrogenation reactor, the vulcanization temperature is 200-400 ℃, and the vulcanization time is 1-8 hours. The temperature of the 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 can be carried out in two steps: firstly, heating to 100-200 ℃ in hydrogen atmosphere, vulcanizing and dehydrating the catalyst for 1-3 hours, then heating to 200-400 ℃ at the heating rate of 1-4 ℃, and processing for 2-4 hours.
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example 1
Weighing a certain amount of Y molecular sieve and pseudo-boehmite, adding sesbania powder, grinding uniformly, acidifying by using 3wt% of nitric acid aqueous solution, fully kneading into gel, extruding into cylindrical strips with the diameter of 1.6mm on a strip extruding machine, drying in a drying 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 forming preparation method, wherein the content of the Y molecular sieve is 70 wt%, and the content of the alumina is 30 wt%.
Weighing 200 g of the catalyst carrier S1, and impregnating a solution containing a certain amount of molybdenum, nickel, phosphorus and triethanolamine on the carrier by an isometric impregnation method, wherein the nitrogen content of the triethanolamine is N/metal (Mo and Ni) molar ratio =0.2/1. Then drying the product in an oven at 80 ℃ for 3 hours, heating the product in a tubular furnace in the presence of nitrogen at 300 ℃ for 2 hours to obtain a passivated hydroisomerization catalyst SC1, which comprises the following components: 15% by weight of molybdenum oxide, 4% by weight of nickel oxide and 2% by weight of phosphorus oxide.
Example 2
Weighing a certain amount of beta molecular sieve and pseudo-boehmite, adding sesbania powder, grinding uniformly, acidifying by using 3wt% of nitric acid aqueous solution, fully kneading into gel, extruding into cylindrical strips with the diameter of 1.6mm on a strip extruding machine, drying for 3 hours at 120 ℃ in a drying oven, and roasting for 3 hours at 550 ℃ in a muffle furnace to obtain a catalyst carrier S2, wherein the content of the beta molecular sieve is 70 wt%, and the content of the alumina is 30 wt%.
Weighing 200 g of the catalyst carrier S2, and impregnating a solution containing a certain amount of molybdenum, nickel, phosphorus and triethanolamine on the carrier by an isometric impregnation method, wherein the nitrogen content of the triethanolamine is N/metal (Mo and Ni) molar ratio =0.2/1. Then drying the mixture in an oven at 80 ℃ for 3 hours, heating the mixture in a tubular furnace in the presence of nitrogen at 300 ℃ for 2 hours to obtain a passivated hydroisomerization catalyst SC2, which comprises the following components: 15% by weight of molybdenum oxide, 4% by weight of nickel oxide and 2% by weight of phosphorus oxide.
Example 3
Weighing 200 g of the catalyst carrier S2, and impregnating a solution containing a certain amount of molybdenum, nickel, phosphorus and dimethylformamide on the carrier by adopting an isometric impregnation method, wherein the nitrogen content of the dimethylformamide is N/metal (Mo and Ni) molar ratio =0.3/1. Then drying the product in an oven at 100 ℃ for 3 hours, heating the product in a tubular furnace in the presence of nitrogen at 350 ℃ for 2 hours to obtain a passivated hydroisomerization catalyst SC3, which comprises the following components: 20% by weight of molybdenum oxide, 5% by weight of nickel oxide and 2% by weight 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 isometric impregnation method, drying the carrier in a drying oven at 120 ℃ for 3 hours, and roasting the carrier in a muffle furnace at 500 ℃ for 2 hours to obtain the hydroisomerization catalyst OC1, wherein the hydroisomerization catalyst OC1 comprises the following components: 15% by weight of molybdenum oxide, 4% by weight of nickel oxide and 2% by weight of phosphorus oxide.
The physicochemical properties of the above four catalysts are shown in table 1:
TABLE 1 physicochemical Properties of catalysts of examples 1 to 3 and comparative example 1
| Catalyst and process for producing the same | Specific surface area, square meter per gram | 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 subjected to performance evaluation using hydrorefined catalytic cracking diesel, and the feedstock properties are shown in table 2. The hydrorefining 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 heavy oil national emphasis laboratory of China university of Petroleum (east China).
TABLE 2 catalytic cracking Diesel Main Properties
The catalyst prepared in examples 1 to 3 and comparative example was evaluated for the hydroisomerization performance of catalytic cracking diesel, and the specific evaluation process was as follows: the catalyst loading was 78 g (100 ml) using a high pressure fixed bed pilot plant. The catalyst needs to be pre-vulcanized before performance evaluation, the vulcanized oil is straight-run diesel containing 2 wt% 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 vulcanization time is 8 hours. After the vulcanization is finished, introducing the hydrocatalytically cracked 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 sampling analysis is carried out after 12 hours of stabilization.
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 in Table 3, the passivated FCC diesel naphthenic ring hydroisomerization catalyst prepared by the process of the present invention has higher naphthenic ring isomerization performance than the conventional in-situ sulfided catalyst, with an indane hydrocarbon yield of about 20.75wt% for the SC2 catalyst and only 12.58wt% for the conventional in-situ sulfided catalyst OC 1. This indicates 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 hydrocarbons is obviously lower than that of the catalyst prepared by the beta molecular sieve.
The catalyst used in example 2 was used to adjust the reaction conditions, and the results of the reaction evaluation are shown in Table 3. The specific evaluation process is as follows: the catalyst needs to be presulfurized before performance evaluation, the vulcanized oil is straight-run diesel containing 2 wt% 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 vulcanization time is 8 hours. After the vulcanization is finished, introducing the hydrocatalytically cracked 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 sampling analysis is carried out after 12 hours of stabilization.
From the results of table 3, it can be seen that the contents of indanes and tetralins are significantly smaller as the reaction temperature increases, while the content of total saturated hydrocarbons increases, indicating that the ring-opening performance of the catalyst is enhanced. However, the naphthene ring isomerization performance of the catalyst is still higher than that of the conventional in-situ sulfided catalyst (OC 1).
Therefore, the method adopts the water solution containing the organic nitride as the passivating agent to prepare the co-impregnation liquid, realizes the selective passivation of a strong acid site in the molecular sieve composite carrier while finishing the loading of the catalyst metal oxide precursor, improves the naphthene ring hydroisomerization activity and selectivity of the catalyst, is particularly suitable for the naphthene ring hydroisomerization reaction in poor catalytic cracking diesel, and is beneficial to the maximum conversion production of low-molecular olefins and aromatic hydrocarbons in the catalytic cracking process.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of a naphthenic ring isomerization catalyst is characterized in that an organic nitride is used as a passivating agent to carry out in-situ passivation on a hydroisomerization catalyst.
2. The method for preparing according to claim 1, characterized in that it comprises the following steps:
preparing an impregnating solution, wherein the impregnating solution comprises an active component, an auxiliary component and the passivating agent;
dipping, dipping the hydroisomerization catalyst carrier by adopting an isovolumetric dipping method, wherein the dipping temperature is 10-100 ℃, and the dipping time is 0.5-3 hours;
drying at 70-120 deg.c for 1-4 hr;
and (3) heating treatment, namely heating treatment in an oxygen-free atmosphere at the heating temperature of 100-400 ℃ for 1-4 hours.
3. The method according to claim 2, wherein the molar ratio of the nitrogen content of said organonitrogen compound to the active ingredient is: n/metal molar ratio =0.1 to 0.5/1.
4. The preparation method of claim 2, wherein the active component is one or more of oxides of Mo and W in the VIB group or Co and Ni in the VIIIB group or precursors thereof, and the content of the oxides in the catalyst is 5-30 wt%.
5. The production method according to claim 2, characterized in that:
the assistant component is P, and the content of P in the catalyst is 0.5 to 3 weight percent based on a simple substance;
the catalyst carrier is a molecular sieve and alumina, and the catalyst carrier is used as a reference, wherein the content of the molecular sieve is 20-70 weight percent, and the content of the alumina is 30-80 weight percent;
the type of the molecular sieve is one or more of Y, ZSM-5 and beta.
6. The method according to any one of claims 1 to 5, wherein the organonitrogen compound is one or more of triethanolamine, diethyleneglycol-olamine, polyacrylamide, and dimethylformamide.
7. A cycloalkane isomerization catalyst produced by the process of any one of claims 1-6.
8. A process for hydroisomerization of catalytically cracked cycle oil, characterized by using the naphthene ring isomerization catalyst according to claim 7.
9. The hydroisomerization process of claim 8, characterized in that:
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;
before the hydroisomerization reaction, carrying out vulcanization treatment on the catalyst in a hydrogenation reactor, wherein the vulcanization treatment temperature is 200-400 ℃, and the vulcanization 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 cycle oil is 500-1500 Nm 3 /m 3 。
10. The hydroisomerization process according to claim 9, characterized in that the sulfurization treatment is to increase the temperature to 100 to 200 ℃ in a hydrogen atmosphere, sulfurize and dehydrate the catalyst for 1 to 3 hours, and then increase the temperature to 200 to 400 ℃ at a rate of 1 to 4 ℃ and treat it for 2 to 4 hours.
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