CN115582143A - Naphthenic ring isomerization catalyst and preparation method and application thereof - Google Patents

Naphthenic ring isomerization catalyst and preparation method and application thereof Download PDF

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CN115582143A
CN115582143A CN202211248172.1A CN202211248172A CN115582143A CN 115582143 A CN115582143 A CN 115582143A CN 202211248172 A CN202211248172 A CN 202211248172A CN 115582143 A CN115582143 A CN 115582143A
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catalyst
hydroisomerization
hours
catalytic cracking
temperature
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CN115582143B (en
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柴永明
王禹
刘宾
刘小波
杨朝合
王志刚
陈小博
袁明江
刘晨光
李胜山
李春义
方堃
张星
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China University of Petroleum East China
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China University of Petroleum East China
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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention discloses a naphthenic ring isomerization catalyst, a preparation method and application thereof. The preparation method adopts a composition of organic nitride and organic sulfide as a vulcanization passivator to carry out vulcanization passivation on the hydroisomerization catalyst. The invention obviously improves the hydroisomerization effect of the naphthenic rings in the catalytic cracking diesel oil, simultaneously has the advantages of effectively enhancing the carbon deposition resistance and improving the liquid yield, has short start-up time, low operation cost and the like, is particularly suitable for the hydroisomerization reaction of the naphthenic rings in the poor catalytic cracking diesel oil, and is beneficial to the maximum conversion production of low molecular olefins and aromatic hydrocarbons in the catalytic cracking process.

Description

Naphthenic ring isomerization catalyst and preparation method and application thereof
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 fuel markets and the continuous increase of the markets of aromatic hydrocarbon (BTX) as a polyester raw material and low-olefin high-octane gasoline components such as alkylate and MTBE, the problem of the shortage of the supply of BTX, C4 alkylate and MTBE raw materials 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 raw material shortage of low-olefin high-octane gasoline components such as BTX, alkylate oil, MTBE and the like is urgently needed to be solved. Aiming at the distinctive 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 exploitation 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 was developed to activate the existing six-membered naphthene ring compounds stably present after hydrogenation and isomerize them into unstable five-membered rings, thereby contributing to the improvement of cracking activity thereof.
Currently, the active metal component of hydroisomerization catalysts is usually in the oxidized state, while the active component on the hydroisomerization catalyst is present in the form of its sulfides in actual use. In addition, due to the existence of strong acid sites on the surface of the molecular sieve in the 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, which is intended to significantly improve the hydroisomerization effect of catalytic cracking diesel, effectively reduce the catalyst preparation and equipment operation costs, achieve high-efficiency conversion of poor-quality catalytic cracking diesel, and maximize the production of low-molecular olefins and aromatics, is a problem to be solved by those skilled in the art.
Disclosure of Invention
Accordingly, 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 naphthene ring isomerizing catalyst features that the composition of organic nitride and organic sulfide is used as sulfurizing passivator to sulfurize and passivate the hydroisomerization catalyst.
Further, the method comprises the steps of: preparing an impregnation liquid, wherein the impregnation liquid comprises an active component, an auxiliary component and the vulcanization passivator; 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 = 0.1-0.5/1, the molar ratio of the sulfur content of the organic sulfide to the active component is: s/metal molar ratio =1 to 4/1.
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.
Further, the auxiliary agent component is P, and the content of P in the catalyst is 0.5-3 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 diamine, polyacrylamide and dimethylformamide, and the organic sulfide is one or more of thiourea, allylthiourea and dimethyl sulfoxide.
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; pretreating the catalyst in a hydrogen atmosphere before the hydroisomerization reaction, wherein the pretreatment temperature is 200-400 ℃, and the pretreatment 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 pretreatment is to heat the catalyst to 100-200 ℃ in a hydrogen atmosphere, dehydrate the catalyst for 1-3 hours, heat the catalyst to 200-400 ℃ at a heating rate of 1-4 ℃ and treat the catalyst 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 a composition containing organic nitride and organic sulfide as an aqueous solution of a vulcanization passivator to prepare an impregnation solution, adopts a Co-impregnation method to load one or more of Mo, W or VIIIB Co and Ni of families VIB on a catalyst carrier, and realizes the vulcanization of a metal oxide precursor and the selective passivation of a strong acid site in a molecular sieve composite carrier by treating the hydroisomerization catalyst at high temperature in an oxygen-free atmosphere. 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, having short start-up time, low operation cost and the like, being particularly suitable for the hydroisomerization reaction of the naphthenic rings in the poor-quality catalytic cracking diesel oil, and being 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, based on the embodiments in the present disclosure, all other embodiments obtained by a person of ordinary skill in the art without making creative efforts shall fall within the protection 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 the composition of organic nitride and organic sulfide as a vulcanization passivator to carry out vulcanization passivation on the hydroisomerization catalyst.
In a specific process, the preparation method of the invention may comprise the following steps: preparing an impregnation liquid, wherein the impregnation liquid comprises an active component, an auxiliary component and the vulcanization passivator; dipping, namely dipping the hydroisomerization catalyst carrier by adopting an isometric dipping method, wherein the dipping temperature is 10-100 ℃, and the dipping time is 0.5-3 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 under 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, diethylene glycol olamine, polyacrylamide and dimethylformamide, the organic nitride can be one or more of thiourea, allylthiourea and dimethyl sulfoxide, 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 molar ratio of the sulfur content of the organosulfide to the active component preferably being: s/metal molar ratio =1 to 4/1.
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 oxides in the catalyst is preferably 5-30 weight percent. The assistant component can be P, and the content of P in the catalyst is preferably 0.5-3 weight percent in terms of simple substance. The catalyst carrier can be selected from a 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, 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, coker wax oil, catalytic cracking diesel oil or catalytic cracking cycle oil. Before the reaction, the catalyst can be pretreated in hydrogen atmosphere, the pretreatment temperature is 200-400 ℃, and the pretreatment 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 pretreatment can be carried out in two steps: firstly, heating to 100-200 ℃ in hydrogen atmosphere, dehydrating the catalyst for 1-3 hours, then heating to 200-400 ℃ at the heating rate of 1-4 ℃, and treating 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 limitations 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 a 3wt% nitric acid aqueous solution, fully kneading into gel, extruding into a cylindrical strip 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 and molding 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, dimethyl sulfoxide and triethanolamine on the carrier by an isometric impregnation method, wherein the sulfur content of the dimethyl sulfoxide is S/metal (Mo and Ni) molar ratio =3/1, and the nitrogen content of the triethanolamine is N/metal (Mo and Ni) molar ratio =0.2/1. Then drying the catalyst in an oven at 80 ℃ for 3 hours, heating the catalyst in a tubular furnace in the presence of nitrogen at 300 ℃ for 2 hours to obtain a vulcanized 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, dimethyl sulfoxide and triethanolamine on the carrier by an isometric impregnation method, wherein the sulfur content of the dimethyl sulfoxide is S/metal (Mo and Ni) molar ratio =3/1, and 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 vulcanized 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, dimethyl sulfoxide and triethanolamine on the carrier by an isometric impregnation method, wherein the sulfur content of the dimethyl sulfoxide is S/metal (Mo and Ni) molar ratio =3/1, and 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 400 ℃ for 2 hours to obtain a vulcanized passivated hydroisomerization catalyst SC3, 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 4
Weighing 200 g of the catalyst carrier S2, and impregnating a solution containing a certain amount of molybdenum, nickel, phosphorus, dimethyl sulfoxide and triethanolamine on the carrier by an isometric impregnation method, wherein the sulfur content of the dimethyl sulfoxide is S/metal (Mo and Ni) molar ratio =3/1, and the nitrogen content of the triethanolamine is N/metal (Mo and Ni) molar ratio =0.3/1. Then drying the catalyst in an oven at 80 ℃ for 3 hours, heating the catalyst in a tubular furnace in the presence of nitrogen at 300 ℃ for 2 hours to obtain a vulcanized passivated hydroisomerization catalyst SC4, 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 5
Weighing 200 g of the catalyst carrier S2, and impregnating a solution containing a certain amount of molybdenum, nickel, phosphorus, thiourea and dimethylformamide on the carrier by adopting an isometric impregnation method, wherein the sulfur content of the thiourea is S/metal (Mo and Ni) molar ratio =4/1, and 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 vulcanized passivated hydroisomerization catalyst SC5, 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, soaking a solution containing a certain amount of molybdenum, nickel and phosphorus on the carrier by adopting an isometric soaking method, then 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 six catalysts are shown in table 1:
TABLE 1 physicochemical Properties of catalysts of examples 1 to 5 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 305 0.32 185
SC2 285 0.33 191
SC3 290 0.34 187
SC4 280 0.33 193
SC5 260 0.31 200
OC1 300 0.32 196
The performance of the six catalysts was evaluated by using hydrorefined catalytic cracking diesel, and the properties of the raw materials 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 heavy oil national emphasis laboratory of China university of Petroleum (east China).
TABLE 2 main properties of catalytically cracked diesel
Figure BDA0003887505830000071
Figure BDA0003887505830000081
The catalysts prepared in examples 1 to 5 were evaluated in the following manner: the catalyst loading was 78 g (100 ml) using a high pressure fixed bed pilot plant. The catalyst needs to be pretreated under hydrogen atmosphere before performance evaluation, and is dehydrated for 2 hours at 120 ℃ and then at 2 ℃ min -1 The temperature rise rate is increased to 300 ℃ and the diesel oil is treated for 3 hours, the pressure and the flow of hydrogen are the same as the reaction evaluation conditions, the diesel oil is catalytically cracked after hydrogenation after the treatment, and the reaction evaluation conditions are as follows: the temperature is 360 ℃, 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 sampling analysis is carried out after 12 hours of stabilization.
Comparative example 1 evaluation of the prepared catalyst. The specific evaluation process is as follows: a high pressure fixed bed pilot plant was used with a catalyst loading of 78 grams (100 ml). The catalyst needs to be pre-vulcanized before performance evaluation, the vulcanized oil is straight-run diesel containing 2wt% of dimethyl disulfide, and the vulcanization conditions are as follows: the temperature is 320 ℃, the hydrogen pressure is 6MPa, and the liquid hourly space velocity is 1.5h -1 The hydrogen-oil ratio was 500/1 (V/V), and the vulcanization time was 8 hours. After vulcanization, adding hydrogenated catalytic cracking diesel oil, wherein the reaction evaluation conditions are as follows: the temperature is 360 ℃, 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 sampling analysis is carried out after 12 hours of stabilization.
The reaction evaluation results are shown in table 3:
TABLE 3 reaction evaluation results of six catalysts
Figure BDA0003887505830000082
Figure BDA0003887505830000091
From the results in Table 3, it can be seen that the sulfurized passivated cracked diesel naphthenic ring hydroisomerization catalyst prepared according to the method of the present invention has higher naphthenic ring isomerization performance than the conventional in-situ sulfurized catalyst, with about 19wt% yield of indane hydrocarbons for SC2, SC3 and SC4 catalysts, and only 12wt% yield of indane hydrocarbons for conventional in-situ sulfurized catalyst OC 1. This shows that the ring-opening cracking activity of the catalyst is effectively inhibited in the sulfurization passivation treatment process, and the isomerization activity and selectivity of the catalyst are remarkably improved. 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 pretreatment conditions and the reaction process conditions were adjusted by using the catalyst of example 4, and the results of the reaction evaluation are shown in table 4. The specific evaluation process is as follows:
pretreatment conditions 1: the catalyst loading was 78 grams (100 ml) using a high pressure fixed bed pilot plant. The catalyst was pretreated under hydrogen atmosphere before performance evaluation, first at 120 ℃ for 2 hours, then at 2 ℃ min -1 The temperature rise rate is increased to 350 ℃ and the diesel oil is treated for 3 hours, the pressure and the flow of hydrogen are the same as the reaction evaluation conditions, the diesel oil is catalytically cracked after hydrogenation after the treatment, and the reaction evaluation conditions are as follows: the temperature is 360 ℃, the hydrogen pressure is 6MPa, and the liquid hourly space velocity is 1.5h -1 Hydrogen-to-oil ratio of 500/1 (V/V), and sampling analysis was carried out 12 hours after stabilization.
Pretreatment conditions 2: the catalyst loading was 78 g (100 m) using a high pressure fixed bed pilot plantl). The catalyst needs to be pretreated under hydrogen atmosphere before performance evaluation, and is dehydrated for 2 hours at 120 ℃ and then at 2 ℃ min -1 When the temperature rise rate is increased to 250 ℃ and the treatment is carried out for 3 hours, the pressure and the flow of hydrogen are the same as the reaction evaluation conditions, the hydrogenated catalytic cracking diesel oil is added after the treatment, and the reaction evaluation conditions are as follows: the temperature is 360 ℃, the hydrogen pressure is 6MPa, and the liquid hourly space velocity is 1.5h -1 Hydrogen-to-oil ratio of 500/1 (V/V), and sampling analysis was carried out 12 hours after stabilization.
Reaction evaluation condition 1: the catalyst loading was 78 g (100 ml) using a high pressure fixed bed pilot plant. The catalyst was pretreated under hydrogen atmosphere before performance evaluation, first at 120 ℃ for 2 hours, then at 2 ℃ min -1 The temperature rise rate is increased to 350 ℃ and the diesel oil is treated for 3 hours, the pressure and the flow of hydrogen are the same as the reaction evaluation conditions, the diesel oil is catalytically cracked after hydrogenation after the treatment, and the reaction evaluation conditions are as follows: the temperature is 380 ℃, the hydrogen pressure is 10MPa, and the liquid hourly space velocity is 1.5h -1 Hydrogen-to-oil ratio of 800/1 (V/V), and sampling analysis was carried out 12 hours after stabilization.
TABLE 4 reaction evaluation results for different pretreatment conditions and evaluation conditions
Figure BDA0003887505830000101
From the results in table 4, it is understood that the pretreatment conditions of the catalyst under a hydrogen atmosphere before performance evaluation did not greatly affect the catalyst performance, but the isomerization performance of the catalyst was slightly improved as the pretreatment temperature was increased. When the pretreatment temperature is increased from 250 ℃ to 350 ℃, the yield of indanes hydrocarbons is increased from 19.19wt% to 19.89wt%. Furthermore, it can be seen that the contents of indanes and tetralins are significantly smaller with increasing reaction temperature, while the content of total saturated hydrocarbons increases, indicating an increased ring-opening performance of the catalyst. 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 organic nitrogen and sulfide as the passivating agent to prepare the co-impregnation liquid, realizes the sulfuration of active metal and the selective passivation of a strong acid site in the molecular sieve composite carrier while completing the loading of the metal oxide precursor of the catalyst, improves the naphthene ring hydroisomerization activity and selectivity of the catalyst, is particularly suitable for the hydroisomerization reaction of naphthene rings in 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.
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 a composition of an organic nitride and an organic sulfide is used as a vulcanization passivator to carry out vulcanization passivation on a hydroisomerization catalyst.
2. The method for preparing according to claim 1, characterized in that it comprises the following steps:
preparing an impregnation liquid, wherein the impregnation liquid comprises an active component, an auxiliary component and the vulcanization passivator;
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 the organonitride to the active ingredient is: n/metal molar ratio = 0.1-0.5/1, the molar ratio of the sulfur content of the organic sulfide to the active component is: s/metal molar ratio =1 to 4/1.
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 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.
6. The preparation method according to any one of claims 1 to 5, wherein the organic nitride is one or more of triethanolamine, diethylene glycol olamine, polyacrylamide and dimethylformamide, and the organic sulfide is one or more of thiourea, allylthiourea and dimethylsulfoxide.
7. A cycloalkane isomerization catalyst produced by the method according to any one of claims 1 to 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;
pretreating the catalyst in a hydrogen atmosphere before the hydroisomerization reaction, wherein the pretreatment temperature is 200-400 ℃, and the pretreatment 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 said pretreatment is carried out by raising the temperature to 100-200 ℃ under a hydrogen atmosphere, dehydrating said catalyst for 1-3 hours, raising the temperature to 200-400 ℃ at a rate of 1-4 ℃ and treating for 2-4 hours.
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