CN108187659B - Supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst and application thereof - Google Patents

Supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst and application thereof Download PDF

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CN108187659B
CN108187659B CN201711397677.3A CN201711397677A CN108187659B CN 108187659 B CN108187659 B CN 108187659B CN 201711397677 A CN201711397677 A CN 201711397677A CN 108187659 B CN108187659 B CN 108187659B
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molybdenum
tungsten
bimetallic oxide
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CN108187659A (en
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靳少华
王磊
孙康
王同济
初乃波
李作金
曹善健
黎源
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Wanhua Chemical Group Co Ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • 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
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
    • C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
    • C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract

The invention provides a supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst and application thereof, wherein the supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst comprises a carrier and a non-stoichiometric molybdenum-tungsten bimetallic oxide loaded on the carrier; the mass of the non-stoichiometric molybdenum-tungsten bimetallic oxide is 6-12 wt% of the mass of the carrier. The catalyst has the characteristics of easy preparation and low preparation cost, and meanwhile, the catalyst composition developed based on the catalyst is particularly suitable for preparing neohexene through the disproportionation of diisobutylene and ethylene, and has the characteristics of high disproportionation activity, high neohexene yield, difficult carbon deposition and inactivation and the like.

Description

Supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst and application thereof
Technical Field
The invention belongs to the technical field of olefin comprehensive utilization, and particularly relates to a supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst which is particularly suitable for preparing neohexene through diisobutylene and ethylene disproportionation, and a preparation method and application thereof.
Background
Neohexene, known by the scientific name 3, 3-dimethyl-1-butene, is an important carbon hexaolefin and is widely applied to the fields of synthetic perfumes, agricultural chemicals and the like. Particularly, in the synthesis of tonalid, the neohexene used as a raw material has higher yield and purer quality compared with other olefins. The neohexene has excellent antiknock property, can be used for improving the octane number of gasoline, can be used for manufacturing brake oil, transmission oil, refrigerant and heat agent, and can be used as a selective adsorbent of acid gas and the like. Furthermore, neohexene is an important intermediate in fine chemicals for the production of 2, 3-dimethyl-1, 3-butadiene, 3-dimethyl-2-butanone, 1,2,4, 5-pyromellitic anhydride, for the production of savory and flavor in the food and flavor industries.
At present, the synthesis method of neohexene mainly comprises the following three methods: catalytic dehydrogenation of neohexane over Al-Cr-K catalyst, dehydrohalogenation of halogenated neohexane, and disproportionation of diisobutylene and ethylene. Wherein, the yield and the selectivity of the neohexene prepared by the catalytic dehydrogenation method of the neohexane are only 11 percent and 35 percent respectively. Most of the halogenated neohexane dehydrohalogenation methods adopt alcoholic solution of alkali or high temperature to remove hydrogen halide; meanwhile, the yield of the halogenated neohexane synthesized by the addition of the halogenated tert-butane and the ethylene is low, about 30 percent, and the reaction needs to be carried out for a long time at a low temperature (-20 ℃), so that a large amount of ethylene is wasted. Disproportionation of diisobutylene from ethylene over transition metal oxide catalysts (e.g., WO)3，MoO3，Re2O7Etc.) the C ═ C double bond in the olefin is cleaved and reformed, giving rise to neohexene. The reaction is as follows:
Figure BDA0001518874100000021
the key technology for preparing neohexene by using diisobutylene and ethylene as raw materials is the preparation of a high-stability olefin double bond isomerization catalyst and the preparation of a high-activity olefin disproportionation catalyst, and particularly, one of the key technologies is how to obtain a catalyst with excellent thermal stability and carbon deposit resistance. Only Chevron Phillips has previously achieved commercial production of neohexene (as reported, for example, in published patent US 4459320), using a disproportionation catalyst of WO3/SiO2Required for the disproportionation reaction of diisobutylene and ethylene under the action of the catalystThe temperature and pressure are high and the reaction requires a long induction period to achieve the optimal catalytic effect. Currently, the company has completely shut down the neohexene production line and implemented technical blockages.
Although the reports about olefin disproportionation technology in China are endless, patent technology for preparing neohexene by a disproportionation method is rarely reported. CN102335631B reports Al2O3The olefin disproportionation technology is a catalyst carrier, but the reacted olefin is an olefin with the carbon number less than or equal to 4, and the application range of the catalyst is limited. CN103739433B and CN102875312B report a method for preparing tetramethylethylene by fluidized bed olefin disproportionation. However, the fluidized bed has the disadvantages of large material back mixing, serious catalyst abrasion, complicated internal components, high operation requirement and the like due to the need of a recovery and dust collection device. In conclusion, the traditional olefin disproportionation technology has the problems of low catalyst activity, overlong induction period, easy abrasion and the like, and is mainly suitable for the reaction of the raw material with less carbon number of the olefin, otherwise, the carbon deposition of the catalyst is inactivated.
According to the patent document CN201280077225.6, the traditional supported WO3The preparation method of the catalyst adopts an impregnation method to impregnate a tungsten source on a carrier, and the dried catalyst can be prepared into the supported WO only after being roasted at high temperature (600-3A catalyst. The disproportionation catalyst active matter prepared by the traditional impregnation method is WO3The activity in olefin disproportionation is low and there is a long induction period. Patent CN201310568498.7 reports a method for preparing reduced tungsten oxide WO by solvothermal method2.72The method of (1), which has disadvantages that a large amount of organic alcohol having reducibility is required, the tungsten source is expensive and extremely unstable in water, especially synthetic WO2.72Is excessively reduced and the disproportionation performance is significantly impaired.
The summary shows that the development of a catalyst which has high disproportionation activity, high new hexene yield, difficult carbon deposition inactivation, easy preparation and environmental protection and economy is one of the difficulties in preparing new hexene by disproportionation of diisobutylene and ethylene.
Disclosure of Invention
The invention provides a load type non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst for making up the defects in the prior art, and the catalyst has the characteristics of easy preparation and low preparation cost; meanwhile, the catalyst composition developed based on the catalyst is particularly suitable for preparing the neohexene by disproportionating diisobutylene and ethylene, and has the characteristics of high disproportionating activity, high neohexene yield, difficult carbon deposition and inactivation and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst in a first aspect, which comprises a carrier and a non-stoichiometric molybdenum-tungsten bimetallic oxide loaded on the carrier; the mass of the non-stoichiometric molybdenum-tungsten bimetallic oxide is 6-12 wt% of the mass of the carrier, and the mass is more preferably 8-10%. Preferably, the chemical composition of the non-stoichiometric molybdenum-tungsten bimetallic oxide is MoxW(1-x)OyWherein x is 0.1 to 0.3, and y is 2.9 to 3.0. The inventor of the application finds that the supported non-stoichiometric molybdenum-tungsten bimetallic oxide of the invention, tungsten oxide and molybdenum oxide in low reduction state, can more easily form a metal-carbene structure with olefin molecules, and can significantly shorten the induction period of the traditional disproportionation catalyst as an active center of the disproportionation reaction, so that the supported non-stoichiometric molybdenum-tungsten bimetallic oxide is more suitable for catalyzing the reaction of diisobutylene and ethylene.
The supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst disclosed by the invention preferably further comprises one or more of alkali metal oxide and alkaline earth metal oxide which are supported on the carrier, so that the catalytic activity of the catalyst can be obviously improved, and the conversion rate is improved; in order to obtain better catalytic effect, the sum of the masses of the alkali metal oxide and the alkaline earth metal oxide is preferably 0.5-2 wt% of the mass of the carrier.
Preferably, the alkali metal oxide comprises one or more of sodium, potassium and cesium oxides; the alkaline earth metal oxide includes one or more of oxides of magnesium and calcium.
Preferably, the carrier includes, but is not limited to, one or more of coarse pore silica gel, mesoporous silica and adjuvant modified silica material.
Preferably, the specific surface area of the coarse-pore silica gel is 300-400 m2(ii)/g, the average pore diameter is 8-10 nm; preferably, the mesoporous silicon comprises SBA-15, COK-12, MCM-41 and the like, and can be commercially available, such as mesoporous silicon supplied by Tianjin Minghan chemical catalyst company, Shanghai Xuefeng molecular sieve company, Shanghai Boyle chemical company and the like; the preferred specific surface area of the mesoporous silicon is 500-800 m2The average pore diameter is preferably 7.5 to 12 nm. The carrier with specific pore diameter and specific surface area is preferred, which is beneficial to improving the catalytic activity of the catalyst.
Preferably, the auxiliary agent in the auxiliary agent modified silicon material comprises an HY molecular sieve, an H beta molecular sieve and Nb2O5、Ta2O5、Al2O3、ZrO2、CeO2The one or more auxiliary agent modified silicon material can be obtained by a process known in the art, for example, mode 1) the auxiliary agent and the silicon material are subjected to mechanical ball milling and mixing; mode 2) the corresponding precursor salt of the auxiliary agent is dissolved in water, dipped on the silicon material, dried and roasted at high temperature to obtain the silicon material. These processes are well known in the art and are not described in detail.
In a second aspect the present invention provides a process for the preparation of a supported non-stoichiometric molybdenum tungsten bimetallic oxide catalyst as described above, comprising the steps of:
1) dissolving metal salt in water to obtain a salt solution, and adjusting the pH value of the salt solution to 7.5-9; the metal salt comprises a tungsten salt and a molybdenum salt; preferably, the metal salt further comprises one or more of an alkali metal salt and an alkaline earth metal salt;
2) dispersing a carrier in the salt solution, and stirring for reaction at the temperature of 200 ℃ and 250 ℃; in a specific embodiment, the carrier is preferably heated in a closed manner to perform stirring reaction, and the stirring speed is preferably 300-500 r/min, so that the carrier can be uniformly dispersed in a salt solution;
3) introducing reducing gas into the reaction system for reduction, and then stopping introducing the reducing gas for aging;
4) washing and drying the product prepared in the step 3); in one embodiment, the product obtained in step 3) is preferably cooled to room temperature, washed, dried and tabletted; preferred drying conditions are: the drying temperature is 50-100 ℃, and the drying time is 12-24 h.
In the method of the present invention, preferably, in step 1), the tungsten salt is selected from one or more of ammonium metatungstate, ammonium paratungstate or sodium tungstate; the molybdenum salt is selected from one or more of ammonium dimolybdate, ammonium tetramolybdate or ammonium heptamolybdate; the alkali metal salt is selected from one or more of sodium, potassium, cesium acetate or oxalate; the alkaline earth metal salt is selected from one or more of magnesium, calcium acetate or oxalate.
In the method, a preferable specific embodiment is that in the step 1), in the salt solution, the mass ratio of water to the metal salt is 50: 1-100: 1;
preferably, in step 1), the pH adjusting agent used for adjusting the pH of the salt solution is one or more selected from the group consisting of ammonia, tetramethylammonium hydroxide, tetrabutylammonium hydroxide.
In the method, a preferable specific embodiment is that in the step 2), the reaction time is 12-36 hours.
In the method of the present invention, preferably, in step 3), the reducing gas is H2A mixed gas of one or more of CO and propylene with an inert gas Ar; h in the mixed gas2The concentration of (b) is preferably 0.5 to 5% by volume, for example, in H2H in the mixed gas of/Ar2The concentration is 0.5-5 v%; the concentration of CO in the mixed gas is preferably 3-20 v%, for example, the concentration of CO in the CO/Ar mixed gas is 3-20 v%; the concentration of propylene in the mixed gas is preferably 5 to 30 v%, for example, the concentration of propylene in the propylene/Ar mixed gas is 5 to 30 v%.
Preferably, in the step 3), the introducing time of the reducing gas is 20-60 min, and the volume space velocity is 3-10 h-1And the aging time is 24-72 h.
In a third aspect, the invention provides a catalyst composition comprising magnesium oxide and a supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst. The magnesium oxide has the effects of purifying raw materials and assisting in catalysis, and is beneficial to prolonging the service life of the main catalyst; the mass ratio of the two is preferably 4: 1-2: 1. (ii) a The supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst is the supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst or the supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst prepared by the method.
In a fourth aspect, the present invention provides a process for producing neohexene by disproportionation of ethylene and diisobutylene in the presence of the catalyst composition described above to produce said neohexene;
preferably, the disproportionation reaction is carried out in a fixed bed, and the feeding volume space velocity of the diisobutylene is preferably 5-50 h-1。
Preferably, the molar ratio of ethylene to diisobutylene is from 4:1 to 2: 1.
Preferably, the disproportionation reaction temperature is 300-400 ℃ to obtain better reaction conversion rate and selectivity; the reaction pressure is preferably 0.1 to 3 MPa.
The technical scheme provided by the invention has the following beneficial effects:
when the catalyst is used for preparing the neohexene through the disproportionation of the diisobutylene and the ethylene hydrocarbon, the single-pass conversion rate of the raw material and the yield of the product neohexene are high, and the catalyst has good stability.
Compared with the traditional impregnation method for preparing the catalyst, the preparation process of the supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst can obtain the oxidized tungsten and molybdenum catalyst without high-temperature roasting, and the molybdenum-tungsten bimetallic oxide with the non-stoichiometric ratio as the active center has no induction period and obviously improved disproportionation activity.
The solvent used in the preparation process of the supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst is water, and belongs to an environment-friendly solvent; a tungsten source or a molybdenum source which is more conventional, low in price and stable in water property is adopted; the synthesized tungsten oxide or molybdenum oxide with low stoichiometric ratio does not have the phenomenon of over reduction, and the prepared catalyst shows specific transmissionGeneral WO3/SiO2More excellent olefin disproportionation performance.
The catalyst of the invention has lower preparation cost and the preparation method is easy to realize. The catalyst composition is used for preparing the neohexene by disproportionating diisobutylene and ethylene, and has the characteristics of high disproportionating activity, high neohexene yield, difficult carbon deposition and inactivation and the like. The single-pass conversion rate of diisobutylene can reach 69-85%, and the selectivity of neohexene can reach 94-99%.
Drawings
Fig. 1 is an XRD spectrum of the catalysts prepared in examples 1,2, 4.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The raw materials used in the examples or comparative examples are all commercially available raw materials, and specific information on part of the raw materials is described below (see table 1):
TABLE 1
Figure BDA0001518874100000061
Figure BDA0001518874100000071
The conversion and selectivity involved in the examples or comparative examples were calculated as follows:
Figure BDA0001518874100000072
Figure BDA0001518874100000073
example 1
Preparation of 6% Mo0.1W0.9O2.9Catalyst SBA-15
1.44g of ammonium heptamolybdate and 18.04g of ammonium metatungstate are added into a 5L reaction kettle, 1.5L of deionized water is added, and the stirring speed is adjusted to 300r/min at room temperature. When the metal salt was completely dissolved, the solution was adjusted to pH 8.0 with ammonia.
300g of SBA-15 (specific surface area 623 m)2/g, mean pore diameter 8nm, Tianjin Minn Kanzhiki Co., Ltd.) was slowly added to the above salt solution, and stirring was continued for 1 hour. Then, the temperature of the reaction kettle is raised to 200 ℃ and kept constant for 24 hours.
Introducing 10 v% of CO/Ar mixed gas into the reaction kettle, wherein the concentration of CO in the mixed gas is 10 v%, and the gas volume space velocity is 8h-1The duration is 20 min. After the introduction of the CO/Ar mixed gas is stopped, the reaction system is continuously aged for 48 hours at the temperature of 200 ℃.
Then, the temperature of the reaction kettle is reduced to room temperature, and the reaction kettle is dried in an oven at 100 ℃ for 12 hours after being filtered and washed by deionized water. The catalyst obtained was designated WS-1.
Its specific surface area is 569m by BET measurement2In terms of/g, the mean pore diameter is 8.6 nm. The carrier is SBA-15, and molybdenum-tungsten double metal oxide Mo is loaded on the carrier0.1W0.9O2.9The mass of (b) is 6% of the mass of the carrier. The contents of Mo and W in the molybdenum-tungsten bimetallic oxide are determined by ICP-AES (inductively coupled plasma atomic emission spectrometry) analysis, and the element valence state is determined by XPS (X-ray photoelectron spectroscopy) analysis. The catalyst of this example may also be referred to as 6% Mo0.1W0.9O2.9The catalyst is SBA-15.
Example 2
Preparation of 8% Mo0.1W0.9O2.9-1% MgO/coarse silica gel catalyst
2.82g of ammonium dimolybdate, 23.16g of ammonium metatungstate and 15.96g of magnesium acetate are added into a 5L reaction kettle, 1.5L of deionized water is added, and the stirring speed is adjusted to 300r/min at room temperature. When the metal salt was completely dissolved, the solution was adjusted to pH 8.5 with ammonia.
300g of coarse-pore silica gel (specific surface area 380 m)2/g, aperture 8.6nm, Qingdao ocean chemical Co., Ltd.) carrier was slowly added to the above salt solution, and stirring was continued for 1 hour.Then, the temperature of the reaction kettle is raised to 210 ℃ and kept constant for 24 hours.
Introducing H into the reaction kettle2Mixed gas of Ar and H2At a concentration of 1 v%, a gas volume space velocity of 3h-1The duration is 30 min. Stopping the introduction of H2After the mixed gas of Ar and Ar, the reaction system is continuously aged for 48 hours at the temperature of 210 ℃.
Then, the temperature of the reaction kettle is reduced to room temperature, and the reaction kettle is dried in an oven at 80 ℃ for 12 hours after being filtered and washed by deionized water. The catalyst obtained was designated WS-2.
The specific surface area is 325m by BET determination2(iv)/g, average pore diameter 9.3 nm. The carrier is coarse-pore silica gel, and molybdenum-tungsten bimetallic oxide Mo loaded on the coarse-pore silica gel0.1W0.9O2.9Is 8% of the mass of the support, the mass of the supported alkaline earth oxide MgO is 1% of the mass of the support, the catalyst being alternatively referred to as 8% Mo0.1W0.9O2.9-1% MgO catalyst.
Example 3
Preparation of 12% Mo0.2W0.8O2.9-1％Na2O/coarse silica gel catalyst
5.99g of ammonium heptamolybdate, 33.36 g of ammonium metatungstate and 6.49g of sodium oxalate are added into a 5L reaction kettle, 1.5L of deionized water is added, and the stirring speed is adjusted to 300r/min at room temperature. When the metal salt was completely dissolved, the solution was adjusted to pH 9.0 with ammonia.
300g of coarse-pore silica gel (specific surface area 380 m)2/g, aperture 8.6nm, Qingdao ocean chemical Co., Ltd.) carrier was slowly added to the above salt solution, and stirring was continued for 1 hour. Then, the temperature of the reaction kettle is raised to 230 ℃ and kept constant for 24 hours.
Introducing 10 v% of CO/Ar mixed gas into the reaction kettle, wherein the concentration of CO in the mixed gas is 10 v%, and the gas volume space velocity is 10h-1The duration is 30 min. After the introduction of the CO/Ar mixed gas is stopped, the reaction system is continuously aged for 48 hours at 230 ℃.
Then, the temperature of the reaction kettle is reduced to room temperature, and the reaction kettle is dried in an oven at 60 ℃ for 12 hours after being filtered and washed by deionized water. The catalyst obtained was prepared and designated WS-3.
The specific surface area is 315 according to BET measurement2In terms of/g, the mean pore diameter is 9.2 nm. The carrier is coarse-pore silica gel, and molybdenum-tungsten bimetallic oxide Mo loaded on the coarse-pore silica gel0.2W0.8O2.9Is 12% of the mass of the carrier, and the supported alkali metal oxide Na2The mass of O is 1% of the mass of the support, and the catalyst is named as 12% Mo0.2W0.8O2.9-1％Na2O/coarse silica gel catalyst.
Example 4
Preparation of 8% Mo0.3W0.7O2.9-2% CaO/MCM-41 catalyst
6.23g of ammonium heptamolybdate, 20.30g of ammonium metatungstate and 16.92g of calcium acetate are added into a 5L reaction kettle, 1.5L of deionized water is added, and the stirring speed is adjusted to 300r/min at room temperature. When the metal salt was completely dissolved, the solution was adjusted to pH 8.0 with ammonia.
300g of MCM-41 (specific surface area 800 m)2/g, mean pore diameter 9nm, Shanghai Boyle chemical Co., Ltd.) the carrier was slowly added to the above salt solution, and stirring was continued for 1 hour. Then, the temperature of the reaction kettle is raised to 210 ℃ and kept constant for 24 hours.
15 v% propylene/Ar mixed gas is introduced into the reaction kettle, the concentration of the propylene in the mixed gas is 15 v%, and the gas volume space velocity is 8h-1The duration is 30 min. After the introduction of the gas mixture was stopped, the reaction was allowed to continue to age at 210 ℃ for 48 h.
Subsequently, the temperature of the reaction vessel was lowered to room temperature, filtered, washed with water, and dried in an oven at 50 ℃ for 12 hours. The catalyst obtained was designated WS-4.
The catalyst has MCM-41 as carrier and Mo-W bimetal oxide Mo carried on the carrier0.3W0.7O2.9Is 8% of the mass of the support and the mass of the supported alkaline earth metal oxide CaO is 2% of the mass of the support, this catalyst being alternatively referred to as 8% Mo0.3W0.7O2.92% CaO/MCM-41 catalyst.
Example 5
Preparation of 10% Mo0.15W0.85O2.9-1％K2O/COK-12 catalyst
3.52g of ammonium dimolybdate, 29.84g of ammonium paratungstate and 5.87g of potassium oxalate are added into a 5L reaction kettle, 2L of deionized water is added, and the stirring speed is adjusted to 300r/min at room temperature. When the metal salt was completely dissolved, the solution was adjusted to pH 8.5 with ammonia.
300g of COK-12 (specific surface area 580 m)2/g, mean pore diameter 7.8nm, Shanghai Boyle chemical Co., Ltd.) the carrier was slowly added to the above salt solution, and stirring was continued for 1 hour. Then, the temperature of the reaction kettle is raised to 250 ℃ and kept constant for 24 hours.
Introducing CO/Ar mixed gas into the reaction kettle, wherein H is contained in the mixed gas2Concentration of (2) is 10 v%, gas volume space velocity is 10h-1The duration is 60 min. After the introduction of the CO/Ar mixed gas is stopped, the reaction system is continuously aged for 48 hours at the temperature of 250 ℃.
Subsequently, the temperature of the reaction vessel was lowered to room temperature, filtered, washed with water, and dried in an oven at 90 ℃ for 12 hours. The catalyst obtained was designated WS-5.
The carrier of the catalyst is COK-12, and molybdenum-tungsten double metal oxide Mo is loaded on the carrier0.15W0.85O2.9Is 10% of the mass of the carrier, and the supported alkali metal oxide K2The mass of O is 1% of the mass of the support, and the catalyst is alternatively called 10% Mo0.15W0.85O2.9-1％K2O/COK-12 catalyst.
Example 6
Preparation of 8% Mo0.1W0.9O2.9-2％Cs2O/Nb2O5Catalyst on coarse-pored silica gel
2.82g of ammonium dimolybdate, 23.16g of ammonium metatungstate and 4.09g of cesium acetate are added into a 5L reaction kettle, 1.5L of deionized water is added, and the stirring speed is adjusted to 300r/min at room temperature. When the metal salt was completely dissolved, the solution was adjusted to pH 8.0 with ammonia.
300gNb2O5Modified coarse pore silica gel (specific surface area 350 m)2(ii)/g, average pore diameter of 8.0nm, is Nb2O5Mixed with coarse silica gel by mechanical ball milling) and slowly added into the salt solution, and continuously stirred for 1 h. Then, the reaction kettle is put intoThe temperature is raised to 230 ℃ and kept constant for 24 h.
Introducing CO/Ar mixed gas into the reaction kettle, wherein the concentration of CO in the mixed gas is 10 v%, and the gas volume space velocity is 5h-1The duration is 20 min. After the introduction of the CO/Ar mixed gas is stopped, the reaction system is continuously aged for 48 hours at 230 ℃.
Subsequently, the temperature of the reaction vessel was lowered to room temperature, filtered, washed with water, and dried in an oven at 100 ℃ for 12 hours. The catalyst obtained was designated WS-6.
The specific surface area is 339m by BET determination2In terms of/g, the mean pore diameter is 9.6 nm. The carrier is Nb2O5Coarse-pore silica gel, molybdenum-tungsten double metal oxide Mo carried thereon0.1W0.9O2.9Is 8% of the mass of the carrier, and the supported alkali metal oxide Cs2The mass of O is 2% of the mass of the support, and the catalyst is alternatively called 8% Mo0.1W0.9O2.9-2％Cs2O/Nb2O5-a coarse pore silica gel catalyst.
The catalysts WS-1, WS-2 and WS-4 are subjected to XRD characterization, and the characterization results are shown in figure 1. Amorphous silicon dioxide broad peaks appear at the diffraction angle of 26 degrees, and XRD spectrograms of the three catalysts all appear to be similar to WO3Characteristic peak of (2), but peak position and standard WO3Is slightly different, which is related to the low valence state of tungsten and the influence of the incorporated molybdenum on its crystal structure. In addition, the XRD diffraction peak of molybdenum-tungsten oxide is not sharp, indicating that it exists in a highly dispersed form on the support. The detection results of the catalysts prepared in other embodiments are basically consistent with the above detection results, and are not repeated.
Examples 7 to 12 (production of neohexene)
The catalytic synthesis of neohexene with the catalysts of examples 1 to 6 was carried out according to the following steps:
20g of the catalyst (prepared in examples 1 to 6) was weighed, mixed with magnesium oxide at a mass ratio of 1:2, and packed in a fixed bed reactor having an inner diameter of 30 mm. The volume space velocity of the diisobutylene is 20h-1Ethylene/diisobutylene molar ratio of 4:1, the reaction pressure is 2.0MPa, and the reaction temperature is 370 ℃. Sampling analysis is carried out after continuous operation for 100hThe results of sampling are shown in Table 2.
Comparative example 1
Preparation of conventional 8% WO3/SiO2Catalyst (impregnation roasting method)
25.50g of ammonium metatungstate was dissolved in 300g of deionized water and the solution was added dropwise to 300g of a coarse-pore silica support using an equal volume impregnation method. After standing for 24h, it was dried in an oven at 100 ℃ for 12 h. Then roasted in a muffle furnace at 550 ℃ for 4h to obtain 8 percent WO3/SiO2The catalyst is designated DB-1.
Comparative example 1 neohexene was produced according to the same process as in examples 7 to 12 except that the catalyst prepared in comparative example 1 was used.
Example 13 (production of neohexene)
20g of the catalyst of example 2 was weighed, mixed with magnesium oxide in a mass ratio of 1:4, and packed into a fixed bed reactor having an inner diameter of 30 mm. The feed volume space velocity of diisobutylene is 50h-1Ethylene/diisobutylene molar ratio of 4:1, the reaction pressure is 2.0MPa, and the reaction temperature is 370 ℃. After 100h of continuous operation, sampling analysis was performed, and the sampling results are shown in Table 2.
Example 14 (production of neohexene)
20g of the catalyst of example 2 was weighed, mixed with magnesium oxide in a mass ratio of 1:4, and packed into a fixed bed reactor having an inner diameter of 30 mm. The feed volume space velocity of diisobutylene is 50h-1Ethylene/diisobutylene molar ratio of 4:1, the reaction pressure is 3.0MPa, and the reaction temperature is 400 ℃. After 100h of continuous operation, sampling analysis was performed, and the sampling results are shown in Table 2.
As can be seen from Table 2: compared with the catalyst of the comparative example 1, the catalyst prepared in the examples 1 to 6 of the present invention has better stability, and the catalyst still has better activity and high product selectivity after continuous reaction for 100 hours, which is mainly because the non-stoichiometric supported molybdenum-tungsten bimetallic oxide catalyst prepared by the present invention can more easily form a firmer metal-carbene structure with olefin molecules, thereby prolonging the olefin disproportionation activity of the catalyst. The alkali metal oxide and/or alkaline earth metal oxide are/is added into the non-stoichiometric supported molybdenum-tungsten bimetallic oxide catalyst, so that the catalytic activity can be obviously further improved, and the conversion rate can be improved.
TABLE 2 comparative results for neohexene production
Figure BDA0001518874100000121
Figure BDA0001518874100000131
Example 10 (production of neohexene)
20g of the catalyst of example 2 was weighed, mixed with magnesium oxide in a mass ratio of 1:2, and packed into a fixed bed reactor having an inner diameter of 30 mm. The feed volume space velocity of the diisobutylene is 20h-1Ethylene/diisobutylene molar ratio of 4:1, the reaction pressure is 2.0MPa, and the reaction temperature is 370 ℃. Sampling analysis is carried out every 25h, and the operation is continuously carried out for 200h, and the sampling results are shown in a table 2.
Table 2 example 10 results
Reaction time/h Diisobutylene conversion% Selectivity to neohexene%
25 85.2 96.8
50 84.9 97.3
75 85.3 97.1
100 85.0 97.0
125 85.1 97.2
150 85.2 96.9
175 84.9 97.3
200 85.3 97.1
The experimental result shows that the catalyst prepared by the invention has good catalytic stability.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.

Claims (20)

1. The supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst is characterized by comprising a carrier and a non-stoichiometric molybdenum-tungsten bimetallic oxide loaded on the carrier; the mass of the non-stoichiometric molybdenum-tungsten bimetallic oxide is 6-12 wt% of the mass of the carrier;
the chemical composition of the non-stoichiometric molybdenum-tungsten bimetallic oxide is MoxW(1-x)OyWherein x is 0.1-0.3, and y is 2.9-3.0;
the catalyst also comprises one or more of alkali metal oxide and alkaline earth metal oxide loaded on the carrier, wherein the sum of the mass of the alkali metal oxide and the mass of the alkaline earth metal oxide is 0.5-2 wt% of the mass of the carrier;
the carrier comprises one or more of coarse silica gel, mesoporous silicon and an auxiliary agent modified silicon material.
2. The supported non-stoichiometric molybdenum tungsten bimetallic oxide catalyst of claim 1, wherein the alkali metal oxide comprises one or more of sodium, potassium and cesium oxides; the alkaline earth metal oxide includes one or more of oxides of magnesium and calcium.
3. The supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst of claim 1 or 2, wherein the coarse-pore silica gel has a specific surface area of 300-400 m2(ii)/g, the average pore diameter is 8-10 nm.
4. The supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst of claim 1 or 2, wherein the mesoporous silicon comprises one or more of SBA-15, COK-12, and MCM-41.
5. The supported non-stoichiometric Mo-W bimetallic oxide catalyst of claim 4, wherein the mesoporous Si has a specific surface area of 500-800 m2(ii)/g, the average pore diameter is 7.5 to 12 nm.
6. The supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst of claim 1 or 2, wherein the promoter comprises an HY molecular sieve in the promoter-modified silicon materialH beta molecular sieve, Nb2O5、Ta2O5、Al2O3、ZrO2、CeO2One or more of (a).
7. A process for preparing a supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst as in any one of claims 1-6, comprising the steps of:
1) dissolving metal salt in water to obtain a salt solution, and adjusting the pH value of the salt solution to 7.5-9; the metal salt comprises a tungsten salt and a molybdenum salt; the metal salt further comprises one or more of an alkali metal salt and an alkaline earth metal salt;
2) dispersing a carrier in the salt solution, and stirring for reaction at the temperature of 200 ℃ and 250 ℃;
3) introducing reducing gas into the reaction system for reduction, and then stopping introducing the reducing gas for aging;
4) washing and drying the product prepared in the step 3).
8. The method according to claim 7, wherein the drying temperature in the step 4) is 50 to 100 ℃.
9. The method according to claim 7, wherein in step 1), the tungsten salt is selected from one or more of ammonium metatungstate, ammonium paratungstate or sodium tungstate; the molybdenum salt is selected from one or more of ammonium dimolybdate, ammonium tetramolybdate or ammonium heptamolybdate; the alkali metal salt is selected from one or more of sodium, potassium, cesium acetate or oxalate; the alkaline earth metal salt is selected from one or more of magnesium, calcium acetate or oxalate.
10. The method according to any one of claims 7 to 9, wherein in the step 1), the mass ratio of water to the metal salt in the salt solution is 50:1 to 100: 1.
11. The method according to claim 10, wherein the pH adjusting agent used for adjusting the pH of the salt solution in step 1) is one or more selected from the group consisting of ammonia, tetramethylammonium hydroxide, tetrabutylammonium hydroxide.
12. The method according to any one of claims 7 to 9, wherein in step 2), the reaction time is 12 to 36 hours.
13. The method according to any one of claims 7 to 9, wherein in step 3) the reducing gas is H2A mixed gas of one or more of CO and propylene and an inert gas Ar.
14. The method of claim 13, wherein the H in the mixture is2The concentration of (A) is 0.5-5 v%; the concentration of the CO in the mixed gas is 3-20 v%; the concentration of the propylene in the mixed gas is 5-30 v%.
15. The method according to claim 13, wherein in the step 3), the introduction time of the reducing gas is 20-60 min, and the volume space velocity is 3-10 h-1And the aging time is 24-72 h.
16. The catalyst composition is characterized by comprising magnesium oxide and a supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst, wherein the mass ratio of the magnesium oxide to the supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst is 4: 1-2: 1; the supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst is the supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst according to any one of claims 1 to 6 or the supported non-stoichiometric molybdenum-tungsten bimetallic oxide catalyst prepared by the method according to any one of claims 7 to 15.
17. A process for producing neohexene wherein ethylene and diisobutylene are disproportionated in the presence of the catalyst composition of claim 16 to produce said neohexene.
18. According to claimThe preparation method of claim 17, wherein the disproportionation is carried out in a fixed bed, and the feed volume space velocity of the diisobutylene is 5 to 50 hours-1。
19. The method of claim 17, wherein the molar ratio of ethylene to diisobutylene is from 4:1 to 2: 1.
20. The method according to claim 17, wherein the disproportionation reaction is carried out at a reaction temperature of 300 to 400 ℃; the reaction pressure is 0.1-3 MPa.
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