CN116173941A - M-WOxZnOZrO 2 Catalyst and application thereof in diisobutylene preparation - Google Patents

M-WOxZnOZrO 2 Catalyst and application thereof in diisobutylene preparation Download PDF

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CN116173941A
CN116173941A CN202211617919.6A CN202211617919A CN116173941A CN 116173941 A CN116173941 A CN 116173941A CN 202211617919 A CN202211617919 A CN 202211617919A CN 116173941 A CN116173941 A CN 116173941A
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solution
catalyst
stirring
isobutene
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黄家辉
苗治理
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention discloses an M-WOxZnOZrO 2 The catalyst and its application in preparing diisobutylene belong to petrochemical technology. M-WOxZnOZrO of the invention 2 Solid solution super acid catalyst, M is one or more than two of La, ce, pr, nd, pm, sm, nb, sn, ga, re, in, al, ni, mn, mo, ti, V, is advantageousThe catalyst is used for catalyzing isobutene to react in a reaction kettle/fixed bed to prepare diisobutene. The method has the advantages of simple process route, mild reaction condition, easy separation of the catalyst from raw materials and products, and the like. The catalyst has good circulation stability, and has good application prospect and industrial application potential in the petrochemical field.

Description

M-WOxZnOZrO 2 Catalyst and application thereof in diisobutylene preparation
Technical Field
The invention belongs to the technical field of petrochemical industry, in particular to M-WOxZnOZrO 2 Catalytic reactionThe agent and the application thereof in the preparation of diisobutylene.
Technical Field
Diisobutylene (diisobutylene) comprises 2, 4-trimethyl-1-pentene and 2, 4-trimethyl-2-pentene as main components. Diisobutylene is mainly used for producing octyl phenol, isooctyl alcohol and the like, is an important organic chemical raw material, can generate self-polymerization or copolymerization reaction, addition reaction, halogenation reaction, alkylation reaction, carbonylation reaction and the like due to the fact that the diisobutylene has C=C double bond, generates a series of fine chemical intermediates, and is widely used in the fields of plastic additives, rubber additives, lubricants, antioxidants, surfactants, synthetic detergents and the like.
Industrially, diisobutylene is generally used for dimerization of carbon tetraolefins to produce high-octane gasoline, and the process of selectively dimerization of isobutene with diisobutylene as a target product is less researched, and is generally carried out by dimerization of isobutene in mixed carbon tetraolefins under the action of an acid catalyst to generate diisobutylene. Various diisobutylene production methods have been developed, mainly sulfuric acid extraction, solid phosphoric acid, molecular sieve, resin, etc. Among the commercial production techniques are sulfuric acid extraction, bayer butene dimerization, diermersol X dimerization, octol butene dimerization, cattil catalytic rectification, etc., most of which aim to remove isobutene in mixed carbon four or to produce mixed carbon eight olefins (diisobutene, dimers of n-butene and n-and iso-butene co-dimers, etc.) or isobutene oligomers, which are all difficult to obtain diisobutene of high purity, and have complicated flow and serious equipment corrosion.
Because of the problems with the use of liquid acid catalysts, many limitations have been imposed, and attention has been focused on the study of novel solid acid catalysts. To date, the solid acid catalysts used for the oligomerization of isobutylating combustion mainly comprise macroporous sulfonic acid resin catalysts, solid phosphoric acid catalysts, molecular sieve catalysts, solid super acid catalysts, oxides, oxide compounds and other catalysts. The solid phosphoric acid method is a common industrial method, and is characterized by mixing isobutene in C4, using solid phosphoric acid as catalyst, and making dimerization reaction in fixed bed reactorThe selectivity can reach 75% (Yao Yaping, yuan Meiqing, xu Jing, etc. "T-49 novel solid phosphoric acid catalyst and application" "Petroleum refining and chemical industry", 2000, 31 (1) P10). Patent CN1810742a discloses a method for preparing diisobutylene with free phosphoric acid as catalyst, and diisobutylene selectivity can reach more than 80%. Patent EP0371938A discloses a solid phosphoric acid catalyst with silica as a support, but the patent does not describe the starting materials and gives specific dimer selectivity. Patent WO01046095A1 discloses a catalyst for producing diisobutylene by superposition of mixed C4 olefins by using an H beta molecular sieve, and found that the silicon-aluminum ratio has a great influence on the product distribution, and when the H beta silicon-aluminum ratio is 100, the conversion rate of isobutene is 100%, the diisobutylene selectivity is 48%, and the deactivation is very fast. Patent CN1087616a discloses an aluminum silicate catalyst for dimerization of C4 fraction isobutene with a dimer selectivity of 65%. Gonzalez et al (Catalysis letters 2006, 110:107-113) studied Ni 2+ The influence of modified zeolite molecular sieve on isobutene dimerization, the authors find that the acid amount of the molecular sieve can be increased after modification, but the problems of quick deactivation, low conversion rate and the like of several molecular sieves are examined. Patent CN104395265a discloses a process for the preparation of isobutene by sugar fermentation, dimerization to diisobutene, without specific selectivity results being given. Patent CN104815695B discloses a method for preparing diisobutylene by using a carbon nanotube supported ionic liquid catalyst, but the preparation of the method is too complex and is not beneficial to industrial application. Patent CN206622082U discloses a device for preparing diisobutylene, triisobutylene and tetraisobutylene by polymerizing isobutene, and the device has a simple structure and is uniformly stirred.
From the above, it can be seen that the solid acid catalyst has been used in the polymerization of isobutene to prepare diisobutene, but has problems of low catalytic activity and selectivity of diisobutene, because of wide distribution of polymerization products of isobutene, the improvement of the selectivity of diisobutene is generally achieved by reducing the reaction rate in the reaction process, for example, 1) controlling the single pass conversion of isobutene and controlling the polymerization rate to improve the selectivity; 2) Reducing the catalyst activity; the method improves the selectivity of diisobutylene by reducing the conversion rate of the isobutene.
Disclosure of Invention
Aiming at the technical problems of low selectivity, complex separation process and the like of diisobutylene in the prior art, the invention aims to provide M-WOxZnOZrO 2 The invention uses W-based solid solution super acid as catalyst and isobutene as raw material to prepare diisobutene, and the M-WOxZnOZrO is prepared 2 Exhibit high activity and selectivity.
In order to achieve the purpose of the invention, the following technical scheme is provided:
the invention provides an M-WOxZnOZrO 2 The solid solution super acid catalyst has M as one or two or more than two of La, ce, pr, nd, pm, sm, nb, sn, ga, re, in, al, ni, mn, mo, ti, V.
Based on the technical proposal, the method further adopts ZnOZrO 2 The solid solution mass, WOx content is 0.1-30%, M content is 0.1-20%, znO and ZrO 2 The molar ratio is 10:1-1:20.
Based on the technical proposal, the method further adopts ZnOZrO 2 The solid solution mass is that WOx content is 1-20% and M content is 1-10%.
Based on the technical scheme, further, the M-WOxZnOZrO 2 The solid solution super acid catalyst is prepared by adopting an impregnation method, a precipitation method and a sol-gel method.
Another aspect of the present invention provides the M-WOxZnOZrO as described above 2 The preparation method of the solid solution super acidic catalyst mainly comprises the following steps:
1) Weighing Zn soluble salt, zr soluble salt and M soluble salt, adding deionized water, stirring and dissolving to obtain solution A;
2) Weighing the W soluble salt, adding deionized water, and stirring for dissolution to obtain a solution B;
3) Slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished;
4) Weighing a certain amount of template agent, adding deionized water, stirring for 2-6h, slowly dripping the obtained solution into the solution C, and continuing stirring for 2-6h after dripping is finished;
5) Slowly dripping a precipitant into the solution obtained in the step 4) under the stirring condition of 40-90 ℃ until the pH value is 7-12, and continuously stirring for 1-8h;
6) Transferring the solution obtained in the step 5) into a hydrothermal kettle, and crystallizing for 6-48h in an environment of 60-180 ℃;
7) Centrifuging and washing after crystallization, washing for 1-5 times by using absolute ethyl alcohol, and vacuum drying to obtain a super acid precursor;
8) Roasting the super acid precursor in air at 300-1000 deg.c for 2-12 hr to obtain M-WOxZnOZrO 2 Solid solution superacid catalysts.
Based on the above technical scheme, in step 4), the template agent is one or more than two of CTAB, n-butanol, glycerol, P123, tetrapropylammonium hydroxide, tween and PEG2000, and the ratio of the total mole number of the template agent to the metal ion is 1:1-1:20.
Based on the technical scheme, further, the precipitant in the step 5) is NH 4 HCO 3 、(NH 4 ) 2 CO 3 、Na 2 CO 3 One or more of NaOH, ammonia water or urea, and the dropping speed is 1-5ml/min.
Based on the technical scheme, the crystallization temperature in the step 6) is 70-100 ℃ and the crystallization time is 6-24h.
Based on the technical scheme, further, the vacuum drying temperature in the step 7) is 50-80 ℃, and the vacuum drying time is 24-48h.
Based on the technical scheme, further, the roasting temperature in the step 8) is 400-600 ℃, and the roasting time is 4-10h.
The invention also provides a method for preparing diisobutylene by isobutene polymerization, which utilizes the M-WOxZnOZrO 2 The solid solution super acidic catalyst catalyzes isobutene to prepare diisobutene in a reaction kettle/fixed bed.
Based on the technical scheme, further, the reaction temperature is 40-100 ℃, the reaction pressure is 0.1-5.0MPa, the reaction time is 2-10h, and the mass ratio of the catalyst to the isobutene is 1:10-1:100.
Based on the technical scheme, one or more of polar substances of methanol, tertiary butanol and MTBE are added in the reaction to serve as inhibitors, and the mass ratio of the inhibitors to the isobutene is 1:20-1:200.
Based on the technical scheme, the reaction pressure is the pressure of the system or the pressure generated by filling inert gas.
Compared with the prior art, the invention has the following advantages:
1) The catalyst disclosed by the invention is simple to prepare, good in repeatability and very high in reaction selectivity;
2) The invention has mild reaction conditions and no equipment corrosion;
3) The method has the advantages of simple and environment-friendly process, no waste acid or waste water generation, no waste acid or waste water treatment, real atomic economical reaction and production cost reduction.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit or scope of the invention, which is therefore not limited to the specific embodiments disclosed below.
Example 1
And (3) preparing a catalyst:
4.46g Zn (NO) was weighed out 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 7.29g of CTAB and 8.40g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 Mixing with ammonia water in equal volumeMixing the precipitate until the pH is 8.0, and stirring for 2h; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Example 2
And (3) preparing a catalyst:
1.45g Ga (NO) was weighed out 3 ) 3 ·9H 2 O、4.46g Zn(NO 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 8.43g of CTAB and 9.36g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst Ga-WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Example 3
And (3) preparing a catalyst:
1.15g La (NO) was weighed out 3 ) 3 ·6H 2 O、4.46g Zn(NO 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 7.29g of CTAB and 8.40g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst La-Wox/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Example 4
And (3) preparing a catalyst:
weigh 0.81g SnCl 4 、4.46g Zn(NO 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 7.78g of CTAB and 8.96g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst Sn-WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Example 5
And (3) preparing a catalyst:
weigh 2.13g C 10 H 5 NbO 20 、4.46g Zn(NO 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 8.12g of CTAB and 9.08g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 Mixing precipitant with ammonia water in equal volumeThe pH is 8.0, and stirring is continued for 2h; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst Nb-WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Example 6
And (3) preparing a catalyst:
1.12g of Nd (NO) was weighed out 3 ) 3 ·6H 2 O、4.46g Zn(NO 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 7.83g of CTAB and 8.72g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuously stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst Nd-WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Example 7
And (3) preparing a catalyst:
weigh 5.15g Al (NO) 3 ) 3 ·9H 2 O、4.46g Zn(NO 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 10.21g of CTAB and 11.76g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuously stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst Al-WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Example 8
And (3) preparing a catalyst:
1.82g Ni (NO) was weighed out 3 ) 2 ·6H 2 O、4.46g Zn(NO 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 8.75g of CTAB and 10.08g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst Ni-WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Example 9
And (3) preparing a catalyst:
1.15g La (NO) was weighed out 3 ) 3 ·6H 2 O、5.15g Al(NO 3 ) 3 ·9H 2 O、4.46g Zn(NO 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 10.94g of CTAB and 12.60g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuously stirring for 2 hours after dripping is finished; slowly dropwise adding 0.5mol/l at 3ml/min under stirring at 70 DEG C(NH 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst La-Al-WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Comparative example 1
And (3) preparing a catalyst:
4.46g Zn (NO) was weighed out 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; weighing 7.29g of CTAB and 8.40g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain solution B, slowly dropwise adding the solution B into the solution A, and continuing stirring for 2 hours after the dropwise adding is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution solid acid precursor; roasting the solid acid precursor in air atmosphere at 500 ℃ for 6 hours to obtain a solid solution catalyst ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 80 ℃ for 2h and 2.0MPa of nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Comparative example 2
And (3) preparing a catalyst:
4.46g Zn (NO) was weighed out 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; weighing 7.29g of CTAB and 8.40g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain solution B, slowly dropwise adding the solution B into the solution A, and continuing stirring for 2 hours after the dropwise adding is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution solid acid precursor; roasting the solid acid precursor in air atmosphere at 500 ℃ for 6 hours to obtain solid solution ZnOZrO 2 . Weighing 1.32g of ammonium metatungstate, adding 50ml of deionized water, stirring for dissolution, adding the solid solution into the solution, stirring overnight, filtering, washing with absolute ethyl alcohol for three times, drying in a 100 ℃ oven for 12 hours to obtain a solid, and roasting the solid in an air atmosphere at 500 ℃ for 4 hours to obtain the supported solid acid catalyst WO X /ZnOZrO 2 (ip)。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Comparative example 3
And (3) preparing a catalyst:
4.46g Zn (NO) was weighed out 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed and 50ml of ammonium metatungstate is addedStirring deionized water for dissolution to obtain a solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 7.29g of CTAB and 8.40g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuing stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 13; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Comparative example 4
And (3) preparing a catalyst:
4.46g Zn (NO) was weighed out 3 ) 2 ·6H 2 O、18.24g Zr(NO 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst WOx/ZnOZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Comparative example 5
And (3) preparing a catalyst:
25.59g Zn (NO) was weighed out 3 ) 2 ·6H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed, 50ml of deionized water is added, and stirring and dissolving are carried out, so as to obtain solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 10.24g of CTAB and 12.60g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuously stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 ℃ for 6 hours to obtain the solid solution super acid catalyst WOx/ZnO.
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Comparative example 6
24.39g of Zr (NO) was weighed out 3 ) 4 ·5H 2 Adding 100ml of deionized water into O, stirring and dissolving to obtain solution A; 1.32g of ammonium metatungstate is weighed and added with 50ml of deionized water to be stirredDissolving to obtain a solution B; slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished; weighing 6.56g of CTAB and 7.56g of Tween 40, adding 100mL of deionized water, dissolving and stirring for 4 hours to obtain a solution, slowly dripping the solution into the solution C, and continuously stirring for 2 hours after dripping is finished; 0.5mol/l (NH) was slowly added dropwise at 3ml/min under stirring at 70 ℃ 4 ) 2 CO 3 The precipitant mixed with ammonia water in equal volume is stirred for 2 hours until the pH value is 8.0; transferring the solution into a hydrothermal kettle with a lining, and crystallizing for 12 hours in an environment of 80 ℃; centrifuging and washing for multiple times after crystallization, and washing for 3 times by using absolute ethyl alcohol; vacuum drying at 80 ℃ for 48 hours to obtain a solid solution super acid precursor; roasting the super acid precursor in air at 500 deg.c for 6 hr to obtain solid solution super acid catalyst WOx/ZrO 2 。
Reaction evaluation:
putting a catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2h reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Comparative example 7
Taking H beta (silicon-aluminum ratio 100) as a catalyst, adding the catalyst, tertiary butanol and liquid isobutene into a reaction kettle, and synthesizing diisobutene under the conditions of 70 ℃ temperature, 2H reaction time and 2.0MPa nitrogen pressure at a stirring speed of 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Comparative example 8
The catalyst, tertiary butanol and liquid isobutene are put into a reaction kettle by taking HY (silicon-aluminum ratio 30) as a catalyst, and diisobutene is synthesized under the conditions that the temperature is 70 ℃, the reaction time is 2h and the nitrogen pressure is 2.0MPa, and the stirring speed is 800 rpm; wherein the mass of the tertiary butanol is 0.2g, the mass of the catalyst is 1.0g, the mass of the isobutene is 20.0g, and the mass ratio of the catalyst to the isobutene is 1:20.
Diisobutylene prepared in examples 1-9 and comparative examples 1-8 was analyzed using conventional experiments and protocols in the art, and the specific results are shown in table 1, wherein:
isobutene conversion calculation:
conversion= (n) Feeding in -n Out of )/n Feeding in *100％；n Feeding in 、n Out of Represents the molar amount of imported and exported isobutene;
diisobutylene selectivity calculation:
selectivity = n DIB /(n Feeding in -n Out of )*100％；n DIB Represents the molar amount of diisobutylene.
TABLE 1 Properties of the catalysts prepared in examples 1-9 and comparative examples 1-8 for the catalytic Synthesis of diisobutylene
Description of the embodiments Catalyst Conversion of isobutene% Diisobutylene selectivity%
Example 1 WOx/ZnOZrO 2 93.8 63.4
Example 2 Ga-WOx/ZnOZrO 2 83.6 80.6
Example 3 La-WOx/ZnOZrO 2 85.0 82.5
Example 4 Sn-WOx/ZnOZrO 2 83.3 85.3
Example 5 Nb-WOx/ZnOZrO 2 88.4 83.8
Example 6 Nd-WOx/ZnOZrO 2 82.9 86.5
Example 7 Al-WOx/ZnOZrO 2 89.3 90.4
Example 8 Ni-WOx/ZnOZrO 2 87.1 86.3
Example 9 La-Al-WOx/ZnOZrO 2 90.3 95.2
Comparative example 1 ZnOZrO 2 4.6 98.7
Comparative example 2 WO X /ZnOZrO 2 (ip) 92.6 44.8
Comparative example 3 WOx/ZnOZrO 2 65.4 53.0
Comparative example 4 WOx/ZnOZrO 2 74.5 48.7
Comparative example 5 WO X /ZnO 95.5 35.4
Comparative example 6 WO X /ZrO 2 93.6 22.7
Comparative example 7 Hβ 94.4 43.4
Comparative example 8 HY 93.5 38.1
As can be seen from the results in Table 1, the catalyst of the present invention not only improves the conversion of diisobutylene but also improves the selectivity of diisobutylene, and the reaction is milder, more green and economical than the comparative example.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of the present invention is not limited thereto. Equivalent substitutions and modifications will occur to those skilled in the art based on the present invention, and are intended to be within the scope of the present invention. The protection scope of the invention is subject to the claims.

Claims (10)

1. M-WOxZnOZrO 2 The solid solution super acid catalyst is characterized in that M is one or more than two of La, ce, pr, nd, pm, sm, nb, sn, ga, re, in, al, ni, mn, mo, ti, V.
2. M-WOxZnOZrO according to claim 1 2 A solid solution superacid catalyst characterized by comprising ZnOZrO 2 The solid solution mass, WOx content is 0.1-30%, M content is 0.1-20%, znO and ZrO 2 The molar ratio is 10:1-1:20.
3. M-WOxZnOZrO according to claim 1 2 The solid solution super acid catalyst is characterized in that the M-WOxZnOZrO 2 The solid solution super acid catalyst is prepared by adopting an impregnation method, a precipitation method and a sol-gel method.
4. The M-WOxZnOZrO of any one of claims 1-3 2 The preparation method of the solid solution super acidic catalyst is characterized by mainly comprising the following steps:
1) Weighing Zn soluble salt, zr soluble salt and M soluble salt, adding deionized water, stirring and dissolving to obtain solution A;
2) Weighing the W soluble salt, adding deionized water, and stirring for dissolution to obtain a solution B;
3) Slowly dripping the solution B into the solution A under stirring, and obtaining a solution C after the dripping is finished;
4) Weighing a certain amount of template agent, adding deionized water, stirring for 2-6h, slowly dripping the obtained solution into the solution C, and continuing stirring for 2-6h after dripping is finished;
5) Slowly dripping a precipitant into the solution obtained in the step 4) under the stirring condition of 40-90 ℃ until the pH value is 7-12, and continuously stirring for 1-8h;
6) Transferring the solution obtained in the step 5) into a hydrothermal kettle, and crystallizing for 6-48h in an environment of 60-180 ℃;
7) Centrifuging and washing after crystallization, washing for 1-5 times by using absolute ethyl alcohol, and vacuum drying to obtain a super acid precursor;
8) Roasting the super acid precursor in air at 300-1000 deg.c for 2-12 hr to obtain M-WOxZnOZrO 2 Solid solution superacid catalysts.
5. The preparation method according to claim 4, wherein in the step 4), the template agent is one or more than two of CTAB, n-butanol, glycerol, P123, tetrapropylammonium hydroxide, tween and PEG2000, and the ratio of the template agent to the total mole number of metal ions is 1:1-1:20; the precipitant in step 5) is NH 4 HCO 3 、(NH 4 ) 2 CO 3 、Na 2 CO 3 One or more of NaOH, ammonia water or urea, and the dropping speed is 1-5ml/min.
6. The method according to claim 4, wherein the crystallization temperature in step 6) is 70 to 100℃and the crystallization time is 6 to 24 hours; the vacuum drying temperature in the step 7) is 50-80 ℃, and the vacuum drying time is 24-48h.
7. The process according to claim 4, wherein the calcination temperature in step 8) is 400 to 600℃and the calcination time is 4 to 10 hours.
8. A process for preparing diisobutene by polymerizing isobutene, wherein M-WOxZnOZrO according to any of claims 1 to 3 is used 2 The solid solution super acidic catalyst catalyzes isobutene to prepare diisobutene in a reaction kettle/fixed bed.
9. The method according to claim 8, wherein the reaction temperature is 40-100 ℃, the reaction pressure is 0.1-5.0MPa, the reaction time is 2-10h, and the mass ratio of the catalyst to the isobutene is 1:10-1:100.
10. The method according to claim 8, wherein one or more of polar methanol, tertiary butanol and MTBE are added as inhibitors, and the mass ratio of the inhibitors to the isobutene is 1:20-1:200.
CN202211617919.6A 2022-12-15 2022-12-15 M-WOxZnOZrO 2 Catalyst and application thereof in diisobutylene preparation Pending CN116173941A (en)

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