CN1781598A - Method for preparing resin assembled heteropoly acid salt catalyst - Google Patents
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Abstract
The preparation process of resin assembled heteropoly acid salt catalyst includes the following steps: 1. soaking cationic exchange resin in exchange solution for the hydrogen ion on the resin and the cation capable of forming insoluble salt with heteropoly acid to exchange in exchange degree controlled in 0.5-95 %; 2. soaking the obtained cation exchange resin in heteropoly acid solution for the hydrogen ion in heteropoly acid solution and cation on the resin to exchange, with the exchanged cation and the heteropoly anion producing insoluble heteropoly acid salt depositing onto the surface of the resin in the supported amount of 1-60 wt%; and 3. washing and drying the obtained resin. The resin assembled heteropoly acid salt catalyst has the features of high acid strength, high acid amount, great specific surface area, water insolubility, etc. and is one kind of high performance compound organic-inorganic catalyst capable of being used in various acid catalyzed reactions.
Description
Technical Field
The invention relates to a preparation method of a resin assembled heteropoly acid salt catalyst.
Background
It is well known that more than 85% of organic reactions need to be carried out with a catalyst, or are economically valuable, while the acid-catalyzed reactions account for the largest proportion of the various catalyzed reactions. The conventional acid catalyst is H2SO4，HF，AlCl3，BF3And the like, the catalysts have good low-temperature catalytic activity, but have strong toxicity and corrosiveness, corrode equipment and pollute the environment, and particularly, the catalysts can form potential hazards to the health of operators, so researchers at home and abroad strive to develop environment-friendly solid acid catalysts to replace liquid acid catalysts in recent decades.
Heteropoly acid and its salt compound are a kind of new solid acid catalytic material with wide application prospect developed in recent years, for this kind of catalytic material, petrochemical, 2000, 29 (1): 49-55 are described in detail. These catalyst materials are characterized by high acid strength and exhibit pure B acid centers, which make heteropolyacids have high activity and selectivity for various acid-catalyzed reactions. However, heteropolyacids as solid acid catalysts also suffer from the following disadvantages: (1) the specific surface area is small and is generally less than 10m2(ii)/g; (2) in case of water, the acid strength of the heteropoly-acid is related to crystal water, the presence of water affects the acid strength of the catalyst, and the heteropoly-acid is easily dissolved in water, so that if the reaction system contains water, the loss of active components is likely to occur; (3) the anhydrous heteropoly acid is in a powder state and is difficult to form. The present solutionThe solution is to load heteropoly acid (salt) on silica, activated carbon, titania, etc.
In order to overcome these disadvantages of heteropolyacids, various methods for supporting heteropolyacids (salts) and their use have been proposed in the prior art. US 6472344B 1, US 2003/0060362 a1 propose a method for preparing a supported heteropolyacid salt catalyst, wherein a porous non-metallic carrier is firstly impregnated with a salt solution, and then is impregnated with a heteropolyacid solution after being dried and roasted to obtain a water-insoluble assembled heteropolyacid salt catalyst; CN 1289641 proposes a molecular sieve-alumina composite carrier supported heteropoly acid catalyst and its application in ammoniation, hydration and etherification reactions; EP 0333076 proposes a titanium dioxide supported heteropolyacid catalyst and its use in the synthesis of methyl tert-butyl ether by etherification of tert-butanol and methanol; EP 0952133A1 proposes a supported heteropolyacid catalyst and an alkylation reaction process of isoparaffin and olefin catalyzed by the supported heteropolyacid catalyst under the supercritical condition; the use of ZrO is proposed in US 6583330B1, US 5391532, US5489733, US 54200922、SiO2、Al2O3A bifunctional catalyst obtained by loading VIII metal and heteropoly acid on an equal carrier, and application thereof in isomerization and alkylation reactions of hydrocarbons; US 5475178, US5324881 propose mesoporous molecular sieve MCM-41 assembled heteropoly acid catalyst and its isomerization reaction in hydrocarbon,The application in alkylation reaction; WO95/13869, US 5866739, US 5919725 propose an SiO2、TiO2、ZrO2An isocarrier-loaded heteropoly acid salt (ammonium, cesium, potassium, rubidium and other salts) catalyst and application thereof in alkylation reaction of aromatic hydrocarbon and olefin; CN1235873A proposes a nanometer silica supported heteropoly acid catalyst and its application in alkylation reaction of aromatic hydrocarbon and olefin; U.S. Pat. No. 4, 2003/0040653, 1 proposes the use of ZrO2A supported heteropolyacid catalyst and application thereof in the synthesis process of alkylbenzene; EP0367408A2 proposes a process for preparing phenol and acetone by catalyzing the decomposition of cumene hydroperoxide by adopting an inert carrier supported heteropoly acid catalyst; CN1130103A proposes a process for hydration of olefins using silica assembled heteropolyacid (salt) catalysts.
As is apparent from the above documents, the supported heteropolyacid (salt) catalysts currently prepared by the conventional supporting method have the following major problems: firstly, when the loaded insoluble heteropolyacid salt catalyst is prepared, the uniform distribution of the active components is difficult to ensure; (II) in the presence of SiO2、TiO2、SiO2、ZrO2When the oxide is a carrier, there is also a disadvantage that the acidity of the catalyst is lowered by the interaction between the heteropoly acid and the carrier.
Disclosure of Invention
The invention provides a preparation method of a resin assembled heteropoly acid salt catalyst, which can uniformly distribute insoluble heteropoly acid acidic salt on the inner surface of resin, the obtained assembled catalyst not only retains the advantages of the resin and the heteropoly acid, but also overcomes the defects of the resin and the heteropoly acid, and is an organic-inorganic composite catalyst with excellent catalytic performance, which can be used for various acid catalytic reactions such as superposition, etherification, alkylation, esterification, hydration, hydrolysis, condensation and the like.
The preparation method of the resin assembled heteropolyacid salt catalyst provided by the invention comprises the following steps:
1) impregnating a hydrogen-type cation exchange resin with a solution containing cations capable of forming an insoluble salt with a heteropoly acid to exchange hydrogen ions on the resin with cations capable of forming an insoluble salt with a heteropoly acid;
2) dipping the cationic resin obtained in the step 1) by using a heteropoly acid solution, exchanging hydrogen ions in the heteropoly acid solution with cations on the resin, and generating insoluble heteropoly acid salt by the exchanged cations and heteropoly anions to precipitate on the surface of the resin;
3) washing and drying the resin assembled with the insoluble heteropolyacid salt obtained in the step 2).
The preparation process of the resin-assembled heteropolyacid salt catalyst provided by the invention can be illustrated by the following two formulas:
in the above formula, Resin-SO3H is a cation exchange resin in the hydrogen form, HnAB12O40Denotes a heteropoly acid, MxHn-xAB12O40Represents an insoluble heteropolyacid acid salt in which n is the valency of the heteropolyanion, x is a positive number between 0 and n and M is a metal ion or an organic cation.
The preparation process of the resin assembly heteropolyacid salt catalyst provided by the invention can be expressed as follows:
the first step is as follows: selection of resins
In principle, the resins used for assembling the heteropolyacid salts can be selected from the various cation exchange resins currently used for catalytic reactions, but in order to obtain better catalytic properties, the resins selected preferably satisfy the following conditions: (1) has the highest exchange capacity; (2) has a pore structure and a specific surface area suitable as a catalyst carrier; (3) has certain particle size and mechanical strength; (4) has high thermal stability.
The resin satisfying the above requirements may be synthesized according to a conventionally known technique, or a commercial resin may be directly purchased. The resin used as catalyst at present is mainly styrene resin with macroporous network structure, which is prepared by suspending and copolymerizing styrene-divinylbenzene in the presence of pore-forming agent to obtain polystyrene resin, and then using concentrated sulfuric acid, fuming sulfuric acid or SO3And carrying out sulfonation to obtain the product. The resin has strong acidity, high exchange capacity, macropore and better thermal stability, so the resin is particularly suitable to be used as a catalyst. Such resins are commercially available, e.g., Roam&Amberlyst series resin produced by Haas, D series, DN series and S series resin produced in China, and the like.
The second step is that: cation exchange
The cations to be exchanged can be either metal or organic, although in principle all cations present in the soluble salt can be selected for exchange, but it is preferred to select those cations which form an insoluble acid salt with the heteropolyacid, so that the acid salt of the heteropolyacid can be assembled on the resinAnd the catalyst can be used in aqueous solution and polar reaction system without loss. Such cations may be metal cations, such as K+，Rb+，Cs+，NH4 +，Ni2+Etc.; it may also be an organic cation such as a quaternary ammonium ion or a quaternary phosphonium ion, for example, a tetramethylammonium ion, a tetraethylammonium ion, a tetrapropylammonium ion, a tetrabutylammonium ion, a diphenyldimethylammonium ion, a dodecyltrimethylammonium ion, a hexadecyltrimethylammonium ion, a tetraethylphosphonium ion, a tetrabutylphosphonium ion, or the like.
The degree of exchange (defined as the percentage of exchanged hydrogen ions in the total amount of exchangeable hydrogen ions of the resin) is controlled during the exchange process, and is generally controlled to be in the range of 0.5-95%, preferably 1-50%. To achieve the desired degree of exchange, conditions such as temperature of exchange, concentration of exchange solution, solid-to-liquid ratio, and exchange time should be controlled. The exchange temperature may be from 0 ℃ to 160 ℃, preferably from room temperature to 90 ℃, the concentration of the exchange solution is from 0.01 to 5mol/L, preferably from 0.1 to 1mol/L, the solid-to-liquid ratio (weight ratio of resin to exchange solution) is from 0.1 to 10: 1, preferably from 1 to 5: 1, and the exchange time is from 5 minutes to 100 hours, preferably from 3 to 10 hours.
After the resin reaches the required exchange degree, the resin is washed, filtered and dried to obtain dry-base resin, and then the heteropoly acid is removed. The purpose of the washing is to wash away the resin-entrained cations to avoid the introduction of cations into the subsequent operation affecting the performance of the catalyst. If the excess cation does not affect or contribute to the performance of the final catalyst, it can be filtered and dried directly without washing. Filtration and drying are the basic operations for preparing the catalyst, and it is noted that the drying process requires temperature and time control, and the temperature cannot exceed the maximum temperature that the resin can withstand.
The third step: impregnated heteropoly acid
The method provided by the invention can be used for assembling various insoluble heteropolyacid acidic salts on the resin.
The heteropoly acid is obtained by condensing more than two kinds of oxygen-containing acid radicals under acidic conditionAnd (4) acid. Heteropolyacids can be classified according to the coordination structure and composition of the heteropolyanion. Heteropolyanions (e.g. PW)12O40 3-) Is formed by the coordination of tetrahedron or octahedron consisting of central atom (also called heteroatom, such as P) and oxygen and a plurality of octahedrons consisting of coordination atom (also called polyatomic atom, such as W) and oxygen according to a certain structure, and the determined structure comprises Keggin structure (XM) with central atom in tetrahedron coordination12O40 n-) And the Dawson structure (X) derived therefrom2M18O62 n-) (ii) a Octahedrally coordinated Anderson structure (XM)6O24 n-) (ii) a Icosahedron coordinated Silverton structure (XM)12O42 n-) And the like. The elements constituting the heteropoly acid are many, and the central atom can be Ti, Zr, V, Nb, Cr, Mn, Fe, Co, Rh, Ni, Pt, Cu, Zn, B, Al, Ga, C, Si, Ge, Sn, P, As, etc.; examples of the element capable of serving as a coordinating atom include Mo, W, V, Nb, Ta, In, Ti, Pb, Fe, Co, Ni, Cu, etc. The catalyst commonly used at present mainly comprises several heteropolyacids with a Keggin structure, such as phosphotungstic acid (H)3PW12O40·xH2O), silicotungstic acid (H)4SiW12O40·xH2O), phosphomolybdic acid (H)3PMo12O40·xH2O), phosphomolybdic acid (H)3PMo12-yVyO40·xH2O), and the like. These structural heteropolyacids are easy to prepare, high in acid strength and good in thermal stability, and therefore are preferred heteropolyacids in the present invention.
The solvent for preparing the impregnation solution can be selected from various solvents capable of dissolving the heteropoly acid without reacting with the heteropoly acid, such as ethanol, acetone, etc., preferably water. The impregnation method may be an equivalent impregnation method or an excess impregnation method. The concentration and dosage of the impregnation liquid are related to the loading amount, the concentration of the heteropoly acid solution is 0.1-1mol/L, and the dosage of the solution is 1-10ml per gram of resin. The impregnation process involves complex chemical and physical processes such as exchange of cations with hydrogen ions and formation of heteropoly acids from the exchanged cations and heteropoly anions, and therefore the impregnation conditions need to be controlled to ensure that the heteropoly acid salts are uniformly distributed on the surface of the resin, preferably in the form of acid salts, to form thedesired supported catalyst. The temperature of the dipping process is 20-100 ℃ and the time is 1-10 hours, and the dipping process is preferably carried out under the condition of stirring. Preferably, the impregnation condition is that 1-5ml of heteropoly acid solution with the concentration of 0.1-0.5mol/L is added into each gram of resin, and the resin is impregnated for 1-5 hours under the condition of stirring at the temperature of 20-80 ℃.
The fourth step: washing and drying process
The resin impregnated with heteropoly acid needs further washing to remove the excess heteropoly acid. If the presence of an excessive amount of the heteropoly-acid does not adversely affect the performance of the catalyst, the catalyst may be directly filtered and dried without washing. In the drying process, the control of temperature and time is very important, the acidity of the heteropoly-acid is generally greatly related to the water content, and therefore, the proper drying temperature and time are controlled to ensure that the final catalyst has the acidity meeting the reaction requirement. The drying temperature should also be controlled within the highest temperature range that the resin can withstand. The drying temperature is generally 50 to 200 ℃ and preferably 90 to 180 ℃. The drying time is from 1 to 50 hours, preferably from 2 to 20 hours.
The resin-assembled heteropolyacid salt catalyst prepared by the process according to the present invention may have an assembled amount (based on the total weight of the catalyst) of heteropolyacid salt of 1 to 60% by weight, preferably 5 to 45% by weight, and most preferably 10 to 35% by weight, and the heteropolyacid is mainly present in the form of an acidic salt of heteropolyacid having a composition MxHn-xAB12O40Where n is the valence of the heteropolyanion and x is a positive number between 0 andn, preferably between 0.05 and 1.
The resin assembled heteropoly acid salt catalyst provided by the invention has the characteristics of high acid strength, large acid amount, large specific surface area, insolubility in water and the like, is a high-performance organic-inorganic composite catalyst, and can be almost used for various acid catalytic reactions. Such as low-carbon olefin polymerization, etherification, esterification, alkylation, olefin hydration, ester compound hydrolysis, condensation, etc.
The resin assembled heteropoly acid catalyst provided by the invention is used for carrying out various reactions, and the adopted technical process is related to the specific reaction. The catalyst can be used in a continuous process or a discontinuous process, and can be used in a slurry bed, a fixed bed, a fluidized bed and other various processes. The resin assembled heteropoly acid catalyst provided by the invention is a granular solid acid catalyst, so that the separation from the product is very convenient. For example, the catalyst can be used in a fixed bed reactor, so that the trouble of separation can be avoided, and even if the catalyst is used in a slurry bed reactor, the catalyst can be easily separated from a product by methods of sedimentation, filtration and the like after reaction, and the catalyst can be recycled. In particular, the resin-assembled heteropoly acid catalyst provided by the invention can be made into a catalyst member like common resin and used in new process such as catalytic distillation.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
This example illustrates the preparation of a resin assembled heteropolyacid acid nickel salt and its use in C4Use in a process for the polymerization of olefins.
100g of Amberlyst15 hydrogen styrene-divinylbenzene resin was placed in a 1000ml beaker and 400ml of 0.1mol/L NiSO was added4Exchanging the solution for 5 hours at room temperature, filtering the solution, washing the solution for 4 times by deionized water, drying the solution for 6 hours at 120 ℃, putting the obtained nickel-containing resin into a 1000ml beaker, adding 400ml of 0.05mol/L phosphotungstic acid solution, stirring the solution for 5 hours at 80 ℃, filtering excessive heteropoly acid solution, and drying the solution at 125 ℃ to obtain the resin group assembled phosphotungstic acid type nickel salt catalyst. The analyzed amount of assembled acid nickel phosphotungstate salt was 19.8 wt%.
20g of the catalyst is loaded into the middle part of a fixed bed reactor with the inner diameter of 12mm and the height of 600mm, and quartz stones are arranged at two ends of the fixed bed reactor. Introducing light C4Olefin is subjected to polymerization reaction under the conditions of 3MPa, 60 ℃ and WHSV of 2h-1Light C4Consists of (in weight percent): isobutane 52.85 percent, 31.19 percent of isobutene, 115.5 percent of butylene, 0.36 percent of n-butane and 0.1 percent of butadiene.
After 10 hours of reaction, a sample is taken for analysis, and the reaction result is as follows: the molar conversion rate of isobutene is 99%, and the molar conversion rate of n-butene is 20%.
Example 2
This example illustrates the preparation of a resin assembled heteropolyacid acidic ammonium salt catalyst and its use in etherification processes.
100g of hydrogen styrene-divinylbenzene resin having the trade name S wasplaced in a 1000ml beaker, and 400ml of 0.1mol/L (NH) was added4)2SO4And exchanging the solution at room temperature for 6 hours, filtering the solution, washing the solution for 4 times by using deionized water, drying the solution at 120 ℃ for 6 hours, putting the obtained resin into a 1000ml beaker, adding 400ml of 0.065mol/L phosphotungstic acid solution, stirring the solution for 5 hours at 80 ℃, filtering the solution, washing the solution for 4 times by using the deionized water, and drying the solution for 5 hours at 150 ℃ to obtain the resin assembled phosphotungstic acid ammonium salt catalyst. The amount of ammonium acid phosphotungstate assembled was analyzed to be 23.3 wt%.
20g of the resin catalyst is loaded into the middle part of a fixed bed reactor with the inner diameter of 12mm and the height of 600mm, and quartz stones are arranged at two ends of the fixed bed reactor for preheating. Methanol and light C are introduced4Olefin is reacted under the conditions of 1MPa, 60 ℃ and WHSV of 2h-1The molar ratio of alcohol to olefin is 1.08: 1. The composition of light C4 was the same as example 1. After 10 hours, a sample was taken and analyzed by gas chromatography, and according to the analysis results, the molar conversion of isobutylene was 97% and the molar selectivity of the product methyl tert-butyl ether (MTBE) was 99.9%.
Example 3
This example illustrates the preparation of a resin assembled heteropolyacid acid potassium salt and its use in an esterification process.
Taking 100g of Amberlyst35 hydrogen type resin, placing the Amberlyst35 hydrogen type resin into a 1000ml beaker, adding 400ml of 0.1mol/L KNO3Exchanging the solution at room temperature for 5 hours, filtering the solution, washing with deionized water for 4 times, drying at 120 ℃ for 6 hours, putting the obtained resin into a 1000ml beaker, adding 400ml of 0.065mol/L phosphotungstic acid solution, stirring at 80 ℃ for 5 hours, and filteringFiltering, washing with deionized water for 4 times, and drying at 150 ℃ to obtain the resin assembled phosphotungstic acid potassium salt catalyst. The assembled amount of the phosphotungstic acid potassium salt obtained by analysis is 24.5 wt%.
Taking 5g of the resin catalyst, filling the resin catalyst into a 250ml three-neck flask with a reflux water diversion device, adding 1mol of glacial acetic acid and 2mol of n-butyl alcohol, heating and refluxing for 2 hours, cooling and filtering the catalyst, measuring the acid value of a product in the flask, and calculating to obtain the molar conversion rate of the acetic acid to be 99.5%.
Example 4
This example illustrates the preparation of resin assembled heteropolyacid acid cesium salt and its use in the alkylation of isobutane butenes.
100g of Amberlyst45 hydrogen form resin was placed in a 1000ml beaker and 400ml of 0.1mol/L CsNO was added3The solution is exchanged for 6 hours at room temperature, the solution is filtered off and washed 4 times with deionized water, 120 timesDrying at the temperature of 1000ml for 6 hours, putting the obtained resin into a beaker with the temperature of 1000ml, adding 400ml of 0.1mol/L phosphotungstic acid solution, stirring for 5 hours at the temperature of 80 ℃, filtering, and drying at the temperature of 175 ℃ to obtain the resin assembled cesium phosphotungstate catalyst. The assembled amount of the acid cesium phosphotungstate salt was analyzed to be 32.5 wt%.
5g of the catalyst is taken and put into a 500ml high pressure reaction kettle, 5mol of n-butane and 1mol of n-butene are added, the mixture is heated and reacted for 2 hours at the temperature of 50 ℃, and then a sample is taken to analyze the product by chromatography. Molar conversion of n-butene of 99%. C8Molar selectivity of saturated alkane of 95 percent, C8The proportion of trimethyl pentane in the product is 86%.
Example 5
This example illustrates the preparation of resin-assembled heteropoly acid quaternary ammonium salts and their use in the alkylation of benzene olefins.
100g of hydrogen type resin with the brand number of Amberlyst 36 is taken and placed in a 1000ml beaker, 400ml of 0.1mol/L tetraethylammonium bromide solution is added for exchange for 6 hours at room temperature, the solution is filtered out, deionized water is used for washing for 4 times, drying is carried out for 6 hours at the temperature of 120 ℃, the obtained resin is placed in a 1000ml beaker, 400ml of 0.065mol/L phosphotungstic acid solution is added for stirring for 5 hours at the temperature of 80 ℃, filtering is carried out, drying is carried out at the temperature of 150 ℃, and the resin assembled tetraethylammonium phosphotungstate catalyst is obtained. The amount of the assembled tetraethylammonium phosphotungstate acid salt analyzed was 24.7 wt%.
5g of the resin catalyst is taken and put into a high-pressure reaction kettle of 250ml, 2mol of benzene and 0.2mol of dodecene are added, the mixture is stirred and reacted for 1 hour under the condition of 80 ℃, and a sample is taken to analyze the product by chromatography. The mol conversion rate of the dodecene is 99.9 percent, the mol yield of the dodecyl benzene is 97 percent, and the distribution of the dodecyl benzene isomers is as follows: 45% of 2-phenyldodecane, 30% of 3-phenyldodecane, 11.9% of 4-phenyldodecane, 7.8% of 5-phenyldodecane and 5.3% of 6-phenyldodecane.
Example 6
This example illustrates the preparation of resin-assembled heteropoly acid quaternary ammonium salts and their use in phenol olefin alkylation processes.
100g of hydrogen type resin with the trade name of D007 is taken and placed in a 1000ml beaker, 400ml of 0.1mol/L dodecyl trimethyl ammonium bromide solution is added for exchange for 6 hours at room temperature, the solution is filtered out, deionized water is used for washing for 4 times, drying is carried out for 6 hours at the temperature of 120 ℃, the obtained resin is placed in a 1000ml beaker, 400ml of 0.05mol/L phosphotungstic acid solution is added for stirring for 5 hours at the temperature of 80 ℃, filtering is carried out, deionized water is used for washing for 4 times, and drying is carried out at the temperature of 120 ℃, thus obtaining the resin assembled phosphotungstic acid type quaternary ammonium salt catalyst. The amount of the assembled acid quaternary ammonium phosphotungstate salt analyzed was 18.8 wt%.
5g of the resin catalyst is taken and put into a 250ml glass stirring reaction kettle, 1mol of phenol and 0.2mol of dodecene are added, the mixture is heated and reacted for 2 hours under the condition of 80 ℃, and a sample is taken for analyzing the product by chromatography. The mol conversion rate of the dodecene is 99.7 percent, the mol yield of the dodecylphenol is 98 percent, and the ratio of the p-dodecylphenol to the o-dodecylphenol is 12.5: 1.
Example 7
This example illustrates the preparation of resin supported cesium acid silicotungstate salts and their use in olefin hydration reactions.
Placing 100g of hydrogen type resin with the trade name of DN-72 in a 1000ml beaker, adding 400ml of 0.1mol/L cesium nitrate solution for exchange for 6 hours at room temperature, filtering the solution, washing with deionized water for 4 times, drying at 120 ℃ for 6 hours, placing the obtained resin in a 1000ml beaker, adding 400ml of 0.1mol/L silicotungstic acid solution, stirring for 5 hours at 80 ℃, filtering, washing with deionized water for 4 times, and drying at 120 ℃ to obtain the resin assembled cesium silicotungstic acid salt catalyst. The amount of cesium acid tungsten silicate salt assembled was analyzed to be 28.5 wt%.
5g of the resin catalyst is taken and put into a 250ml high-pressure reaction kettle, 1mol of cyclohexene and 5mol of water are added for reaction for 1 hour under the condition of 120 ℃ and self pressure, and a sample is taken for chromatographic analysis of the product. The cyclohexene molar conversion rate is 99.5%, and the cyclohexanol molar yield is 99%.
Example 8
This example illustrates the preparation of resin-assembled ammonium acid silicotungstates and their use in methyl acetate reactions.
100g of Amberlyst35 hydrogen form resin was placed in a 1000ml beaker and 400ml of 0.1mol/L (NH) was added4)2SO4Exchanging the solution for 5 hours at room temperature, filtering the solution, washing the solution for 4 times by using deionized water, drying the solution for 6 hours at 120 ℃, putting the obtained resin into a 1000ml beaker, adding 400ml of 0.1mol/L silicotungstic acid solution, stirring the solution for 5 hours at 80 ℃, filtering the solution, washing the solution for 4 times by using deionized water, and drying the solution at 150 ℃ to obtain the resin assembled silicotungstic acid type ammonium salt catalyst. The amount of assembled ammonium silicotungstate was analyzed to be 26.3 wt%.
5g of the resin catalyst is taken and put into a 250ml high-pressure reaction kettle, 1mol of methyl acetate and 5mol of water are added, the reaction is carried out for 3 hours under the condition of 50 ℃ and the autogenous pressure, and the product is sampled and analyzed by chromatography. Themolar conversion of methyl acetate was 45%.
Claims (15)
1. A preparation method of a resin assembled heteropoly acid salt catalyst comprises the following steps:
1) impregnating hydrogen type cation exchange resin with exchange solution containing cation capable of forming insoluble salt with heteropoly acid to exchange hydrogen ion on the resin with cation capable of forming insoluble salt with heteropoly acid, and controlling exchange degree at 0.5-95%;
2) impregnating the cationic resin obtained in the step 1) with a heteropoly acid solution, so that hydrogen ions in the heteropoly acid solution exchange with cations on the resin, and the exchanged cations and heteropoly anions generate insoluble heteropoly acid acidic salt to be precipitated on the surface of the resin, wherein the assembling amount of the heteropoly acid salt is 1-60 wt% based on the total weight of the catalyst;
3) washing and drying the resin assembled with the insoluble heteropolyacid salt obtained in the step 2).
2. The process according to claim 1, wherein the resin is a styrene-divinylbenzene resin.
3. A process according to claim 1, wherein the cation capable of forming an insoluble acid salt with the heteropolyacid is selected from K+、Rb+、Cs+、NH4 +、Ni2+Or an organic cation selected from quaternary ammonium ions, quaternary phosphonium ions.
4. The method according to claim 3, wherein the quaternary ammonium ion or the quaternary phosphonium ion is selected from the group consisting of tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, diphenyldimethylammonium ion, dodecyltrimethylammonium ion, hexadecyltrimethylammonium ion, tetraethylphosphonium ion and tetrabutylphosphonium ion.
5. The process according to claim 1, wherein the heteropoly-acid is a heteropoly-acid having a Keau structure.
6. A process according to claim 1 or 5, wherein the heteropoly-acids are phosphotungstic acid, silicotungstic acid, phosphomolybdic acid.
7. The method according to claim 1, wherein the degree of exchange in step 1 is controlled to be 1 to 50%.
8. The process according to claim 1, wherein the exchange temperature is 0 ℃ to 160 ℃, the concentration of the exchange solution is 0.01 to 5mol/L, the solid-liquid weight ratio is 0.1 to 10: 1, and the exchange time is 5 minutes to 100 hours.
9. The process according to claim 8, wherein the exchange temperature is 20 ℃ to 90 ℃, the concentration of the exchange solution is 0.1 to 1mol/L, the solid-liquid weight ratio is 1 to 5: 1, and the exchange time is 3 to 10 hours.
10. The process according to claim 1, wherein the impregnation conditions are: the concentration of the heteropoly acid solution is 0.1-1mol/L, the dosage of the solution is 1-10ml per gram of resin, the dipping temperature is 20-100 ℃, and the time is 1-10 hours.
11. The method of claim 10, wherein the impregnation conditions are: the concentration of the heteropoly acid solution is 0.1-0.5mol/L, the dosage of the solution is 1-5ml per gram of resin, and the solution is soaked for 1-5 hours under the conditions of 20-80 ℃ and stirring.
12. The process according to claim 1, wherein the drying temperature is 50 to 200 ℃ and the drying time is 1 to 50 hours.
13. The process according to claim 1, wherein the drying temperature is 90 to 180 ℃ and the drying time is 2 to 20 hours.
14. The process according to claim 1, wherein the heteropolyacid salt is incorporated in an amount of 5 to 45% by weight based on the total weight of the catalyst.
15. The process according to claim 1 or 14, wherein the heteropolyacid salt is incorporated in an amount of 10 to 35% by weight based on the total weight of the catalyst.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102059133A (en) * | 2010-12-10 | 2011-05-18 | 厦门大学 | Recovery method of catalyst for preparing epoxy fatty acid methyl ester (FAME) |
| CN101485990B (en) * | 2009-03-10 | 2011-11-02 | 润泽制药(苏州)有限公司 | Solid supported heteropoly acid catalyst and preparation method thereof |
| CN105536870A (en) * | 2015-12-21 | 2016-05-04 | 崔贤长 | Catalyst for synthesizing methyl tert-butyl ether and preparation method for methyl tert-butyl ether |
| CN109718854A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of solid acid catalysts and the preparation method and application thereof |
| CN113976178A (en) * | 2021-10-19 | 2022-01-28 | 沈阳工业大学 | Preparation method and application of CPS (CPS) supported heteropoly acid ionic liquid catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4898995A (en) * | 1988-10-24 | 1990-02-06 | Texaco Chemical Company | Method for production of phenol/acetone from cumene hydroperoxide |
| WO1995013869A1 (en) * | 1993-11-19 | 1995-05-26 | Exxon Research & Engineering Company | Heteropoly compounds and use in aromatic alkylation |
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2004
- 2004-11-30 CN CNB2004100963161A patent/CN100443174C/en active Active
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101485990B (en) * | 2009-03-10 | 2011-11-02 | 润泽制药(苏州)有限公司 | Solid supported heteropoly acid catalyst and preparation method thereof |
| CN102059133A (en) * | 2010-12-10 | 2011-05-18 | 厦门大学 | Recovery method of catalyst for preparing epoxy fatty acid methyl ester (FAME) |
| CN102059133B (en) * | 2010-12-10 | 2012-07-04 | 厦门大学 | Recovery method of catalyst for preparing epoxy fatty acid methyl ester (FAME) |
| CN105536870A (en) * | 2015-12-21 | 2016-05-04 | 崔贤长 | Catalyst for synthesizing methyl tert-butyl ether and preparation method for methyl tert-butyl ether |
| CN109718854A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | A kind of solid acid catalysts and the preparation method and application thereof |
| CN113976178A (en) * | 2021-10-19 | 2022-01-28 | 沈阳工业大学 | Preparation method and application of CPS (CPS) supported heteropoly acid ionic liquid catalyst |
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| CN100443174C (en) | 2008-12-17 |
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