CN100336594C - Macropore composite resin catalyst for preparing alkylidene diatomic alcohol - Google Patents
Macropore composite resin catalyst for preparing alkylidene diatomic alcohol Download PDFInfo
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- CN100336594C CN100336594C CNB2004100676260A CN200410067626A CN100336594C CN 100336594 C CN100336594 C CN 100336594C CN B2004100676260 A CNB2004100676260 A CN B2004100676260A CN 200410067626 A CN200410067626 A CN 200410067626A CN 100336594 C CN100336594 C CN 100336594C
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Abstract
The present invention relates to macro-porous composite resin catalyst for preparing alkylidene dihydric alcohol, which mainly solves the problems of short service life and poor heat resistance of catalyst which is used in the prior art under the conditions of high conversion rate and high selectivity. The present invention adopts monomer, co-monomer, nanometer material, initiator, first auxiliary agent and second auxiliary agent to prepare composite resin and uses the technical scheme that compounds containing OH<->, Cl<->, HSO4<->, HCO3<-> and HCOO<-> have an ion exchange to prepare the catalyst, and thereby, the present invention solves the problems. The present invention can be used in industrial production of alkylidene dihydric alcohol.
Description
Technical field
The present invention relates to a kind of macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol.
Background technology
Ethylene glycol, propane diols are important aliphatic dihydroxy alcohols, and wherein the ethylene glycol purposes is the most extensive, and main application is to produce mylar, comprises fiber, film and engineering plastics.Also can directly be used as cooling agent and antifreezing agent, also be simultaneously to produce the indispensable materials of product such as alkyd resins, plasticizer, paint, adhesive, surfactant, explosive and capacitor electrolyte.
In ethylene glycol compounds, the range of application of diethylene glycol (DEG), triethylene glycol or senior polyethylene glycol is narrower than the range of application of ethylene glycol.Therefore, in order to improve the selectivity that oxirane is converted into ethylene glycol, industrial often is with excessive water, and promptly 20～25 times to the mole of oxirane, is used for above-mentioned hydration reaction.At this moment, reaction does not need catalyst, and the oxirane conversion ratio generates the selectivity 88～91% of ethylene glycol near 100%.Therefore, the glycol concentration of gained mostly was about 10～20% most after reaction finished.In the recovery and purification step of ethylene glycol, must from the mixture of ethylene glycol and water, remove excessive water by still-process, this needs lot of energy.For example, when the mol ratio of water and oxirane is 20, removes the required heat energy consumption of no water that is approximately 19 times of ethylene glycol by evaporation and need 170 kilocalories for every mole of ethylene glycol.This means that producing 1 ton of ethylene glycol will expend about 5.5 tons of steam.For this reason, various countries research institution has carried out deep research to the catalyzing epoxyethane hydration preparing ethylene glycol one after another, and reducing the mol ratio of water and oxirane, raising selectivity and yield reach and cut down the consumption of energy and the purpose of material consumption.
Preparing ethandiol by catalyzing epoxyethane hydration is divided into two kinds of methods, and a kind of is direct hydration method, i.e. oxirane direct and water effect generation monoethylene glycol under catalyst action; Another kind is the ethylene carbonate method, promptly oxirane under catalyst action, elder generation and CO
2Reaction generates ethylene carbonate, and ethylene carbonate is hydrolyzed into monoethylene glycol in the presence of catalyst then.
Once adopting liquid acid in early days is catalyst, and as sulfuric acid, the ethylene glycol yield is 88～90%, and shortcoming is an etching apparatus.Had for the shortcoming that overcomes liquid acid once proposes to use--SO
3H,--PO (OH)
2The storng-acid cation exchange resin of active group.Hydration can continued operation under low temperature, low pressure, and resin is through regeneration, the repeated use of washing back.Industrial do not have widely used reason to be: if want to improve the yield of ethylene glycol, water and ethylene glycol proportioning are big, and product design is low, puies forward dense difficulty; Ion exchange resin is after using a period of time in addition, and tradable volume descends more, can not restore fully after the regeneration.The base catalysis hydration is used industrial failing, mainly be oxirane can be in large quantities with ethylene glycol and the condensed ethandiol continuation effect that generates by ethylene glycol, generate the product that contracts of ethylene glycol more, reduced the yield of ethylene glycol.Because all there are some shortcomings in acid, base catalysis hydration, thereby the hydration of present industrial employing on-catalytic.In order to improve reaction rate, industrial reaction temperature is generally 150～200 ℃, pressure 0.8～2.0MPa.
Can obtain higher conversion ratio, good selectivity and low water/epoxyalkane ratio with the EP-A-156449 disclosed method.According to the document, epoxyalkane is hydrolyzed in the presence of the anionic material of containing metal thing improving optionally, and preferably having has the electropositive of affinity to cooperate the solid material at center to metalate anion.Described solid material is anion exchange resin preferably, and metalate anion is molybdate, tungstate radicle, metavanadic acid root, pyrovanadic acid hydrogen root and pyrovanadium acid radical anion.The trouble of this method is that the product stream of alkylene glycol containing also contains a large amount of metalate anion that displace from the electropositive cooperation center of the anionic solid material of containing metal thing.Proposed to simplify method for product recovery with water-insoluble vanadate and molybdate.But when using these metalate anion salt, resulting selectivity is starkly lower than the selectivity when using the water-soluble metal thing.
EP-A-226799 discloses the method for preparing ethylene glycol and/or propane diols in the presence of a kind of catalyst composition at carboxylic acid and carboxylate (both can by being used in combination arbitrarily) by the hydration of corresponding alkylene oxide hydrocarbon.These acid/salt composites are the solution form, and they must be separated from product.
JP-A-57-139026 discloses a kind of at halogen-type anion exchange resin and CO
2Co-exist in down the method for alkylene oxide and water reaction.RU-C-2001901 points out that above-mentioned document invention disclosed has the shortcoming that generates carbonate in reactant mixture, because boiling point is approaching, carbonate is difficult to separate from glycol.
(the USPatent:5 of Shell company of the U.S., 874,653, WO:99/23053), the Shvets V.F. of Mendeleev Chemical Engineering Univ., Russia, (WO:99/12876, RU:2,149,864) etc. have developed a series of anion exchange resin that have quaternary ammonium group by styrene and divinyl benzene crosslinked is catalyst.Use this catalyst system and catalyzing, the conversion ratio of oxirane is near 100%, and the selectivity of ethylene glycol can reach 95%.Yet the remarkable shortcoming of this catalyst system and catalyzing be to use the life-span short, heat resistance is poor.Simultaneously, even if in lower temperature range (＜95 ℃), the expansion of catalyst is still relatively more serious.Although thereby above-mentioned research work obtained very big progress, but still can't realize industrialization.
Summary of the invention
To be the catalyst that uses in the conventional art have higher conversion and optionally under the condition to technical problem to be solved by this invention, exist catalyst short service life, the problem of poor heat resistance provides a kind of new macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol.This catalyst is used for having catalyst conversion ratio height when the epoxyalkane catalysis hydration prepares the alkylene dihydric alcohol reaction, product alkylene dihydric alcohol selectivity height, while catalyst long service life, the characteristics that heat resistance is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol, and compound resin comprises following component by weight percentage:
(1) monomer 20～50%;
(2) comonomer 3～20%;
(3) nano material 0.1～10%;
(4) initator 0.1～2%;
(5) auxiliary agent one 0.1～2%;
(6) auxiliary agent 2 20～60%;
Wherein monomer is selected from least a in methyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, butadiene, styrene or the acrylonitrile; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT, nano magnesia or the nano zine oxide; Initator is selected from least a in benzoyl peroxide or the azodiisobutyronitrile; Auxiliary agent one is selected from least a in polyvinyl alcohol, bentonite, calcium carbonate or the gelatin; Auxiliary agent two is selected from least a in aliphatic hydrocarbon, polystyrene, gasoline, aliphatic acid or the paraffin; Compound resin carries out ion-exchange and makes catalyst with being selected from the compound that contains hydroxyl, chlorine root, bisulfate ion, bicarbonate radical or formate anion, and the exchanging equivalent of resin is 2.0～4.5 milliequivalents/gram compound resin.
The monomer preferred version is selected from styrene in the technique scheme; The comonomer preferred version is selected from divinylbenzene; The nano material preferred version is selected from CNT; The initator preferred version is selected from benzoyl peroxide; Auxiliary agent one preferred version is selected from polyvinyl alcohol; Auxiliary agent two preferred versions are selected from polystyrene or gasoline; The exchanging equivalent preferred version of resin is 3.0～3.5 milliequivalents/gram compound resin; The alkylene dihydric alcohol preferred version is ethylene glycol or propane diols.
CNT among the present invention is multi-walled carbon nano-tubes (MWNTs), is prepared by chemical vapour deposition technique.Composite is obtained by situ aggregation method or improvement in-situ compositing by CNT and monomer.CNT also can adopt SWCN (SWNTs), and composite material and preparation method thereof also can adopt arc process, solid-phase pyrolysis etc.
The preparation method of the compound resin that uses among the present invention may further comprise the steps:
(1) auxiliary agent one being made into weight percent concentration is 2～5% water solution A;
(2) with monomer, comonomer and initator and auxiliary agent two, wiring solution-forming B;
(3) solution A and solution B are mixed, reacted 0～8 hour down at 70～90 ℃; Add nano material, reacted 2～8 hours down at 70～90 ℃; Be warming up to 90～100 ℃ of reactions 2～8 hours, after reaction finished, inclining supernatant liquid, washed with water, filtered then, dry compound pearl body, and wherein the nano material in above-mentioned reactant mixture adds wiring solution-forming B in step (2); Perhaps add reaction system after 0～8 hour in solution A and solution B hybrid reaction;
(4) 100～500% of the compound pearl body weight of adding chloromethyl ether and 20～70% zinc chloride catalyst in compound pearl body, under 30～50 ℃, compound pearl body is carried out Friedel-crafts reaction, reaction time is 8～20 hours, 20～70% of the compound pearl body weight of adding dichloroethanes after the suction strainer washing, 70～200% trimethylamine hydrochloride and 60～180% NaOH, 25～40 ℃ of reactions 5～20 hours, reaction finishes back adding NaOH and makes the transition, be washed to neutrality then, promptly get composite resin material, wherein monomer is selected from methyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, butadiene, at least a in styrene or the acrylonitrile; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT, nano magnesia or the nano zine oxide; Initator is selected from least a in benzoyl peroxide or the azodiisobutyronitrile; Auxiliary agent one is selected from least a in polyvinyl alcohol, bentonite, calcium carbonate or the gelatin; Auxiliary agent two is selected from least a in aliphatic hydrocarbon, polystyrene, gasoline, aliphatic acid or the paraffin.
The Preparation of catalysts method of using among the present invention may further comprise the steps:
(1) gets above-mentioned composite resin material and pack in the metal tube, feed distilled water backwash resin bed, feed distilled water then and just washing 20～40 minutes as vector resin;
(2) washed resin bed 20～40 minutes with 500～1500% (weight ratio, as follows) methanol solution, dry up with nitrogen;
(3) be made into 2～10% aqueous solution with 10～40% oxirane and washed resin bed 20～40 minutes, with distillation washing 20～30 minutes;
(4) be made into the 1 mol aqueous solution with 150～300% hydrochloric acid and washed resin bed 40～60 minutes, be washed till with distilled water and flow out liquid and be neutral;
(5) be made into the 1 mol aqueous solution with 150～300% MY and washed resin bed 40～60 minutes, wherein M
+Be selected from Na
+Or K
+, Y
-Be selected from OH
-, Cl
-, HCOO
-, HCO
3 -Or HSO
4 -, being washed till outflow liquid with distilled water and being neutral, nitrogen dries up the back and takes out.
The present invention is by containing OH with compound resin with being selected from
-, Cl
-, HCOO
-, HCO
3 -Or HSO
4 -Anionic compound carries out ion-exchange and makes catalyst, is used for the epoxyalkane catalysis hydration and prepares alkylene dihydric alcohol when reaction, and the inventor is surprised to find catalyst and has following advantage:
1, activity of such catalysts height.Compare with existing technology, reaction velocity can be by existing 2 hours
-1Bring up to 3～6 hours
-1Thereby, the production capacity of raising device.
2, the mol ratio of water and oxirane is low.Compare with existing ethylene glycol production technology, catalyst of the present invention can make water than obviously reducing, can reduce to 10: 1 by 20～25: 1 of existing technology, thus the energy consumption of greatly reducing.
3, alkylene dihydric alcohol selectivity and yield improve.Compare with existing technology, catalyst of the present invention can make the alkylene dihydric alcohol selectivity improve, and can be increased to 95～97% by 88～91% of existing ethylene glycol production technology, thereby greatly reduce material consumption.
4, the good stability of catalyst, the life-span is long.Can turn round continuously more than half a year, the conversion ratio of oxirane is not seen tangible reduction, and the selectivity of alkylene dihydric alcohol remains unchanged substantially.
5, this catalyst does not have corrosion to equipment, environmentally safe.
Obtained better technical effect.
The invention will be further elaborated below by embodiment.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified, can not be interpreted as limiting the scope of the invention.
The specific embodiment
The preparation method of compound resin
[embodiment]
In 500 milliliters of there-necked flasks, add 200 ml distilled waters and 0.9 gram gelatin, start the stirring intensification polyvinyl alcohol is all dissolved.Stop to stir, cold slightly back adds monomer mixture solution (29.2 gram styrene, 5.8 gram divinylbenzenes (weight content 40%), 1.2 gram CNTs, 35.6 grams 200 that contain initator
#Gasoline, 0.35 gram benzoyl peroxide), start stirring, be warming up to 85 ℃, reacted 4 hours.Be warming up to 95 ℃ about 2 hours.After reaction finished, inclining supernatant liquid, with 85 ℃ of hot washes several times, more several times, filter then with cold wash, drying, weigh compound pearl body.The functionalization of compound pearl body: in 500 milliliters of there-necked flasks, add the 20.6 compound pearl body A of gram and 80 milliliters of chloromethyl ethers, start to stir and be warmed up to 30 ℃, adding 8 gram zinc chloride is catalyst, under 39～40 ℃, compound pearl body A is carried out Friedel-crafts reaction, reaction time is 10 hours, and suction strainer is with washings such as acetone.Add 8.5 grams, two oxidative ethanes, 18.5 gram trimethylamine hydrochlorides, 75 milliliters of 20% weight sodium hydroxides, reaction is about 12 hours about 30 ℃.After reaction finished, progressively thin up to proportion equaled at 1.0 o'clock, washing, and hydro-oxidation sodium is washed to neutrality after transition, promptly gets composite resin material.
Method for preparing catalyst
Catalyst A
Get 40 milliliters of catalyst carrier resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 minutes, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with methanol solution; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to flowing out liquid; Washed 50 minutes with 1 mol HCl solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to flowing out liquid; Washed flow rate of liquid 10 ml/min 70 minutes with 10% (weight) HCOONa solution; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to flowing out liquid; Nitrogen purges after 1.5 hours and takes out.
Catalyst B
Get 25 milliliters of catalyst carrier resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 ml/min, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with methanol solution; Washed 30 minutes flow rate of liquid 10 ml/min with 3% weight aqueous solution of ethylene oxide; Washed 50 minutes with 1 mol HCl solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to flowing out liquid; Washed 100 minutes with the 5% weight NaOH aqueous solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to flowing out liquid; With 2% weight CO
2The aqueous solution is at 2.0 MPa CO
2Washed flow rate of liquid 15 ml/min under the atmosphere 100 minutes; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to flowing out liquid; Nitrogen purges after 1.5 hours and takes out.
Catalyst C
Get 25 milliliters of catalyst carrier resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 minutes, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with 3% weight aqueous solution of ethylene oxide; Washed 50 minutes with 1 mol HCl solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to flowing out liquid; With 1 mol NaHCO
3Solution was washed 50 minutes, and flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to flowing out liquid; With 2% weight CO
2The aqueous solution is at 2.0 MPa CO
2Washed flow rate of liquid 15 ml/min under the atmosphere 100 minutes; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to flowing out liquid; Nitrogen purges after 1.5 hours and takes out.
Catalyst D
Get 30 milliliters of catalyst carrier resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 minutes, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with 3% weight aqueous solution of ethylene oxide; Washed 100 minutes with 1 mol HCl solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to flowing out liquid; With 10% weight NaHSO
4Solution was washed 60 minutes, flow rate of liquid 10 ml/min; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to flowing out liquid; Nitrogen purges after 1.5 hours and takes out.
Catalyst E
Get 25 milliliters of catalyst carrier resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 minutes, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with methanol solution; Washed 30 minutes flow rate of liquid 10 ml/min with 3% weight aqueous solution of ethylene oxide; Feed distilled water washing 20 minutes, flow rate of liquid 20 ml/min; With 2% weight CO
2The aqueous solution is at 2.0 MPa CO
2Washed flow rate of liquid 15 ml/min under the atmosphere 100 minutes; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to flowing out liquid; Nitrogen purges after 1.5 hours and takes out.
[embodiment 1～5]
It is 10 millimeters that above-mentioned catalyst A, B, C, D, E each 15 milliliters (granularity 20～40 orders) are filled in a diameter respectively successively, in long 350 millimeters the stainless steel fixed bed reactors, uses metering pump massage that than charging in 12: 1 raw water and oxirane.Reacting system pressure is 1.2 MPas, and 90 ℃ of reaction temperatures, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[comparative example 1]
With granularity be 15 milliliters on 20～40 purpose porcelain rings to fill in a diameter be 10 millimeters, in long 350 millimeters the stainless steel fixed bed reactors, with raw water and oxirane with the metering pump massage you than charging in 12: 1.Reacting system pressure is 1.5 MPas, and 90 ℃ of reaction temperatures, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[embodiment 6]
It is 10 millimeters that above-mentioned catalyst C15 milliliter (granularity 20～40 orders) is filled in a diameter, in long 350 millimeters the stainless steel fixed bed reactors, with raw water and oxirane your ratio of metering pump massage charging in 22: 1.Reacting system pressure is 1.2 MPas, and 90 ℃ of reaction temperatures, liquid air speed are 6 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[embodiment 7]
It is 10 millimeters that above-mentioned catalyst C15 milliliter (granularity 20～40 orders) is filled in a diameter, in long 350 millimeters the stainless steel fixed bed reactors, with raw water and oxirane your ratio of metering pump massage charging in 5: 1.Reacting system pressure is 1.2 MPas, and 90 ℃ of reaction temperatures, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[embodiment 8]
It is 10 millimeters that 15 milliliters of above-mentioned catalyst B (granularity 20～40 orders) are filled in a diameter, in long 350 millimeters the stainless steel fixed bed reactors, with raw water and oxirane your ratio of metering pump massage charging in 10: 1.Reacting system pressure is 1.2 MPas, and 90 ℃ of reaction temperatures, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[embodiment 9]
It is 10 millimeters that above-mentioned catalyst C15 milliliter (granularity 20～40 orders) is filled in a diameter, in long 350 millimeters the stainless steel fixed bed reactors, with raw water and oxirane your ratio of metering pump massage charging in 15: 1.Reacting system pressure is 1.2 MPas, and 90 ℃ of reaction temperatures, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
The reactivity worth of table 1 different catalysts
| Sequence number | Catalyst | EO conversion ratio % | EG selectivity % |
| Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 comparative examples 1 embodiment 6 embodiment 7 embodiment 8 embodiment 9 | A B C D E - C C B C | 98.7 99.2 99.14 98.85 97.92 10.63 98.0 99.26 98.98 99.08 | 86.72 94.83 97.89 71.32 38.94 92.09 98.35 93.24 94.58 97.82 |
[embodiment 10]
Above-mentioned catalyst C24 milliliter is incorporated in one 300 milliliters the stainless steel gap reactor, adds 4.9 moles of raw waters and 0.48 mole of expoxy propane.Reacting system pressure is 1.2 MPas, 120 ℃ of reaction temperatures, and the reaction time is 3.5 hours, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography.The expoxy propane conversion ratio is 99.4%, and the propane diols selectivity is 95.8%.
Claims (9)
1, a kind of macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol, compound resin comprises following component by weight percentage:
(1) monomer 20～50%;
(2) comonomer 3～20%;
(3) nano material 0.1～10%;
(4) initator 0.1～2%;
(5) auxiliary agent one 0.1～2%;
(6) auxiliary agent 2 20～60%;
Wherein monomer is selected from least a in methyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, butadiene, styrene or the acrylonitrile; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT, nano magnesia or the nano zine oxide; Initator is selected from least a in benzoyl peroxide or the azodiisobutyronitrile; Auxiliary agent one is selected from least a in polyvinyl alcohol, bentonite, calcium carbonate or the gelatin; Auxiliary agent two is selected from least a in aliphatic hydrocarbon, polystyrene, gasoline, aliphatic acid or the paraffin; Compound resin carries out ion-exchange and makes catalyst with being selected from the compound that contains hydroxyl, chlorine root, bisulfate ion, bicarbonate radical or formate anion, and the exchanging equivalent of resin is 2.0～4.5 milliequivalents/gram compound resin.
2, according to the described macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol of claim 1, it is characterized in that monomer is selected from styrene.
3, according to the described macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol of claim 1, it is characterized in that comonomer is selected from divinylbenzene.
4, according to the described macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol of claim 1, it is characterized in that nano material is selected from CNT.
5, according to the described macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol of claim 1, it is characterized in that initator is selected from benzoyl peroxide.
6,, it is characterized in that auxiliary agent one is selected from polyvinyl alcohol according to the described macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol of claim 1.
7,, it is characterized in that auxiliary agent two is selected from polystyrene or gasoline according to the described macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol of claim 1.
8, according to the described macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol of claim 1, the exchanging equivalent that it is characterized in that resin is 3.0～3.5 milliequivalents/gram compound resin.
9,, it is characterized in that alkylene dihydric alcohol is ethylene glycol or propane diols according to the described macropore composite resin catalyst that is used to prepare alkylene dihydric alcohol of claim 1.
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| DE102006045504A1 (en) * | 2006-09-27 | 2008-04-03 | Lanxess Deutschland Gmbh | Crosslinked anion exchange resin based on polystyrene substituted in position 4 with cationic trialkylammonio-alkylaminomethyl groups, used for desalinisation of water in cooling circuits or as a catalyst |
| CN102212177B (en) * | 2011-04-07 | 2012-12-26 | 天津南开和成科技有限公司 | Porous resin with surface hydrophily |
| CN109575292B (en) * | 2017-09-29 | 2021-05-11 | 中国石油化工股份有限公司 | Ion exchange resin and use thereof |
| CN115518689B (en) * | 2021-06-24 | 2023-10-31 | 中国石油化工股份有限公司 | Catalyst for preparing glycol by epoxy alkane hydration and preparation method and application thereof |
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