CN109647521A - Polyoxymethylene dimethyl ether catalyst for preparing - Google Patents

Polyoxymethylene dimethyl ether catalyst for preparing Download PDF

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Publication number
CN109647521A
CN109647521A CN201710941274.4A CN201710941274A CN109647521A CN 109647521 A CN109647521 A CN 109647521A CN 201710941274 A CN201710941274 A CN 201710941274A CN 109647521 A CN109647521 A CN 109647521A
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catalyst
cation exchange
grams
exchange resin
acid
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CN109647521B (en
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杨为民
高晓晨
缪晓春
高焕新
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/08—Ion-exchange resins
    • B01J31/10—Ion-exchange resins sulfonated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/30—Ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • C07C41/50—Preparation of compounds having groups by reactions producing groups
    • C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
    • B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
    • B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to polyoxymethylene dimethyl ether catalyst for preparing, mainly solve the problems, such as the prior art using methanol, dimethoxym ethane and paraformaldehyde as that there are catalyst activities in reaction raw materials synthesizing polyoxymethylene dimethyl ether technique is low, selectivity is low, by using polyoxymethylene dimethyl ether catalyst for preparing, the catalyst is metal ion-modified cation exchange resin, the modified metal includes the technical solution of IIA metal, be can be used in the industrial production of polyoxymethylene dimethyl ether.

Description

Polyoxymethylene dimethyl ether catalyst for preparing
Technical field
The present invention relates to polyoxymethylene dimethyl ether catalyst for preparing.
Background technique
In recent years, as the industrial revolution influences the resource grid goed deep into increasingly and China is distinctive " more coals, have gas at few oil " Office, China's oil resource growing tension, petroleum supply pressure unprecedentedly increase.It is expected that 10~20 years following, China's oil supply rate Only~50%.How to be become using the energy crisis that China's coal resources abundant solve China and is badly in need of solving for researcher Certainly the problem of.Therefore the attention that novel oil product substitute is increasingly subject to people is developed by coal-based methanol.
Dimethyl ether is proposed as a kind of procetane earliest, however since its own cold starting performance is poor, room temperature Lower vapour pressure is high, is easy to produce vapour lock makes dimethyl ether significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether, That is Polyoxymethylene dimethyl ethers (PODE), is the common name of a substance, and skeleton symbol can be expressed as CH3O(CH2O)nCH3, octane number (> 30) with higher and oxygen content (42~51%).When the value of n is 2~10, object Rationality matter, combustibility and diesel oil are very close, preferably resolve dimethyl ether and lack as existing for derv fuel blend component It falls into.Therefore polyoxymethylene dimethyl ether can be used as novel cleaning diesel component, and the additive amount in diesel oil, can up to 30% (v/v) To improve the combustion position of diesel oil within the engine, the thermal efficiency is improved, reduces particulate matter and CO in tail gasxAnd NOxRow It puts.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be reducedxDischarging 7~10%, PM reduces by 5~35%.By coal Ji Jia Alcohol synthesis PODE can not only replace part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, reduce diesel combustion to the danger of environment Evil has important strategic importance and good economic value.
CN 101048357A (method for preparing polyoxymethylene dimethyl ether) is described using inorganic acid, sulfonic acid, heteropoly acid, acid Property ion exchange resin, zeolite, aluminium oxide etc. be used as catalyst, be reactant synthesizing polyoxymethylene by dimethoxym ethane and metaformaldehyde The method of dimethyl ether.But using the conversion ratio of existing catalyst and selectivity all up for improving.
Cation exchange resin is shown good as solid acid catalyst in the esterification of Aquo System, etherification reaction Catalytic perfomance, but its acid strength is lower.It generallys use and prepares support type resin, make activity by increasing acidity of catalyst It is improved.Metal-modified resin can be used, new acid site is formed on a catalyst, can't be handed over by other metal ions It changes, which solves in the case where catalyst keeps high activity in industrial application for polyoxymethylene dimethyl ether synthesis and it is acid not The problem of meeting metal ion contained in raw material replaces and inactivates.
Summary of the invention
The first technical problem to be solved by the present invention is that the prior art is former for reaction with methanol, dimethoxym ethane and paraformaldehyde There is a problem of that n=2-10 selectivity of product is low in material synthesizing polyoxymethylene dimethyl ether technique, a kind of new polyformaldehyde diformazan is provided Ether catalyst for preparing.The catalyst has the advantages that the selectivity of product of n=2-10 is high.
The second technical problem to be solved by the present invention is to provide a kind of using catalyst described in one of above-mentioned technical problem Preparation method.
The third technical problem to be solved by the present invention is the application of catalyst described in one of above-mentioned technical problem.
One of in order to solve the above-mentioned technical problem, technical scheme is as follows:
Polyoxymethylene dimethyl ether catalyst for preparing, the catalyst are metal ion-modified cation exchange resin, institute Stating modified metal includes IIA metal.Modified sulfonic acid polystyrene cation exchange resin, significantly improves to n=2~10 The selectivity of PODE.
In above-mentioned technical proposal, the modified metal includes Ga.
In above-mentioned technical proposal, the IIA metal preferably is selected from least one of Ra, Be, Mg, Ca, Sr and Ba.
In above-mentioned technical proposal, the modified metal further includes Ga and IIA metal simultaneously, and Ga and IIA metal is mentioning Height has synergistic effect to the selectivity aspect of the PODE of n=2~10.Ratio between Ga and IIA metal is not particularly limited, As long as Ga and IIA metal is existed simultaneously can obtain comparable synergy in catalyst.
As non-restrictive, the mass ratio of Ga and IIA metal is 0.01~100, within this range further non-limit Qualitative citing such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,10 etc..
In above-mentioned technical proposal, the modified metal includes at least two in IIA metal, such as, but not limited to Ra With Be, Mg and Ca, Sr and Ba, the selectivity to the PODE of n=2~10 is being improved between the element two-by-two in the IIA metal Aspect has synergistic effect.At this point, the ratio between Ra and Be, Mg and Ca, Sr and Ba is not particularly limited, if it is above-mentioned two-by-two IIA metallic element is existed simultaneously can obtain comparable synergy in catalyst.
As non-restrictive, the mass ratio between Ra and Be, Mg and Ca, Sr and Ba is 0.01~100, in this range Interior further non-restrictive such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,10 etc..
In above-mentioned technical proposal, the content of modified metal is not particularly limited in catalyst, such as, but not limited to catalyst The content of middle modified metal is greater than 0 and to be less than or equal to 9.8w%.
In above-mentioned technical proposal, the full exchange capacity of the resin is 3.0~5.9mmol/g.
In above-mentioned technical proposal, the resin can be gel-type or macroporous type.
In above-mentioned technical proposal, the resin is preferably sulfonic acid polystyrene cation exchange resin.
In above-mentioned technical proposal, the sulfonic acid polystyrene includes crosslinked polystyrene skeleton and sulfonic acid group.
In order to solve the above-mentioned technical problem two, technical scheme is as follows:
The preparation method of catalyst described in any one of technical solution of one of above-mentioned technical problem, is included in catalytic amount Acid in the presence of, the cation exchange resin and the suspension containing the modified metal-oxide and/or hydroxide are connect Touching carries out ion exchange.
In above-mentioned technical proposal, the acid is not particularly limited, if can with containing the modified metal-oxide and/or The salt that hydroxide reacts can be dissolved in solvent used in the suspension and be ok, under this principle such as, but not limited to At least one of hydrochloric acid, nitric acid or carboxylic acid of C2~C10.
In above-mentioned technical proposal, the carboxylic acid can be hydroxyl substituted carboxylic acid, such as, but not limited to hydroxyacetic acid, lactic acid, Tartaric acid, citric acid etc..
In above-mentioned technical proposal, the carboxylic acid can be the monoacid of C2~C10, such as, but not limited to acetic acid etc..
To solve above-mentioned technical problem three, technical solution of the present invention is as follows:
Catalyst is in synthesizing polyoxymethylene dimethyl ethers described in any one of technical solution of one of above-mentioned technical problem Using.
The synthetic method of polyoxymethylene dimethyl ethers for example can be, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein Methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, the dosage of methanol and dimethoxym ethane cannot be simultaneously 0, raw material is contacted with catalyst described above, and reaction generates polyoxymethylene dimethyl ether.
In above-mentioned technical proposal, catalyst amount is preferably the 0.05~10% of raw material weight；More preferably raw material weight 0.1~5%.
In above-mentioned technical proposal, reaction temperature is preferably 70~200 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 0.2~6MPa.
In above-mentioned technical proposal, the reaction time is preferably 1 to 20 hour, and more 4 to 12 hours.
In above-mentioned technical proposal, the sum of dosage of methanol and dimethoxym ethane and the mass ratio of paraformaldehyde are preferably in raw material (0.4~5): 1；Methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0.2~10): (0.5~10): 1.
In the case where the composition of catalyst of the present invention is clear, the preparation of catalyst is not particularly limited, Ke Yican Ion-exchange process commonly used in the prior art is examined to be prepared.It such as may include following steps: by sulfonic acid sodium form polystyrene Cation exchange resin is washed with deionized water to outflow clear water, impregnates 1 with 0.5~20% strong acid (such as hydrochloric acid or sulfuric acid) ~12h impregnates 1~12h with deionized water or alcohol solution dipping, is washed with deionized later to pH=6 to get this hair is arrived The bright sulfonic acid polystyrene cation exchange resin.When sulfonic acid type of the present invention can also be directly obtained from commercially available channel Polystyrol cation exchange resin, rather than sulfonic acid sodium form, may be used to the preparation of catalyst of the present invention.
Using catalyst of the invention, the PODE yield of n=2~10 is good, and the selectivity of product of n=2~10 is up to 89.6%, Achieve preferable technical effect.
Heretofore described full exchange capacity is in terms of butt resin.
Below by embodiment, the present invention is further elaborated, the raw material paraformaldehyde used in embodiment and comparative example The degree of polymerization be 5, selectivity of product on the basis of paraformaldehyde by target of the polyoxymethylene dimethyl ether that the degree of polymerization is 2~10 produce Object calculates.
Specific embodiment
[embodiment 1]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur The Ga (OH) that acid type polystyrene cation exchange resin and 300ml are 2 grams containing Ga31 drop ice vinegar is added in aqueous suspension mixing Acid, mixing stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtain the catalyst that Ga content is 2w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 2]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, the Ra (OH) for being 2 grams containing Ra with 300ml under nitrogen protection2Aqueous suspension mixing, adds Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Ra content is 2w%'s Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 3]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, the Be (OH) for being 2 grams containing Be with 300ml under nitrogen protection2Aqueous suspension mixing, adds Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Be content is 2w%'s Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 4]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, the Mg (OH) for being 2 grams containing Mg with 300ml under nitrogen protection2Aqueous suspension mixing, adds Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Mg content is 2w%'s Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 5]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, the Ca (OH) for being 2 grams containing Ca with 300ml under nitrogen protection2Aqueous suspension mixing, adds Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Ca content is 2w%'s Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 6]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, the Sr (OH) for being 2 grams containing Sr with 300ml under nitrogen protection2Aqueous suspension mixing, adds Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Sr content is 2w%'s Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 7]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, the Ba (OH) for being 2 grams containing Ba with 300ml under nitrogen protection2Aqueous suspension mixing, adds Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Ba content is 2w%'s Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 8]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, with 300ml containing the Ga (OH) that Ga is 1 gram and Ra is 1 gram under nitrogen protection3And Ra (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven Constant weight, obtaining Ga content is the catalyst that 1w% and Ra content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 9]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, with 300ml containing the Ga (OH) that Ga is 1 gram and Be is 1 gram under nitrogen protection3And Be (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven Constant weight, obtaining Ga content is the catalyst that 1w% and Be content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 10]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, with 300ml containing the Ga (OH) that Ga is 1 gram and Mg is 1 gram under nitrogen protection3And Mg (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven Constant weight, obtaining Ga content is the catalyst that 1w% and Mg content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 11]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, with 300ml containing the Ga (OH) that Ga is 1 gram and Ca is 1 gram under nitrogen protection3And Ca (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven Constant weight, obtaining Ga content is the catalyst that 1w% and Ca content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 12]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, with 300ml containing the Ga (OH) that Ga is 1 gram and Sr is 1 gram under nitrogen protection3And Sr (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven Constant weight, obtaining Ga content is the catalyst that 1w% and Sr content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 13]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin, with 300ml containing the Ga (OH) that Ga is 1 gram and Ba is 1 gram under nitrogen protection3And Ba (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven Constant weight, obtaining Ga content is the catalyst that 1w% and Ba content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 14]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Ra is 0.5 gram and Be is 0.5 gram Ga(OH)3、Ra(OH)2With Be (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, Dry to constant weight in vacuum oven, it be 0.5w% and Be content is urging for 0.5w% that obtain Ga content, which be 1w%, Ra content, Agent.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 15]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Mg is 0.5 gram and Ca is 0.5 gram Ga(OH)3、Mg(OH)2With Ca (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, Dry to constant weight in vacuum oven, it be 0.5w% and Ca content is urging for 0.5w% that obtain Ga content, which be 1w%, Mg content, Agent.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 16]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Sr is 0.5 gram and Ba is 0.5 gram Ga(OH)3、Sr(OH)2With Ba (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, Dry to constant weight in vacuum oven, it be 0.5w% and Ba content is urging for 0.5w% that obtain Ga content, which be 1w%, Sr content, Agent.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 17]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Ra is 0.4 gram, Be is 0.3 gram and Mg For 0.3 gram of Ga (OH)3、Ra(OH)2、Be(OH)2With Mg (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixes, 24 hours are stood at room temperature, dry to constant weight in vacuum oven, it is 0.4w%, Be that obtain Ga content, which be 1w%, Ra content, Content is the catalyst that 0.3w% and Mg content is 0.3w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 18]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Ca is 0.4 gram, Sr is 0.3 gram and Ba For 0.3 gram of Ga (OH)3、Ca(OH)2、Sr(OH)2With Ba (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixes, 24 hours are stood at room temperature, dry to constant weight in vacuum oven, it is 0.4w%, Sr that obtain Ga content, which be 1w%, Ca content, Content is the catalyst that 0.3w% and Ba content is 0.3w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 19]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Ra is 0.25 gram, Be is 0.25 gram, The Ga (OH) that Mg is 0.25 gram and Ca is 0.25 gram3、Ra(OH)2、Be(OH)2、Mg(OH)2With Ca (OH)2It is mixed to mix aqueous suspension It closes, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, and dry to constant weight in vacuum oven, obtaining Ga content is It is 0.25w%, Mg content is the catalysis that 0.25w% and Ca content is 0.25w% that 1w%, Ra content, which are 0.25w%, Be content, Agent.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 20]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Ra is 0.25 gram, Be is 0.25 gram, The Ga (OH) that Sr is 0.25 gram and Ba is 0.25 gram3、Ra(OH)2、Be(OH)2、Sr(OH)2With Ba (OH)2It is mixed to mix aqueous suspension It closes, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, and dry to constant weight in vacuum oven, obtaining Ga content is It is 0.25w%, Sr content is the catalysis that 0.25w% and Ba content is 0.25w% that 1w%, Ra content, which are 0.25w%, Be content, Agent.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 21]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Mg is 0.25 gram, Ca is 0.25 gram, The Ga (OH) that Sr is 0.25 gram and Ba is 0.25 gram3、Mg(OH)2、Ca(OH)2、Sr(OH)2With Ba (OH)2It is mixed to mix aqueous suspension It closes, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, and dry to constant weight in vacuum oven, obtaining Ga content is It is 0.25w%, Sr content is the catalysis that 0.25w% and Ba content is 0.25w% that 1w%, Mg content, which are 0.25w%, Ca content, Agent.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 22]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Ra is 0.2 gram, Be is 0.2 gram, Mg For the Ga (OH) that 0.2 gram, Ca are 0.2 gram and Sr is 0.2 gram3、Ra(OH)2、Be(OH)2、Mg(OH)2、Ca(OH)2With Sr (OH)2 Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, and it is dry to constant weight in vacuum oven, It is 0.2w%, Be content be 0.2w%, Mg content is that 0.2w%, Ca content are that obtain Ga content, which be 1w%, Ra content, 0.2w% and Sr content is the catalyst of 0.2w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 23]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Ra is 0.2 gram, Be is 0.2 gram, Mg For the Ga (OH) that 0.2 gram, Ca are 0.2 gram and Ba is 0.2 gram3、Ra(OH)2、Be(OH)2、Mg(OH)2、Ca(OH)2With Ba (OH)2 Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, and it is dry to constant weight in vacuum oven, It is 0.2w%, Be content be 0.2w%, Mg content is that 0.2w%, Ca content are that obtain Ga content, which be 1w%, Ra content, 0.2w% and Ba content is the catalyst of 0.2w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[embodiment 24]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur Acid type polystyrene cation exchange resin with 300ml containing Ga is 1 gram under nitrogen protection, Ra is 0.2 gram, Be is 0.2 gram, Mg For the Ga (OH) that 0.15 gram, Ca are 0.15 gram, Sr is 0.15 gram and Ba is 0.15 gram3、Ra(OH)2、Be(OH)2、Mg(OH)2、Ca (OH)2、Sr(OH)2With Ba (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, Vacuum oven is dry to constant weight, and it be 0.2w%, Be content is 0.2w%, Mg content that obtain Ga content, which be 1w%, Ra content, It is 0.15w%, Sr content for 0.15w%, Ca content is the catalyst that 0.15w% and Ba content is 0.15w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 2 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 130 DEG C and 4h is reacted under 0.5MPa self-generated pressure, is extracted after sample is centrifugated by gas chromatographic analysis.It include polyformaldehyde diformazan in product Ether and unreacted material benzenemethanol and paraformaldehyde, composition distribution such as table 1.
[comparative example 1]
In proportion for embodiment 1, difference is only that the catalyst used is poly- for drying sulfonic acid type described in embodiment 1 2 grams of styrene cation exchange resin, other process conditions are same as Example 1, the results are shown in Table 1.
Table 1
N is the degree of polymerization, product CH3O(CH2O)nCH3。

Claims (10)

1. polyoxymethylene dimethyl ether catalyst for preparing, the catalyst is metal ion-modified cation exchange resin, described Modified metal includes IIA metal.
2. catalyst according to claim 1, it is characterized in that IIA metal in Ra, Be, Mg, Ca, Sr and Ba at least It is a kind of.
3. catalyst according to claim 1, it is characterized in that the content of modified metal is greater than 0 and to be less than etc. in catalyst In 9.8w%.
4. catalyst according to claim 1, it is characterized in that the full exchange capacity of the resin is 3.0~5.9mmol/g.
5. catalyst according to claim 1, it is characterized in that the resin is gel-type or macroporous type.
6. catalyst according to claim 1, it is characterized in that the resin is sulfonic acid polystyrene cation exchange tree Rouge.
7. catalyst according to claim 6, it is characterized in that the sulfonic acid polystyrene includes crosslinked polystyrene bone Frame and sulfonic acid group.
8. the preparation method of catalyst described in any one of claim 1~7, including in the presence of the acid of catalytic amount, by institute It states cation exchange resin and contacts progress ion exchange with the suspension containing the modified metal-oxide and/or hydroxide.
9. the preparation method of catalyst according to claim 8, it is characterized in that the acid is hydrochloric acid, nitric acid or C2~C10 At least one of carboxylic acid.
10. application of the catalyst described in any one of claim 1~7 in synthesizing polyoxymethylene dimethyl ethers.
CN201710941274.4A 2017-10-10 2017-10-10 Catalyst for preparing polyformaldehyde dimethyl ether Active CN109647521B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL159360B (en) * 1968-06-24 1979-02-15 Sir Soc Italiana Resine Spa PROCESS FOR PREPARING ACRYLIC ACID AND / OR METHACRYLIC ACID.
CN1506444A (en) * 2002-12-13 2004-06-23 中国石油天然气股份有限公司 Method for modifying catalytically cracked gasoline
CN106582834A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Catalyst for preparation of polyoxymethylene dimethyl ether

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL159360B (en) * 1968-06-24 1979-02-15 Sir Soc Italiana Resine Spa PROCESS FOR PREPARING ACRYLIC ACID AND / OR METHACRYLIC ACID.
CN1506444A (en) * 2002-12-13 2004-06-23 中国石油天然气股份有限公司 Method for modifying catalytically cracked gasoline
CN106582834A (en) * 2015-10-16 2017-04-26 中国石油化工股份有限公司 Catalyst for preparation of polyoxymethylene dimethyl ether

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