CN109647519A - Polyoxymethylene dimethyl ethers catalyst - Google Patents

Polyoxymethylene dimethyl ethers catalyst Download PDF

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Publication number
CN109647519A
CN109647519A CN201710941053.7A CN201710941053A CN109647519A CN 109647519 A CN109647519 A CN 109647519A CN 201710941053 A CN201710941053 A CN 201710941053A CN 109647519 A CN109647519 A CN 109647519A
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catalyst
exchange resin
cation exchange
acid
grams
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CN109647519B (en
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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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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

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

Abstract

The present invention relates to the catalyst of polyoxymethylene dimethyl ether preparation, 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 the catalyst of polyoxymethylene dimethyl ether preparation, the catalyst is metal ion-modified cation exchange resin；The modified metal includes the technical solution of IIIA metal, be can be used in the industrial production of polyoxymethylene dimethyl ether.

Description

Polyoxymethylene dimethyl ethers catalyst
Technical field
The present invention relates to the catalyst of polyoxymethylene dimethyl ethers preparation.
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 Base ether catalyst.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, the catalyst are metal ion-modified cation exchange resin；The modification Metal includes IIIA metal.
In above-mentioned technical proposal, the preferred Ga of IIIA metal.
In above-mentioned technical proposal, the modified metal includes VIIB metal.
Ga and VIIB metal have synergistic effect in terms of improving to the selectivity of the PODE of n=2~10.Ga and VIIB gold Ratio between category is not particularly limited, as long as Ga and VIIB metal is existed simultaneously can obtain comparable collaboration in catalyst Effect.As non-restrictive, the mass ratio of Ga and VIIB metal is 0.01~100, further non-limiting within this range Property citing such as 0.10,0.50,0.80,1.0,1.5,2.0,3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0 etc..
In above-mentioned technical proposal, the VIIB metal preferably is selected from least one of Mn or Tc.
In above-mentioned technical proposal, still more preferably VIIB metal includes simultaneously that Mn and Tc, at this time Mn and Tc are being improved There is synergistic effect to the selectivity aspect of the PODE of n=2~10.At this point, the ratio between Mn and Tc is not particularly limited, only Comparable synergy can be obtained in catalyst by wanting Mn and Tc to exist simultaneously.As non-restrictive, the matter of Mn and Tc Amount than being 0.01~100, within this range further non-restrictive such as 0.10,0.50,0.80,1.0,1.5,2.0, 3.0,4.0,5.0,6.0,7.0,8.0,9.0,10.0 etc..
In above-mentioned technical proposal, the content of modified metal is not particularly limited in catalyst, such as, but not limited to modified gold The content of category is greater than 0 and to be less than or equal to 10w%.
In above-mentioned technical proposal, the full exchange capacity of the resin is 3.0~6.0mmol/g.F
In above-mentioned technical proposal, the resin can be gel-type or macroporous type.
In above-mentioned technical proposal, the cation exchange resin is preferably sulfonic acid polystyrene cation exchange resin.
In above-mentioned technical proposal, the sulfonic acid polystyrene cation exchange resin includes crosslinked polystyrene bone Frame 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 89.4%, 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 Mn (OH) for being 2 grams containing Mn 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 Mn 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 Tc (OH) for being 2 grams containing Tc 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 Tc 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, with 300ml containing the Ga (OH) that Ga is 1 gram and Mn is 1 gram under nitrogen protection3And Mn (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 Mn 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.
From embodiment 4 and embodiment 1 and embodiment 2 on year-on-year basis it is found that Ga and Mn is improving the choosing to the PODE of n=2~10 There is synergistic effect in terms of selecting property.
[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, with 300ml containing the Ga (OH) that Ga is 1 gram and Tc is 1 gram under nitrogen protection3And Tc (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 Tc 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.
From embodiment 5 and embodiment 1 and embodiment 3 on year-on-year basis it is found that Ga and Tc is improving the choosing to the PODE of n=2~10 There is synergistic effect in terms of selecting property.
[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, with 300ml containing the Tc (OH) that Tc is 1 gram and Mn is 1 gram under nitrogen protection2And Mn (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 Tc content is the catalyst that 1w% and Mn 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 6 and embodiment 2 and embodiment 3 are on year-on-year basis as can be seen that Mn and Tc is being improved to the PODE's of n=2~10 Selectivity aspect has synergistic effect.
[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 with 300ml containing Ga is 1 gram under nitrogen protection, Tc is 0.5 gram and Mn is 0.5 gram Ga(OH)3、Tc(OH)2With Mn (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 Mn content is urging for 0.5w% that obtain Ga content, which be 1w%, Tc 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 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 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 100 DEG C and 4h is reacted under 0.6MPa 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 1.5 grams and Mn is 0.5 gram under nitrogen protection3With Mn(OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry in vacuum oven To constant weight, obtaining Ga content is the catalyst that 1.5w% and Mn content is 0.5w%.
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 90 DEG C and 4h is reacted under 0.2MPa 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 1.5 grams and Tc is 0.5 gram under nitrogen protection3With Tc(OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry in vacuum oven To constant weight, obtaining Ga content is the catalyst that 1.5w% and Tc content is 0.5w%.
2, the synthesis of polyoxymethylene dimethyl ether
0.5 gram of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, at 120 DEG C With react 4h under 0.8MPa self-generated pressure, extract after sample centrifuge separation by gas chromatographic analysis.It include polyformaldehyde two in product Methyl 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 Ga is 1.5 grams under nitrogen protection, Tc is 0.25 gram and Mn is 0.25 Gram Ga (OH)3、Tc(OH)2With Mn (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, it is small to stand 24 at room temperature for mixing When, dry to constant weight in vacuum oven, it is that 0.25w% and Mn content is that obtain Ga content, which be 1.5w%, Tc content, The catalyst of 0.25w%.
2, the synthesis of polyoxymethylene dimethyl ether
Be added 3 grams of catalyst in 300 milliliters of tank reactors, 100 grams of methanol and 100 grams of paraformaldehydes, at 110 DEG C and 4h is reacted under 0.3MPa 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 (9)

1. polyoxymethylene dimethyl ether catalyst, the catalyst is metal ion-modified cation exchange resin；The modified gold Belonging to includes IIIA metal.
2. 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 10w%.
3. catalyst according to claim 1, it is characterized in that the full exchange capacity of the resin is 3.0~6.0mmol/g.
4. catalyst according to claim 1, it is characterized in that the resin is gel-type or macroporous type.
5. catalyst according to claim 1, it is characterized in that the cation exchange resin is sulfonic acid polystyrene sun Ion exchange resin.
6. catalyst according to claim 1, it is characterized in that the sulfonic acid polystyrene cation exchange resin includes Crosslinked polystyrene skeleton and sulfonic acid group.
7. the preparation method of catalyst described in any one of claim 1~6, 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.
8. the preparation method of catalyst according to claim 7, it is characterized in that the acid is hydrochloric acid, nitric acid or C2~C10 At least one of carboxylic acid.
9. application of the catalyst described in any one of claim 1~6 in synthesizing polyoxymethylene dimethyl ethers.
CN201710941053.7A 2017-10-10 2017-10-10 Polyoxymethylene dimethyl ether catalyst Active CN109647519B (en)

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CN105585456A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Preparation method for polyoxymethylene dimethyl ethers
CN105585460A (en) * 2014-10-24 2016-05-18 中国石油化工股份有限公司 Method for synthesizing polyoxymethylene dimethyl ethers

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CN104549502A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst for synthesis of polyoxymethylene dimethyl ether and application of catalyst
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