CN109651102A - The preparation method of polyoxymethylene dimethyl ether - Google Patents
The preparation method of polyoxymethylene dimethyl ether Download PDFInfo
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- CN109651102A CN109651102A CN201710941225.0A CN201710941225A CN109651102A CN 109651102 A CN109651102 A CN 109651102A CN 201710941225 A CN201710941225 A CN 201710941225A CN 109651102 A CN109651102 A CN 109651102A
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- 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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- 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
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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Abstract
The present invention relates to the preparation methods of polyoxymethylene dimethyl ether, solve the prior art mainly with methanol, dimethoxym ethane and paraformaldehyde are low for there are catalyst activities in reaction raw materials synthesizing polyoxymethylene dimethyl ether technique, the low problem of selectivity, by using the preparation method of polyoxymethylene dimethyl ether, including, with methanol, dimethoxym ethane and paraformaldehyde are 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 0 simultaneously, raw material is contacted with catalyst, reaction generates polyoxymethylene dimethyl ether, the catalyst is metal ion-modified cation exchange resin, the modified metal includes the technical solution of IIA metal, it can be used in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to the preparation methods of polyoxymethylene dimethyl ether.
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 technical problem to be solved by the present invention is to the prior arts to close by reaction raw materials of methanol, dimethoxym ethane and paraformaldehyde
At there is a problem of that n=2-10 selectivity of product is low in polyoxymethylene dimethyl ether technique, the new polyoxymethylene dimethyl ether of one kind is provided
Preparation method.This method has the advantages that the selectivity of product of n=2-10 is high.
In order to solve the above-mentioned technical problem, technical scheme is as follows:
The preparation method of polyoxymethylene dimethyl ether, including, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein first
Alcohol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, the dosage of methanol and dimethoxym ethane is not
It can simultaneously be 0, raw material is contacted with catalyst, and reaction generates polyoxymethylene dimethyl ether, and the catalyst is metal ion
Change
The cation exchange resin of property, the modified metal includes IIA metal.
Modified sulfonic acid polystyrene cation exchange resin, significantly improves the selectivity to the PODE of n=2~10.
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, methanol in raw material: dimethoxym ethane: the mass ratio of paraformaldehyde is (0.2~10): (0.5~
10)∶1。
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 above-mentioned technical proposal, the catalyst can be using the method preparation included the following steps: in catalytic amount
In the presence of acid, the cation exchange resin is contacted with the suspension containing the modified metal-oxide and/or hydroxide
Carry 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..
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 the present 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 compared with
Good 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. the preparation method of polyoxymethylene dimethyl ether, including, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: first contracting
Aldehyde: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, the dosage of methanol and dimethoxym ethane cannot be 0 simultaneously, raw material with urge
Agent contact, reaction generate polyoxymethylene dimethyl ether, and the catalyst is metal ion-modified cation exchange resin, described to change
Property metal includes IIA metal.
2. according to the method described in claim 1, it is characterized in that catalyst amount is the 0.05~10% of raw material weight.
3. according to the method described in claim 1, it is characterized in that reaction temperature is 70~200 DEG C.
4. according to the method described in claim 1, it is characterized in that reaction pressure is 0.2~6MPa.
5. according to the method described in claim 1, it is characterized in that the reaction time is preferably 1 to 20 hour.
6. according to the method described in claim 1, it is characterized in that methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0.2~10)
: (0.5~10): 1.
7. according to the method described in claim 1, it is characterized in that IIA metal in Ra, Be, Mg, Ca, Sr and Ba at least one
Kind.
8. according to the method described in claim 1, it is characterized in that the content of modified metal is greater than 0 and to be less than or equal in catalyst
9.8w%.
9. according to the method described in claim 1, it is characterized in that the full exchange capacity of the resin is 3.0~5.9mmol/g.
10. according to the method described in claim 1, it is characterized in that the resin is gel-type or macroporous type.
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| 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 |
| CN107915601A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The method of synthesizing polyoxymethylene dimethyl ethers |
| CN107915602A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | Polyoxymethylene dimethyl ethers catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN107915601A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The method of synthesizing polyoxymethylene dimethyl ethers |
| CN107915602A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | Polyoxymethylene dimethyl ethers catalyst |
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