CN106588595A - Synthetic method of polyoxymethylene dimethyl ethers - Google Patents
Synthetic method of polyoxymethylene dimethyl ethers Download PDFInfo
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- CN106588595A CN106588595A CN201510661213.3A CN201510661213A CN106588595A CN 106588595 A CN106588595 A CN 106588595A CN 201510661213 A CN201510661213 A CN 201510661213A CN 106588595 A CN106588595 A CN 106588595A
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- catalyst
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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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Abstract
The invention relates to a synthetic method of polyoxymethylene dimethyl ethers. The method mainly solves the problem that a heterogeneous catalyst has low selectivity for catalysis of polyoxymethylene dimethyl ethers in the prior art. A polyoxymethylene dimethyl ether catalyst is used, acidic cation exchange resin is used as a main component, and Cu ion which is loaded on the main active component is used as a modifier. The technical scheme can better solve the technical problem, and can be applied to industrial production of polyoxymethylene dimethyl ethers.
Description
Technical field
The present invention relates to the synthetic method of polyoxymethylene dimethyl ether.
Background technology
In recent years, with the industrial revolution affect increasingly deeply and China's distinctive " many coals, few oil, there is gas " resource grid
Office, China's oil resource growing tension, oil supply pressure unprecedentedly increases.It is estimated following 10～20 years, China's oil
Supply rate only～50%.How the energy crisis for solving China using the coal resources of China's abundant is become as scientific research work
Author's urgent problem.Therefore the attention that new oil product succedaneum is increasingly subject to people is developed by coal-based methanol.
Dimethyl ether is proposed as earliest a kind of procetane, yet with its own cold starting performance is poor, room temperature
Lower vapour pressure is high, easily produce vapour lock causes dimethyl ether significantly raised as the cost of vehicle alternative fuel.Polyformaldehyde two
Methyl ether, i.e. Polyoxymethylene dimethyl ethers (PODE), are the common names of a class material, and its skeleton symbol can be with table
It is shown as CH3O(CH2O)nCH3, with higher octane number (>30) with oxygen content (42～51%).When n value be 2～
When 10, its physical property, combustibility and diesel oil closely, preferably resolve dimethyl ether and adjust as derv fuel
The defect existed with component.Therefore polyoxymethylene dimethyl ether can be used as new cleaning diesel component, the addition in diesel oil
Amount can improve diesel oil combustion position within the engine up to 30% (v/v), improve the thermal efficiency, in reducing tail gas
Particulate matter and COxAnd NOxDischarge.It is reported that, add 5～30% CH3OCH2OCH3NO can be reducedx
7～10%, PM of discharge reduces by 5～35%.Synthesizing PODE by coal-based methanol not only can replace part diesel oil, also
Can improve the efficiency of combustion of diesel oil, reduce harm of the diesel combustion to environment, with important strategic importance and good
Economic worth.In addition, CH3O(CH2O)2CH3It is very strong to the solvability of hydro carbons, can be separately as without aromatic hydrocarbons
Solvent using or be used in mixed way with existing solvent naphtha, performance is better than existing aromatic solvent naphtha.
CN 101048357A (method for preparing polyoxymethylene dimethyl ether) describe using mineral acid, sulfonic acid, heteropoly acid,
Acid-exchange resin, zeolite, aluminium oxide etc., as catalyst, are reactant conjunction by dimethoxym ethane and metaformaldehyde
Into the method for polyoxymethylene dimethyl ether.
But prior art is low to the polyoxymethylene dimethyl ether selectivity of polymerization degree n=2.
The content of the invention
One of the technical problem to be solved is polyoxymethylene dimethyl ether selectivity of the prior art to polymerization degree n=2
A kind of low problem, there is provided synthetic method of new polyoxymethylene dimethyl ether, the method has the poly- first to polymerization degree n=2
The high advantage of aldehyde dimethyl ether selectivity.
The two of the technical problem to be solved are the preparation methoies of used catalyst in one of above-mentioned technical problem.
The three of the technical problem to be solved are another kind of preparations of used catalyst in one of above-mentioned technical problem
Method.
To solve one of above-mentioned technical problem, technical scheme is as follows：The synthetic method of polyoxymethylene dimethyl ether,
Generate dimethyl ether and polyoxymethylene dimethyl ether including making dimethoxym ethane that generation polycondensation reaction is contacted with catalyst, the catalyst with
Active component based on acid cation exchange resin, to be carried on the Cu ions in the main active component as modifying agent.
The Cu ions are selected from Cu (II) and/or Cu (I).
In above-mentioned technical proposal, reaction temperature is preferably 90～160 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 1～50bar in terms of gauge pressure.
In above-mentioned technical proposal, dimethoxym ethane liquid volume air speed is preferably 5～300h-1。
In above-mentioned technical proposal, described acid cation exchange resin is preferably storng-acid cation exchange resin.
In above-mentioned technical proposal, by weight, Cu ion concentrations are preferably 0.1～10% in the catalyst.
In above-mentioned technical proposal, described acid cation exchange resin is preferably sulfonic acid polystyrene crosslinked resin.
In above-mentioned technical proposal, described acid cation exchange resin is preferably gel-type or macropore.
To solve the two of above-mentioned technical problem, technical scheme is as follows：Any one of one of above-mentioned technical problem
The preparation method of the catalyst, comprises the following steps：
(1) make the acid cation exchange resin carry out ion-exchange reactionss with Cu (II) compound and obtain Cu (II)
Modified acid cation exchange resin.The modified acid cation exchange resins of Cu (II) can be used as polyformaldehyde of the present invention
The catalyst of the synthetic method of dimethyl ether is used.
In above-mentioned technical proposal, preferably also comprise the steps：
(2) Cu (II) in the modified acid cation exchange resins of the Cu (II) is reduced to using reducing agent
Cu (I) is modified acid cation exchange resin.The modified acid cation exchange resins of Cu (I) show to the selectivity of PODE2
Write better than the modified acid cation exchange resins of Cu (II).
In above-mentioned technical proposal, described reducing agent preferably be selected from hydrogen, azanol and its salt (salt preferred hydrochlorate),
First azanol and its salt (salt preferred hydrochlorate), sulfurous acid, sulfurous acid acid salt (the salt preferred as alkali salt,
Such as potassium salt or sodium salt) and sulfurous acid normal salt (the salt preferred as alkali salt, such as potassium salt or sodium salt) at least
It is a kind of.Most preferably azanol and its salt.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
Another kind of preparation method of catalyst any one of case, including making the acid cation exchange resin and Cu (I)
Compound carries out ion-exchange reactionss and obtains the catalyst.
In above-mentioned technical proposal, Cu (I) compound is such as, but not limited to Red copper oxide, Cu-lyt., protobromide
Copper, Hydro-Giene (Water Science). or oxalic acid are cuprous.
The chemical equation of polyoxymethylene dimethyl ether synthetic reaction of the present invention is：
CH3OCH2OCH3(dimethoxym ethane) --- --- → CH3OCH3(dimethyl ether)+CH3O(CH2O)nCH3
The selective computational methods of polyoxymethylene dimethyl ether are as follows in the present invention：
CH3O(CH2O)nCH3Selectivity=n × (CH3O(CH2O)nCH3Mole growing amount)/dimethoxym ethane molar consumption
As n=2
CH3O(CH2O)2CH3Selectivity=2 × (CH3O(CH2O)2CH3Mole growing amount)/dimethoxym ethane molar consumption
Using technical scheme, the selectivity of the polyoxymethylene dimethyl ether of n=2 is up to 73%, can be used for polyformaldehyde
In the commercial production of dimethyl ether.
Further instruction is given below by example to the present invention.
Specific embodiment
【Embodiment 1】
1st, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, with the hydrogen shape ion exchange that the trade mark is Amberlyst-15
Resin (exchange capacity is 1.7eq/L) 100mL mixes, and shakes on shaking table after 5h, filters, successively with water, weight concentration
Alcohol water blend for 75% rinses resin, then adds the solution of oxammonium hydrochloride. (20g oxammonium hydrochloride .s is molten resin
Solution is 75% ethanol water in 100mL weight concentrations) in, shake 3 hours on shaking table, it is stored at room temperature 5 minutes,
Topple over clear liquid, add weight concentration to be that 75% ethanol water is washed 2 times, each ethanol water 50mL is filtered,
90 DEG C are vacuum dried 10 hours, obtain Cu (I)/Amberlyst-15 catalyst that Cu contents are 5g/L.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 100 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
【Comparative example 1】
1st, the acquisition of catalyst
Hydrogen shape ion exchange resin with Amberlyst-15 is as catalyst.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 100 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
【Embodiment 2】
1st, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, with the hydrogen shape ion exchange that the trade mark is Amberlyst-15
Shake on resin 100mL mixing shaking tables after 5h, filter, successively with alcohol water blend that water, weight concentration are 75%
Resin is rinsed, 90 DEG C are vacuum dried 10 hours, obtain Cu (II)/Amberlyst-15 catalyst that Cu contents are 5g/L.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 100 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
【Embodiment 3】
1st, the acquisition of catalyst
With the CuOAc100mL normal hexane suspensions containing 0.5gCu, with the amberlite that the trade mark is Amberlyst-15
Fat 100mL mixes, and shakes after 72h on shaking table under nitrogen protection, filters, and with normal hexane resin, room temperature nitrogen are rinsed
Dry up dry 24 hours, obtain Cu (I)/Amberlyst-15 resin catalysts that Cu contents are 5g/L.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 100 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
【Embodiment 4】
1st, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, with the hydrogen shape ion exchange that the trade mark is Amberlyst-15
Resin 100mL mixes, and shakes on shaking table after 5h, filters, water-soluble with ethanol that water, weight concentration are 75% successively
Liquid rinses resin, then adds the solution of oxammonium hydrochloride. (20g oxammonium hydrochloride .s to be dissolved in into 100mL weight dense resin
Spend for 75% ethanol water) in, shake 3 hours on shaking table, it is stored at room temperature 5 minutes, topple over clear liquid, add weight
Amount concentration is that 75% ethanol water is washed 2 times, and each ethanol water 50mL is filtered, 90 DEG C of vacuum drying 10
Hour, obtain Cu (I)/Amberlyst-15 catalyst that Cu contents are 5g/L.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 120 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
【Embodiment 5】
1st, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, with the hydrogen shape ion exchange that the trade mark is Amberlyst-15
Resin 100mL mixes, and shakes on shaking table after 5h, filters, water-soluble with ethanol that water, weight concentration are 75% successively
Liquid rinses resin, then adds the solution of oxammonium hydrochloride. (20g oxammonium hydrochloride .s to be dissolved in into 100mL weight dense resin
Spend for 75% ethanol water) in, shake 3 hours on shaking table, it is stored at room temperature 5 minutes, topple over clear liquid, add weight
Amount concentration is that 75% ethanol water is washed 2 times, and each ethanol water 50mL is filtered, 90 DEG C of vacuum drying 10
Hour, obtain Cu (I)/Amberlyst-15 catalyst that Cu contents are 5g/L.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 140 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
【Embodiment 6】
1st, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, with the hydrogen shape ion exchange that the trade mark is Amberlyst-39
Resin (exchange capacity 1.15eq/L) 100mL mixes, and shakes on shaking table after 5h, filters, successively with water, weight concentration
Alcohol water blend for 75% rinses resin, then adds the solution of oxammonium hydrochloride. (20g oxammonium hydrochloride .s is molten resin
Solution is 75% ethanol water in 100mL weight concentrations) in, shake 3 hours on shaking table, it is stored at room temperature 5 minutes,
Topple over clear liquid, add weight concentration to be that 75% ethanol water is washed 2 times, each ethanol water 50mL is filtered,
90 DEG C are vacuum dried 10 hours, obtain Cu (I)/Amberlyst-15 catalyst that Cu contents are 5g/L.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 100 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
【Embodiment 7】
1st, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, with the hydrogen shape ion exchange that the trade mark is Amberlyst-36
Resin (exchange capacity 1.95eq/L) 100mL mixes, and shakes on shaking table after 5h, filters, dense with water, weight successively
The alcohol water blend flushing resin for 75% is spent, then resin the solution of oxammonium hydrochloride. is added into (by 20g oxammonium hydrochloride .s
100mL weight concentrations are dissolved in for 75% ethanol water) in, shake 3 hours on shaking table, it is stored at room temperature 5 minutes,
Topple over clear liquid, add weight concentration to be that 75% ethanol water is washed 2 times, each ethanol water 50mL is filtered,
90 DEG C are vacuum dried 10 hours, obtain Cu (I)/Amberlyst-36 catalyst that Cu contents are 5g/L.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 100 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
【Embodiment 8】
1st, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, with the hydrogen shape ion exchange that the trade mark is Amberlyst-35
Resin (exchange capacity 1.9eq/L) 100mL mixes, and shakes on shaking table after 5h, filters, dense with water, weight successively
The alcohol water blend flushing resin for 75% is spent, then resin the solution of oxammonium hydrochloride. is added into (by 20g oxammonium hydrochloride .s
100mL weight concentrations are dissolved in for 75% ethanol water) in, shake 3 hours on shaking table, it is stored at room temperature 5 minutes,
Topple over clear liquid, add weight concentration to be that 75% ethanol water is washed 2 times, each ethanol water 50mL is filtered,
90 DEG C are vacuum dried 10 hours, obtain Cu (I)/Amberlyst-35 catalyst that Cu contents are 5g/L.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 100 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
【Embodiment 9】
1st, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, (hands over hydrogen shape ion exchange resin of the trade mark for CT251
Capacity is changed for 1.9eq/L) 100mL mixing, shake on shaking table after 5h, filter, successively with water, weight concentration as 75%
Alcohol water blend rinse resin, then by resin add oxammonium hydrochloride. solution (20g oxammonium hydrochloride .s are dissolved in
100mL weight concentrations are 75% ethanol water) in, shake 3 hours on shaking table, it is stored at room temperature 5 minutes, topple over
Clear liquid, adds weight concentration to be that 75% ethanol water is washed 2 times, and each ethanol water 50mL is filtered, 90 DEG C
Vacuum drying 10 hours, obtains Cu (I)/CT251 catalyst that Cu contents are 5g/L.
2nd, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction is carried out on fixed-bed reactor, adopt internal diameter for a height of 550mm of 12mm stainless steel reaction
Device, the loadings of catalyst are 10mL, and reaction temperature is 100 DEG C, and the liquid volume air speed of dimethoxym ethane is 60h-1, instead
Answer the gas chromatographic analysiss of product Jing Agilent 6890.
Composition and composite result for ease of comparing catalyst is listed in table 1.
Can be seen that through Cu (I), Cu (II) modified strong-acid ion exchange resin, its selectivity from the data of table 1
Significantly better than resin before modified, and Cu (I) the modified resin resin reaction modified compared with Cu (II) is better.
Table 1
Claims (9)
1. the synthetic method of polyoxymethylene dimethyl ether, including make dimethoxym ethane contact with catalyst generation polycondensation reaction generate dimethyl ether and
Polyoxymethylene dimethyl ether, catalyst active component based on acid cation exchange resin, to be carried on the main work
Property component on Cu ions be modifying agent.
2. synthetic method according to claim 1, is characterized in that reaction temperature is 90～160 DEG C.
3. synthetic method according to claim 1, is characterized in that reaction pressure is calculated as 1～50bar with gauge pressure.
4. synthetic method according to claim 1, is characterized in that dimethoxym ethane liquid volume air speed is 5～300h-1。
5. synthetic method according to claim 1, is characterized in that described acid cation exchange resin for highly acid sun
Ion exchange resin.
6. synthetic method according to claim 1, is characterized in that by weight, Cu ion concentrations in the catalyst
For 0.1～10%.
7. synthetic method according to claim 5, is characterized in that described acid cation exchange resin and gathers for sulfonic acid type
Styrene crosslinked resin.
8. synthetic method according to claim 5, it is characterized in that described acid cation exchange resin for gel-type or
Macropore.
9. the preparation method of catalyst described in any one of claim 1～8, comprises the following steps：
The acid cation exchange resin is set to carry out ion-exchange reactionss with Cu (II) compound and obtain Cu (II) changing
Property acid cation exchange resin.
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Cited By (8)
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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 |
| CN106582836A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for PODE (polyoxymethylene dimethyl ether) |
| CN106582837A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Catalyst for producing polyoxymethylene dimethyl ether |
| CN109651108A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | With the process of methanol and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651100A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of methanol-fueled CLC polyoxymethylene dimethyl ether |
| CN109651096A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of dimethoxym ethane and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651097A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | With the process of methanol and paraformaldehyde production polyoxymethylene dimethyl ether |
| CN109651099A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of methanol and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
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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 |
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| CN109651100A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of methanol-fueled CLC polyoxymethylene dimethyl ether |
| CN109651096A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of dimethoxym ethane and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651097A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | With the process of methanol and paraformaldehyde production polyoxymethylene dimethyl ether |
| CN109651099A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | By the process of methanol and paraformaldehyde synthesizing polyoxymethylene dimethyl ether |
| CN109651099B (en) * | 2017-10-10 | 2022-04-01 | 中国石油化工股份有限公司 | Process method for synthesizing polyformaldehyde dimethyl ether from methanol and paraformaldehyde |
| CN109651097B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Process for producing polyformaldehyde dimethyl ether from methanol and paraformaldehyde |
| CN109651100B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Process for synthesizing polyformaldehyde dimethyl ether from methanol |
| CN109651096B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Process method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde |
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