CN106588595B - The synthetic method of polyoxymethylene dimethyl ether - Google Patents
The synthetic method of polyoxymethylene dimethyl ether Download PDFInfo
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- CN106588595B CN106588595B CN201510661213.3A CN201510661213A CN106588595B CN 106588595 B CN106588595 B CN 106588595B CN 201510661213 A CN201510661213 A CN 201510661213A CN 106588595 B CN106588595 B CN 106588595B
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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 present invention relates to the synthetic methods of polyoxymethylene dimethyl ether, mainly solve the problems, such as that heterogeneous catalysis catalysis polyoxymethylene dimethyl ether is selectively low in the prior art, by using polyoxymethylene dimethyl ether catalyst, with acid cation exchange resin for main active component, using the Cu ion being carried in the main active component as the technical solution of modifying agent, it preferably solves the technical problem, can be used in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to the synthetic 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.In addition to this, CH3O(CH2O)2CH3To the solvability of hydro carbons
It is very strong, it can use separately as no aromatic solvent or be used in mixed way with existing solvent naphtha, performance is molten better than existing aromatic hydrocarbons
Agent oil.
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 the prior art is selectively low to the polyoxymethylene dimethyl ether of polymerization degree n=2.
Summary of the invention
The first technical problem to be solved by the present invention is that the prior art selects the polyoxymethylene dimethyl ether of polymerization degree n=2
Property low problem, provide a kind of synthetic method of new polyoxymethylene dimethyl ether, this method has the polyformaldehyde to polymerization degree n=2
The high advantage of dimethyl ether selectivity.
The second technical problem to be solved by the present invention is the preparation method of used catalyst in one of above-mentioned technical problem.
The third technical problem to be solved by the present invention is another system of used catalyst in one of above-mentioned technical problem
Preparation Method.
One of to solve above-mentioned technical problem, technical scheme is as follows: the synthetic method of polyoxymethylene dimethyl ether, packet
Including, which contacts dimethoxym ethane with catalyst, occurs polycondensation reaction generation dimethyl ether and polyoxymethylene dimethyl ether, and the catalyst is with acid sun
Ion exchange resin is main active component, using the Cu ion being carried in the main active component as modifying agent.The Cu ion
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, the acid cation exchange resin is preferably storng-acid cation exchange resin.
In above-mentioned technical proposal, by weight, Cu ion concentration is preferably 0.1~10% in the catalyst.
In above-mentioned technical proposal, the acid cation exchange resin is preferably sulfonic acid polystyrene crosslinked resin.
In above-mentioned technical proposal, the acid cation exchange resin is preferably gel-type or macropore.
To solve above-mentioned technical problem two, technical scheme is as follows: any one of one of above-mentioned technical problem
The preparation method of the catalyst, comprising the following steps:
(1) make the acid cation exchange resin obtain Cu (II) with Cu (II) compound progress ion-exchange reactions to change
Property acid cation exchange resin.The modified acid cation exchange resin of Cu (II) can be used as polyoxymethylene dimethyl ether of the present invention
The catalyst of synthetic method uses.
In above-mentioned technical proposal, it is also preferable to include following steps:
(2) Cu (II) in the Cu (II) modified acid cation exchange resin is reduced to by Cu (I) using reducing agent
Modified acid cation exchange resin.The modified acid cation exchange resin of Cu (I) is significantly better than Cu to the selectivity of PODE2
(II) modified acid cation exchange resin.
In above-mentioned technical proposal, the reducing agent preferably is selected from hydrogen, azanol and its salt (the preferred hydrochloride of salt), first
Azanol and its salt (the preferred hydrochloride of salt), sulfurous acid, sulfurous acid acid salt (the salt preferred as alkali salt, such as sylvite
At least one of or sodium salt) and sulfurous acid normal salt (the salt preferred as alkali salt, such as sylvite or sodium salt).Most preferably azanol
And its salt.
To solve above-mentioned technical problem three, technical scheme is as follows: the technical side of one of above-mentioned technical problem
Another preparation method of catalyst described in any one of case, including make the acid cation exchange resin and Cu (I) chemical combination
Object carries out ion-exchange reactions and obtains the catalyst.
In above-mentioned technical proposal, Cu (I) compound be such as, but not limited to cuprous oxide, stannous chloride, cuprous bromide,
Cuprous iodide or oxalic acid are cuprous.
The chemical equation of polyoxymethylene dimethyl ether synthetic reaction of the present invention are as follows:
CH3OCH2OCH3(dimethoxym ethane) --- --- → CH3OCH3(dimethyl ether)+CH3O(CH2O)nCH3
The calculation method of polyoxymethylene dimethyl ether selectivity is as follows in the present invention:
CH3O(CH2O)nCH3Selectivity=n × (CH3O(CH2O)nCH3Mole production quantity)/dimethoxym ethane molar consumption
As n=2
CH3O(CH2O)2CH3Selectivity=2 × (CH3O(CH2O)2CH3Mole production quantity)/dimethoxym ethane molar consumption
Using technical solution of the present invention, the selectivity of the polyoxymethylene dimethyl ether of n=2 is up to 73%, can be used for polyformaldehyde
In the industrial production of dimethyl ether.
Further instruction is given to the present invention below by example.
Specific embodiment
[embodiment 1]
1, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, the hydrogen shape amberlite for being Amberlyst-15 with the trade mark
Rouge (exchange capacity 1.7eq/L) 100mL is mixed, and after shaking 5h on shaking table, filtering is successively 75% with water, weight concentration
Alcohol water blend rinses resin, and 20g hydroxylamine hydrochloride (is then dissolved in 100mL weight by the solution that hydroxylamine hydrochloride is added in resin
Concentration is 75% ethanol water) in, it shakes 3 hours, is stored at room temperature 5 minutes on shaking table, topple over clear liquid, weight concentration, which is added, is
75% ethanol water washs 2 times, each ethanol water 50mL, filtering, and 90 DEG C are dried in vacuo 10 hours, and obtaining Cu content is
Cu (I)/Amberlyst-15 catalyst of 5g/L.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
[comparative example 1]
1, the acquisition of catalyst
Using the hydrogen shape ion exchange resin of Amberlyst-15 as catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
[embodiment 2]
1, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, the hydrogen shape amberlite for being Amberlyst-15 with the trade mark
On rouge 100mL mixing shaking table shake 5h after, filtering, successively with water, weight concentration be 75% alcohol water blend rinse resin, 90
DEG C vacuum drying 10 hours, obtain Cu content be 5g/L Cu (II)/Amberlyst-15 catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
[embodiment 3]
1, the acquisition of catalyst
With the CuOAc100mL n-hexane suspension containing 0.5gCu, the ion exchange resin for being Amberlyst-15 with the trade mark
100mL is mixed, and under nitrogen protection after shaking 72h on shaking table, filtering rinses resin with n-hexane, and room temperature nitrogen drying dry 24 is small
When, obtain Cu (I)/Amberlyst-15 resin catalyst that Cu content is 5g/L.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
[embodiment 4]
1, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, the hydrogen shape amberlite for being Amberlyst-15 with the trade mark
Rouge 100mL is mixed, and after shaking 5h on shaking table, filtering successively rinses resin with water, the alcohol water blend that weight concentration is 75%,
Then 20g hydroxylamine hydrochloride (it is water-soluble for 75% ethyl alcohol to be dissolved in 100mL weight concentration by the solution that hydroxylamine hydrochloride is added in resin
Liquid) in, it shakes 3 hours, is stored at room temperature 5 minutes on shaking table, topple over clear liquid, weight concentration is added as the washing of 75% ethanol water
2 times, each ethanol water 50mL, filtering, 90 DEG C be dried in vacuo 10 hours, obtain Cu content be 5g/L Cu (I)/
Amberlyst-15 catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
[embodiment 5]
1, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, the hydrogen shape amberlite for being Amberlyst-15 with the trade mark
Rouge 100mL is mixed, and after shaking 5h on shaking table, filtering successively rinses resin with water, the alcohol water blend that weight concentration is 75%,
Then 20g hydroxylamine hydrochloride (it is water-soluble for 75% ethyl alcohol to be dissolved in 100mL weight concentration by the solution that hydroxylamine hydrochloride is added in resin
Liquid) in, it shakes 3 hours, is stored at room temperature 5 minutes on shaking table, topple over clear liquid, weight concentration is added as the washing of 75% ethanol water
2 times, each ethanol water 50mL, filtering, 90 DEG C be dried in vacuo 10 hours, obtain Cu content be 5g/L Cu (I)/
Amberlyst-15 catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
[embodiment 6]
1, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, the hydrogen shape amberlite for being Amberlyst-39 with the trade mark
Rouge (exchange capacity 1.15eq/L) 100mL is mixed, after shaking 5h on shaking table, filtering, successively with water, the wine that weight concentration is 75%
Smart aqueous solution rinses resin, and 20g hydroxylamine hydrochloride (it is dense to be then dissolved in 100mL weight by the solution that hydroxylamine hydrochloride is added in resin
Degree is 75% ethanol water) in, it shakes 3 hours, is stored at room temperature 5 minutes on shaking table, topple over clear liquid, weight concentration, which is added, is
75% ethanol water washs 2 times, each ethanol water 50mL, filtering, and 90 DEG C are dried in vacuo 10 hours, and obtaining Cu content is
Cu (I)/Amberlyst-15 catalyst of 5g/L.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
[embodiment 7]
1, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, the hydrogen shape amberlite for being Amberlyst-36 with the trade mark
Rouge (exchange capacity 1.95eq/L) 100mL is mixed, after shaking 5h on shaking table, filtering, successively with water, the wine that weight concentration is 75%
Smart aqueous solution rinses resin, and 20g hydroxylamine hydrochloride (it is dense to be then dissolved in 100mL weight by the solution that hydroxylamine hydrochloride is added in resin
Degree is 75% ethanol water) in, it shakes 3 hours, is stored at room temperature 5 minutes on shaking table, topple over clear liquid, weight concentration, which is added, is
75% ethanol water washs 2 times, each ethanol water 50mL, filtering, and 90 DEG C are dried in vacuo 10 hours, and obtaining Cu content is
Cu (I)/Amberlyst-36 catalyst of 5g/L.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
[embodiment 8]
1, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL, the hydrogen shape amberlite for being Amberlyst-35 with the trade mark
Rouge (exchange capacity 1.9eq/L) 100mL is mixed, after shaking 5h on shaking table, filtering, successively with water, the wine that weight concentration is 75%
Smart aqueous solution rinses resin, and 20g hydroxylamine hydrochloride (it is dense to be then dissolved in 100mL weight by the solution that hydroxylamine hydrochloride is added in resin
Degree is 75% ethanol water) in, it shakes 3 hours, is stored at room temperature 5 minutes on shaking table, topple over clear liquid, weight concentration, which is added, is
75% ethanol water washs 2 times, each ethanol water 50mL, filtering, and 90 DEG C are dried in vacuo 10 hours, and obtaining Cu content is
Cu (I)/Amberlyst-35 catalyst of 5g/L.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
[embodiment 9]
1, the acquisition of catalyst
With the Cu (OAc) containing 0.5gCu2Aqueous solution 100mL (is exchanged with the hydrogen shape ion exchange resin that the trade mark is CT251
Capacity is 1.9eq/L) 100mL mixing, after shaking 5h on shaking table, filtering is successively water-soluble with water, alcohol that weight concentration is 75%
Liquid rinses resin, and then by the solution of resin addition hydroxylamine hydrochloride, (20g hydroxylamine hydrochloride, which is dissolved in 100mL weight concentration, is
75% ethanol water) in, it shakes 3 hours, is stored at room temperature 5 minutes on shaking table, topple over clear liquid, addition weight concentration is 75% second
Alcohol solution washs 2 times, each ethanol water 50mL, filtering, and 90 DEG C are dried in vacuo 10 hours, and obtaining Cu content is 5g/L's
Cu (I)/CT251 catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Synthetic reaction carries out on fixed-bed reactor, uses internal diameter for the stainless steel reactor of a height of 550mm of 12mm,
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, reaction product is through pacifying
Prompt 6890 gas chromatographic analysis of human relations.
For the composition of catalyst and composite result are listed in table 1 convenient for comparing.
It can be seen that the strong-acid ion exchange resin modified by Cu (I), Cu (II), selectivity from the data of table 1
Significantly better than resin before modified, and Cu (I) modified resin is compared with the resin reaction better effect that Cu (II) is modified.
Table 1
Claims (9)
1. the synthetic method of polyoxymethylene dimethyl ether, including make dimethoxym ethane contacted with catalyst occur polycondensation reaction generate dimethyl ether and
Polyoxymethylene dimethyl ether, the catalyst with acid cation exchange resin be main active component, to be carried on the main active group
Cu ion on point is modifying agent.
2. synthetic method according to claim 1, it is characterized in that reaction temperature is 90~160 DEG C.
3. synthetic method according to claim 1, it is characterized in that reaction pressure is calculated as 1~50bar with gauge pressure.
4. synthetic method according to claim 1, it is characterized in that dimethoxym ethane liquid volume air speed is 5~300h-1。
5. synthetic method according to claim 1, it is characterized in that the acid cation exchange resin is highly acid sun
Ion exchange resin.
6. synthetic method according to claim 1, it is characterized in that by weight, Cu ion concentration is in the catalyst
0.1~10%.
7. synthetic method according to claim 5, it is characterized in that the acid cation exchange resin is poly- for sulfonic acid type
Styrene crosslinked resin.
8. synthetic method according to claim 5, it is characterized in that the acid cation exchange resin be gel-type or
Macropore.
9. the preparation method of catalyst described in any one of claim 1~8, comprising the following steps:
It is mixed, is filtered with acid cation exchange resin with Cu (II) compound water solution, successively rinsed with water, alcohol water blend
Then resin resin is added in the ethanol solution of hydroxylamine hydrochloride, stand, and topples over clear liquid, and ethanol water washing, mistake is added
Filter, it is dry, obtain Cu (I) modified acid cation exchange resin catalyst.
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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 |
| 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 |
| 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) |
| 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 |
| 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 |
| 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 |
| CN109651108B (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 by using methanol and paraformaldehyde |
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| CN1044417A (en) * | 1989-01-28 | 1990-08-08 | 天津大学 | Be used for the resin-carried copper catalyst and the preparation thereof of itrile group hydration |
| CN103524779A (en) * | 2012-10-08 | 2014-01-22 | 中国科学院化学研究所 | Cuprous oxide/ion exchange resin composite and preparation method thereof |
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| US2449469A (en) * | 1944-11-02 | 1948-09-14 | Du Pont | Preparation of polyformals |
| CN104549443B (en) * | 2013-10-28 | 2017-04-19 | 中国石油化工股份有限公司 | polyformaldehyde dimethyl ether catalyst and application thereof |
| CN104549502B (en) * | 2013-10-28 | 2018-01-09 | 中国石油化工股份有限公司 | Catalyst and its application for polyoxymethylene dimethyl ether synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044417A (en) * | 1989-01-28 | 1990-08-08 | 天津大学 | Be used for the resin-carried copper catalyst and the preparation thereof of itrile group hydration |
| CN103524779A (en) * | 2012-10-08 | 2014-01-22 | 中国科学院化学研究所 | Cuprous oxide/ion exchange resin composite and preparation method thereof |
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