CN106582837A - Catalyst for producing polyoxymethylene dimethyl ether - Google Patents
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Abstract
The invention relates to a catalyst for producing polyoxymethylene dimethyl ether. The catalyst is mainly used for solving the problem of processes for synthesizing the polyoxymethylene dimethyl ether from methanol, methylal and paraformaldehyde in the prior art that catalysts are low in activity and low in selectivity. Through adopting the technical scheme that the catalyst for producing the polyoxymethylene dimethyl ether is metal ion modified sulfonic acid type polystyrene cation exchange resin, the sulfonic acid type polystyrene cation exchange resin comprises a crosslinked polystyrene skeleton and a sulfonic acid group, and metal comprises at least one of IB-family metal elements, the catalyst can be applied to the industrial production of the polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to the catalyst of polyoxymethylene dimethyl ethers production.
Background technology
In recent years, with the industrial revolution affect increasingly deeply and China's distinctive " many coals, few oil, there is gas " resource general layout, 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 researcher 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, and yet with its own cold starting performance is poor, vapour pressure is high, easily produce vapour lock under room temperature causes dimethyl ether significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether, i.e. Polyoxymethylene dimethyl ethers (PODE), are the common names of a class material, and its skeleton symbol can be expressed as CH3O(CH2O)nCH3, with higher octane number (>30) with oxygen content (42～51%).When the value of n is 2～10, its physical property, combustibility and diesel oil closely, preferably resolve the defect that dimethyl ether exists as derv fuel blend component.Therefore polyoxymethylene dimethyl ether can be used as new cleaning diesel component, and the addition in diesel oil can improve diesel oil combustion position within the engine up to 30% (v/v), improve the thermal efficiency, reduces particulate matter and CO in tail gasxAnd NOxDischarge.It is reported that, add 5～30% CH3OCH2OCH3NO can be reducedx7～10%, PM of discharge reduces by 5～35%.Synthesizing PODE by coal-based methanol not only can replace part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, harm of the diesel combustion to environment be reduced, with important strategic importance and good economic worth.
CN 101048357A (method for preparing polyoxymethylene dimethyl ether) are described using mineral acid, sulfonic acid, heteropoly acid, acid-exchange resin, zeolite, aluminium oxide etc. as catalyst, by dimethoxym ethane and metaformaldehyde for reactant synthesizing polyoxymethylene dimethyl ether method.But all await improving using the conversion ratio and selectivity of existing catalyst.
Cation exchange resin shows good catalytic perfomance as solid acid catalyst in the esterification, etherification reaction in Aquo System, but its acid strength is relatively low.Generally using support type resin is prepared, by increasing acidity of catalyst activity is improved.Metal-modified resin can be adopted, new acid site is formed on a catalyst, can't by other metal ion exchanged, which solves in the case of in polyoxymethylene dimethyl ether synthesis, catalyst keeps highly active in commercial Application and its acidity will not by raw material in the contained metal ion problem that replaces and inactivate.
The content of the invention
One of the technical problem to be solved be prior art with methanol, dimethoxym ethane and paraformaldehyde as reaction raw materials synthesizing polyoxymethylene dimethyl ether technique in there is a problem of that n=2-10 selectivity of product is low, there is provided a kind of catalyst of new polyoxymethylene dimethyl ethers production.The catalyst has the advantages that the selectivity of product of n=2-10 is high.
The two of the technical problem to be solved are to provide a kind of synthetic method of one of the employing above-mentioned technical problem polyoxymethylene dimethyl ether of the catalyst.
In order to solve one of above-mentioned technical problem, technical scheme is as follows：
The catalyst of polyoxymethylene dimethyl ethers production, the catalyst is metal ion-modified sulfonic acid polystyrene cation exchange resin, and the sulfonic acid polystyrene cation exchange resin includes crosslinked polystyrene skeleton and sulfonic acid group；The metal includes at least one in IB races element.
In above-mentioned technical proposal, preferably, at least one in IB races element preferred Cu or Ag, most has choosing to include Cu and Ag simultaneously, two kinds of metals have synergism in terms of the selectivity to the PODE of n=2～10 is improved.
In above-mentioned technical proposal, the content of metal described in catalyst is preferably greater than 0 and less than or equal to 10w%.
In above-mentioned technical proposal, the CEC of the resin is preferably 3.0～5.0mmol/g.The exchange capacity is in terms of butt resin.
In above-mentioned technical proposal, the resin can be gel-type or macroporous type.
In order to solve the two of above-mentioned technical problem, technical scheme is as follows：
The synthetic method of polyoxymethylene dimethyl ethers, with methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0～10): (0～10): 1, methanol can not be simultaneously 0 with the consumption of dimethoxym ethane, raw material is contacted with catalyst described above, and reaction generates polyoxymethylene dimethyl ether.
In above-mentioned technical proposal, catalyst amount is preferably the 0.05～10% of raw material weight；More preferably the 0.1～5% of raw material weight.
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 response time is preferably 1 to 20 hour, more 4 to 12 hours.
In above-mentioned technical proposal, methanol is preferably (0.4～5) with the consumption sum of dimethoxym ethane with the mass ratio of paraformaldehyde in raw material: 1；Methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0.2～10): (0.5～10): 1.
In the case where the composition of catalyst of the present invention is clear, the preparation of catalyst is not particularly limited, and may be referred to ion-exchange process commonly used in the prior art and is prepared.For example may include following steps：Sulfonic acid sodium form polystyrol cation exchange resin deionized water is washed till after outflow clear water, 1～12h is soaked with 0.5～20% strong acid (such as hydrochloric acid or sulphuric acid), deionized water or alcohol solution dipping soak 1～12h, it is washed with deionized afterwards to pH=6, that is, obtains sulfonic acid polystyrene cation exchange resin of the present invention.When sulfonic acid polystyrene cation exchange resin of the present invention, rather than sulfonic acid sodium form can also be directly obtained from commercially available channel, may be used to the preparation of catalyst of the present invention.With at least one precursor compound in Cu and Ag, deionized water or ethanol solution are configured to the solution of variable concentrations, and with ion exchange resin of the present invention ion-exchange treatment is carried out, and are finally washed with deionized, it is dried, that is, catalyst of the present invention is obtained.
Using the catalyst of the present invention, the PODE yields of n=2～10 are good, and n=2～10 selectivity of product is up to 86.3%, achieves preferable technique effect.
Heretofore described CEC is in terms of butt resin.
Below by embodiment, the present invention is further elaborated, and the degree of polymerization of the raw material paraformaldehyde adopted in embodiment and comparative example is 5, and selectivity of product is calculated with the polyoxymethylene dimethyl ether that the degree of polymerization is 2～10 on the basis of paraformaldehyde as target product.
Specific embodiment
【Embodiment 1】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the Cu (NO that Cu is 2 grams3)2Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 2】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the AgNO that Ag is 2 grams3Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Ag contents for 2w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 3】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.Take and be 1 gram containing Ag with 300ml equivalent to the sulfonic acid polystyrene cation exchange resin of 98 grams of butt resin and mix containing the copper nitrate silver nitrate mixed aqueous solution that Cu is 1 gram, 24 hours are stood under room temperature, finally it is washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, the catalyst that Ag contents are that 1w%, Cu content is 1w% is obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 4】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 95 grams of butt resin is taken with 300ml containing the Cu (NO that Cu is 5 grams3)2Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 5w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 5】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the Cu (NO that Cu is 2 grams3)2Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 110 DEG C and 0.8MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 6】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the Cu (NO that Cu is 2 grams3)2Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 150 DEG C and 0.5MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 7】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 95 grams of butt resin is taken with 300ml containing the AgNO that Ag is 5 grams3Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Ag contents for 5w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.6MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 8】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the AgNO that Ag is 2 grams3Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Ag contents for 2w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 110 DEG C and 0.5MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 9】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the Cu (NO that Cu is 2 grams3)2Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
0.5 gram of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 10】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the Cu (NO that Cu is 2 grams3)2Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Cu contents for 2w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
5 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 130 DEG C and 0.5MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Embodiment 11】
1st, the preparation of catalyst
The deionized water of sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed till after outflow clear water, with the soak with hydrochloric acid 4h of 4w%, it is washed with deionized afterwards to pH=6, after 60 DEG C of dryings, sulfonic acid polystyrene cation exchange resin is obtained, its CEC is 4.10mmol/g.The sulfonic acid polystyrene cation exchange resin equivalent to 98 grams of butt resin is taken with 300ml containing the AgNO that Ag is 2 grams3Aqueous solution, under room temperature 24 hours are stood, and are finally washed with deionized to pH=6, in vacuum drying oven drying to constant weight, that is, catalyst of the Ag contents for 2w% are obtained.
2nd, the synthesis of polyoxymethylene dimethyl ether
2 grams of catalyst, 100 grams of methanol and 100 grams of paraformaldehydes are added in 300 milliliters of tank reactors, 4h is reacted under 110 DEG C and 2MPa self-generated pressures, extracted after sample centrifugation by gas chromatographic analysiss.Comprising polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde in product, its composition distribution such as table 1.
【Comparative example 1】
For embodiment 1 in proportion, the catalyst for adopting is differed only in be dried 2 grams of sulfonic acid polystyrene cation exchange resin described in embodiment 1, other process conditions are same as Example 1, the results are shown in Table 1.
Table 1
N is the degree of polymerization, and product is CH3O(CH2O)nCH3。
Claims (9)
1. the catalyst of polyoxymethylene dimethyl ethers production, the catalyst is metal ion-modified sulfonic acid polystyrene
Cation exchange resin, the sulfonic acid polystyrene cation exchange resin includes crosslinked polystyrene skeleton and sulfonic group
Group；The metal includes at least one in IB races element.
2. catalyst according to claim 1, the content that it is characterized in that modified metal in catalyst is more than 0 and little
In equal to 10w%.
3. catalyst according to claim 1, the CEC that it is characterized in that the resin is 3.0～5.0mmol/
g。
4. catalyst according to claim 1, is characterized in that the resin for gel-type or macroporous type.
5. the synthetic method of polyoxymethylene dimethyl ethers, with methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: first
Acetal: the mass ratio of paraformaldehyde is (0～10): (0～10): 1, methanol can not be simultaneously 0 with the consumption of dimethoxym ethane,
Raw material is contacted with catalyst described in claim 1, and reaction generates polyoxymethylene dimethyl ether.
6. synthetic method according to claim 5, it is characterised in that catalyst amount is the 0.05～10% of raw material weight.
7. synthetic method according to claim 5, it is characterised in that reaction temperature is 70～200 DEG C.
8. synthetic method according to claim 5, it is characterised in that reaction pressure is 0.2～6MPa.
9. synthetic method according to claim 5, it is characterised in that the response time is 1 to 20 hour.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107320382A (en) * | 2017-07-31 | 2017-11-07 | 上海中翊日化有限公司 | A kind of composition containing dried tremella extract and the application in personal care articles |
| CN109651098A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The production method of 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 |
| CN109647516A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The catalyst of polyoxymethylene dimethyl ether preparation |
| 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 |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3888799B2 (en) * | 1999-05-14 | 2007-03-07 | 三井化学株式会社 | Method for producing bisphenol A |
| CN103420816A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether preparation method |
| CN103638973A (en) * | 2013-12-16 | 2014-03-19 | 中国科学院广州能源研究所 | Preparation method of sulfoacid-type cation exchange resin catalyst |
| CN103739458A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Preparation method of polyoxymethylene dimethyl ethers |
| CN104549502A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for synthesis of polyoxymethylene dimethyl ether and application of catalyst |
| CN104549443A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether catalyst and application thereof |
| CN106588595A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Synthetic method of polyoxymethylene dimethyl ethers |
-
2015
- 2015-10-16 CN CN201510673500.6A patent/CN106582837A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3888799B2 (en) * | 1999-05-14 | 2007-03-07 | 三井化学株式会社 | Method for producing bisphenol A |
| CN103420816A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether preparation method |
| CN103739458A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Preparation method of polyoxymethylene dimethyl ethers |
| CN104549502A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Catalyst for synthesis of polyoxymethylene dimethyl ether and application of catalyst |
| CN104549443A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether catalyst and application thereof |
| CN103638973A (en) * | 2013-12-16 | 2014-03-19 | 中国科学院广州能源研究所 | Preparation method of sulfoacid-type cation exchange resin catalyst |
| CN106588595A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Synthetic method of polyoxymethylene dimethyl ethers |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107320382A (en) * | 2017-07-31 | 2017-11-07 | 上海中翊日化有限公司 | A kind of composition containing dried tremella extract and the application in personal care articles |
| CN109651098A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The production method of 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 |
| CN109647516A (en) * | 2017-10-10 | 2019-04-19 | 中国石油化工股份有限公司 | The catalyst of polyoxymethylene dimethyl ether preparation |
| 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 |
| 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 |
| 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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