CN105772062A - Method for catalyzing and producing methylal by means of modified molecular sieve supported catalyst - Google Patents
Method for catalyzing and producing methylal by means of modified molecular sieve supported catalyst Download PDFInfo
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- CN105772062A CN105772062A CN201610212209.3A CN201610212209A CN105772062A CN 105772062 A CN105772062 A CN 105772062A CN 201610212209 A CN201610212209 A CN 201610212209A CN 105772062 A CN105772062 A CN 105772062A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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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
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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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
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Abstract
The invention belongs to the field of methylal oxidative catalysis and synthesis and particularly relates to a method for catalyzing and producing methylal by means of a modified molecular sieve supported catalyst.In the preparation process, raw material methyl alcohol is subjected to oxidative catalysis and synthesis reaction to obtain methylal under the condition that a synthesis catalyst and the molecular sieve supported catalyst exist, wherein the oxidative catalysis and synthesis reaction is conducted for 5-7 h at the temperature of 80-100 DEG C, and contents or volume fractions of the synthesis catalyst and the molecular sieve supported catalyst in an oxidative catalysis reaction system in the oxidative catalysis and synthesis reaction process are 0.5-3% and 3-15% respectively.The prepared product is easy to separate, high in purity and yield and little in three-waste pollution, industrial large-scale production is easy, and the product yield reaches 72% or above.
Description
Technical field
The invention belongs to methylal oxidation and catalyze and synthesize field, specifically a kind of method utilizing modified molecular screen solid-carried catalyst catalytic production dimethoxym ethane.
Background technology
Methanol is as a kind of important basic chemical industry product, it is possible to become gas to prepare by ECDCs containing carbon resource such as coal, natural gas or biomass.The synthetic technology of methanol is increasingly mature, and production cost also in continuous reduction, which results in the serious superfluous of methanol production capacity.Especially with coal-based methanol industrial expansion, oil product and chemicals technical research that methanol oxidation is converted into more high added value propose an urgent demand.
Methanol can be converted into numerous oil products with more high added value and chemicals, for instance methyl formate (MF), dimethoxym ethane (DMM), polyoxymethylene dimethyl ether (PODEn) etc. are chemicals and the oil dopes of the great using value generated after the reactions such as oxidation and dehydration occur methanol in different catalysts.Wherein, MF is described as omnipotent chemical intermediate, is often used to produce Methanamide, dimethylformamide, acetic acid, pharmaceuticals and fumigant.DMM is a kind of colourless, five poisonous creatures: scorpion, viper, centipede, house lizard, toad and eco-friendly chemicals, it is possible to as diesel fuel additives and efficient organic solvent, play a significant role at the energy and environmental area.The character of PODEn and diesel oil are sufficiently close to, there is higher oxygen content and Cetane number, directly can mix breathe out with diesel oil, it is effectively improved the combustion position in Diesel engine, improve the thermal efficiency, reduce pollutant emission, and without Diesel engine structure is carried out any change, utilizing methanol and derivant synthesis PODEn thereof is Development of Novel Coal Chemical Industry and the new way making up petroleum resources shortage increasingly.Being prepared methanol by coal based synthetic gas, the exploitation again through Downstream Products of Methanol industrial chain extends, and converts methanol into the chemical products and oil product with important use, as a non-petroleum path being about to, in recent years, has caused the extensive concern of researcher.
And methanol oxidation is prepared dimethoxym ethane (DMM) and obtained in method, tradition methylal synthesis technique is to realize from methanol through two-step method, and namely first methanol oxidation generates formaldehyde, and then methanol and formaldehyde condensation generate dimethoxym ethane.Although traditional handicraft is comparatively ripe, but two-step method is utilized to prepare the process energy consumption height of dimethoxym ethane, technological process length, cost height.Therefore, methanol oxidation selective oxidation one-step method is prepared dimethoxym ethane and is received the concern of a large amount of personnel, is also the new direction trend prepared of methylal synthesis.
Molecular sieve has the pore passage structure of uniqueness, surface acidity, ion exchange property and good heat stability, and its pore passage structure and surface acidity can with multiple method modulation in a big way, and utilize the condensation course that methanol prepares PODEn to rely primarily on the acid effect of catalyst, plus molecular sieve catalyst separate, renewable, but due to molecular sieve selectivity and molecular sieve self to prepare modifying process relevant, obtain the high selective molecular sieve catalyst of PODEn, it is necessary to molecular sieve catalyst and molecular modification process are made appropriate process.
Summary of the invention
It is an object of the invention in the technique overcoming current catalysis synthesis process to prepare dimethoxym ethane product still ubiquity preparation time length, react insufficient, the problem such as complex procedures, production efficiency are low, produce low conversion rate, catalyst life is short, catalytic selectivity is poor, it is provided that a kind of method utilizing modified molecular screen solid-carried catalyst catalytic production dimethoxym ethane.
The solution of the present invention is by being achieved in that: a kind of method utilizing modified molecular screen solid-carried catalyst catalytic production dimethoxym ethane, it is characterized in that, material benzenemethanol, under synthetic catalyst and Supported on Zeolite catalyst existent condition, carries out oxidation catalysis synthetic reaction and obtains dimethoxym ethane；Described oxidation catalysis synthetic reaction is reaction 5 ~ 7h when temperature 80 ~ 100 DEG C；Content in oxidation catalysis reaction system of synthetic catalyst and Supported on Zeolite catalyst or volume fraction respectively 0.5 ~ 3% and 3 ~ 15% in described oxidation catalysis synthetic reaction process.
As the further restriction of the inventive method, described synthetic catalyst is 4A zeolite Na12Al12Si12O48·27H2Any one or their mixture in O, lamina sodium silicate, polyacrylic acid, sodium metasilicate.
As the further restriction of the inventive method, described Supported on Zeolite method for preparing catalyst comprises the following steps:
null1) prepared by carrier: be dissolved in the deionized water of 150-250mol in the aluminum source of 2-5mol silicon source and 0.01-0.05mol，Strong stirring 10-20min，Both are made fully to dissolve，Add the template of 0.4-0.8mol，Sulfuric acid regulation solution pH=10-15 is used after stirring 20-30min，Add the auxiliary agent that mass fraction is 2-3%，Gained mixed solution is obtained concentrated gel material as evaporation 5-10h in baking oven 100-120 DEG C，Concentrated gel material is sealed，Crystallization 10-24h in 150-180 DEG C of crystallizing kettle，Sample is filtered washing and dry，550-650 DEG C of roasting 5-8h，Obtain ZSM-5 or MCM-22 or the HZSM-5 type molecular sieve carrier with microcellular structure；
2) load of catalyst activity component: catalyst and carrier are that 1:8 ~ 10 are put into stirring in purified water and made it be completely dissolved according to mass ratio, carrier and purified water mass ratio are 1:10, rear dipping 24 hours, dry moisture, 3-5h is activated, thus preparing Supported on Zeolite catalyst at 180-250 DEG C.
As the further restriction of the present invention, described silicon source is any one in silica gel or waterglass；Described aluminum source is any one in aluminum sulfate or sodium metaaluminate.
As the further restriction of the present invention, described template is any one in n-butylamine, ethylenediamine, triethylamine and ethanolamine or their combination in any.
Further restriction as the present invention, it is characterised in that described auxiliary agent is any one in Lanthanum (III) nitrate, cobalt acetate, magnesium acetate.
The present invention possesses following good result: utilize the generation of the synthetic reaction of oxidation catalyst and immobilized dose of modified molecular screen promotion dimethoxym ethane, reduce the energy consumption of production in the presence of a catalyst and shorten the time of reaction, and decrease the formation of the acetal compound etc. of methyl formate and higher molecular weight, realize the reduction of production cost, improve the quality of product, reduce environmental pollution.The feature that modified molecular screen has Stability Analysis of Structures, catalysis activity and selectivity is high that the present invention uses; make catalytic oxidation process gentle; the easily separated purity of product prepared is high, yield is high, three-waste pollution is few, is conducive to industrial scale to produce, and product yield reaches more than 72%.
Detailed description of the invention
Describing the present invention below in conjunction with embodiment and prepare the synthetic method of dimethoxym ethane, these descriptions are not that present invention is further limited.
Embodiment 1
It is 4A zeolite Na that the present embodiment uses synthetic catalyst12Al12Si12O48·27H2O.The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 250mol by the aluminum sulfate of 2mol waterglass and 0.01mol, strong stirring 10min, it is made fully to dissolve, add the n-butylamine of 0.4mol, stirring 20min, use sulfuric acid regulation solution pH=10, it is subsequently adding the Lanthanum (III) nitrate that mass fraction is 2%, gained mixed solution is added baking oven and obtains concentrated gel material at 100 DEG C of evaporation 5h, concentrated gel material is sealed, crystallization 10h in 150 DEG C of crystallizing kettles, is filtered washing and dry, 550 DEG C of roasting 5h to sample.Take 12 phosphotungstic acid 5g to put into stirring in the water of 400g and make it be completely dissolved, be subsequently adding carrier vector 40g, stir 1-2 hour, impregnate 24 hours, then dry moisture, activate 3.5h at 250 DEG C, thus preparing solid-carried catalyst ZSM-5, prepare dimethoxym ethane with this catalyst reaction.
The present embodiment according to material benzenemethanol, carries out oxidation catalysis synthetic reaction and obtains dimethoxym ethane under synthetic catalyst and Supported on Zeolite catalyst existent condition；Described oxidation catalysis synthetic reaction is the reaction 5h when temperature 100 DEG C；Content in oxidation catalysis reaction system of synthetic catalyst and Supported on Zeolite catalyst or volume fraction respectively 0.8% and 10% in oxidation catalysis synthetic reaction process.
The product yield that the present embodiment obtains reaches 72.5%.
Embodiment 2
It is lamina sodium silicate that the present embodiment uses synthetic catalyst.The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 250mol by the sodium metaaluminate of 3mol waterglass and 0.03mol, strong stirring 10min, it is made fully to dissolve, add the ethylenediamine of 0.6mol, stirring 30min, use sulfuric acid regulation solution pH=11, it is subsequently adding the Lanthanum (III) nitrate that mass fraction is 2%, gained mixed solution is added baking oven and obtains concentrated gel material at 100 DEG C of evaporation 5h, concentrated gel material is sealed, crystallization 10h in 150 DEG C of crystallizing kettles, is filtered washing and dry, 600 DEG C of roasting 6h to sample.Take 12 phosphotungstic acid 5g to put into stirring in the water of 500g and make it be completely dissolved, be subsequently adding carrier vector 50g, stir 1 hour, impregnate 24 hours, then dry moisture, activate 4h at 200 DEG C, thus preparing solid-carried catalyst MCM-22, prepare dimethoxym ethane with this catalyst reaction.
The present embodiment according to material benzenemethanol, carries out oxidation catalysis synthetic reaction and obtains dimethoxym ethane under synthetic catalyst and Supported on Zeolite catalyst existent condition；Described oxidation catalysis synthetic reaction is the reaction 6h when temperature 90 DEG C；Content in oxidation catalysis reaction system of synthetic catalyst and Supported on Zeolite catalyst or volume fraction respectively 0.5% and 5% in described oxidation catalysis synthetic reaction process.
The product yield that the present embodiment obtains reaches 73.2%.
Embodiment 3
It is polyacrylic acid that the present embodiment uses synthetic catalyst.The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 250mol by the sodium metaaluminate of 4mol waterglass and 0.05mol, strong stirring 20min, it is made fully to dissolve, add n-butylamine and the ethylenediamine (molal quantity 1:1) of 0.6mol, stirring 30min, use sulfuric acid regulation solution pH=11, it is subsequently adding the Lanthanum (III) nitrate that mass fraction is 2%, gained mixed solution is added baking oven and obtains concentrated gel material at 100 DEG C of evaporation 5h, concentrated gel material is sealed, crystallization 10h in 150 DEG C of crystallizing kettles, sample is filtered washing and dry, 600 DEG C of roasting 6h.Take 12 phosphotungstic acid 5g to put into stirring in the water of 600g and make it be completely dissolved, be subsequently adding carrier vector 60g, stir 1 hour, impregnate 24 hours, then dry moisture, activate 3h at 200 DEG C, thus preparing solid-carried catalyst HZSM-5, prepare dimethoxym ethane with this catalyst reaction.
The present embodiment according to material benzenemethanol, carries out oxidation catalysis synthetic reaction and obtains dimethoxym ethane under synthetic catalyst and Supported on Zeolite catalyst existent condition；Described oxidation catalysis synthetic reaction is the reaction 7h when temperature 80 DEG C；Content in oxidation catalysis reaction system of synthetic catalyst and Supported on Zeolite catalyst or volume fraction respectively 2% and 3% in described oxidation catalysis synthetic reaction process.
The product yield that the present embodiment obtains reaches 74%.
Embodiment 4
It is sodium metasilicate that the present embodiment uses synthetic catalyst.The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 250mol by the aluminum sulfate of 5mol waterglass and 0.05mol, strong stirring 20min, it is made fully to dissolve, add the ethanolamine of 0.8mol, stirring 30min, use sulfuric acid regulation solution pH=11, it is subsequently adding the magnesium acetate that mass fraction is 2%, gained mixed solution is added baking oven and obtains concentrated gel material at 120 DEG C of evaporation 10h, concentrated gel material is sealed, crystallization 24h in 180 DEG C of crystallizing kettles, is filtered washing and dry, 650 DEG C of roasting 8h to sample.Take 12 phosphotungstic acid 5g to put into stirring in the water of 500g and make it be completely dissolved, be subsequently adding carrier vector 50g, stir 2 hours, impregnate 24 hours, then dry moisture, activate 5h at 230 DEG C, thus preparing solid-carried catalyst ZSM-5, prepare dimethoxym ethane with this catalyst reaction.
The present embodiment according to material benzenemethanol, carries out oxidation catalysis synthetic reaction and obtains dimethoxym ethane under synthetic catalyst and Supported on Zeolite catalyst existent condition；Described oxidation catalysis synthetic reaction is the reaction 7h when temperature 80 DEG C；Content in oxidation catalysis reaction system of synthetic catalyst and Supported on Zeolite catalyst or volume fraction respectively 3% and 15% in described oxidation catalysis synthetic reaction process.
The product yield that the present embodiment obtains reaches 76%.
Embodiment 5
It is lamina sodium silicate and the mixture of sodium metasilicate mass ratio 1:1 that the present embodiment uses synthetic catalyst.The preparation process of the Supported on Zeolite catalyst that the present invention uses is: be dissolved in the deionized water of 150mol by the aluminum sulfate of 4.5mol silica gel and 0.04mol, strong stirring 15min, both are made fully to dissolve, add the n-butylamine of 0.6mol, triethylamine and ethanolamine (molal quantity 1:1:1), sulfuric acid regulation solution pH=10 is used after stirring 20min, add the cobalt acetate that mass fraction is 3%, gained mixed solution is obtained concentrated gel material as evaporation 10h in baking oven 110 DEG C, concentrated gel material is sealed, crystallization 18h in 180 DEG C of crystallizing kettles, sample is filtered washing and dry, 550 DEG C of roasting 8h, obtain the MCM-22 type molecular sieve carrier with microcellular structure；
Taking catalyst and carrier according to mass ratio is that 1:8 ~ 10 are put into stirring in purified water and made it be completely dissolved, carrier and purified water mass ratio are 1:10, rear dipping 24 hours, dry moisture, 5h is activated, thus preparing reactive distillation coupled method to produce the solid-carried catalyst of butyl acetate at 180 DEG C.Dimethoxym ethane is prepared with this catalyst reaction.
The present embodiment according to material benzenemethanol, carries out oxidation catalysis synthetic reaction and obtains dimethoxym ethane under synthetic catalyst and Supported on Zeolite catalyst existent condition；Described oxidation catalysis synthetic reaction is the reaction 6h when temperature 85 DEG C；Content in oxidation catalysis reaction system of synthetic catalyst and Supported on Zeolite catalyst or volume fraction respectively 2.5% and 12% in described oxidation catalysis synthetic reaction process.
The product yield that the present embodiment obtains reaches 72.5%.
The above embodiment of the present invention scheme is only the description of the invention and can not limit the present invention, claim indicates the scope of product constituent of the present invention, component ratio, preparation method parameter, and the scope of parameter of the present invention is not pointed out in above-mentioned explanation, therefore, any change in the implication suitable with claims of the present invention and scope, all will be understood that in the scope being included in claims.
The present invention reacts research staff's long-term work experience accumulation through multidigit methylal synthesis; and created by creative work; the feature that modified molecular screen has Stability Analysis of Structures, catalysis activity and selectivity is high that the present invention uses; make hydrolysis reaction gentle; the easily separated purity of product prepared is high, yield is high, three-waste pollution is few, is conducive to industrial scale to produce.Product yield reaches more than 72%.
Claims (6)
1. the method utilizing modified molecular screen solid-carried catalyst catalytic production dimethoxym ethane, it is characterised in that material benzenemethanol, under synthetic catalyst and Supported on Zeolite catalyst existent condition, carries out oxidation catalysis synthetic reaction and obtains dimethoxym ethane；
Described oxidation catalysis synthetic reaction is reaction 5 ~ 7h when temperature 80 ~ 100 DEG C；
Content in oxidation catalysis reaction system of synthetic catalyst and Supported on Zeolite catalyst or volume fraction respectively 0.5 ~ 3% and 3 ~ 15% in described oxidation catalysis synthetic reaction process.
2. the method utilizing modified molecular screen solid-carried catalyst catalytic production dimethoxym ethane according to claim 1, it is characterised in that described synthetic catalyst is 4A zeolite Na12Al12Si12O48·27H2Any one or their mixture in O, lamina sodium silicate, polyacrylic acid, sodium metasilicate.
3. the method utilizing modified molecular screen solid-carried catalyst catalytic production dimethoxym ethane according to claim 1, it is characterised in that described Supported on Zeolite method for preparing catalyst comprises the following steps:
null1) prepared by carrier: be dissolved in the deionized water of 150-250mol in the aluminum source of 2-5mol silicon source and 0.01-0.05mol，Strong stirring 10-20min，Both are made fully to dissolve，Add the template of 0.4-0.8mol，Sulfuric acid regulation solution pH=10-15 is used after stirring 20-30min，Add the auxiliary agent that mass fraction is 2-3%，Gained mixed solution is obtained concentrated gel material as evaporation 5-10h in baking oven 100-120 DEG C，Concentrated gel material is sealed，Crystallization 10-24h in 150-180 DEG C of crystallizing kettle，Sample is filtered washing and dry，550-650 DEG C of roasting 5-8h，Obtain ZSM-5 or MCM-22 or the HZSM-5 type molecular sieve carrier with microcellular structure；
2) load of catalyst activity component: catalyst and carrier are that 1:8 ~ 10 are put into stirring in purified water and made it be completely dissolved according to mass ratio, carrier and purified water mass ratio are 1:10, rear dipping 24 hours, dry moisture, 3-5h is activated, thus preparing Supported on Zeolite catalyst at 180-250 DEG C.
4. the method utilizing modified molecular screen solid-carried catalyst catalytic production dimethoxym ethane according to claim 3, it is characterised in that described silicon source is any one in silica gel or waterglass；Described aluminum source is any one in aluminum sulfate or sodium metaaluminate.
5. the method utilizing modified molecular screen solid-carried catalyst catalytic production dimethoxym ethane according to claim 3, it is characterised in that described template is any one in n-butylamine, ethylenediamine, triethylamine and ethanolamine or their combination in any.
6. the method utilizing modified molecular screen solid-carried catalyst catalytic production dimethoxym ethane according to claim 3, it is characterised in that described auxiliary agent is any one in Lanthanum (III) nitrate, cobalt acetate, magnesium acetate.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107233885A (en) * | 2017-05-28 | 2017-10-10 | 湖北绿色家园材料技术股份有限公司 | A kind of preparation method for air oxidation catalyst |
| CN109134210A (en) * | 2017-06-19 | 2019-01-04 | 镇江瑞德新材料科技研发有限公司 | A method of polyoxymethylene dimethyl ether is produced using molecular catalyst |
| CN112742411A (en) * | 2020-12-29 | 2021-05-04 | 安徽省福泰精细化工有限责任公司 | Preparation method of catalyst for methylal synthesis |
| CN113184873A (en) * | 2021-04-23 | 2021-07-30 | 内蒙古超牌新材料股份有限公司 | Preparation method of molecular sieve, low-nitrogen-adsorption hollow glass drying agent and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224431A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof |
| WO2012024896A1 (en) * | 2010-08-23 | 2012-03-01 | 中国石油化工股份有限公司 | Non-adhesive molecular sieve catalyst and preparation method therefor |
| CN103121927A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of polymethoxymethylal |
| CN103121926A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of polymethoxy acetal |
| CN103772161A (en) * | 2012-10-17 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ethers |
-
2016
- 2016-04-07 CN CN201610212209.3A patent/CN105772062A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224431A (en) * | 2008-01-30 | 2008-07-23 | 中国科学院山西煤炭化学研究所 | Catalyst for methanol oxidation to methylal by one step, preparing method and applications thereof |
| WO2012024896A1 (en) * | 2010-08-23 | 2012-03-01 | 中国石油化工股份有限公司 | Non-adhesive molecular sieve catalyst and preparation method therefor |
| CN103121927A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of polymethoxymethylal |
| CN103121926A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Preparation method of polymethoxy acetal |
| CN103772161A (en) * | 2012-10-17 | 2014-05-07 | 中国石油化工股份有限公司 | Method for preparing polyoxymethylene dimethyl ethers |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107233885A (en) * | 2017-05-28 | 2017-10-10 | 湖北绿色家园材料技术股份有限公司 | A kind of preparation method for air oxidation catalyst |
| CN107233885B (en) * | 2017-05-28 | 2021-02-09 | 湖北绿色家园材料技术股份有限公司 | Preparation method of catalyst for air oxidation |
| CN109134210A (en) * | 2017-06-19 | 2019-01-04 | 镇江瑞德新材料科技研发有限公司 | A method of polyoxymethylene dimethyl ether is produced using molecular catalyst |
| CN112742411A (en) * | 2020-12-29 | 2021-05-04 | 安徽省福泰精细化工有限责任公司 | Preparation method of catalyst for methylal synthesis |
| CN113184873A (en) * | 2021-04-23 | 2021-07-30 | 内蒙古超牌新材料股份有限公司 | Preparation method of molecular sieve, low-nitrogen-adsorption hollow glass drying agent and preparation method thereof |
| CN113184873B (en) * | 2021-04-23 | 2022-12-02 | 内蒙古超牌新材料股份有限公司 | Preparation method of molecular sieve, low-nitrogen-adsorption hollow glass drying agent and preparation method thereof |
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Application publication date: 20160720 |