CN109651106B - Method for preparing polyformaldehyde dimethyl ether - Google Patents
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- CN109651106B CN109651106B CN201710935012.7A CN201710935012A CN109651106B CN 109651106 B CN109651106 B CN 109651106B CN 201710935012 A CN201710935012 A CN 201710935012A CN 109651106 B CN109651106 B CN 109651106B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
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Abstract
The invention relates to a method for preparing polyformaldehyde dimethyl ether, which mainly solves the problems of low catalyst activity and low selectivity in the process of synthesizing the polyformaldehyde dimethyl ether by taking methanol, methylal and paraformaldehyde as reaction raw materials in the prior art.
Description
Technical Field
The invention relates to a method for preparing polyoxymethylene dimethyl ethers.
Background
In recent years, with the influence of industrial revolution, the petroleum resources in China are increasingly tense and the pressure of petroleum supply is unprecedentedly increased along with the unique resource pattern of 'more coal, less oil and gas'. The petroleum supply rate in China is only 50% in the future 10-20 years. How to solve the energy crisis of China by using abundant coal resources of China becomes a problem which needs to be solved urgently by researchers. Therefore, people pay more attention to the development of novel oil substitutes from coal-based methanol.
Dimethyl ether was originally proposed as an additive for diesel fuel, but the cost of dimethyl ether as an alternative fuel for vehicles is significantly increased due to its poor cold start performance, high vapor pressure at normal temperature and easy generation of vapor lock. Polyoxymethylene dimethyl ethers (PODE) is a generic term for a class of substances, and can be represented by the general formula CH3O(CH2O)nCH3Having a higher octane number (>30) And oxygen content (42-51%). When the value of n is 2-10, the physical property and the combustion performance of the dimethyl ether are very close to those of diesel oil, and the defects of dimethyl ether as a blending component of the vehicle diesel oil are overcome. Therefore, the polyoxymethylene dimethyl ether can be used as a novel clean diesel oil component in diesel oilThe additive amount can reach 30% (v/v), the combustion condition of diesel oil in an engine can be improved, the heat efficiency is improved, and particulate matters and CO in tail gas are reducedxAnd NOxAnd (4) discharging. Reportedly, 5-30% CH is added3OCH2OCH3Can reduce NOxThe emission is 7-10%, and the PM is reduced by 5-35%. The PODE synthesized by the coal-based methanol can replace part of diesel oil, improve the combustion efficiency of the diesel oil, reduce the harm of the combustion of the diesel oil to the environment, and has important strategic significance and good economic value.
CN 101048357a (method for preparing polyoxymethylene dimethyl ether) introduces a method for synthesizing polyoxymethylene dimethyl ether by using methylal and trioxymethylene as reactants and using inorganic acid, sulfonic acid, heteropoly acid, acidic ion exchange resin, zeolite, alumina, etc. as catalysts. However, the conversion and selectivity of the existing catalysts are to be improved.
The cation exchange resin as solid acid catalyst shows excellent catalytic reaction performance in esterification and etherification reaction of water-containing system, but the acid strength is lower. It is common to prepare supported resins, the activity of which is enhanced by increasing the acidity of the catalyst. The metal modified resin can be adopted to form a new acid center on the catalyst, and the new acid center can not be exchanged by other metal ions, so that the problem that the acidity of the catalyst can not be replaced by metal ions contained in raw materials to be inactivated under the condition that the catalyst keeps high activity in industrial application of polyformaldehyde dimethyl ether synthesis is solved.
Disclosure of Invention
The invention aims to solve the technical problem that the product selectivity of n-2-10 is low in the process of synthesizing the polyformaldehyde dimethyl ether by taking methanol, methylal and paraformaldehyde as reaction raw materials in the prior art, and provides a novel method for preparing the polyformaldehyde dimethyl ether. The method has the advantage of high product selectivity of n-2-10.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the method for preparing the polyformaldehyde dimethyl ether comprises the steps of taking methanol, methylal and paraformaldehyde as raw materials, wherein the mass ratio of the methanol to the methylal to the paraformaldehyde is (0-10) to 1, the using amounts of the methanol and the methylal cannot be 0 at the same time, contacting the raw materials with a catalyst, and reacting to generate the polyformaldehyde dimethyl ether, wherein the catalyst is cation exchange resin modified by metal ions, and the metal comprises VIII group metal.
In the technical scheme, the dosage of the catalyst is preferably 0.05-10% of the weight of the raw materials; more preferably 0.1 to 5% by weight of the raw material.
In the technical scheme, the reaction temperature is preferably 70-200 ℃.
In the technical scheme, the reaction pressure is preferably 0.2-6 MPa.
In the above technical scheme, the reaction time is preferably 1 to 20 hours, more preferably 4 to 12 hours.
In the technical scheme, the mass ratio of the methanol to the methylal to the paraformaldehyde is preferably (0.2-10) to (0.5-10) to 1.
In the above technical solution, the metal further includes IIIA metal.
In the above technical solution, the group IIIA metal is preferably Ga. Ga and a VIII group element have a synergistic effect in increasing the selectivity of PODE (peroxidase) to n-2-10. The ratio between Ga and the group VIII element is not particularly limited as long as the Ga and the group VIII element are present in the catalyst at the same time and a comparable synergistic effect can be obtained.
The mass ratio of Ga to the group VIII element is, by way of non-limiting example, 0.01 to 100, and further non-limiting examples within this range include 0.1, 0.5, 0.8, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10, and the like.
In the above technical solution, the group VIII element is selected from at least one of Fe, Co and Ni.
In the above aspect, it is more preferable that the modified metal includes Ga and at least two selected from Fe, Co and Ni, and in this case, the two VIII elements have a synergistic effect in increasing the selectivity to n-2 to 10 PODE. At this time, the ratio among Ni, Co and Fe is not particularly limited as long as at least two of Ni, Co and Fe are simultaneously present in the catalyst to achieve comparable synergistic effects, such as, but not limited to, between Co and Ni, and between Ni and Fe.
The mass ratio of the above-mentioned two VIII elements, for example, Co to Ni and Ni to Fe is 0.01 to 100 by way of non-limiting example, and further non-limiting examples within this range include 0.1, 0.5, 0.8, 1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, 10 and the like.
In the most preferred embodiment, the modifying metal contains Fe, Co, Ni and Ga at the same time, and in this case, the selectivity to PODE having n of 2 to 10 is most preferable.
In the above-mentioned technical solution, the content of the modified metal in the catalyst is not particularly limited, but is not limited to, for example, the content of the modified metal in the catalyst is more than 0 and 9.8w% or less.
In the technical scheme, the total exchange capacity of the resin is preferably 3.0-5.9 mmol/g.
In the above technical solution, the resin may be of a gel type or a macroporous type.
In the above technical scheme, the catalyst can be prepared by a method comprising the following steps: and (c) contacting the sulfonic polystyrene cation exchange resin with the suspension containing the modified metal oxide in the presence of a catalytic amount of acid to effect ion exchange.
In the above technical scheme, the acid is not particularly limited as long as the salt obtained by the reaction with the modified metal oxide can be dissolved in the solvent used for the suspension, and the acid is, for example, but not limited to, at least one of hydrochloric acid, nitric acid and carboxylic acids having a carbon number of 2 to 10.
In the above technical scheme, the carboxylic acid may be a hydroxy-substituted carboxylic acid, such as but not limited to glycolic acid, lactic acid, tartaric acid, citric acid, and the like.
In the above technical scheme, the carboxylic acid may be a C2-C10 monobasic acid, such as but not limited to acetic acid and the like.
In the case where the composition of the catalyst of the present invention has been clarified, the preparation of the catalyst is not particularly limited and can be carried out by referring to an ion exchange method which is generally used in the prior art. For example, the following steps can be included: washing the sodium sulfonate type polystyrene cation exchange resin with deionized water until clear water flows out, soaking the resin in 0.5-20% strong acid (such as hydrochloric acid or sulfuric acid) for 1-12 h, soaking the resin in deionized water or an ethanol solution for 1-12 h, and then washing the resin with deionized water until the pH value is 6, thus obtaining the sulfonic acid type polystyrene cation exchange resin. While the sulfonic acid type polystyrene cation exchange resin of the present invention is also directly available from commercial sources, it can be used for the preparation of the catalyst of the present invention, rather than the sodium sulfonate type.
By adopting the method, the yield of PODE with n-2-10 is good, the selectivity of the product with n-2-10 is as high as 88.3%, and a better technical effect is achieved.
The total exchange capacity in the present invention is based on dry resin.
The present invention is further illustrated by the following examples, wherein the polymerization degree of the raw material paraformaldehyde used in the examples and comparative examples is 5, and the product selectivity is calculated by taking paraformaldehyde as a reference and taking polyoxymethylene dimethyl ether with the polymerization degree of 2-10 as a target product.
Detailed Description
[ example 1 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin on a dry basis were taken and 300ml of Ga (OH) containing 2 g of Ga3Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ga content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 2 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to dry resin was taken and mixed with 300ml of Ni (OH) 2 g under nitrogen2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ni content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 3 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and reacting with 300ml of Co-containing polystyrene cation exchange resin under the protection of nitrogenIs 2 g of Co (OH)2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Co content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 4 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to dry resin was taken and mixed with 300ml of 2 g Fe (OH) containing Fe under nitrogen2Mixing the water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Fe content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 5 ]
1. Preparation of the catalyst
Washing sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, and washing with deionized waterSoaking the polystyrene cation exchange resin in 4 w% hydrochloric acid for four times, soaking the polystyrene cation exchange resin in 4 w% hydrochloric acid for 4h each time, washing the polystyrene cation exchange resin with deionized water until the eluate has no chloride ion, and drying the polystyrene cation exchange resin at 60 ℃ to obtain the polystyrene cation exchange resin with the total exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Ga (OH) containing 1 g of Ga and 1 g of Ni under the protection of nitrogen3And Ni (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ga content of 1 w% and the Ni content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 6 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and reacting with 300ml of Ga (OH) containing 1 g of Ga and 1 g of Co under the protection of nitrogen3And Co (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ga content of 1 w% and the Co content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 7 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and reacting with 300ml of Ga (OH) containing 1 g of Ga and 1 g of Fe under the protection of nitrogen3And Fe (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ga content of 1 w% and the Fe content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 8 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking with 4 w% hydrochloric acid for four times, each time using 4 w% hydrochloric acid 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, each time for 4h, washing with deionized water until the eluate has no chloride ion, and drying at 60 deg.CThen, the sulfonic acid type polystyrene cation exchange resin is obtained, and the total exchange capacity of the resin is 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to the dry resin was taken and mixed with 300ml of Ga (OH) containing 1 g of Ga, 0.5 g of Co and 0.5 g of Ni under the protection of nitrogen3、Co(OH)2And Ni (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ga content of 1 w%, the Co content of 0.5 w% and the Ni content of 0.5 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 9 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin equivalent to dry resin is taken and mixed with 300ml of Ga (OH) containing 1 g of Ga, 0.5 g of Co and 0.5 g of Fe under the protection of nitrogen3、Co(OH)2And Fe (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ga content of 1 w%, the Co content of 0.5 w% and the Fe content of 0.5 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 10 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. 98 g of sulfonic polystyrene cation exchange resin corresponding to the dry resin was taken and mixed with 300ml of Ga (OH) containing 1 g of Ga, 0.5 g of Ni and 0.5 g of Fe under the protection of nitrogen3、Ni(OH)2And Fe (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ga content of 1 w%, the Ni content of 0.5 w% and the Fe content of 0.5 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 11 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking the resin with 4 w% hydrochloric acid for four times, soaking the resin with 4 w% hydrochloric acid for 4h each time, washing the resin with deionized water until the eluate has no chloride ions, and drying the resin at 60 ℃ to obtain the sulfonic type polystyrene cationIon exchange resin with a total exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to the dry resin, and reacting with 300ml of Ga (OH) containing 1 g of Ga, 0.4 g of Co, 0.3 g of Ni and 0.3 g of Fe under the protection of nitrogen3、Co(OH)2、Ni(OH)2And Fe (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ga content of 1 w%, the Co content of 0.4 w%, the Ni content of 0.3 w% and the Fe content of 0.3 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 130 ℃ and 0.5MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ example 12 ]
1. Preparation of the catalyst
Washing the sodium sulfonate type polystyrene cation exchange resin 7320 with deionized water until clear water flows out, soaking for four times with 4 w% hydrochloric acid, soaking for 4h each time with 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320, washing with deionized water until the eluate has no chloride ions, and drying at 60 ℃ to obtain the sulfonic type polystyrene cation exchange resin with the full exchange capacity of 4.10 mmol/g. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to the dry resin, and reacting with 300ml of Ga (OH) containing 1 g of Ga, 0.4 g of Co, 0.3 g of Ni and 0.3 g of Fe under the protection of nitrogen3、Co(OH)2、Ni(OH)2And Fe (OH)2Mixing the mixed water suspension, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hours, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Ga content of 1 w%, the Co content of 0.4 w%, the Ni content of 0.3 w% and the Fe content of 0.3 w%.
2. Synthesis of polyformaldehyde dimethyl ether
2 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde are added into a 300ml tank reactor, the mixture is reacted for 4 hours at 90 ℃ and 0.6MPa autogenous pressure, and a sample is extracted, centrifuged and analyzed by gas chromatography. The product contains the dimethyl ether of paraformaldehyde and unreacted raw materials of methanol and polyformaldehyde, and the composition distribution is shown in table 1.
[ COMPARATIVE EXAMPLE 1 ]
The same ratio as in example 1 was used except that the catalyst used was 2 g of the dry sulfonic acid type polystyrene cation exchange resin described in example 1 and the other process conditions were the same as in example 1, and the results are shown in Table 1.
TABLE 1
n is polymerization degree, and the product is CH3O(CH2O)nCH3。
Claims (9)
1. The method for preparing the polyformaldehyde dimethyl ether comprises the steps of taking methanol, methylal and paraformaldehyde as raw materials, wherein the mass ratio of the methanol to the methylal to the paraformaldehyde is (0-10) to 1, the using amounts of the methanol and the methylal cannot be 0 at the same time, contacting the raw materials with a catalyst to react to generate the polyformaldehyde dimethyl ether, wherein the catalyst is cation exchange resin modified by metal ions, and the metal is Ga and at least one selected from Fe, Co and Ni.
2. The method of claim 1, wherein the amount of the catalyst is 0.05 to 10% by weight based on the weight of the raw material.
3. The method according to claim 1, wherein the reaction temperature is 70 to 200 ℃.
4. The method according to claim 1, wherein the reaction pressure is 0.2 to 6 MPa.
5. The process as claimed in claim 1, wherein the reaction time is from 1 to 20 hours.
6. The method according to claim 1, wherein the mass ratio of methanol to methylal to paraformaldehyde is (0.2 to 10) to (0.5 to 10) to 1.
7. The method as set forth in claim 1, wherein the content of the modifying metal in the catalyst is more than 0 and 9.8w% or less.
8. The method of claim 1, wherein the resin has a total exchange capacity of 3.0 to 5.9 mmol/g.
9. The method of claim 1, wherein the resin is of the gel type or macroporous type.
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| CN201710935012.7A CN109651106B (en) | 2017-10-10 | 2017-10-10 | Method for preparing polyformaldehyde dimethyl ether |
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| CN201710935012.7A CN109651106B (en) | 2017-10-10 | 2017-10-10 | Method for preparing polyformaldehyde dimethyl ether |
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| CN107915607A (en) * | 2016-10-09 | 2018-04-17 | 中国石油化工股份有限公司 | The preparation method of polyoxymethylene dimethyl ether |
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