CN109651101B - Synthesis method of polyoxymethylene dimethyl ether - Google Patents
Synthesis method of polyoxymethylene dimethyl ether Download PDFInfo
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- CN109651101B CN109651101B CN201710940924.3A CN201710940924A CN109651101B CN 109651101 B CN109651101 B CN 109651101B CN 201710940924 A CN201710940924 A CN 201710940924A CN 109651101 B CN109651101 B CN 109651101B
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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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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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Abstract
The invention relates to a method for synthesizing polyoxymethylene dimethyl ethers, which mainly solves the problems of low catalyst activity and low selectivity in the process of synthesizing polyoxymethylene dimethyl ethers by taking methanol, methylal and paraformaldehyde as reaction raw materials in the prior art, and the method for synthesizing polyoxymethylene dimethyl ethers comprises the steps of taking methanol, methylal and paraformaldehyde as raw materials, wherein the mass ratio of methanol to methylal to paraformaldehyde is (0-10) to 1, the use amounts of methanol and methylal cannot be 0 at the same time, contacting the raw materials with a catalyst to generate polyoxymethylene dimethyl ethers through reaction, and the catalyst is metal ion modified cation exchange resin; the technical scheme that the modified metal comprises IIIA metal can be used in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical Field
The invention relates to a synthesis method of polyoxymethylene dimethyl ether.
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 component, the addition amount in the diesel can reach 30% (v/v), the combustion condition of the diesel in an engine can be improved, the thermal 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 polyoxymethylene dimethyl ether by taking methanol, methylal and paraformaldehyde as reaction raw materials in the prior art, and provides a novel method for synthesizing polyoxymethylene 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 synthesizing the polyoxymethylene dimethyl ethers 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 polyoxymethylene dimethyl ethers, wherein the catalyst is metal ion modified cation exchange resin; the modifying metal comprises a IIIA 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 sum of the using amounts of methanol and methylal in the raw materials to paraformaldehyde is preferably (0.4-5) to 1; the mass ratio of the methanol to the methylal to the paraformaldehyde is (0.2-10) to (0.5-10) to 1.
In the above technical solution, Ga is preferred as the IIIA metal.
In the above technical solution, the modified metal includes VIIB metal.
Ga and VIIB metal have a synergistic effect in improving selectivity to PODE with n being 2-10. The ratio between the Ga and VIIB metals is not particularly limited, as long as a comparable synergistic effect is achieved with both Ga and VIIB metals present in the catalyst. The mass ratio of Ga to VIIB metal is, by way of non-limiting example, 0.01 to 100, and further non-limiting examples within this range include 0.10, 0.50, 0.80, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, and the like.
In the above technical solution, the VIIB metal is preferably at least one of Mn or Tc.
In the above technical solution, it is further preferable that the VIIB metal includes both Mn and Tc, and in this case, Mn and Tc have a synergistic effect in increasing selectivity to PODE having n 2 to 10. At this time, the ratio between Mn and Tc is not particularly limited as long as Mn and Tc are present in the catalyst at the same time to achieve a comparable synergistic effect. The mass ratio of Mn to Tc is, by way of non-limiting example, 0.01 to 100, and further non-limiting examples within this range include 0.10, 0.50, 0.80, 1.0, 1.5, 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, and the like.
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, more than 0 and not more than 10 w%.
In the technical scheme, the total exchange capacity of the resin is 3.0-6.0 mmol/g. F
In the above technical solution, the resin may be of a gel type or a macroporous type.
In the above technical solution, the cation exchange resin is preferably sulfonic acid type polystyrene cation exchange resin.
In the above technical scheme, the sulfonic acid type polystyrene cation exchange resin comprises a crosslinked polystyrene skeleton and a sulfonic acid group.
In the above technical scheme, the catalyst can be prepared by a method comprising the following steps: ion exchange is carried out by contacting the cation exchange resin with a suspension containing the modified metal oxide and/or hydroxide in the presence of a catalytic amount of acid.
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 and/or hydroxide can be dissolved in the solvent used for the suspension, and in this principle, for example, but not limited to, at least one of hydrochloric acid, nitric acid, and C2 to C10 carboxylic acids.
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 89.4%, 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 acid polystyrene cation exchange resin corresponding to the dry resin was mixed with 300ml of Mn (OH) 2 g of Mn under nitrogen protection2Mixing 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 Mn 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. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to dry resin was taken and mixed with 300ml of Tc (OH) containing 2 g of Tc under nitrogen2Mixing the aqueous suspensions, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hr, and drying in vacuum oven to constant temperatureAnd weighing to obtain the catalyst with the Tc content of 2w percent.
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. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to the dry resin, and reacting the resin with 300ml of Ga (OH) containing 1 g of Ga and 1 g of Mn under the protection of nitrogen3And Mn (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 Mn 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.
In example 4, in comparison with examples 1 and 2, Ga and Mn have a synergistic effect in increasing the selectivity to PODE having n of 2 to 10.
[ example 5 ]
1. Preparation of the catalyst
Sulfonic acidThe sodium polystyrene cation exchange resin 7320 is washed by deionized water until clear water flows out, and is soaked by 4 w% hydrochloric acid for four times, 4 w% hydrochloric acid which is 10 times of the dry weight of the sodium polystyrene cation exchange resin 7320 is used for each time, the sodium polystyrene cation exchange resin is soaked for 4h, then the sodium polystyrene cation exchange resin is washed by deionized water until no chloride ion exists in the eluate, and the sodium polystyrene cation exchange resin is dried at 60 ℃ to obtain the sulfonic polystyrene cation exchange resin, wherein the total exchange capacity of the sulfonic polystyrene cation exchange resin is 4.10 mmol/g. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to the dry resin was taken and mixed with 300ml of Ga (OH) containing 1 g of Ga and 1 g of Tc under nitrogen protection3And Tc (OH)2Mixing the mixed aqueous 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 Tc 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.
In example 5, in comparison with examples 1 and 3, Ga and Tc have a synergistic effect in increasing the selectivity to PODE having n of 2 to 10.
[ 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. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to the dry resin was taken and mixed with 300ml of Tc (OH) containing 1 g of Tc and 1 g of Mn under nitrogen protection2And Mn (OH)2The mixed water is mixed with the suspension liquid,adding 1 drop of glacial acetic acid, mixing, standing for 24 hours at room temperature, and drying in a vacuum drying oven to constant weight to obtain the catalyst with the Tc content of 1w percent and the Mn content of 1w percent.
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.
In example 6, compared with examples 2 and 3, it can be seen that Mn and Tc have a synergistic effect in increasing the selectivity to PODE with n being 2-10.
[ 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. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to the dry resin was mixed with 300ml of Ga (OH) containing 1 g of Ga, 0.5 g of Tc and 0.5 g of Mn under nitrogen protection3、Tc(OH)2And Mn (OH)2Mixing the mixed aqueous 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 Tc content of 0.5 w% and the Mn 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 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 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 100 ℃ 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.
[ 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 acid polystyrene cation exchange resin corresponding to the dry resin was mixed with 300ml of Ga (OH) containing 1.5 g of Ga and 0.5 g of Mn under nitrogen protection3And Mn (OH)2Mixing the mixed aqueous suspensions, adding 1 drop of glacial acetic acid, mixing, standing at room temperature for 24 hr, and vacuum-filteringAnd drying the catalyst in a drying oven to constant weight to obtain the catalyst with the Ga content of 1.5w percent and the Mn content of 0.5w percent. 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 0.2MPa 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 acid polystyrene cation exchange resin corresponding to the dry resin was taken and mixed with 300ml of Ga (OH) containing 1.5 g of Ga and 0.5 g of Tc under nitrogen protection3And Tc (OH)2Mixing the mixed aqueous 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 1.5 w% and the Tc content of 0.5 w%. 2. Synthesis of polyformaldehyde dimethyl ether
0.5 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 120 ℃ and 0.8MPa autogenous pressure, and a sample is extracted, centrifuged and separated, and then 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 polystyrene cation exchange resin 7320 with deionized water until the clear water flows out, soaking with 4 w% hydrochloric acid for four times, each time using the sodium sulfonate polystyrene cation exchange resin7320 soaking 4 w% hydrochloric acid 10 times of the dry weight of the resin for 4h, washing with deionized water until no chloride ion exists in the eluate, and drying at 60 deg.C to obtain sulfonic polystyrene cation exchange resin with total exchange capacity of 4.10 mmol/g. 98 g of sulfonic acid polystyrene cation exchange resin corresponding to the dry resin was mixed with 300ml of Ga (OH) containing 1.5 g of Ga, 0.25 g of Tc and 0.25 g of Mn under nitrogen protection3、Tc(OH)2And Mn (OH)2Mixing the mixed aqueous 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 1.5 w%, the Tc content of 0.25 w% and the Mn content of 0.25 w%.
2. Synthesis of polyformaldehyde dimethyl ether
A300 ml tank reactor was charged with 3 g of catalyst, 100 g of methanol and 100 g of paraformaldehyde, reacted at 110 ℃ under 0.3MPa autogenous pressure for 4 hours, and a sample was withdrawn, 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 (10)
1. The method for synthesizing the polyoxymethylene dimethyl ethers 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 polyoxymethylene dimethyl ethers, wherein the catalyst is metal ion modified cation exchange resin; the modifying metal is Ga.
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 in the raw material is (0.2-10) to (0.5-10) 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 10w% or less.
8. The method of claim 1, wherein the resin has a total exchange capacity of 3.0 to 6.0 mmol/g.
9. The method of claim 1, wherein the resin is of the gel type or macroporous type.
10. The method as set forth in claim 1, wherein said cation exchange resin is a sulfonic acid type polystyrene cation exchange resin.
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