CN109651099B - Process method for synthesizing polyformaldehyde dimethyl ether from methanol and paraformaldehyde - Google Patents
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Abstract
The invention relates to a process for synthesizing polyoxymethylene dimethyl ether, which solves the problem of low yield of the product of the process for synthesizing polyoxymethylene dimethyl ether by using methanol and paraformaldehyde as raw materials, and comprises a reaction zone and a separation zone, wherein the reaction zone comprises a nitrogen storage tank, a methanol storage tank, a mixing tank with a heater, a drying pipe and a bubbling reactor, the process steps of the reaction zone are that paraformaldehyde is heated in the mixing tank to form formaldehyde gas, the formaldehyde gas is blown by nitrogen and conveyed to the drying pipe for dewatering, the formaldehyde gas enters the bubbling reactor, the formaldehyde gas reacts with methanol and a mixture recycled and introduced into the reactor to generate polyoxymethylene dimethyl ether under the action of a solid acid catalyst, the separation zone comprises an anion exchange resin bed layer, a rectification module and a product storage tank, the process steps of the separation zone are that the reactor discharge enters the rectification module after being deacidified by an anion exchange resin bed layer, and the tri-and tetra-polymers of polyoxymethylene dimethyl ether enter the product storage tank, the technical problem is solved well.
Description
Technical Field
The invention relates to a method for synthesizing polyoxymethylene dimethyl ethers, in particular to a method for synthesizing polyoxymethylene dimethyl ethers by taking paraformaldehyde as a raw material.
Background
The resource pattern of China has the characteristics of rich coal, less oil and gas, and the vigorous industrial development of China puts increasing requirements on petroleum supply. However, in recent years, petroleum resources in China are increasingly tense, and the pressure of petroleum supply is increasing unprecedentedly. According to statistics, the foreign dependence of China in 2011 reaches 56.5%, and the petroleum is increased by 1.7% compared with 2010. Since the country is first to be the pure import country of petroleum in 1993, the external dependence of petroleum in China is increased by 6% of the year, and the 2009 breaks through 50% of the warning line. 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 fuel oil substitutes from coal base.
In addition, due to the dual pressure of air pollution and energy shortage, energy conservation and emission reduction become a subject of social development. Thus, the petrochemical industry has long been working on developing new emission-reduced diesel fuels. Many emerging alternative diesel fuels have been developed, including: GTL diesel, biodiesel, ethanol diesel, dimethyl ether, diesel oil oxygen-containing compounds, emulsified diesel oil and the like. Most of them are produced by synthetic method without using petroleum, basically do not contain impurities of sulfur, nitrogen and aromatic hydrocarbon, and are very clean diesel oil or diesel oil blending components, which are highly valued in recent years, and all countries are making great effort to develop and popularize. Among them, the use of diesel blending components does not require additional devices or changes in engine structure, and thus is considered to be a convenient and effective measure.
Dimethyl ether is firstly proposed as an additive of diesel oil, and the addition of a proper amount of dimethyl ether into the diesel oil can effectively reduce particulate matters and CO in tail gasxAnd NOxAnd (4) discharging. However, dimethyl ether has some defects due to its physical properties, such as poor cold start performance, high vapor pressure at normal temperature, easy generation of vapor lock, storage, transportation, low-pressure liquefaction and other high costs, which obviously increase the cost of dimethyl ether as an alternative fuel for vehicles. 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 cetane number (>40) And oxygen content (42-51%). When the value of n is 1, the polyformaldehyde dimethyl ether is methylal, and the methylal serving as the vehicle fuel additive component can improve the energy utilization efficiency and reduce the exhaust emission, but is still easy to cause air lock. When the value of n is 2-6, the physical property and the combustion performance of the diesel oil are very close to those of diesel oil, and the dimethyl ether and the methylal serving as the diesel oil for vehicles are better solvedThe diesel oil blending component has the defects. Therefore, the polyoxymethylene dimethyl ether can be used as a novel clean diesel component, the addition amount in the diesel can reach more than 10 percent (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. The optimal chain length of the polyoxymethylene dimethyl ethers mixed with diesel oil is n =3, 4. When n =2, the flash point of polyoxymethylene dimethyl ether is too low, and when n is too large, polyoxymethylene dimethyl ether may precipitate and clog at a low temperature. Reportedly, 5-30% CH is added3OCH2OCH3Can greatly reduce NOxAnd (5) discharging.
The middle of PODE is paraformaldehyde segment, and two ends are sealed by methyl. PODE is generally synthesized from a compound which provides paraformaldehyde (formaldehyde, trioxane, paraformaldehyde, etc.) and a compound which provides a blocked methyl group (methanol, dimethyl ether, methylal, etc.). PODE can be synthesized by dehydrating methanol and formaldehyde or paraformaldehyde and trioxymethylene under the catalysis of acid. The production of synthesis gas from coal gasification, methanol from synthesis gas, formaldehyde from methanol oxidation, and paraformaldehyde or trioxymethylene from formaldehyde have long been industrialized. 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. The development and synthesis of PODE can convert rich coal resources in China into liquid alternative fuels, reduce the import dependence of China on petroleum and further have great significance to national energy safety.
Polyoxymethylene dimethyl ethers in laboratories can be prepared by heating paraformaldehyde with low polymerization degree or reacting paraformaldehyde with methanol at 150-180 ℃ in the presence of trace amounts of sulfuric acid or hydrochloric acid. Since polyoxymethylene dimethyl ethers have great application values in the field of diesel additives, a large number of companies and research institutes have been researching feasible industrial production technologies for a long time.
EP2228359A1 describes a process for preparing polyoxymethylene dimethyl ethers from methanol as starting material. The method uses a molecular sieve modified by ammonium molybdate and ferric nitrate as a catalyst, and methanol and air (oxygen) are oxidized in one step at the temperature of more than 200 ℃ to obtain the polyoxymethylene dimethyl ether. The method has relatively low production cost, but the preparation process of the catalyst is complex, and the selectivity of the polyoxymethylene dimethyl ether is not ideal.
EP1070755 describes a process for preparing polyoxymethylene dimethyl ethers having 2 to 6 formaldehyde units per molecule by reacting methylal with paraformaldehyde in the presence of trifluorosulfonic acid. WO2006/045506A1 describes that a series of products with n = 1-10 are obtained by BASF company by using sulfuric acid and trifluoromethanesulfonic acid as catalysts and methylal, paraformaldehyde and trioxymethylene as raw materials. The above methods all adopt protonic acid as a catalyst, which is cheap and easy to obtain, but has the defects of strong corrosivity, difficult separation, large environmental pollution and high requirement on equipment.
US6160174 and US6265528 describe that the BP company obtains polyoxymethylene dimethyl ether by a gas-solid reaction using methanol, formaldehyde, dimethyl ether and methylal as raw materials and cation exchange resin as a catalyst. However, this method has the advantages of easy separation of catalyst, easy circulation, low conversion rate, low yield and complex process.
The CN 101768057A takes methanol and trioxymethylene as raw materials and takes solid superacid as a catalyst to catalyze and synthesize polyformaldehyde dimethyl ether, although a good raw material conversion rate is obtained, due to the strong acidity of the solid superacid and the irregular pore structure, the selectivity of a byproduct methylal in a product is 20-50%, the flash point of a diesel oil mixture is reduced due to the large amount of methylal, the quality of the diesel oil mixture is damaged, and the product is not suitable for being used as an additive of diesel oil. CN 101048357A introduces a synthesis process for synthesizing polyoxymethylene dimethyl ethers by taking methylal and trioxymethylene as raw materials. We also developed a solid acid catalyst (molecular sieve CN 200910056820.1, solid super acid CN 200910056819.9) to prepare polyoxymethylene dimethyl ether from methanol and trioxymethylene.
However, the processes all adopt trioxymethylene as a reaction raw material, and the price of the trioxymethylene is 14000 yuan/ton according to market research; compared with the price of paraformaldehyde, the price of the paraformaldehyde is only 5000 yuan/ton. We have found that the production cost of polyoxymethylene dimethyl ether from paraformaldehyde can be greatly reduced.
CN 101182367A discloses a process method for synthesizing polyformaldehyde dimethyl ether by using acid ionic liquid as a catalyst and formaldehyde as synthetic trioxymethylene and then using trioxymethylene and methanol. Although the method has high one-way yield, the used ionic liquid catalyst is expensive and difficult to separate, and the operation difficulty is higher. US5,959,156 describes a process for the synthesis of polyoxymethylene dimethyl ethers starting from dimethyl ether and methanol using a novel heterogeneous promoted condensation catalyst. Although the process is low in cost, the product yield is not ideal.
Disclosure of Invention
The invention aims to solve the technical problem that the yield of a product is low in the process of synthesizing polyformaldehyde dimethyl ether by taking methanol and paraformaldehyde as raw materials in the prior art, and provides a novel method for synthesizing polyformaldehyde dimethyl ether. The method has the advantages of low price of raw material paraformaldehyde, low production cost and high yield.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a process for synthesizing polyoxymethylene dimethyl ether from methanol and paraformaldehyde includes such steps as heating paraformaldehyde in mixing tank to become formaldehyde gas, purging with nitrogen gas, drying in drying tube, removing water, bubbling in reactor, under the action of a solid acid catalyst, the materials react with methanol and a mixture recycled and introduced into a reactor to generate polyformaldehyde dimethyl ether, a separation zone comprises an anion exchange resin bed layer, a rectification module and a product storage tank, the process step of the separation zone is that the discharged materials of the reactor enter the rectification module after being deacidified by the anion exchange resin bed layer, the materials are separated by the rectification module, the tri-polymer and the tetra-polymer of the polyformaldehyde dimethyl ether enter the product storage tank, and other components are circulated to the reactor.
In the technical scheme, the mass ratio of the methanol to the paraformaldehyde is preferably 0.02-50: 1. The reaction temperature is preferably 50-250 ℃; the reaction pressure is 0.01-20.0 MPa. The reaction residence time is preferably 0.5-10.0 h. The temperature of the mixing tank is preferably 200 to 300 ℃, and more preferably 240 to 280 ℃. Recovering a first fraction comprising methylal, a second fraction comprising methanol polyoxymethylene dimethyl ether dimers, and a fourth fraction comprising higher degree of polymerization (n >4) polyoxymethylene dimethyl ether separated by a rectification module into the reactor mixture; preferably, the rectification module also separates a third fraction containing the tri-and tetramers of polyoxymethylene dimethyl ether. The rectification module preferably consists of 3 rectification columns. The first fraction is preferably taken off at the top of the first rectification column, the second fraction is preferably taken off at the top of the second rectification column, the third fraction is preferably taken off at the top of the third rectification column and the fourth fraction is preferably taken off at the bottom of the third rectification column. The first, second, and fourth fractions are preferably recycled to the reactor after removal of water by a water remover. The operating pressure of the first rectifying tower is preferably 0.2-2 MPa, the operating pressure of the second rectifying tower is preferably 0.02-1.2 MPa, and the operating pressure of the third rectifying tower is preferably 0.001-0.6 MPa. The theoretical plate number of the first rectifying tower is preferably 15-25, the theoretical plate number of the second rectifying tower is preferably 15-30, and the theoretical plate number of the third rectifying tower is preferably 15-35.
In the above technical scheme, the solid acid catalyst is selected from one or more of the following catalysts: sulfonic acid type polystyrene cation exchange resin, metal modified sulfonic acid type polystyrene cation exchange resin, molecular sieve, dinitrobenzoic acid, ethylene diamine tetraacetic acid, alumina, titanium dioxide, more preferably metal modified sulfonic acid type polystyrene cation exchange resin.
In the technical scheme, the sulfonic acid type polystyrene cation exchange resin comprises a crosslinked polystyrene skeleton and sulfonic acid groups; the modifying metal includes Cu.
In the above technical solution, preferably, the modified metal further includes an auxiliary metal selected from Mn, Cu and an auxiliary metal having a synergistic effect in improving selectivity to PODE with n =2 to 10. The ratio between Cu and the auxiliary metal is not particularly limited as long as Cu and the auxiliary metal are simultaneously present in the catalyst to achieve a comparable synergistic effect.
The mass ratio of Cu to the auxiliary metal 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-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.
In the above technical solution, the resin may be of a gel type or a macroporous type.
In the above technical solution, the catalyst can be prepared by a method comprising contacting the sulfonic acid type polystyrene cation exchange resin with a suspension containing the modified metal oxide and/or hydroxide in the presence of a catalytic amount of acid to perform 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 and/or hydroxide 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 C2-C10 carboxylic acid.
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 above technical solution, the drying agent used in the drying tube and the dehydrator is preferably selected from at least one of the following drying agents: ion exchange resin, molecular sieve and silica gel.
In the above technical scheme, the rectifying tower is preferably a packed tower, and the packing is preferably stainless steel or ceramic with a regular structure.
The invention has the following advantages: firstly, the yield and the selectivity are high, and the sum of n =3 and n =4 products accounts for the sum of n = 2-5 products; secondly, the production cost is low; thirdly, recycling the by-products by adopting a rectification method; and a better technical effect is achieved.
Drawings
The invention will be described in further detail with reference to fig. 1. FIG. 1 is a process flow diagram of the present invention.
The method comprises the following steps that nitrogen (material flow 2) output by a nitrogen storage tank 1 sweeps paraformaldehyde (material flow 3) to a mixing tank 4, the mixing tank 4 is connected with a heater 5, the paraformaldehyde is heated to be gas in the mixing tank 4, the output material flow 6 (the mixed gas of the nitrogen, the formaldehyde and the water vapor) is dried through a drying pipe 7 to remove water vapor to obtain a material 8, the material 8 is fed to a bubbling reactor 9, meanwhile, a material flow 14 (liquid phase methanol) output by a methanol storage tank 13 is fed to the reactor 9, a material 19 (the main component is methylal) with water removed is recovered from the top of a rectifying tower 15, and a material 24 (the main component is a di-polymer, a penta-polymer and a hexamer of the methanol and the polyformaldehyde dimethyl ether) with water removed by a water remover 23. The reactor discharge 10 is deacidified by an anion exchange resin bed layer 12 to obtain a material 11, and the material 11 enters a rectifying tower 15 for separation. Unreacted methylal is discharged from the top of the rectifying tower 15 (stream 17), and is subjected to water removal by a water remover 18 and then is introduced into the bubbling reactor 9 again. The bottom discharge 16 of the rectifying tower 15 enters a rectifying tower 20 for further separation. Unreacted methanol and the generated polyoxymethylene dimethyl ether dimer are discharged from the top of the rectifying tower 20 (material flow 22), and are introduced into the bubbling reactor 9 again after being dehydrated by a dehydrator 23. The bottom discharge 21 of the rectifying tower 20 enters a rectifying tower 25 for further separation. The trimer and tetramer of polyoxymethylene dimethyl ether are discharged from the top of the rectifying tower 25 (stream 27) and enter a product storage tank 28. Polyoxymethylene dimethyl ether with higher polymerization degree (n is more than 4) is discharged from the bottom of the rectifying tower 25 (material flow 26), is dehydrated by a dehydrator 23 and then is introduced into the bubbling reactor 9 again. The nitrogen brought into the device during feeding is condensed by a condenser at the top of the rectifying tower 15 and then discharged from a non-condensable gas outlet of the condenser (not shown in the figure).
The invention is further illustrated by the following examples.
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 outSoaking the polystyrene cation exchange resin in 4w% hydrochloric acid for four times, soaking the polystyrene cation exchange resin in 4w% hydrochloric acid for 4h each time, washing the polystyrene cation exchange resin with deionized water until no chloride ion exists in the eluate, 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. 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to the dry resin was taken in combination with 300ml of Cu (OH) containing 2 g of Cu2Mixing 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 Cu content of 2 w%.
2. Synthesis of polyformaldehyde dimethyl ether
In the reaction process shown in the attached figure, the reactor 9 has a volume of 2L, and is provided with an electric stirring device and an electric heating sleeve for heating.
150g of catalyst is filled in the bubbling reactor 9, a nitrogen purging device is used, 10000g of paraformaldehyde is continuously added into a mixing tank, the temperature of the mixing tank is 250 ℃, and the formaldehyde gas generated after heating is dehydrated by a drying pipe and then enters the bubbling reactor 9; while adding anhydrous methanol to the bubbling reactor 9, the mixed solution (methanol, formaldehyde and PODE) recovered cyclicallyn=1,2,5, 6), the feed rates were 62.5g/h and 140g/h, respectively. The operating conditions of the bubble reactor 9 were a reaction temperature of 150 ℃ and a reaction pressure of 2.0 MPa. The reaction discharge enters an anion exchange resin bed layer.
The reactor discharge 10 enters a rectifying tower 15 for separation after being deacidified by an anion exchange resin bed layer 12, the operating pressure is 1.10MPa, and the theoretical plate number is 20. Unreacted methylal is discharged from the top of the rectifying tower 15 (stream 17), and is subjected to water removal by a water remover 18 and then is introduced into the bubbling reactor 9 again. The bottom material discharged from the rectifying tower 15 enters a rectifying tower 20 for next separation, the operating pressure is 0.56MPa, and the theoretical plate number is 20. Unreacted methanol and the generated polyoxymethylene dimethyl ether dimer are discharged from the top of the rectifying tower 20 (material flow 22), and are introduced into the bubbling reactor 9 again after being dehydrated by a dehydrator 23. The bottom discharge 21 of the rectifying tower 20 enters a rectifying tower 25 for next separation, the operating pressure is 0.30MPa, and the theoretical plate number is 20. The trimer and tetramer of polyoxymethylene dimethyl ether are discharged from the top of the rectifying tower 25 (stream 27) and enter a product storage tank 28. Polyoxymethylene dimethyl ether with higher polymerization degree (n is more than 4) is discharged from the bottom of the rectifying tower 25 (material flow 26), is dehydrated by a dehydrator 23 and then is introduced into the bubbling reactor 9 again. The reaction was continued for 80h and the product was sampled on-line and analyzed by gas chromatography, the results of which are given 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 4w% hydrochloric acid, soaking for 4h each time with 4w% 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
Otherwise, the reaction was continued for 80 hours as in example 1, and the product was sampled on-line and analyzed by gas chromatography, and the results of the experiment are 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 4w% hydrochloric acid, soaking for 4h each time with 4w% 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 resin containing 1 g of Cu and 1 g of Mn under the protection of nitrogenCu(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 Cu content of 1w% and the Mn content of 1 w%.
2. Synthesis of polyformaldehyde dimethyl ether
Otherwise, the reaction was continued for 80 hours as in example 1, and the product was sampled on-line and analyzed by gas chromatography, and the results of the experiment are shown in Table 1.
TABLE 1
n is polymerization degree, and the product is CH3O(CH2O)nCH3。
Claims (13)
1. A process for synthesizing polyoxymethylene dimethyl ether from methanol and paraformaldehyde includes such steps as heating paraformaldehyde in mixing tank to become formaldehyde gas, purging with nitrogen gas, drying in drying tube, removing water, bubbling in reactor, under the action of a solid acid catalyst, the materials react with methanol and a mixture recycled and introduced into a reactor to generate polyformaldehyde dimethyl ether, a separation zone comprises an anion exchange resin bed layer, a rectification module and a product storage tank, the process step of the separation zone is that the discharged materials of the reactor enter the rectification module after being deacidified by the anion exchange resin bed layer, the materials are separated by the rectification module, the tri-polymer and the tetra-polymer of the polyformaldehyde dimethyl ether enter the product storage tank, and other components circulate to the reactor;
the solid acid catalyst is metal modified sulfonic acid type polystyrene cation exchange resin, and the metal is the combination of Cu and Mn.
2. The process method for synthesizing polyoxymethylene dimethyl ethers according to claim 1, wherein the mass ratio of methanol to paraformaldehyde is 0.02 to 50: 1.
3. The process method for synthesizing polyoxymethylene dimethyl ethers according to claim 1, wherein the reaction temperature is 50 to 250 ℃; the reaction pressure is 0.01-20.0 MPa.
4. The process for synthesizing polyoxymethylene dimethyl ethers according to claim 1, wherein the reaction residence time is 0.5 to 10.0 hours.
5. The process for synthesizing polyoxymethylene dimethyl ethers according to claim 1, wherein the temperature of the mixing tank is 200 to 300 ℃.
6. The process for synthesizing polyoxymethylene dimethyl ethers according to claim 1, wherein the recovering the mixture fed to the reactor comprises a first fraction containing methylal, a second fraction containing dimers of polyoxymethylene dimethyl ethers containing methanol, and a fourth fraction containing polyoxymethylene dimethyl ethers having higher degree of polymerization n >4 separated by a rectification module; the rectification module also separates a third fraction containing the tri-and tetramers of the polyoxymethylene dimethyl ethers.
7. The process for synthesizing polyoxymethylene dimethyl ethers as claimed in claim 6, wherein said rectifying module is composed of 3 rectifying columns.
8. The process for synthesizing polyoxymethylene dimethyl ethers as claimed in claim 7, wherein the first fraction is taken from the top of the first rectifying column, the second fraction is taken from the top of the second rectifying column, the third fraction is taken from the top of the third rectifying column, and the fourth fraction is taken from the bottom of the third rectifying column.
9. The process of claim 6, wherein the first, second, and fourth fractions are recycled to the reactor after being dewatered by a dehydrator.
10. The process for synthesizing polyoxymethylene dimethyl ethers according to claim 7, wherein the operating pressure of the first rectification column is 0.2 to 2MPa, the operating pressure of the second rectification column is 0.02 to 1.2MPa, and the operating pressure of the third rectification column is 0.001 to 0.6 MPa.
11. The process method for synthesizing polyoxymethylene dimethyl ethers according to claim 1, wherein the mass ratio of Cu to Mn is 0.01 to 100.
12. The process for synthesizing polyoxymethylene dimethyl ethers according to claim 1, wherein the content of the metal is more than 0 and 10w% or less.
13. The process for synthesizing polyoxymethylene dimethyl ethers according to claim 1, wherein the total exchange capacity of the resin is 3.0 to 6.0 mmol/g.
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