CN109651097B - Process for producing polyformaldehyde dimethyl ether from methanol and paraformaldehyde - Google Patents
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- C—CHEMISTRY; METALLURGY
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- C07C41/48—Preparation of compounds having groups
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- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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Abstract
The invention relates to a process method for producing polyoxymethylene dimethyl ethers from methanol and paraformaldehyde. The technological process of producing polyoxymethylene dimethyl ether with methanol and paraformaldehyde includes heating paraformaldehyde in a mixing tank to form formaldehyde gas, nitrogen purging to transfer the formaldehyde gas to a drying pipe for dewatering, spraying to form methanol solution, and reaction with the mixture in a liquid phase reactor under the action of solid acid catalyst to produce polyoxymethylene dimethyl ether.
Description
Technical Field
The invention relates to a process method for producing polyoxymethylene dimethyl ethers from methanol and paraformaldehyde.
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'. 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. 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.
The dimethyl ether of the traditional diesel additive can effectively reduce particles 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 defects of dimethyl ether and methylal serving as blending components of the diesel oil for vehicles are overcome. 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 and chemicals, improve the combustion and emission performance of diesel oil, effectively supplement part of oil supply gaps, reduce the import dependence of China on oil and further have great significance on 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 produced by a process for producing polyoxymethylene dimethyl ethers by using methanol and paraformaldehyde as raw materials in the prior art is low, and provides a novel process method for producing polyoxymethylene dimethyl ethers, which has the advantage of high yield.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a process for preparing 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 to remove water, loading it in spray tower, counter-current contacting with methanol in spray tower to form methanol solution of formaldehyde, loading it in liquid-phase reactor, reacting with the mixture recovered in reactor to obtain polyoxymethylene dimethyl ether under the action of solid acid catalyst to obtain polyoxymethylene dimethyl ether, separating by anionic exchange resin bed, rectifying module and product storage tank, the tri-polymer and the tetramer of the polyoxymethylene dimethyl ether enter a product storage tank, unreacted raw material methanol is circulated to the methanol 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 80-240 ℃. The reaction pressure is preferably 0.01 to 15.0 MPa. The reaction residence time is preferably 0.5-10.0 h. The operating pressure of the spray tower is preferably 0.1-5.0 MPa, and the operating temperature is preferably 45-65 ℃.
The mixture in the technical scheme preferably comprises a first fraction containing methylal, a third fraction containing polyformaldehyde dimethyl ether dimers and a fifth fraction containing polyformaldehyde dimethyl ether with higher polymerization degree (n >4), which are separated by a rectification module; the rectification module also preferably separates a second fraction containing methanol and a fourth fraction containing tri-and tetramers of polyoxymethylene dimethyl ether.
The rectification module in the technical scheme preferably consists of 4 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, the fourth fraction is preferably taken off at the top of the fourth rectification column, and the fifth fraction is preferably taken off at the bottom of the fourth rectification column. The first fraction, the third fraction and the fifth fraction are preferably recycled to the liquid phase reactor after being dewatered by a dehydrator, and the second fraction is preferably recycled to the methanol storage tank after being dewatered by the dehydrator.
In the above technical solution, the operating pressure of the first rectifying tower is preferably 0.2 to 2MPa, the operating pressure of the second rectifying tower is preferably 0.1 to 1.5MPa, the operating pressure of the third rectifying tower is preferably 0.05 to 1.2MPa, and the operating pressure of the fourth rectifying tower is preferably 0.001 to 0.6 MPa.
In the technical scheme, the number of theoretical plates of the first rectifying tower is preferably 15-25, the number of theoretical plates of the second rectifying tower is preferably 15-30, the number of theoretical plates of the third rectifying tower is preferably 15-35, and the number of theoretical plates of the fourth rectifying tower is preferably 15-40.
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 scheme, the catalyst can be prepared by a method comprising the following steps: the sulfonic acid type polystyrene cation exchange resin is contacted with the 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.
Nitrogen gas (commodity circulation 2) of nitrogen gas storage tank 1 output sweeps paraformaldehyde (commodity circulation 3) to mixing tank 4, mixing tank 4 links to each other with heater 5, and paraformaldehyde heats to gas in mixing tank 4, and the commodity circulation 6 of output (for the gas mixture of nitrogen gas, formaldehyde gas, vapor) gets material 8 through drying tube 7 drying and water vapor removal, and material 8 feeds into spray column 9, and liquid phase methyl alcohol (commodity circulation 25) by the output of methyl alcohol storage tank 24 is to spray column 9 reverse feeding simultaneously, forms methyl alcohol solution commodity circulation 10 of formaldehyde. The stream 10 is fed to a liquid phase reactor 11, and also fed to the liquid phase reactor 10 are a stream 19 (mainly liquid phase methylal) which is output after water removal by a water remover 18, and a stream 30 (mainly dimer of polyoxymethylene dimethyl ethers, and polyoxymethylene dimethyl ethers having higher polymerization degree (n > 4)) which is output after water removal by a water remover 29. The reactor discharge 12 is deacidified by an anion exchange resin bed layer 13 to obtain a material 14, and the material 14 enters a rectifying tower 15 for separation. Unreacted methylal is discharged from the top of the rectifying tower 15 (material flow 16), and is subjected to water removal by a water remover 18 and then is introduced into the liquid phase reactor 11 again. The bottom discharge 17 of the rectifying tower 15 enters a rectifying tower 20 for next separation. Unreacted methanol is discharged from the top of the rectifying tower 20 (stream 21), and is subjected to water removal by a water remover 23 and then is introduced into a methanol storage tank 24 again. The bottom discharge 22 of the rectification column 20 enters a rectification column 26 for further separation. The dimer 27 of the polyoxymethylene dimethyl ether is discharged from the top of the rectifying tower 26, dewatered by a dehydrator 29 and then introduced into the liquid phase reactor 11 again. The material 28 discharged from the bottom of the rectifying tower 26 enters a rectifying tower 31, and the trimer and the tetramer of the polyoxymethylene dimethyl ether are discharged from the top of the rectifying tower 31 (material flow 32) and enter a product storage tank 34. Polyoxymethylene dimethyl ether with higher polymerization degree (n is more than 4) is discharged from the bottom of the rectifying tower 31 (material flow 33), is dewatered by a dehydrator 29 and then is introduced into the liquid phase reactor 11 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
Sodium sulfonate typeThe polystyrene cation exchange resin 7320 is washed by deionized water until clear water flows out, and is soaked by 4w% hydrochloric acid for four times, 4w% hydrochloric acid which is 10 times of the dry weight of the sodium sulfonate type polystyrene cation exchange resin 7320 is used for each time, the soaking time is 4h, then the polystyrene cation exchange resin is washed by deionized water until no chloride ion exists in the washing liquid, and the polystyrene cation exchange resin is obtained after drying at 60 ℃, wherein the full exchange capacity of the polystyrene cation exchange resin is 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 volume of the spray tower 9 is 5L, the volume of the reactor 11 is 2L, and the reactor is provided with an electric stirring device and is heated by an electric heating sleeve.
150g of catalyst is filled in a liquid phase reactor 11, a nitrogen purging device is used, 10000g of paraformaldehyde is continuously added into a mixing tank, the temperature of the mixing tank is 250 ℃, formaldehyde gas generated after heating enters a spray tower 9 after being dehydrated by a drying pipe and is in countercurrent contact with methanol in the spray tower, the feeding speed of the methanol is 62.5 g/h, the operating pressure of the spray tower is 0.3MPa, and the operating temperature is 55 ℃; the methanol solution of formaldehyde formed was fed to the liquid phase reactor 11, and simultaneously, a mixed solution of methylal and polyoxymethylene dimethyl ethers (n =2,5, 6) was fed to the liquid phase reactor 11 at feed rates of 44.5g/h and 46.0g/h, respectively. The liquid phase reactor 11 was operated under conditions of a reaction temperature of 110 ℃ and a reaction pressure of 0.50 MPa. The reaction discharge enters an anion exchange resin bed layer.
The reactor discharge 12 is deacidified by an anion exchange resin bed layer 13 and then enters a rectifying tower 15 for separation, the operating pressure is 1MPa, and the theoretical plate number is 20. Unreacted methylal is discharged from the top of the rectifying tower 15 (material flow 16), and is subjected to water removal by a water remover 18 and then is introduced into the liquid phase reactor 11 again. The material discharged from the bottom of the rectifying tower 15 enters a rectifying tower 20 for next separation, the operating pressure is 1MPa, and the theoretical plate number is 20. Unreacted methanol is discharged from the top of the rectifying tower 20 (stream 21), and is subjected to water removal by a water remover 23 and then is introduced into a methanol storage tank 24 again. The bottom discharge 22 of the rectifying tower 20 enters a rectifying tower 26 for next separation, the operating pressure is 1MPa, and the theoretical plate number is 20. Discharging the dimer of the polyoxymethylene dimethyl ether from the top of the rectifying tower 26, removing water by a dehydrator 29, and then introducing into the liquid phase reactor 11 again. The trimer and tetramer of polyoxymethylene dimethyl ether are discharged from the top of the rectifying tower 31 (stream 32) at an operating pressure of 0.3MPa and a theoretical plate number of 20, and enter a product storage tank 34. Polyoxymethylene dimethyl ether with higher polymerization degree (n is more than 4) is discharged from the bottom of the rectifying tower 31 (material flow 33), is dewatered by a dehydrator 29 and then is introduced into the liquid phase reactor 11 again. The reaction was continued for 80h and the product was sampled on-line and analyzed by gas chromatography and the results 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 2.
[ example 3 ]
1. Preparation of the catalyst
The sodium sulfonate polystyrene cation exchange resin 7320 is washed with deionized water until the clear water flows out, and then soaked with 4w% hydrochloric acid for four times, each time using the sodium sulfonate polystyrene cation exchange resin equivalent to sodium sulfonate type polySoaking 4w% hydrochloric acid 10 times of dry weight of styrene cation exchange resin 7320 for 4h each time, 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. Taking 98 g of sulfonic acid type polystyrene cation exchange resin corresponding to dry resin, and mixing with 300ml of Cu (OH) containing 1 g of Cu and 1 g of Mn under the protection of nitrogen2And 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 preparing 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 to remove water, loading it in spray tower, counter-current contacting with methanol in spray tower to form methanol solution, loading it in liquid-phase reactor, reacting with the mixture recovered in reactor to obtain polyoxymethylene dimethyl ether under the action of solid acid catalyst, separating by anionic exchange resin bed, rectifying module and product storage tank, enabling tri-and tetramers of the polyformaldehyde dimethyl ether to enter a product storage tank, circulating unreacted raw material methanol to the methanol storage tank, and circulating other components 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 producing polyoxymethylene dimethyl ethers according to claim 1, wherein the mass ratio of methanol to paraformaldehyde is 0.02 to 50: 1.
3. The process for producing polyoxymethylene dimethyl ethers according to claim 1, wherein the reaction temperature is 80 to 240 ℃.
4. The process for producing polyoxymethylene dimethyl ethers according to claim 1, wherein the reaction pressure is 0.01 to 15.0 MPa.
5. The process for producing polyoxymethylene dimethyl ethers according to claim 1, wherein the reaction residence time is 0.5 to 10.0 hours.
6. The process method for producing polyoxymethylene dimethyl ethers according to claim 1, wherein the operating pressure of the spray tower is 0.1 to 5.0 MPa, and the operating temperature is 45 to 65 ℃.
7. The process for producing polyoxymethylene dimethyl ethers according to claim 1, wherein the mixture comprises a first fraction containing methylal, a third fraction containing polyoxymethylene dimethyl ether dimers and a fifth fraction containing polyoxymethylene dimethyl ethers having a higher degree of polymerization n >4 separated by a rectification module; the rectification module also separates a second fraction containing methanol and a fourth fraction containing tri-and tetramers of polyoxymethylene dimethyl ether.
8. The process for producing polyoxymethylene dimethyl ethers according to claim 7, wherein said rectification module comprises 4 rectification columns.
9. The process for producing polyoxymethylene dimethyl ethers according to claim 8, wherein the first fraction is discharged from the top of a first rectification column, the second fraction is discharged from the top of a second rectification column, the third fraction is discharged from the top of a third rectification column, the fourth fraction is discharged from the top of a fourth rectification column, and the fifth fraction is discharged from the bottom of the fourth rectification column.
10. The process for producing polyoxymethylene dimethyl ethers of claim 7, wherein the first, third and fifth fractions are recycled to the liquid phase reactor after being dewatered by a dehydrator, and the second fraction is recycled to the methanol storage tank after being dewatered by a dehydrator.
11. The process for producing polyoxymethylene dimethyl ethers according to claim 1, wherein the mass ratio of Cu to Mn is 0.01 to 100.
12. The process for producing 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 producing 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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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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