WO2021052328A1 - 一种聚甲氧基二甲醚及其混合物的制备方法 - Google Patents

一种聚甲氧基二甲醚及其混合物的制备方法 Download PDF

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WO2021052328A1
WO2021052328A1 PCT/CN2020/115358 CN2020115358W WO2021052328A1 WO 2021052328 A1 WO2021052328 A1 WO 2021052328A1 CN 2020115358 W CN2020115358 W CN 2020115358W WO 2021052328 A1 WO2021052328 A1 WO 2021052328A1
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formaldehyde
macromolecules
catalyst
dmmn
polyol
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PCT/CN2020/115358
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English (en)
French (fr)
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蔡依进
王兴路
蔡依超
郑吉振
孙华
李文强
陈海龙
徐圣凯
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山东辰信新能源有限公司
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Priority claimed from CN201910884450.4A external-priority patent/CN112521255B/zh
Priority claimed from CN201910921323.7A external-priority patent/CN112574013A/zh
Application filed by 山东辰信新能源有限公司 filed Critical 山东辰信新能源有限公司
Publication of WO2021052328A1 publication Critical patent/WO2021052328A1/zh
Priority to US17/560,796 priority Critical patent/US20220112148A1/en

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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
    • 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
    • C07C41/58—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
    • C07C45/38—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a primary hydroxyl group

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  • the present disclosure belongs to the technical field of energy and chemical industry, in particular, a preparation method of polymethoxy dimethyl ether and a mixture thereof is designed.
  • the cetane number is as high as 76, the oxygen content is 47%-50%, and there is no sulfur and no aromatics. Adding 10% to 20% of polymethoxy dimethyl ether to diesel can significantly reduce the cold filter filter point of diesel, improve the combustion quality of diesel in the engine, and increase thermal efficiency.
  • DMM3, DMM4, DMM5 and DMM3-8 are also a class of solvents with extremely strong dissolving power. They can be used in paints, coatings, inks, adhesives, cleaning agents, electrolyte solvents, etc.
  • Polymethoxy dimethyl ether is usually prepared by reacting methanol or methylal with trioxane or paraformaldehyde in the presence of an acidic catalyst.
  • the basic reaction equation is as follows:
  • trioxane is synthesized using concentrated formaldehyde under the conditions of sulfuric acid catalysis. In the presence of water, a large amount of reflux is required, the heat of vaporization of water is large, and the energy consumption is high. Solvent extraction and dehydration are required, which leads to high synthesis cost.
  • trioxymethylene has a high melting point (61°C), which is easy to sublime, and is prone to pipeline blockage and dangerous accidents. For example, in the process of storage and transportation, once mixed with strong acidic substances, paraformaldehyde will polymerize to form high molecular polymers, which will cause equipment scrapping, pipeline destruction, and dangerous accidents.
  • Paraformaldehyde is a solid form prepared from an aqueous formaldehyde solution after vacuum dehydration and then polymerization, granulation, pulverization, and drying, although the manufacturing cost is reduced.
  • the reaction activity is low, and it is inconvenient to feed materials from synthesis to application in the process of continuous production.
  • formaldehyde has a strong odor and toxicity, which is harmful to the health of workers.
  • gaseous formaldehyde and methylal undergo a catalytic reaction in the presence of a catalyst to prepare a DMMn synthetic solution, which is processed and separated to obtain DMM3-8.
  • the preparation method of gaseous formaldehyde in this process uses monohydric alcohols such as isobutanol as auxiliary agents, resulting in low atom utilization rate and low boiling point of auxiliary agents. It is easy to enter the synthetic liquid and finished products with formaldehyde, and the price is relatively high. Not conducive to industrialization. More importantly, after this adjuvant is formed into hemiacetal, the water solubility is enhanced, it is very difficult to form a layer with water, or special separation equipment is required. In the subsequent distillation and dehydration process, due to the influence of balance, the reformed auxiliary additives will be steamed out and mixed into the dilute formaldehyde solution.
  • trioxane which is too late to decompose, will vaporize with the gaseous formaldehyde, which is likely to cause blockage of the conveying pipeline.
  • the cost of trioxane is relatively high, which is not conducive to industrialization.
  • the polyol remaining after the gasification of formaldehyde is returned and applied to the next batch of formaldehyde concentration to prepare flowing polyoxymethylene with lower moisture content.
  • the polyol includes, but is not limited to: ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, glycerol, butylene glycol, neopentyl Diol, trimethylolpropane, or a mixture of two or more of them.
  • the aqueous formaldehyde solution includes: a commercial formaldehyde aqueous solution or gaseous formaldehyde containing vapor, hydrogen, and methanol formed by catalytic dehydrogenation or oxidation of methanol.
  • the formaldehyde content of the aqueous formaldehyde solution is 10%-85%, preferably 30%-70%.
  • the mixture of formaldehyde and polyol in the heating dehydration step under the vacuum condition, is dehydrated to a moisture content of less than 15%, preferably less than 1.0%.
  • the dehydration temperature of the mixture of formaldehyde and polyol is 30°C to 110°C, preferably 60°C to 100°C.
  • the temperature for heating and vaporizing the flowing polyoxymethylene containing relatively low moisture is 110°C to 300°C, preferably 120°C to 180°C.
  • the catalyst is an acid catalyst.
  • the acid catalyst includes: a liquid acid catalyst, a solid acid catalyst or a gas acid catalyst.
  • the solid acid catalyst includes: titanium silicate molecular sieve, mordenite, sodium bisulfate, aluminum sulfate, ferric chloride, sulfonic acid resin, fluorosulfonic acid resin, sulfuric acid, phosphoric acid adsorbed Silica gel particles, or their mixtures.
  • the mass ratio of the formaldehyde to the polyol is 1.0:0.02 to 20.0, and preferably 1:0.2 to 2.0.
  • the temperature of the catalytic reaction is 30°C to 200°C, preferably 50°C to 120°C.
  • the polyol includes: ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, glycerol, butylene glycol, pentaerythritol, neopentyl glycol Or trimethylolpropane.
  • the aqueous formaldehyde solution includes: aqueous formaldehyde solution in commercial form or gaseous formaldehyde containing vapor formed by catalytic dehydrogenation and oxidation of methanol.
  • the formaldehyde content of the aqueous formaldehyde solution is 5%-85%, preferably 30%-70%.
  • the acid catalyst includes: a liquid acid catalyst, a solid acid catalyst, or a gas acid catalyst.
  • the solid acid catalyst includes: titanium silicate molecular sieve, mordenite, sodium bisulfate, aluminum sulfate, ferric chloride, sulfonic acid resin, fluorosulfonic acid resin, sulfuric acid, phosphoric acid adsorbed Silica gel particles or their mixtures.
  • the formaldehyde, polyols and macromolecules are dehydrated to a moisture weight of less than 10 wt%, preferably less than 1.0 wt%.
  • the ratio of the mass of the formaldehyde to the mass of the polyol and the macromolecule is 1.0:0.1 ⁇ 10.0, preferably 1:0.2 ⁇ 1.8.
  • the catalytic reaction temperature is controlled at 30°C to 180°C, preferably 50°C to 80°C.
  • the macromolecules are used in the next batch of synthetic formaldehyde concentration or directly used in the synthesis reaction.
  • Figure 1 is the process flow of the present disclosure, that is, after the aqueous formaldehyde solution and polyol are mixed in the mixer, they enter the vacuum dehydrator. After dehydration, the flowing polyoxymethylene with lower moisture is obtained, and the flowing polyoxymethylene enters the gasifier gas.
  • the pure gaseous formaldehyde is obtained by chemical conversion, and then the obtained gaseous formaldehyde and methylal, the last batch of low-boiling substances and macromolecules are mixed and enter the catalytic reactor, and the catalytic reaction occurs in the presence of the catalyst and at a certain temperature. After the reaction liquid is purified, it enters the separation system for separation to separate low boilers, macromolecules and finished DMMn products.
  • the residual polyol is returned to the mixer and used in the next batch of formaldehyde concentration to prepare the flowing polyformaldehyde with lower moisture content.
  • the recovered low boilers are separated from a small amount of accumulated moisture, they are returned to the system and mixed with gaseous formaldehyde to continue to participate in the catalytic reaction.
  • the present disclosure provides a new synthesis technical route and process of gaseous formaldehyde and DMMn.
  • the whole process runs in a liquid or gaseous state.
  • the raw materials of the method are easy to obtain and easy to implement. Continuity and automation, high total yield, high product purity, low cost, low waste water pollution, safety and environmental protection, suitable for industrial production.
  • the present disclosure aims to solve a series of problems existing in the synthesis of polymethoxy dimethyl ether by using paraformaldehyde, trioxane or formaldehyde aqueous solution, and provides a new synthetic technical route and process.
  • the raw materials of the method are easily available. , It is easy to realize continuity and automation, the total yield is higher, the cost is lower, the waste water is less and the pollution is small, it is safe and environmentally friendly, and suitable for industrial production.
  • a preparation method of polymethoxy dimethyl ether is to mix an aqueous formaldehyde solution and a polyol in a certain proportion, and then heat and dehydrate under vacuum conditions.
  • DDMn polymethoxy dimethyl ether
  • flowable polyformaldehyde with lower moisture content is obtained, and the flowable polyformaldehyde containing lower moisture is heated and gasified to obtain purer gaseous formaldehyde.
  • the obtained gaseous formaldehyde is combined with methylal and applied in the presence of a catalyst. Batches of low boilers and macromolecules are mixed, and a catalytic reaction occurs at a certain temperature.
  • the catalyst is filtered out and the synthetic liquid is purified, and the atmospheric pressure and vacuum distillation are carried out respectively to separate low boilers, macromolecules, and macromolecules.
  • the finished product of DMMn, and then the finished product of DMMn is subjected to vacuum distillation to obtain each single component.
  • the residual polyol is returned and used in the next batch of formaldehyde concentration to prepare the flowing polyformaldehyde with lower moisture content.
  • the recovered low-boiling matter is separated from a small amount of accumulated moisture, it is returned to the system to realize the cyclic production of DMMn.
  • the preparation method of polymethoxy dimethyl ether (DMM3-8) described in one or more embodiments of the present disclosure has easy-to-obtain raw materials, and the whole process is liquid and gaseous, which is convenient to realize continuity and automation. High rate, high product purity, low cost, low waste water pollution, safety and environmental protection, suitable for industrial production.
  • a method for preparing polymethoxy dimethyl ether and a mixture thereof is to mix the aqueous formaldehyde solution with polyol and the applied macromolecules in a certain proportion, and then vacuum Heat to remove water under conditions to obtain almost anhydrous, flowable polyoxymethylene etherate with low polymerization degree.
  • This anhydrous etherate is combined with methylal, the previous batch of low-boiling substances, macromolecules, etc. in the presence of a catalyst.
  • Catalytic reaction occurs at a certain temperature. After the reaction reaches equilibrium, the catalyst is filtered out, and the atmospheric pressure and vacuum distillation are performed respectively to separate low boilers, macromolecules and finished DMMn products. The finished DMMn products are then subjected to vacuum distillation to obtain Each single component.
  • the separated low boilers and macromolecules are returned and used in the next batch of synthesis.
  • a method for preparing polymethoxy dimethyl ether and a mixture thereof raw materials are readily available, simple and effective, easy to achieve continuity and automation, high yield, and low cost , Waste water pollution is small, safe and environmentally friendly, suitable for industrial production.
  • the formaldehyde content of the aqueous formaldehyde solution is 10%-85%, such as 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55 %, 60%, 65%, 70%, 75% or 80%.
  • the mixture of formaldehyde and polyol in the heating and dehydration step under the vacuum condition, is dehydrated to a moisture content of less than 15%, such as less than 1.0%, and for example 0.1-14, such as 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.8%, 0.6%, 0.4%, or 0.2%.
  • the dehydration temperature of the mixture of formaldehyde and polyol is 30°C to 110°C, for example, 35°C, 40°C, 45°C, 50°C, 55°C. °C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C or 150°C.
  • the temperature for heating and vaporizing the flowing polyoxymethylene containing lower moisture is 110°C to 300°C, such as 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C or 290°C.
  • the mass ratio of the formaldehyde to the polyol is 1.0:0.02 to 20.0, such as 1:0.04, 1:0.06, 1:0.08, 1 : 1.10, 1: 1.20, 1: 1.40, 1: 1.60, 1: 1.80, 1: 2.00, 1: 3.00, 1: 4.00, 1: 5.00, 1: 6.00, 1: 7.00, 1: 8.00, 1: 9.00 , 1:10.00, 1:11.00, 1:12.00, 1:13.00, 1:14.00, 1:15.00, 1:16.00, 1:17.00, 1:18.00 or 1:19.00.
  • the temperature of the catalytic reaction is 30°C to 200°C, for example, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C , 130°C, 140°C, 150°C, 160°C, 170°C, 180°C or 190°C.
  • the formaldehyde content of the aqueous formaldehyde solution is 5%-85%, such as 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%.
  • the formaldehyde, polyols and macromolecules are dehydrated to a moisture weight of less than 10%, such as 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1%, 0.8%, 0.6%, 0.4% or 0.2% (by weight percentage).
  • the ratio of the mass of the formaldehyde to the mass of the polyol and the macromolecule is 1.0:0.1 ⁇ 10.0, preferably 1:0.2 ⁇ 1.8.
  • One or more embodiments of the present disclosure use an aqueous formaldehyde solution (or gaseous formaldehyde synthesis gas) as the raw material for the source of formaldehyde, which simplifies the production and lowers the product cost.
  • aqueous formaldehyde solution or gaseous formaldehyde synthesis gas
  • One or more embodiments of the present disclosure use polyhydric alcohol as a carrier and auxiliary to prepare hemiacetal etherate, which has low cost, high efficiency, easy operation, and does not pollute subsequent materials.
  • One or more embodiments of the present disclosure solve the problem that polyoxymethylene itself forms an insoluble and infusible solid state with low activity and difficult to transport when it is removed to an anhydrous state.
  • reaction process of one or more embodiments of the present disclosure has a higher yield through proper control.
  • the production capacity of a single device can be made relatively large.
  • One or more embodiments of the present disclosure should use solid acid catalysts, which have good catalytic effects, and are safe and environmentally friendly.
  • the formaldehyde in one or more embodiments of the present disclosure is still an easy-flowing liquid after simply removing the water, which is convenient for realizing continuous production and automatic control.
  • Example 1 After mixing 400g of formaldehyde aqueous solution (37%) and 60g of ethylene glycol, evacuating and heating to remove water, 193.2g of anhydrous flowing polyoxymethylene is obtained, and the anhydrous flowing polyoxymethylene is gradually heated to 160 °C, the formaldehyde is gradually gasified to obtain gaseous formaldehyde, and then the dry and anhydrous gaseous formaldehyde is passed into a mixture of 10g catalyst and 280g methylal. Catalytic reaction occurs at a certain temperature.
  • the catalyst is filtered out to obtain 356.7g reaction balance liquid, 91.7g residual ethylene glycol (total loss 24.8g), then 356.7g reaction balance liquid was subjected to atmospheric and vacuum distillation, respectively, to separate 250.8g of low boilers, 15.5g of macromolecules and finished DMMn 72.4g (loss of 18.0g), the finished product of DMMn is then subjected to vacuum distillation to obtain each single component.
  • the residual ethylene glycol is returned and used in the next batch of formaldehyde concentration to prepare anhydrous flowing polyformaldehyde.
  • Example 2 After mixing 400 g of formaldehyde aqueous solution (37%) and 91 g of ethylene glycol recovered from the previous batch, vacuum and heat to remove water, 222.5 g of anhydrous flowing polyformaldehyde was obtained, and the anhydrous flowing polyformaldehyde was then After gradually heating to 160°C, the formaldehyde is gradually gasified to obtain gaseous formaldehyde, and then the dry and anhydrous gaseous formaldehyde is passed into a mixture of 10g catalyst and 280g methylal. Catalytic reaction occurs at a certain temperature.
  • reaction balance liquid After the reaction reaches equilibrium, The catalyst was filtered out to obtain 384.7g of reaction balance liquid and 93.5g of residual ethylene glycol (total loss of 24.3g). Then 384.7g of reaction balance liquid was subjected to atmospheric and reduced pressure distillation, respectively, to separate 264.0g of low boilers and macromolecules. 22.9g and 77.3g of DMMn product (loss of 20.5g). The DMMn product is then subjected to vacuum distillation to obtain each single component. After the gasification of the formaldehyde, the residual ethylene glycol is returned and used in the next batch of formaldehyde concentration to prepare anhydrous flowing polyformaldehyde.
  • Example 3 After mixing 400g of formaldehyde aqueous solution (37%) and 93.5g of ethylene glycol recovered from the previous batch, vacuum and heat to remove water, obtain 226.7g of anhydrous flowing polyformaldehyde, anhydrous flowing polyformaldehyde After gradually heating to 160°C, the formaldehyde is gradually gasified to obtain gaseous formaldehyde, and then the dry and anhydrous gaseous formaldehyde is passed into the one with 10g of catalyst, 264.0g of recovered low boilers, and 22.9g of macromolecules plus 196g of methylal. In the mixture, a catalytic reaction occurs at a certain temperature.
  • reaction equilibrium liquid 90.0g of residual ethylene glycol (a total loss of 26g), and then 593.6g of reaction equilibrium liquid is subjected to atmospheric pressure.
  • vacuum distillation separated 397.3g of low boilers, 35.5g of macromolecules, and 128.8g of finished DMMn (loss of 32.0g).
  • the finished DMMn was subjected to vacuum distillation to obtain each single component.
  • the residual ethylene glycol is returned and used in the next batch of formaldehyde concentration to prepare anhydrous flowing polyformaldehyde.
  • Example 4 After mixing 400g of aqueous formaldehyde solution (37%) and 60g of glycerol, evacuating and heating to remove water, 191.1g of anhydrous flowing polyformaldehyde is obtained, and the anhydrous flowing polyoxymethylene is gradually heated to 160 °C, the formaldehyde is gradually gasified to obtain gaseous formaldehyde, and then the dry and anhydrous gaseous formaldehyde is passed into a mixture of 10g catalyst and 280g methylal. Catalytic reaction occurs at a certain temperature.
  • the catalyst is filtered out to obtain 360.7g reaction balance liquid, 92.0g residual glycerol (total loss 18.4g), then 360.7g reaction balance liquid was subjected to atmospheric and vacuum distillation, respectively, to separate 246.8g of low boilers, 17.2g of macromolecules and finished DMMn 74.4g (loss of 22.3g), the finished product of DMMn is subjected to vacuum distillation to obtain each single component.
  • the residual glycerol after the gasification of formaldehyde is returned and used in the next batch of formaldehyde concentration to prepare anhydrous flowing polyformaldehyde.
  • Example 5 After mixing 400g of formaldehyde aqueous solution (37%), 30g of diethylene glycol and 30g of trimethylolpropane, evacuating and heating to remove water, 193.1g of anhydrous flowing polyformaldehyde was obtained, and 193.1g of anhydrous flowing polyformaldehyde was obtained. After the formaldehyde is gradually heated to 160°C, the formaldehyde is gradually gasified to obtain gaseous formaldehyde, and then the dry and anhydrous gaseous formaldehyde is passed into a mixture of 10g catalyst and 280g methylal. Catalytic reaction occurs at a certain temperature, and the reaction reaches equilibrium.
  • reaction balance liquid 357.7g of reaction balance liquid
  • 94.5g of residual diethylene glycol and trimethylolpropane mixture total loss of 20.9g
  • 357.7g of reaction balance liquid was subjected to atmospheric and vacuum distillation, respectively, to separate out 250.0g of low boilers, 20.5g of macromolecules, and 73.4g of finished DMMn (loss of 13.8g).
  • the finished DMMn is then subjected to vacuum distillation to obtain individual components.
  • the residual diethylene glycol and trimethylolpropane mixture is returned and used in the next batch of formaldehyde concentration to prepare anhydrous flowing polyformaldehyde.
  • the solid residue is 0.6g (a total loss of 22g), and then 387.8g of the reaction balance liquid is subjected to atmospheric and vacuum distillation respectively to separate 295.9g of low boilers, 15.2g of macromolecules and 50.4g of finished DMMn (loss of 26.3g), DMMn
  • the finished product is then subjected to vacuum distillation to obtain each single component.
  • the formaldehyde is solid after polymerization in this process, which is difficult to transport and transfer.
  • the water content of the paraformaldehyde obtained is still high, as high as 3.5%, which affects the equilibrium conversion rate of the synthetic solution and results in a low yield.
  • the 744.5g of DMM1, DMM2, etc. obtained in the previous batch were subjected to special separation under normal pressure to obtain 404.5g of DMM1, etc. (can be applied to the next batch of synthesis); 25g of methanol water, etc., (can be used for methylal synthesis); DMM2 308.5g (can be applied to the next batch of synthesis).
  • reaction liquid 1621.8g , Firstly distill out 647.4g of DMM1 and others at normal pressure; 496.3g of DMM2 and others, then distill out 323.5g of DMM3-8 at -0.098MP, and 119.6g of residual macromolecules, which are used for the next batch of synthesis.
  • the present disclosure solves the problems of difficult preparation, transportation, and low activity of solid paraformaldehyde existing with paraformaldehyde as a raw material; high cost, serious equipment corrosion, and risk of pipeline blockage when using paraformaldehyde as a raw material; and
  • the aqueous formaldehyde solution is used as the raw material, the equilibrium conversion rate is low, the content of formaldehyde and hemiacetal is high, it is difficult to separate and obtain the finished product, and the water accumulation cannot be recycled.
  • the present disclosure is the company's extensive research on various synthetic routes and synthesis of DMMn After the technology, when the low-cost synthesis of DMMn cannot be completed, another way of thinking, careful research and experimental verification of the technical results obtained, finally make the raw materials of the present disclosure easy to obtain, the process is simple and effective, the cost is low, the process is simple and smooth, and the synthesis The conversion rate is high and it is easy to separate.
  • the present disclosure has low investment costs, low production and start-up risks, and high operating profits.
  • the present disclosure provides a method for preparing polymethoxy dimethyl ether and a mixture thereof.
  • the present disclosure uses aqueous formaldehyde solution (or gaseous formaldehyde synthesis gas) as the raw material for the source of formaldehyde, which simplifies the production and lowers the product cost; adopts polyhydric alcohol as a carrier auxiliary agent to prepare hemiacetal etherate, which has low cost, high efficiency and easy Operation, does not pollute subsequent materials; solves the problem that polyoxymethylene itself forms an insoluble and insoluble solid state with low activity and difficult to transport when it is removed to anhydrous state; it is suitable for continuous process and is easy to realize automatic control; solid acid catalyst can be used with good catalytic effect , Safe and environmentally friendly; formaldehyde is still easy to flow liquid after simply removing the water, which is convenient for continuous production and automatic control.
  • aqueous formaldehyde solution or gaseous formaldehyde synthesis gas

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Abstract

本公开提供了一种聚甲氧基二甲醚(DMMNn，一般n＝3～8或2-8)及其混合物的制备方法，包括：甲醛水溶液和多元醇的混合物在真空条件下加热脱水制得含较低水分的流动聚甲醛，再经过加热气化得到较纯的气态甲醛，再在催化剂存在下和甲缩醛、套用的上批次低沸物和大分子等混合，进行催化反应，滤出催化剂并净化合成液，分别进行常压及减压蒸馏，分离得低沸物、大分子和DMMn成品，DMMn成品再经减压精馏，可得到各单组分产物，其中甲醛气化后残余的多元醇返回，套用于下批的甲醛浓缩；或者包括：甲醛水溶液和多元醇及套用的上批次的大分子混合物在真空条件下加热脱除水分，得到无水的可流动的聚甲醛醚化物，在催化剂存在下和甲缩醛、套用的上批次低沸物、大分子等，发生催化反应，滤出催化剂，分别进行常压及减压蒸馏，分离出低沸物、大分子和DMMn成品，DMMn成品再经减压精馏，可得到各单组分，分离得到的低沸物和大分子返回，套用于下批的合成。

Description

一种聚甲氧基二甲醚及其混合物的制备方法
相关申请的交叉引用
本申请要求于2019年9月27日提交中国专利局的申请号为2019109213237、名称为“一种聚甲氧基二甲醚(DMMn)的制备方法”的中国专利申请以及于2019年9月19日提交中国专利局的申请号为201910884450.4、名称为“一种聚甲醛二甲基醚及其混合物的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本公开属于能源化工技术领域，尤其是设计了一种聚甲氧基二甲醚及其混合物的制备方法。
背景技术
聚甲氧基二甲醚又称聚甲醛二甲醚，英文名称：Polyoxymethylene dimethyl ethers，简称PODE或DMMn，是一类以二甲氧基甲烷为母体、亚甲氧基为主链的低分子量缩醛类聚合物，其通式表示为：CH3O(CH2O)nCH3。其聚合度为3-8或2-8的聚甲氧基二甲醚，简称DMMn(n＝2-8或3-8)用于清洁柴油调和组分。其物理化学性质与柴油相近，在不需要对车辆发动机供油系统进行改造的情况下，可以将其调和到柴油中使用。其十六烷值高达76，含氧量47％～50％，无硫无芳烃。在柴油中添加聚甲氧基二甲醚10％～20％，能显著降低柴油冷滤点，可改善柴油在发动机中的燃烧质量，提高热效率。同时DMM3、DMM4、DMM5和DMM3-8也是一类溶解能力极强的溶剂。它们可应用于油漆、涂料、油墨、粘合剂、清洗剂、电解液溶剂等。
聚甲氧基二甲醚通常由甲醇或甲缩醛与三聚甲醛或多聚甲醛在酸性催化剂存在下反应制得，反应基本方程式如下：
Figure PCTCN2020115358-appb-000001
酸性催化剂催化合成聚甲氧基二甲醚的过程是一个平衡反应。少量水的存在，就促使平衡逆向移动，使得反应液中残余大量的甲醛、甲醇和半缩醛等，而产物混合物中目标产物的含量较低，给提纯和低成本制备聚甲氧基二甲醚造成困难。所以人们便想到用无水或者低水分含量的甲醛，这就想到利用三聚甲醛、多聚甲醛、合成无水或者低水分的气态甲醛、或者想到用较浓的甲醛水溶液来合成并在合成过程中想法脱除体系的水。
但是，三聚甲醛是在硫酸催化的条件下使用浓甲醛合成。在有水情况下，需要大量回流，水的汽化热较大，能耗较高，还要用溶剂萃取、脱水，导致其合成成本较高。而且三聚甲醛熔点较高(61℃)，易升华，容易发生管道堵塞，出现危险事故等。例如，三聚甲醛在储存及运输过程中，一旦混入到强酸性物质就会聚合形成高分子聚合物，使设备报废，管道毁坏，出现危险事故。
而多聚甲醛是由甲醛水溶液，在真空脱水后再聚合、造粒或粉碎、干燥等工序制得的固体形态，虽然制造成本有所降低。但是在作为反应物的情况下，因其不溶不熔的性质，反应活性较低，在连续化生产的过程中，从合成到应用投料都不方便。而且，甲醛气味较大，毒性较大，有损工人健康。
国内也有用较高浓度甲醛水溶液和甲醇或甲缩醛反应制备聚甲氧基二甲醚(DMM3-8)的报道。虽然从理论上看，工艺流畅、方便操作，但是实际操作中存在各种技术问题，例如合成液再脱水较困难、转化率很低、甲醛残余多，难于分离等问题，工艺不成熟，难于实现工业化。
据报道，用气体甲醛与甲缩醛在催化剂存在下，发生催化反应，制备DMMn合成液，经处理及分离后得到DMM3-8。但是该工艺中气态甲醛的制备方法，是用异丁醇等一元醇作为辅剂，导致原子利用率低，辅剂沸点较低，容易随着甲醛进入合成液和成品中，而且价格较高，不利于工业化。其更重要的是，这种辅剂形成半缩醛后，水溶性增强，与水形 成分层十分困难，或者需要特殊的分离设备。在其后续的蒸馏脱水过程中，由于平衡的影响，重新形成的辅助添加剂会被蒸出混合到稀的甲醛溶液中。
用甲醇或甲缩醛在氧化反应器中利用空气氧化制取甲醛气体；再将制备的甲醛气体通入冷却器中冷却至20～99℃，再进入气水分离器脱除冷凝水后得甲醛气体。事实证明，氧化甲醇形成的甲醛气体含有30％左右的生成水分，在降低到20～99℃时很容易形成甲醛水合物而液化或者发生聚合反应而液化或固化，不利于实现工业化。
其它制备无水气态甲醛的常规方法还有：1、将多聚甲醛加热解聚，制备气态甲醛，但是多聚甲醛本身具备的结合水就在4％-12％左右，大大影响DMMn合成的收率及中间产物的进一步循环套用。不但固体聚甲醛制备比较繁琐，而且进一步的投料及输送都不利于规模化、连续化的规模生产，且存在较大的安全隐患。2、三聚甲醛在酸性催化剂的作用下，加热分解气化。这样会存在来不及分解的三聚甲醛随气态甲醛气化而出，容易形成输送管道堵塞，而且三聚甲醛成本较高，不利于实现工业化。
发明内容
本公开提供一种聚甲氧基二甲醚(DMMNn，优选地n＝3～8)的制备方法，包括以下步骤：
-甲醛水溶液和多元醇按照一定比例混合后，真空条件下加热脱水一步制得含较低水分的流动聚甲醛，
-含较低水分的流动聚甲醛再经过加热气化得到较纯的气态甲醛，
-由获得的气态甲醛在催化剂存在下和甲缩醛、套用的上批次低沸物和大分子等混合，在一定温度下发生催化反应，
-反应达到平衡后,滤出催化剂并净化合成液，分别进行常压及减压蒸馏，分离出低沸物、大分子和DMMn成品，以及
-DMMn成品再经减压精馏，可得到各单组分DMMn产物，
其中，将甲醛气化后残余的多元醇返回并套用于下批的甲醛浓缩，以制备含较低水分的流动聚甲醛。
在一种或多种实施方式中，所述多元醇包括，但不限于：乙二醇、1,2-丙二醇、1,3-丙二醇、二甘醇、丙三醇、丁二醇、新戊二醇、三羟甲基丙烷、或它们之间两种或者两种以上的混合物。
在一种或多种实施方式中，所述甲醛水溶液包括：商品形式的甲醛水溶液或甲醇通过催化脱氢或氧化形成的含水蒸汽、氢气和甲醇的气态甲醛。
在一种或多种实施方式中，所述甲醛水溶液的甲醛含量为10％-85％，优选 30％-70％。
在一种或多种实施方式中，在所述真空条件下加热脱水步骤中，将甲醛和多元醇的混合物脱水到水分小于15％，优选的小于1.0％。
在一种或多种实施方式中，在所述真空条件下加热脱水步骤中，甲醛和多元醇的混合物脱水温度为30℃～110℃，优选60℃～100℃。
在一种或多种实施方式中，对所述含较低水分的流动聚甲醛进行加热气化的温度为110℃～300℃，优选120℃～180℃。
在一种或多种实施方式中，所述催化剂为酸性催化剂，优选地所述酸性催化剂包括：液体酸性催化剂、固体酸性催化剂或气体酸性催化剂。
在一种或多种实施方式中，所述固体酸性催化剂包括：钛硅分子筛、丝光沸石、硫酸氢钠、硫酸铝、氯化铁、磺酸树脂、氟磺酸树脂、吸附有硫酸、磷酸的硅胶颗粒、或它们的混合物。
在一种或多种实施方式中，在甲醛水溶液和多元醇按照一定比例混合步骤中，甲醛和多元醇质量比为1.0:0.02～20.0，其中优选1:0.2～2.0。
在一种或多种实施方式中，所述催化反应的温度为30℃～200℃，优选50℃～120℃。
本公开提供一种聚甲氧基二甲醚(DMMn，优选地n＝2-8)及其混合物的制备方法，包括以下步骤：
-甲醛水溶液和多元醇及套用的上批次的大分子按照一定比例混合后，真空条件下加热脱除水分，得到无水的可流动的聚甲醛醚化物，
-所述无水的聚甲醛醚化物在酸性催化剂存在下与甲缩醛、套用的上批次低沸物、大分子等，在一定温度下发生催化反应，
-反应达到平衡后,滤出催化剂，分别进行常压及减压蒸馏，分离出低沸物、大分子和DMMn成品，
-DMMn成品再经减压精馏，可得到各单组分DMMn产物，
-将分离得到的低沸物和大分子返回并套用于下批的合成。
在一种或多种实施方式中，所述多元醇包括：乙二醇、1,2-丙二醇、1,3-丙二醇、二甘醇、丙三醇、丁二醇、季戊四醇、新戊二醇或三羟甲基丙烷。
在一种或多种实施方式中，所述甲醛水溶液包括：商品形式的甲醛水溶液或甲醇通过催化脱氢、氧化形成的含水蒸汽的气态甲醛。
在一种或多种实施方式中，甲醛水溶液的甲醛含量为5％-85％，优选30％-70％。
在一种或多种实施方式中，所述酸性催化剂包括：液体酸性催化剂、固体酸性催化剂或气体酸性催化剂。
在一种或多种实施方式中，所述固体酸性催化剂包括：钛硅分子筛、丝光沸石、硫酸氢钠、硫酸铝、氯化铁、磺酸树脂、氟磺酸树脂、吸附有硫酸、磷酸的硅胶颗粒或它们的混合物。
在一种或多种实施方式中，在真空条件下加热脱除水分步骤中，将甲醛和多元醇及大分子脱水到水分重量小于10wt％，优选地小于1.0wt％。
在一种或多种实施方式中，在甲醛水溶液和多元醇及套用的上批次的大分子按照一定比例混合的步骤中，甲醛的质量和多元醇及大分子的质量之比为1.0:0.1～10.0，优选1:0.2～1.8。
在一种或多种实施方式中，所述催化反应温度控制在30℃～180℃，优选50℃～80℃。
在一种或多种实施方式中，所述大分子套用于下一批合成的甲醛浓缩或者直接套用于合成反应。
附图说明
为了更清楚地说明本公开实施方式的技术方案，下面将对实施方式中所需要使用的附图作简单地介绍，应当理解，以下附图仅示出了本公开的某些实施方式，因此不应被看作是对范围的限定，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他相关的附图。
附图1是本公开的工艺流程，即甲醛水溶液和多元醇在混合器内混合后，进入真空脱水器，脱水后得到的含较低水分的流动聚甲醛，流动聚甲醛再进入气化器气化得到较纯气态甲醛，再由获得的气态甲醛和甲缩醛、套用的上批次低沸物和大分子等混合后进入催化反应器，在催化剂存在下和一定温度下发生催化反应，反应后反应液经净化后，进入分离系统进行分离，分离出低沸物、大分子和DMMn成品。甲醛气化后残余的多元醇返回混合器，套用于下批的甲醛浓缩，去制备含较低水分的流动聚甲醛。回收的低沸物经过分离出少量累积的水分后，返回系统和气态甲醛混合，继续参与催化反应。
具体实施方式
为使本公开实施方式的目的、技术方案和优点更加清楚，下面将对本公开实施方式中的技术方案进行清楚、完整地描述。实施方式中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
除非本文另有定义，否则结合本公开使用的科学和技术术语应具有本领域普通技术人员通常理解的含义。以下描述示例性方法和材料，但是与本文描述的那些类似或等同的方 法和材料也可以用于本公开的实践或测试中。
本公开为了克服已知气体甲醛的制备方法存在的现实问题，提供一种新的气体甲醛和DMMn的合成技术路线及工艺过程，整个过程以液态或气态状态运行，该方法原料易得、便于实现连续化和自动化，总收率较高、产品纯度较高，成本较低，废水污染性小，安全环保，适合工业化生产。
本公开就是为了解决现有的用多聚甲醛、三聚甲醛或者甲醛水溶液合成聚甲氧基二甲醚存在的一系列问题，提供一种新的合成技术路线及工艺过程，该方法原料易得、便于实现连续化和自动化，总收率较高、成本较低，废水少而且污染性小，安全环保，适合工业化生产。
在一种或多种实施方式中，一种聚甲氧基二甲醚(DMMn一般n＝3-8)制备方法是以甲醛水溶液和多元醇按照一定比例混合后，真空条件下加热脱水，经此一步便得到含较低水分的流动聚甲醛，含较低水分的流动聚甲醛再经过加热气化得到较纯气态甲醛，再由获得的气态甲醛在催化剂存在下和甲缩醛、套用的上批次低沸物和大分子等混合，在一定温度下发生催化反应，反应达到平衡后,滤出催化剂并净化合成液，分别进行常压及减压蒸馏，分离出低沸物、大分子和DMMn成品，DMMn成品再经减压精馏，可得到各单组分。甲醛气化后残余的多元醇返回，套用于下批的甲醛浓缩，去制备含较低水分的流动聚甲醛。回收的低沸物经过分离出少量累积的水分后，返回系统，实现DMMn的循环生产。
基本流程见附图(图1)。
其中获得流动聚甲醛及气体甲醛的主要反应式示例如下：
Figure PCTCN2020115358-appb-000002
本公开一种或多种实施方式中所述的一种聚甲氧基二甲醚(DMM3-8)的制备方法，原料易得，全流程为液态和气态，便于实现连续化和自动化，收率较高、产品纯度较高，成本较低，废水污染性小，安全环保，适合工业化生产。
本公开的一种或多种实施方式中的一种聚甲氧基二甲醚及其混合物的制备方法是以甲醛水溶液和多元醇及套用的上批次的大分子按照一定比例混合后，真空条件下加热脱除水分，得到几乎无水的可流动的低聚合度聚甲醛醚化物，该无水的醚化物在催化剂存在下和甲缩醛、套用的上批次低沸物、大分子等，在一定温度下发生催化反应，反应达到平衡后, 滤出催化剂，分别进行常压及减压蒸馏，分离出低沸物、大分子和DMMn成品，DMMn成品再经减压精馏，可得到各单组分。分离得到的低沸物和大分子返回，套用于下批的合成。
基本反应流程如下：
Figure PCTCN2020115358-appb-000003
本公开的一种或多种实施方式中的一种聚甲氧基二甲醚及其混合物的制备方法，原料易得，简单有效，便于实现连续化和自动化，收率较高，成本较低，废水污染性小，安全环保，适合工业化生产。
在一种或多种实施方式中，所述甲醛水溶液的甲醛含量为10％-85％，例如15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％或80％。
在一种或多种实施方式中，在所述真空条件下加热脱水步骤中，将甲醛和多元醇的混合物脱水到水分小于15％，例如小于1.0％，再例如0.1-14，诸如13％、12％、11％、10％、9％、8％、7％、6％、5％、4％、3％、2％、1％、0.8％、0.6％、0.4％或0.2％。
在一种或多种实施方式中，在所述真空条件下加热脱水步骤中，甲醛和多元醇的混合物脱水温度为30℃～110℃，例如35℃、40℃、45℃、50℃、55℃、60℃、65℃、70℃、75℃、80℃、85℃、90℃、95℃、100℃或150℃。
在一种或多种实施方式中，对所述含较低水分的流动聚甲醛进行加热气化的温度为110℃～300℃，例如120℃、130℃、140℃、150℃、160℃、170℃、180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃、260℃、270℃、280℃或290℃。
在一种或多种实施方式中，在甲醛水溶液和多元醇按照一定比例混合步骤中，甲醛和多元醇质量比为1.0:0.02～20.0，例如1:0.04、1:0.06、1:0.08、1:1.10、1:1.20、1:1.40、1:1.60、1:1.80、1:2.00、1:3.00、1:4.00、1:5.00、1:6.00、1:7.00、1:8.00、1:9.00、1:10.00、1:11.00、1:12.00、1:13.00、1:14.00、1:15.00、1:16.00、1:17.00、1:18.00或1:19.00。
在一种或多种实施方式中，所述催化反应的温度为30℃～200℃、例如40℃、50℃、60℃、70℃、80℃、90℃、100℃、110℃、120℃、130℃、140℃、150℃、160℃、170℃、180℃或190℃。
在一种或多种实施方式中，甲醛水溶液的甲醛含量为5％-85％，例如10％、15％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％、70％、75％或80％。
在一种或多种实施方式中，在真空条件下加热脱除水分步骤中，将甲醛和多元醇及大分子脱水到水分重量小于10％，例如9％、8％、7％、6％、5％、4％、3％、2％、1％、0.8％、0.6％、0.4％或0.2％(以重量百分比计)。
在一种或多种实施方式中，在甲醛水溶液和多元醇及套用的上批次的大分子按照一定比例混合的步骤中，甲醛的质量和多元醇及大分子的质量之比为1.0:0.1～10.0，优选1:0.2～1.8。
具体体现在以下几方面：
1、本公开的一种或多种实施方式采用甲醛水溶液(或者气态甲醛合成气)作为甲醛来源的原料，使生产更简单化，产品成本较低。
2、本公开的一种或多种实施方式采用多元醇为载体辅剂制备半缩醛醚化物，成本低、效率高、易操作、不污染后续物料。
3、本公开的一种或多种实施方式解决了聚甲醛本身在脱到无水状态时形成不溶不熔的活性低、难于输送的固体状态。
4、本公开的一种或多种实施方式的连续化过程便于实现自动化控制。
5、本公开的一种或多种实施方式的反应过程，通过适当控制，收率较高。
6、本公开的一种或多种实施方式的连续化装置，单套装置的产能可以做的比较大。
7、本公开的一种或多种实施方式应可用固体酸性催化剂，催化效果好，安全环保。
8、本公开的一种或多种实施方式的甲醛在简单脱干净水分后仍然为容易流动的液体，便于实现连续化生产和自动化控制。
实施例
实施例1：将400g甲醛水溶液(37％)和乙二醇60g混合后，抽真空、加热脱除水分，得到无水的流动聚甲醛193.2g，无水的流动聚甲醛再经过逐步加热到160℃，甲醛逐步气化得气态甲醛，再将干燥无水的气态甲醛通入到有10g催化剂、280g甲缩醛混合物中，在一定温度下发生催化反应，反应达到平衡后,滤出催化剂，得到反应平衡液356.7g，残余乙二醇91.7g(共损失24.8g)，再将反应平衡液356.7g分别进行常压及减压蒸馏，分离出低沸物250.8g、大分子15.5g和DMMn成品72.4g(损失18.0g)，DMMn成品再经减压精馏，可得到各单组分。甲醛气化后残余的乙二醇返回，套用于下批的甲醛浓缩，去制备无水的流动聚甲醛。
实施例2：将400g甲醛水溶液(37％)和上批次回收的乙二醇91g混合后，抽真空、 加热脱除水分，得到无水的流动聚甲醛222.5g，无水的流动聚甲醛再经过逐步加热到160℃，甲醛逐步气化得气态甲醛，再将干燥无水的气态甲醛通入到有10g催化剂、280g甲缩醛混合物中，在一定温度下发生催化反应，反应达到平衡后,滤出催化剂，得到反应平衡液384.7g，残余乙二醇93.5g(共损失24.3g)，再将反应平衡液384.7g分别进行常压及减压蒸馏，分离出低沸物264.0g、大分子22.9g和DMMn成品77.3g(损失20.5g)，DMMn成品再经减压精馏，可得到各单组分。甲醛气化后残余的乙二醇返回，套用于下批的甲醛浓缩，去制备无水的流动聚甲醛。
实施例3：将400g甲醛水溶液(37％)和上批次回收的乙二醇93.5g混合后，抽真空、加热脱除水分，得到无水的流动聚甲醛226.7g，无水的流动聚甲醛再经过逐步加热到160℃，甲醛逐步气化得气态甲醛，再将干燥无水的气态甲醛通入到有10g催化剂、回收的低沸物264.0g、大分子22.9g补加196g甲缩醛的混合物中，在一定温度下发生催化反应，反应达到平衡后,滤出催化剂，得到反应平衡液593.6g，残余乙二醇90.0g(共损失26g)，再将反应平衡液593.6g分别进行常压及减压蒸馏，分离出低沸物397.3g、大分子35.5g和DMMn成品128.8g(损失32.0g)，DMMn成品再经减压精馏，可得到各单组分。甲醛气化后残余的乙二醇返回，套用于下批的甲醛浓缩，去制备无水的流动聚甲醛。
实施例4：将400g甲醛水溶液(37％)和丙三醇60g混合后，抽真空、加热脱除水分，得到无水的流动聚甲醛191.1g，无水的流动聚甲醛再经过逐步加热到160℃，甲醛逐步气化得气态甲醛，再将干燥无水的气态甲醛通入到有10g催化剂、280g甲缩醛混合物中，在一定温度下发生催化反应，反应达到平衡后,滤出催化剂，得到反应平衡液360.7g，残余丙三醇92.0g(共损失18.4g)，再将反应平衡液360.7g分别进行常压及减压蒸馏，分离出低沸物246.8g、大分子17.2g和DMMn成品74.4g(损失22.3g)，DMMn成品再经减压精馏，可得到各单组分。甲醛气化后残余的丙三醇返回，套用于下批的甲醛浓缩，去制备无水的流动聚甲醛。
实施例5：将400g甲醛水溶液(37％)和二甘醇30g、三羟甲基丙烷30g混合后，抽真空、加热脱除水分，得到无水的流动聚甲醛193.1g，无水的流动聚甲醛再经过逐步加热到160℃，甲醛逐步气化得气态甲醛，再将干燥无水的气态甲醛通入到有10g催化剂、280g甲缩醛混合物中，在一定温度下发生催化反应，反应达到平衡后,滤出催化剂，得到反应平衡液357.7g，残余二甘醇和三羟甲基丙烷混合物94.5g(共损失20.9g)，再将反应平衡液357.7g分别进行常压及减压蒸馏，分离出低沸物250.0g、大分子20.5g和DMMn成品73.4g(损失13.8g)，DMMn成品再经减压精馏，可得到各单组分。甲醛气化后残余的二甘醇和三羟甲基丙烷的混合物返回，套用于下批的甲醛浓缩，去制备无水的流动聚甲醛。
对比例1
将400g甲醛水溶液(37％)，以同样的条件抽真空、加热脱除水分，得到无水的不可流动的多聚甲醛130.4g，将该不可流动的聚甲醛再经过逐步加热到160℃，甲醛逐步气化得气态甲醛，再将气态甲醛通入到有10g催化剂、280g甲缩醛混合物中，在一定温度下发生催化反应，反应达到平衡后,滤出催化剂，得到反应平衡液387.8g，残余固体残渣0.6g(共损失22g)，再将反应平衡液387.8g分别进行常压及减压蒸馏，分离出低沸物295.9g、大分子15.2g和DMMn成品50.4g(损失26.3g)，DMMn成品再经减压精馏，可得到各单组分。但是该过程甲醛聚合后是固体，难于输送及转移。小试规模的间歇实验中，得到的多聚甲醛含水量仍较高，高达3.5％，影响合成液的平衡转化率致使收率较低。
对比例2
将400g甲醛水溶液(37％)和异丁醇60g混合后，混溶无分层现象，抽真空、加热脱除水分，得到固体聚甲醛161.5g，其甲醛含量79.8、水分2.32％，异丁醇损失31.2g，固体聚甲醛不利于输送等操作，在本实验中不具备继续合成的意义。
表1实施例与比较例中DMMn成品质量与损失质量的比较
Figure PCTCN2020115358-appb-000004
在表1中可以看出，实施例中的成品质量远高于比较例1中的成品质量(由于比较2中固体聚甲醛不利于输送等操作，该实验无法也没有意义继续进行)。而且实施例中质量损失与成品质量的比例也远低于比较例1中的结果。
实施例6：
取37％甲醛水溶液800g和60g乙二醇混合后，真空条件下于95℃以下脱除水分，得到无水的可流动的聚甲醛醚化物326.4g，将该可流动的聚甲醛醚化物转入具有10g酸性磺酸树脂和560g甲缩醛的混合物中、在50-80温度下发生催化反应，反应达到平衡后,滤出催化剂得到反应液866.4g，先常压蒸馏出DMM1、DMM2等583.4g，在于-0.098MP蒸出161gDMM3-8，残余大分子97g，用于套下批的合成。
实施例7：
取37％甲醛水溶液800g和120g乙二醇混合后，真空条件下于95℃以下脱除水分，得到无水的可流动的聚甲醛醚化物391.5g，将该可流动的聚甲醛醚化物转入具有10g酸性磺酸树脂和800g甲缩醛的混合物中、在50-80温度下发生催化反应，反应达到平衡后,滤出催化剂得到反应液1152.5g，先常压蒸馏出DMM1、DMM2等644.5g，在于-0.098MP蒸出 328gDMM3-8，残余大分子158g，用于套下批的合成。
实施例8：
将上批次得到的DMM1、DMM2等744.5g，于常压下进行特殊分离，得DMM1等404.5g(可套用于下批合成)；获得甲醇水等25g(可用于甲缩醛合成)；DMM2等308.5g(可套用于下批合成)。
实施例9：
取37％甲醛水溶液800g、70乙二醇和上批次大分子134g混合后，真空条件下于95℃以下脱除水分，得到无水的可流动的聚甲醛醚化物443.8g，将该可流动的聚甲醛醚化物转入具有10g酸性磺酸树脂、920g甲缩醛和279g回收的DMM2等的混合物中、在50-80温度下发生催化反应，反应达到平衡后,滤出催化剂得到反应液1621.8g，先常压蒸馏出DMM1等647.4g；DMM2等496.3g，后再于-0.098MP蒸出323.5gDMM3-8，残余大分子119.6g，用于套下批的合成。
实施例10：
取37％甲醛水溶液800g和60g甘油混合后，真空条件下于95℃以下脱除水分，得到无水的可流动的聚甲醛醚化物328.1g，将该可流动的聚甲醛醚化物转入具有10g酸性磺酸树脂和800g甲缩醛的混合物中、在50-80温度下发生催化反应，反应达到平衡后,滤出催化剂得到反应液1113g，先常压蒸馏出DMM1、DMM2等742.5g，在于-0.098MP蒸出236.5gDMM3-8，残余大分子112g，用于套下批的合成。
实施例11：
取37％甲醛水溶液800g和60g二甘醇混合后，真空条件下于95℃以下脱除水分，得到无水的可流动的聚甲醛醚化物325.4g，将该可流动的聚甲醛醚化物转入具有10g酸性磺酸树脂和800g甲缩醛的混合物中、在50-80温度下发生催化反应，反应达到平衡后,滤出催化剂得到反应液1106.4g，先常压蒸馏出DMM1、DMM2等744.9g，在于-0.098MP蒸出235.5gDMM3-8，残余大分子106g，用于套下批的合成。
实施例12：
取37％甲醛水溶液800g和60g1,2-丙二醇混合后，真空条件下于95℃以下脱除水分，得到无水的可流动的聚甲醛醚化物327g，将该可流动的聚甲醛醚化物转入具有10g酸性磺酸树脂和800g甲缩醛的混合物中、在50-80温度下发生催化反应，反应达到平衡后,滤出催化剂得到反应液1110g，先常压蒸馏出DMM1、DMM2等759g，在于-0.098MP蒸出230gDMM3-8，残余大分子102g，用于套下批的合成。
对比例3：
将37％甲醛水溶液800g真空条件下于95℃以下脱除水分，得到无水的不可流动的多聚甲醛颗粒252g，将该多聚甲醛转入具有10g酸性磺酸树脂和800g甲缩醛的混合物中、在50-80温度下发生催化反应，反应24小时后，仍含有大量多聚甲醛颗粒，无法分离催化剂和进一步获得产品。
本公开解决了目前以多聚甲醛为原料存在的固体多聚甲醛难于制备、输送、活性低的问题；以三聚甲醛为原料时的成本高、设备腐蚀严重、管道堵塞风险的问题；和以甲醛水溶液为原料时的，平衡转化率低、甲醛和半缩醛含量高，难于分离获得成品，水分累积无法循环生产等系列问题；本公开是本公司在大量研究DMMn的各种合成路线及合成技术以后，无法完成DMMn低成本合成的情况下，另辟思路，仔细研究和努力实验验证而获得的技术成果，最终使得本公开原料易得，工艺简单有效，成本较低，工序简单流畅，合成转化率较高，容易分离。本公开投资成本较低，生产开车风险较低，经营利润丰厚。
最后要说明的是：以上所述仅为本公开的优选间歇合成实施例而已，并不用于限制本公开，尽管参照前述实例对本公开进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换，或者只是利用本公开的技术改做为连续化工程。凡在本公开的精神和原则之内，所做的的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。
工业实用性
本公开提供一种聚甲氧基二甲醚及其混合物的制备方法。本公开采用甲醛水溶液(或者气态甲醛合成气)作为甲醛来源的原料，使生产更简单化，产品成本较低；采用多元醇为载体辅剂制备半缩醛醚化物，成本低、效率高、易操作、不污染后续物料；解决了聚甲醛本身在脱到无水状态时形成不溶不熔的活性低、难于输送的固体状态；适合连续化过程便于实现自动化控制；可用固体酸性催化剂，催化效果好，安全环保；甲醛在简单脱干净水分后仍然为容易流动的液体，便于实现连续化生产和自动化控制。

Claims (21)

  1. 一种聚甲氧基二甲醚(DMMNn，优选地n＝3～8)的制备方法，包括以下步骤：
    -甲醛水溶液和多元醇按照一定比例混合后，真空条件下加热脱水一步制得含较低水分的流动聚甲醛，
    -含较低水分的流动聚甲醛再经过加热气化得到较纯的气态甲醛，
    -由获得的气态甲醛在催化剂存在下和甲缩醛、套用的上批次低沸物和大分子等混合，在一定温度下发生催化反应，
    -反应达到平衡后,滤出催化剂并净化合成液，分别进行常压及减压蒸馏，分离出低沸物、大分子和DMMn成品，以及
    -DMMn成品再经减压精馏，可得到各单组分DMMn产物，
    其中，将甲醛气化后残余的多元醇返回并套用于下批的甲醛浓缩，以制备含较低水分的流动聚甲醛。
  2. 根据权利1所述的方法，其中所述多元醇包括：乙二醇、1,2-丙二醇、1,3-丙二醇、二甘醇、丙三醇、丁二醇、新戊二醇、三羟甲基丙烷、或它们之间两种或者两种以上的混合物。
  3. 根据权利1所述的方法，其中所述甲醛水溶液包括：商品形式的甲醛水溶液或甲醇通过催化脱氢或氧化形成的含水蒸汽、氢气和甲醇的气态甲醛。
  4. 根据权利1至3中任一项所述的方法，其中所述甲醛水溶液的甲醛含量为10％-85％，优选30％-70％。
  5. 根据权利1所述的方法，其中在所述真空条件下加热脱水步骤中，将甲醛和多元醇的混合物脱水到水分小于15％，优选的小于1.0％。
  6. 根据权利1至5中任一项所述的方法，其中在所述真空条件下加热脱水步骤中，甲醛和多元醇的混合物脱水温度为30℃～110℃，优选60℃～100℃。
  7. 根据权利1所述的方法，其中对所述含较低水分的流动聚甲醛进行加热气化的温度为110℃～300℃，优选120℃～180℃。
  8. 根据权利1所述的方法，其中所述催化剂为酸性催化剂，优选地所述酸性催化剂包括：液体酸性催化剂、固体酸性催化剂或气体酸性催化剂。
  9. 根据权利8所述的方法，其中所述固体酸性催化剂包括：钛硅分子筛、丝光沸石、硫酸氢钠、硫酸铝、氯化铁、磺酸树脂、氟磺酸树脂、吸附有硫酸、磷酸的硅胶颗粒、或它们的混合物。
  10. 根据权利1所述的方法，其中在甲醛水溶液和多元醇按照一定比例混合步骤中， 甲醛和多元醇的质量比为1.0:0.02～20.0，优选1:0.2～2.0。
  11. 根据权利1所述的方法，其中所述催化反应的温度为30℃～200℃，优选50℃～120℃。
  12. 一种聚甲氧基二甲醚(DMMn，优选地n＝2-8)及其混合物的制备方法，包括以下步骤：
    -甲醛水溶液和多元醇及套用的上批次的大分子按照一定比例混合后，真空条件下加热脱除水分，得到无水的可流动的聚甲醛醚化物，
    -所述无水的聚甲醛醚化物在酸性催化剂存在下与甲缩醛、套用的上批次低沸物、大分子等，在一定温度下发生催化反应，
    -反应达到平衡后,滤出催化剂，分别进行常压及减压蒸馏，分离出低沸物、大分子和DMMn成品，
    -DMMn成品再经减压精馏，可得到各单组分DMMn产物，
    -将分离得到的低沸物和大分子返回并套用于下批的合成。
  13. 根据权利12所述的方法，其中所述多元醇包括：乙二醇、1,2-丙二醇、1,3-丙二醇、二甘醇、丙三醇、丁二醇、季戊四醇、新戊二醇或三羟甲基丙烷。
  14. 根据权利12所述的方法，其中所述甲醛水溶液包括：商品形式的甲醛水溶液或甲醇通过催化脱氢、氧化形成的含水蒸汽的气态甲醛。
  15. 根据权利12至14中任一项所述的方法，其中甲醛水溶液的甲醛含量为5％-85％，优选30％-70％。
  16. 根据权利12所述的方法，其中所述酸性催化剂包括：液体酸性催化剂、固体酸性催化剂或气体酸性催化剂。
  17. 根据权利16所述的方法，其中所述固体酸性催化剂包括：钛硅分子筛、丝光沸石、硫酸氢钠、硫酸铝、氯化铁、磺酸树脂、氟磺酸树脂、吸附有硫酸、磷酸的硅胶颗粒或它们的混合物。
  18. 根据权利12所述的方法，其中在真空条件下加热脱除水分步骤中，将甲醛和多元醇及大分子脱水到水分重量小于10wt％，优选地小于1.0wt％。
  19. 根据权利12所述的方法，其中在甲醛水溶液和多元醇及套用的上批次的大分子按照一定比例混合的步骤中，甲醛的质量与多元醇及大分子的质量之比为1.0:0.1～10.0，优选1:0.2～1.8。
  20. 根据权利12所述的方法，其中所述催化反应温度控制在30℃～180℃，优选50℃～80℃。
  21. 根据权利12所述的方法，所述大分子套用于下一批合成的甲醛浓缩或者直接 套用于合成反应。
PCT/CN2020/115358 2019-09-19 2020-09-15 一种聚甲氧基二甲醚及其混合物的制备方法 WO2021052328A1 (zh)

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