CN112521255B - Preparation method of polyoxymethylene dimethyl ether and mixture thereof - Google Patents
Preparation method of polyoxymethylene dimethyl ether and mixture thereof Download PDFInfo
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- CN112521255B CN112521255B CN201910884450.4A CN201910884450A CN112521255B CN 112521255 B CN112521255 B CN 112521255B CN 201910884450 A CN201910884450 A CN 201910884450A CN 112521255 B CN112521255 B CN 112521255B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention belongs to the technical field of energy and chemical industry, and provides a preparation method of a fuel additive, an environment-friendly solvent-polyoxymethylene dimethyl ether (DMMn, generally n=2-8) and a mixture thereof, which comprises the following steps: mixing formaldehyde aqueous solution, polyalcohol and macromolecule of the upper batch of the sleeve according to a certain proportion, heating under vacuum condition to remove water to obtain anhydrous flowable polyoxymethylene etherate, carrying out catalytic reaction on the anhydrous etherate, methylal, low-boiling substances of the upper batch of the sleeve, macromolecule and the like under a certain temperature, filtering out the catalyst after the reaction reaches equilibrium, respectively carrying out normal pressure and reduced pressure distillation, separating out low-boiling substances, macromolecules and DMMn finished products, and carrying out reduced pressure rectification on the DMMn finished products to obtain each single component. The separated low-boiling substances and macromolecules return to be used for the synthesis of the next batch.
Description
1. Technical field: the invention belongs to the technical field of energy and chemical industry, and particularly relates to a preparation method of polyoxymethylene dimethyl ether and a mixture thereof.
2. Technical background: polyoxymethylene dimethyl ether is also called polymethoxy dimethyl ether, english name: polyoxymethylene dimethyl ethers, PODE or DMMn for short, is a low molecular weight acetal polymer with dimethoxy methane as a matrix and methyleneoxy as a main chain, and has the general formula shown as follows: CH3O (CH 2O) nCH3. The polymethoxy dimethyl ether with the polymerization degree of 2-8 is abbreviated as DMMn (n=2-8), is used for cleaning diesel oil blending components, has physical properties similar to diesel oil, and does not need to modify an oil supply system of a vehicle engine when blended into the diesel oil. The cetane number of the diesel oil is up to 76, the oxygen content is 47-50%, the diesel oil is mixed with 10-20% of the diesel oil without sulfur and aromatic hydrocarbon, the cold filter plugging point of the diesel oil can be obviously reduced, the combustion quality of the diesel oil in an engine can be improved, and the heat efficiency is improved. Meanwhile, DMM2, DMM3, DMM4 and DMM5 are solvents with extremely strong dissolving capacity and are applied to paint, coating, printing ink, adhesives, cleaning agents, electrolyte solvents and the like.
Polyoxymethylene dimethyl ethers (DMM 2-8) are generally prepared by reacting methanol or methylal with trioxymethylene or paraformaldehyde in the presence of an acidic catalyst, the basic equation of the reaction being as follows:
however, the trioxymethylene is synthesized by sulfuric acid catalysis, a large amount of reflux is carried out in the production process under the condition of water, the vaporization heat of the water is high, the energy consumption is high, the solvent is used for extraction and dehydration, the synthesis cost per se is high, the melting point of the trioxymethylene is high (61 ℃), the trioxymethylene is easy to sublimate, the pipeline is easy to be blocked, and if the trioxymethylene is in the conveying process, insoluble high polymer is extremely easy to form once contacting strong acid, so that equipment and the pipeline are destroyed, dangerous accidents and the like occur;
the paraformaldehyde is in a solid form prepared by the steps of carrying out vacuum dehydration on an aqueous formaldehyde solution, then carrying out polymerization, granulating or crushing, drying and the like, although the manufacturing cost is reduced, the paraformaldehyde is further used as a reactant, has low reactivity due to the insoluble and infusible property, is inconvenient to feed from synthesis to application in the continuous production process, has large formaldehyde smell and toxicity, and is harmful to the health of workers.
There is also a report in China that polyoxymethylene dimethyl ether (DMM 3-8) is prepared by reacting a formaldehyde aqueous solution with higher concentration with methanol or methylal, and although the process is smooth and convenient to operate in theory, the equilibrium conversion rate is very low and the formaldehyde residue is much because of the existence of a large amount of water, and the separation is difficult, so the process is not mature and the industrialization is difficult to realize.
3. The invention comprises the following steps:
(1) The invention aims to: the invention aims to solve a series of problems existing in the existing synthesis of polyoxymethylene dimethyl ether by using paraformaldehyde, trioxymethylene or formaldehyde aqueous solution, and provides a new synthesis technical route and a new technical process.
(2) The technical scheme is as follows: the invention relates to a preparation method of polyoxymethylene dimethyl ether and a mixture thereof, which comprises the steps of mixing formaldehyde aqueous solution, polyalcohol and macromolecule of the upper batch used mechanically according to a certain proportion, heating under vacuum condition to remove water, obtaining nearly anhydrous flowable polyoxymethylene etherate with low polymerization degree, wherein the anhydrous etherate is subjected to catalytic reaction with methylal, low boiling substance of the upper batch used mechanically, macromolecule and the like under a certain temperature, filtering out the catalyst after the reaction reaches equilibrium, respectively carrying out normal pressure and reduced pressure distillation, separating out low boiling substance, macromolecule and DMMn finished product, and carrying out reduced pressure rectification on the DMMn finished product to obtain each single component. The separated low-boiling substances and macromolecules return to be used for the synthesis of the next batch. The basic reaction flow is as follows:
(3) The technical effects are as follows: the preparation method of the polyoxymethylene dimethyl ether and the mixture thereof has the advantages of easily available raw materials, simplicity, effectiveness, convenience for realizing continuity and automation, higher yield, lower cost, small wastewater pollution, safety and environmental protection, and is suitable for industrial production.
The specific aspects are as follows:
1. the invention adopts formaldehyde aqueous solution (or gaseous formaldehyde synthetic gas) as raw material of formaldehyde source, which simplifies the production and reduces the cost of the product.
2. The formaldehyde is still a liquid easy to flow after simply removing clean water, and is convenient for realizing continuous production and automatic control.
3. The reaction process of the invention is properly controlled, and the yield is higher.
4. The continuous device of the invention has larger capacity of a single device.
5. The invention can be used as solid acid catalyst, with good catalytic effect, safety and environmental protection.
5. The specific embodiments of the present invention are as follows:
example 1:
mixing 800g of 37% formaldehyde aqueous solution and 60g of glycol, removing water under vacuum condition at the temperature of below 95 ℃ to obtain 326.4g of anhydrous flowable polyoxymethylene etherate, transferring the flowable polyoxymethylene etherate into a mixture of 10g of acid sulfonic acid resin and 560g of methylal, carrying out catalytic reaction at the temperature of 50-80 ℃ to obtain 866.4g of reaction solution, distilling 583.4g of DMM1, DMM2 and the like at normal pressure, distilling 161g of DMM3-8 at-0.098 MP, and using 97g of residual macromolecules for the synthesis of the next batch.
Example 2:
mixing 800g of 37% formaldehyde aqueous solution and 120g of glycol, removing water under vacuum condition at the temperature of below 95 ℃ to obtain 391.5g of anhydrous flowable polyoxymethylene etherate, transferring the flowable polyoxymethylene etherate into a mixture of 10g of acidic sulfonic acid resin and 800g of methylal, carrying out catalytic reaction at the temperature of 50-80 ℃ to obtain 1152.5g of reaction solution, distilling 644.5g of DMM1, DMM2 and the like under normal pressure, distilling 328g of DMM3-8 under the condition of-0.098 MP, and using 158g of residual macromolecules for synthesis of the next batch.
Example 3:
744.5g of DMM1, DMM2 and the like obtained in the previous batch are subjected to special separation under normal pressure to obtain 404.5g of DMM1 and the like (which can be sleeved for the next batch synthesis); 25g of methanol water or the like (usable for methylal synthesis) was obtained; DMM2, etc. 308.5g (which can be used as a sleeve for the next synthesis).
Example 4:
mixing 800g of 37% formaldehyde aqueous solution, 70 ethylene glycol and 134g of macromolecules in the previous batch, removing water at a temperature below 95 ℃ under vacuum condition to obtain 443.8g of anhydrous flowable polyoxymethylene etherate, transferring the flowable polyoxymethylene etherate into a mixture of 10g of acidic sulfonic acid resin, 920g of methylal, 279g of recovered DMM2 and the like, carrying out catalytic reaction at 50-80 ℃, filtering out the catalyst to obtain 1621.8g of reaction liquid after the reaction reaches equilibrium, and distilling 647.4g of DMM1 and the like at normal pressure; 496.3g of DMM2 and the like, and then 323.5g of DMM3-8 and 119.6g of residual macromolecules are distilled out at-0.098 MP and used for the synthesis of the next batch.
Example 5:
mixing 800g of 37% formaldehyde aqueous solution and 60g of glycerin, removing water under vacuum condition at the temperature of below 95 ℃ to obtain 328.1g of anhydrous flowable polyoxymethylene etherate, transferring the flowable polyoxymethylene etherate into a mixture of 10g of acidic sulfonic acid resin and 800g of methylal, carrying out catalytic reaction at the temperature of 50-80 ℃ to obtain 1113g of reaction liquid, firstly distilling 742.5g of DMM1, DMM2 and the like under normal pressure, distilling 236.5g of DMM3-8 under the condition of-0.098 MP, and using 112g of residual macromolecules for synthesis of next batch.
Example 6:
mixing 800g of 37% formaldehyde aqueous solution and 60g of diglycol, removing water under vacuum condition at the temperature of below 95 ℃ to obtain 325.4g of anhydrous flowable polyoxymethylene etherate, transferring the flowable polyoxymethylene etherate into a mixture of 10g of acidic sulfonic acid resin and 800g of methylal, carrying out catalytic reaction at the temperature of 50-80 ℃ to obtain 1106.4g of reaction solution, distilling 744.9g of DMM1, DMM2 and the like at normal pressure, distilling 235.5g of DMM3-8 at-0.098 MP, and using 106g of residual macromolecules for synthesis of next batch.
Example 7:
mixing 800g of 37% formaldehyde aqueous solution with 60g of 1, 2-propylene glycol, removing water under vacuum condition at the temperature of 95 ℃ to obtain 327g of anhydrous flowable polyoxymethylene etherate, transferring the flowable polyoxymethylene etherate into a mixture of 10g of acidic sulfonic acid resin and 800g of methylal, carrying out catalytic reaction at the temperature of 50-80 g, filtering out the catalyst to obtain 1110g of reaction solution after the reaction reaches equilibrium, distilling 759g of DMM1, DMM2 and the like at normal pressure, distilling 230g of DMM3-8 at-0.098 MP, and using residual macromolecule 102 for synthesis of the next batch.
Example 8: (comparative example) a 37% aqueous formaldehyde solution, 800g, was dehydrated under vacuum at 95 c to obtain 252g of anhydrous, non-flowable paraformaldehyde particles, which were transferred into a mixture of 10g of an acidic sulfonic acid resin and 800g of methylal, and reacted catalytically at 50-80 c for 24 hours, and still contained a large amount of paraformaldehyde particles, and the catalyst could not be separated and further obtained.
The invention solves the problems that solid paraformaldehyde is difficult to prepare, convey and has low activity existing in the prior art by taking paraformaldehyde as a raw material; the problems of high cost, serious equipment corrosion and pipeline blockage risk when trioxymethylene is used as a raw material; and when formaldehyde aqueous solution is used as raw material, the equilibrium conversion rate is low, formaldehyde and hemiacetal content is high, it is difficult to separate and obtain finished products, water accumulation can not be recycled, and other problems; the invention is a technical result obtained by carefully researching and striving experimental verification under the condition that DMMn low-cost synthesis cannot be completed after a great deal of research on various synthetic routes and synthetic technologies of DMMn by the company, and finally, the invention has the advantages of easily obtained raw materials, simple and effective process, low cost, simple and smooth working procedure, higher synthesis conversion rate and easy separation. The invention has low investment cost, low production and driving risk and high operation profit.
Finally, the following is to be described: the above description is only a preferred batch synthesis example of the present invention, and is not intended to limit the present invention, but although the present invention has been described in detail with reference to the foregoing examples, it will be apparent to those skilled in the art that modifications may be made to the technical solutions described in the foregoing examples, or equivalents may be substituted for some of the technical features thereof, or continuous engineering may be performed by using the techniques of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (1)
1. The preparation method of the polyoxymethylene dimethyl ether and the mixture thereof is characterized by comprising the following steps: mixing formaldehyde aqueous solution with 30-70% of content, ethylene glycol and macromolecules of the upper batch according to a proportion, heating under vacuum condition to remove water, dehydrating to water content less than 1%, obtaining anhydrous flowable polyoxymethylene etherate, carrying out catalytic reaction on the anhydrous polyoxymethylene etherate, methylal and the macromolecules of the upper batch at 50-80 ℃ in the presence of an acid catalyst, filtering out the catalyst after the reaction reaches equilibrium, respectively carrying out normal pressure and reduced pressure distillation, separating out low-boiling substances, macromolecules and DMMn finished products, carrying out reduced pressure distillation on the DMMn finished products, obtaining single components, returning the separated low-boiling substances and macromolecules, and applying the separated low-boiling substances and macromolecules to the next batch of synthesis; the macromolecular sleeve is used for the next formaldehyde concentration process of synthesis or directly used for synthesis reaction; in the DMMn finished product, n=2-8;
the acidic catalyst comprises: liquid acid catalyst, solid acid catalyst, gas acid catalyst; the solid acid catalyst comprises: titanium silicalite, mordenite, sodium bisulfate, aluminum sulfate, ferric chloride, sulfonic acid resins, fluorosulfonic acid resins, silica gel particles adsorbed with sulfuric acid and phosphoric acid, and mixtures thereof.
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| CN201910884450.4A CN112521255B (en) | 2019-09-19 | 2019-09-19 | Preparation method of polyoxymethylene dimethyl ether and mixture thereof |
| PCT/CN2020/115358 WO2021052328A1 (en) | 2019-09-19 | 2020-09-15 | Preparation method for polyoxymethylene dimethyl ether and mixture thereof |
| US17/560,796 US20220112148A1 (en) | 2019-09-19 | 2021-12-23 | Preparation method for polyoxymethylene dimethyl ether and mixture thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105541568A (en) * | 2016-02-03 | 2016-05-04 | 凯瑞环保科技股份有限公司 | Preparation method and device of polymethoxy dimethyl ether reaction raw material |
| CN107266296A (en) * | 2017-07-13 | 2017-10-20 | 湖北三里枫香科技有限公司 | A kind of alkyl polyoxyether PODEn production technology device and method |
| CN107353188A (en) * | 2016-05-10 | 2017-11-17 | 北京旭阳科技有限公司 | A kind of method for preparing anhydrous gaseous formaldehyde |
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| DE102009035503A1 (en) * | 2009-07-31 | 2011-02-10 | Man Nutzfahrzeuge Ag | Use of polyoxymethylene di (alkylpolyglycol) ethers as an additive to diesel fuels to reduce soot emissions in compression ignition engines |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105541568A (en) * | 2016-02-03 | 2016-05-04 | 凯瑞环保科技股份有限公司 | Preparation method and device of polymethoxy dimethyl ether reaction raw material |
| CN107353188A (en) * | 2016-05-10 | 2017-11-17 | 北京旭阳科技有限公司 | A kind of method for preparing anhydrous gaseous formaldehyde |
| CN107266296A (en) * | 2017-07-13 | 2017-10-20 | 湖北三里枫香科技有限公司 | A kind of alkyl polyoxyether PODEn production technology device and method |
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