CN106957402B - A kind of preparation method of low cost polymethoxy dibutyl ethers - Google Patents
A kind of preparation method of low cost polymethoxy dibutyl ethers Download PDFInfo
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- CN106957402B CN106957402B CN201710209006.3A CN201710209006A CN106957402B CN 106957402 B CN106957402 B CN 106957402B CN 201710209006 A CN201710209006 A CN 201710209006A CN 106957402 B CN106957402 B CN 106957402B
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- polymethoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/30—Chemical modification by after-treatment
- C08G2/34—Chemical modification by after-treatment by etherification
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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
Abstract
The invention discloses a kind of preparation methods of inexpensive polymethoxy dibutyl ethers.Method includes the following steps: (1) mixes butanol and paraformaldehyde according to the ratio that molar ratio is 1:1.5~1:2.5, mixture is pumped into reaction kettle again, under the action of acidic catalyst, reacted under conditions of 70~180 DEG C, 0.1~2.0MPa；(2) step (1) gained reactant is pumped into compression rectification tower, at 110~190 DEG C of 0.1~0.8MPa of tower top pressure, temperature；0.1~0.8MPa of tower bottom pressure, it under conditions of 170~243 DEG C of temperature, is separated, isolates polymethoxy dibutyl ethers from tower bottom；(3) purifies and separates.The method of the present invention can effectively promote the yield and purity of polymethoxy dibutyl ethers, meanwhile, also extracting n-butyl alcohol can be recycled as far as possible, reduce production cost.
Description
Technical field
The invention belongs to field of energy and chemical technologys, and in particular to a kind of preparation side of low cost polymethoxy dibutyl ethers
Method.
Background technique
Polymethoxy dialkyl ether is a kind of oxygenated fuel of good performance, has high cetane number, high oxygen-containing, low condensation point
Outstanding advantages of with low cold filter plugging point, can significantly improve the performance of diesel oil, be greatly promoted the complete of diesel oil after reconciling with diesel oil
It burns, diesel exhaust smoke intensity is greatly reduced；For this purpose, carried out a large amount of research to it both at home and abroad, but most of at present all concentrate
In this product of polymethoxy dimethyl ether, and performance it is more excellent, can be separately as the poly- methoxy of the non-methyl blocking of fuel
Base dialkyl ether studies less, only minimal amount of report, and current research also rests on laboratory stage, has no industry
The report of metaplasia production method or apparatus.
Currently, the preparation method of most of polymethoxy dialkyl ether, is that raw material is placed in reaction kettle to synthesize and add
Pressure rectifying obtains polymethoxy dialkyl ether product, but this is also only a kind of laboratory preparation production method, and does not consider to produce
The separation of moisture and its recycling of unreacted material in by-product after product separation, be unable to reach industrial high efficiency rate, it is low at
This requirement.
Polymethoxy dibutyl ethers are as one of polymethoxy dialkyl ether, due to being limited by reacting, butanol
Aldol condensation generates a large amount of water, these water and raw material bring water and raw material butanol, aldehydes and gathers in synthesis with aldehydes
Methoxyl group dibutyl ethers product will form complicated azeotropic mixture, can not separate by conventional method.
Disclosed patent has no to the play-by-play of separation moisture, the unreacted butanol of recycling at present, refers only to adopt
It is dehydrated with temp.-changing adsorption technology, since water content is big in reaction system, using temp.-changing adsorption dehydration, there is only one-time investments
The problems such as the problems such as huge, production energy consumption, there is also adsorbents to be easy blocking failure, replacement is difficult, it is unfavorable for industrializing.
Summary of the invention
For above-mentioned deficiency in the prior art, the present invention provides a kind of preparation side of inexpensive polymethoxy dibutyl ethers
Method can effectively promote the yield of polymethoxy dibutyl ethers, reduce production cost.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of preparation method of low cost polymethoxy dibutyl ethers, comprising the following steps:
(1) butanol and paraformaldehyde are mixed according to the ratio that molar ratio is 1:1.5~1:2.5, then mixture is pumped into
In reaction kettle, under the action of acidic catalyst, reacted under conditions of 70~180 DEG C, 0.1~2.0MPa, reaction formula
It is as follows:
2C4H9OH+HO(CH2O)nH→C4H9O(CH2O)nC4Hq+2H2O；
(2) step (1) gained reactant is pumped into compression rectification tower, in 0.1~0.8MPa of tower top pressure, temperature 110
~190 DEG C, 0.1~0.8MPa of tower bottom pressure, under conditions of 170~243 DEG C of temperature, separated, isolate poly- first from tower bottom
Oxygroup dibutyl ethers get light component from tower top；
(3) purifies and separates: stratification after the isolated light component of tower top is cooled to 40~60 DEG C separates organic phase I
And water phase, and the extraction salt (extraction is than R=0.5~2) that concentration is 60%~65% is added into water phase and carries out first time extraction,
Organic phase II is collected, then the extraction salt (extraction is than R=0.5~2) that concentration is 50%~55% is added into organic phase II and carries out
Reextraction collects organic phase III, merges organic phase I and organic phase III, obtains n-butanol, and is back in reaction system as former
Material.
Further, the acidic catalyst in step (1) is sulfuric acid, hydrochloric acid, type ZSM 5 molecular sieve or highly acidic cation
Exchanger resin.
Further, acidic catalyst additional amount is the 2%~5% of mixture weight in step (1).
Further, tower top isolates light component in step (2), and light component includes butanol, water, dibutoxy methane or two
The mixture of isobutoxy methane or di-secondary butoxy-methane, formaldehyde, tower bottom isolate polymethoxy dibutyl ethers.
Further, polymethoxy dibutyl ethers are polymethoxy diisobutyl ether or polymethoxy di-secondary in step (2)
Butyl ether；Wherein, n is the integer greater than 1.
Further, salting liquid KF, KCl, KBr, KI, NaCl, NaI, LiCl, LiBr, K2CO3、Na2CO3Or Na2SO4。
Further, extraction conditions are as follows: extracting extraction salt used for the first time is saturated solution or supersaturated solution or solid
Salt, it is saturated salt solution or solid salt that second, which extracts extraction salt used,.
The polymethoxy dibutyl ethers that above-mentioned preparation method is prepared.
The invention has the benefit that
The present invention has successfully been isolated out in polymethoxy dibutyl ethers production process and is difficult to using conventional method separation
Alcohol-water mixture, effectively recycled unreacted raw material low-carbon alcohols in waste water makes to produce to significantly improve raw material availability
Energy consumption and cost are greatly reduced.
Extraction salting liquid evaporated, be concentrated after can be recycled, and cycle-index on effect of extracting substantially without influence.
Specific embodiment
A specific embodiment of the invention is described below, in order to facilitate understanding by those skilled in the art this hair
It is bright, it should be apparent that the present invention is not limited to the ranges of specific embodiment, for those skilled in the art,
As long as various change is in the spirit and scope of the present invention that the attached claims limit and determine, these variations are aobvious and easy
See, all are using the innovation and creation of present inventive concept in the column of protection.
Embodiment 1
A kind of preparation method of low cost polymethoxy dibutyl ethers, comprising the following steps:
(1) butanol and paraformaldehyde (in terms of formaldehyde) are mixed according to the ratio that molar ratio is 1:1.5, then mixture is pumped
Enter in reaction kettle, and the type ZSM 5 molecular sieve for accounting for mixture weight 2% is added thereto, in nitrogen atmosphere, 70 DEG C, 0.1MPa
Under conditions of react, obtain reactant；
(2) step (1) gained reactant is pumped into compression rectification tower, at 110 DEG C of tower top pressure 0.1MPa, temperature；Tower
Bottom pressure 0.1MPa, it under conditions of 170 DEG C of temperature, is separated, isolates butanol, water, dibutoxy methane or two from tower top
The light component of isobutoxy methane or di-secondary butoxy-methane, formaldehyde mixing, tower bottom isolate polymethoxy dibutyl ethers；
(3) stratification after the isolated light component of tower top is cooled to 40 DEG C, separates organic phase I and water phase, and to water
The supersaturated solution of potassium carbonate (extraction is than R=1.5) that concentration is 60% is added in phase and carries out first time extraction, collects organic phase
II, then the unsaturated carbonate potassium solution (extraction is than R=1.3) that concentration is 53.9% is added into organic phase II and carries out reextraction,
Organic phase III is collected, merges organic phase I and organic phase III, obtains n-butanol, and is back in reaction kettle as raw material.
Embodiment 2
A kind of preparation method of low cost polymethoxy dibutyl ethers, comprising the following steps:
(1) butanol and paraformaldehyde (in terms of formaldehyde) are mixed according to the ratio that molar ratio is 1:1.6, then mixture is pumped
Enter in reaction kettle, and the cation exchange resin for accounting for mixture weight 5% is added thereto, in nitrogen atmosphere, 70 DEG C, 0.5MPa
Under conditions of react, obtain reactant；
(2) step (1) gained reactant is pumped into compression rectification tower, at 114 DEG C of tower top pressure 0.4MPa, temperature；Tower
Bottom pressure 0.6MPa, it under conditions of 225 DEG C of temperature, is separated, isolates butanol, water, dibutoxy methane or two from tower top
The light component of isobutoxy methane or di-secondary butoxy-methane, formaldehyde mixing, tower bottom isolate polymethoxy dibutyl ethers；
(3) stratification after the isolated light component of tower top is cooled to 40 DEG C, separates organic phase I and water phase, and to water
The supersaturated Klorvess Liquid (extraction is than R=1.5) that concentration is 60% is added in phase and carries out first time extraction, collects organic phase
II, then the saturated potassium chloride solution (extraction is than R=1.4) that concentration is 58% is added into organic phase II and carries out reextraction, it receives
Collect organic phase III, merge organic phase I and organic phase III, obtain n-butanol, and is back in reaction kettle as raw material.
Embodiment 1,2 resulting polymethoxy dibutyl ethers and n-butanol are detected, the result is shown in tables 1.
1 product purity of table and yield detection
Claims (8)
1. a kind of preparation method of low cost polymethoxy dibutyl ethers, which comprises the following steps:
(1) butanol and paraformaldehyde are mixed according to the ratio that molar ratio is 1:1.5~1:2.5, then mixture is pumped into reaction
In kettle, under the action of acidic catalyst, reacted under conditions of 70~180 DEG C, 0.1~2.0MPa, reaction formula is as follows:
2C4H9OH+HO(CH2O)nH→C4H9O(CH2O)nC4H9+2H2O；
(2) step (1) gained reactant is pumped into compression rectification tower, in 0.1~0.8MPa of tower top pressure, temperature 110~190
DEG C, 0.1~0.8MPa of tower bottom pressure, under conditions of 170~243 DEG C of temperature, separated, isolate polymethoxy two from tower bottom
Butyl ether gets light component from tower top；
(3) purifies and separates: stratification after the isolated light component of tower top is cooled to 40~60 DEG C separates organic phase I and water
Phase, and the extraction salt that concentration is 60%~65% is added into water phase, extraction carries out first time extraction than R=0.5~2, collects
Organic phase II, then the extraction salt that concentration is 50%~55% is added into organic phase II, extraction carries out secondary than R=0.5~2
Organic phase III is collected in extraction, is merged organic phase I and organic phase III, is obtained n-butanol, and is back in reaction system as raw material.
2. the preparation method of low cost polymethoxy dibutyl ethers according to claim 1, which is characterized in that step (1)
Described in acidic catalyst be sulfuric acid, hydrochloric acid, type ZSM 5 molecular sieve or storng-acid cation exchange resin.
3. the preparation method of low cost polymethoxy dibutyl ethers according to claim 1, which is characterized in that step (1)
Described in acidic catalyst additional amount be mixture weight 2%~5%.
4. the preparation method of low cost polymethoxy dibutyl ethers according to claim 1, which is characterized in that step (2)
Middle tower top isolates light component, and the light component includes butanol, water, dibutoxy methane or two isobutoxy methane or di-secondary fourth
The mixture of oxygroup methane, formaldehyde, tower bottom isolate polymethoxy dibutyl ethers.
5. the preparation method of low cost polymethoxy dibutyl ethers according to claim 4, which is characterized in that step (2)
Described in polymethoxy dibutyl ethers be polymethoxy diisobutyl ether or polymethoxy di-sec-butyl ether；Wherein, n is greater than 1
Integer.
6. the preparation method of low cost polymethoxy dibutyl ethers according to claim 1, which is characterized in that the extraction
Salt is KF, KCl, KBr, KI, NaCl, NaI, LiCl, LiBr, K2CO3、Na2CO3Or Na2SO4。
7. the preparation method of low cost polymethoxy dibutyl ethers according to claim 1, which is characterized in that the extraction
Condition are as follows: the extraction salt used of extraction for the first time is saturated solution or supersaturated solution or solid salt, second of extraction extraction used
Salt is saturated salt solution or solid salt.
8. the polymethoxy dibutyl ethers that the described in any item preparation methods of claim 1~7 are prepared.
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Citations (4)
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|---|---|---|---|---|
| CN103739458A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Preparation method of polyoxymethylene dimethyl ethers |
| CN103772164A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院兰州化学物理研究所 | Reaction system for continuously preparing polyoxymethylene dialkyl ether, and process thereof |
| CN104803833A (en) * | 2014-01-27 | 2015-07-29 | 北京东方红升新能源应用技术研究院有限公司 | Liquid phase temperature swing adsorption separating dehydration method for preparing polymethoxydialkyl ether |
| CN105753666A (en) * | 2016-05-10 | 2016-07-13 | 中国人民解放军总后勤部油料研究所 | Method for preparing polyoxymethylene dimethyl ether |
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2017
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Patent Citations (4)
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| CN103739458A (en) * | 2012-10-17 | 2014-04-23 | 中国石油化工股份有限公司 | Preparation method of polyoxymethylene dimethyl ethers |
| CN103772164A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院兰州化学物理研究所 | Reaction system for continuously preparing polyoxymethylene dialkyl ether, and process thereof |
| CN104803833A (en) * | 2014-01-27 | 2015-07-29 | 北京东方红升新能源应用技术研究院有限公司 | Liquid phase temperature swing adsorption separating dehydration method for preparing polymethoxydialkyl ether |
| CN105753666A (en) * | 2016-05-10 | 2016-07-13 | 中国人民解放军总后勤部油料研究所 | Method for preparing polyoxymethylene dimethyl ether |
Non-Patent Citations (1)
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| 盐效萃取分离共沸蒸馏后的正丁醇-水混合物;王雨等;《北京化工大学学报(自然科学版)》;20141231;第41卷(第3期);摘要 |
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Address after: Dazhou City, Sichuan Province, 635000 River Road District No. 25 Patentee after: Sichuan Daxing Energy Co., Ltd Patentee after: Institute of Military New Energy Technology, Institute of Systems Engineering, Academy of Military Sciences Address before: No.25 Xihe Road, Tongchuan District, Dazhou City, Sichuan Province Patentee before: SICHUAN DAXING ENERGY Co.,Ltd. Patentee before: INSTITUTE OF OIL PLANT, LOGISTIC SUPPORT DEPARTMENT OF THE CENTRAL MILITARY COMMISSION |
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Effective date of registration: 20211108 Address after: Dazhou City, Sichuan Province, 635000 River Road District No. 25 Patentee after: Sichuan Daxing Energy Co., Ltd Patentee after: Institute of Military New Energy Technology, Institute of Systems Engineering, Academy of Military Sciences Patentee after: Beijing Dongfang Hongsheng New Energy Application Technology Research Institute Co.,Ltd. Address before: Dazhou City, Sichuan Province, 635000 River Road District No. 25 Patentee before: Sichuan Daxing Energy Co., Ltd Patentee before: Institute of Military New Energy Technology, Institute of Systems Engineering, Academy of Military Sciences |