CN109096062A - Method for purifying polymethoxy dimethyl ether - Google Patents
Method for purifying polymethoxy dimethyl ether Download PDFInfo
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- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/48—Preparation of compounds having groups
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Abstract
Long-term continuous production is difficult to caused by being to solve formaldehyde during rectification method purification polymethoxy dimethyl ether and there are problems that operate, using the technical solution included the following steps: the reaction equilibrium mixture that reaction synthesis unit obtains, dimethoxym ethane is removed in the first knockout tower first, obtains the first tower bottoms；First tower bottoms enters purification kettle, contacts with chemical pretreatment solution, obtains comprising PODE2~8Purification feed liquid；Purification feed liquid enters Second distillation column, isolates the second fraction comprising PODE2, first alcohol and water from top, tower reactor obtains the second tower bottoms；Second fraction enters third distillation column, isolates the third fraction comprising first alcohol and water by third distillation column tower top, obtains third tower bottoms, as the PODE2 product of high-purity；Second tower bottoms enters the 4th rectifying column, and the 4th rectifying column product cut is isolated in the 4th the top of the distillation column；The 4th rectifying column product cut is PODE3~4Or PODE3~5。
Description
Technical field
The present invention relates to the methods for purifying polymethoxy dimethyl ether, more particularly to are the reaction of raw material from paraformaldehyde
Obtained in high-purity PODE is prepared in reaction mixture containing polymethoxy dimethyl ether3~4Product or PODE3~5The method of product.
Background technique
With sharply increasing for modern society's energy consumption, the growing tension of petroleum resources, environmental pressure is also increasing,
There is an urgent need to develop new cleaning diesel fuels.Using oxygenatedchemicals be diesel fuel additives, without in addition increase device or
Change engine structure, is a kind of convenient, effective measures, becomes the new approaches of development of oil industry.
Polymethoxy dimethyl ether (PODE) is a kind of oxygenatedchemicals, general formula are as follows: CH3O(CH2O)nCH3, wherein n is >=1
Integer (general value, for the PODE of different n, is hereafter indicated less than 10 with PODEn).Polymethoxy dimethyl ether, especially n
=3~5 condensate not only has suitable fusing point and boiling point, while oxygen content with higher (47%~49%) and 16
Alkane value (78~100) is conducive to improve the combustion position of diesel oil within the engine, improves the thermal efficiency, reduce pollutant emission；Cause
This, PODE3~5It is the diesel-dope ideal composition of great application prospect, may be used as part and replace diesel oil, improve bavin
The efficiency of combustion of oil.
In recent years, the preparation of PODE has received widespread attention, and has a large amount of patent report.Formaldehyde and methanol are raw material conjunction
At in the method for PODE, water is inevitable as reaction product, this also becomes the fatal defects of the synthetic route.The reason is that in acid
Under the conditions of property, the presence of water is easy to that polymethoxy dimethyl ether is caused to hydrolyze to form hemiacetal, and hemiacetal is difficult to from polymethoxy two
It is removed in methyl ether, so that the separating-purifying of polymethoxy dimethyl ether is more complicated.
The method of source control moisture is to gather using dimethoxym ethane and metaformaldehyde or for cheap paraformaldehyde as raw material preparation
Methoxyl group dimethyl ether, however all focused in most patent reports in raw material route selection and the selection of catalyst, for rear
Continuous separating-purifying does not do further investigation report.United States Patent (USP) US2449269 and US5746785 describe a kind of dimethoxym ethane with
The method that paraformaldehyde (or formalin of concentration) synthesizes polymethoxy dimethyl ether in the presence of sulfuric acid and formic acid.European patent
EP1070755A1, which discloses to react in the presence of three fluosulfonic acid by dimethoxym ethane with paraformaldehyde, prepares polymethoxy dimethyl ether
Method, the conversion ratio of dimethoxym ethane are 54%, PODE2~5Yield be 51.2%.CN103664549A and CN103880614A is used
Paraformaldehyde is that raw material synthesizes polymethoxy dimethyl ether by catalyst of solid super-strong acid, includes unreacted raw material in product
Dimethoxym ethane and paraformaldehyde, in the composition of reaction mixture, in addition to dimethoxym ethane, polymethoxy dimethyl ether, also not comprising 8.3%
The paraformaldehyde of reaction.
For in the preparation method of polymethoxy dimethyl ether, not only there is product in reaction mixture, unreacted raw material is molten
Formaldehyde (or paraformaldehyde) of the solution in system, even there are also by-product carbinol etc., to obtain pure PODE for diesel oil addition,
It needs to carry out separating-purifying to reaction mixture.The polymethoxy dimethyl ether introduced in CN101048357A and CN102786397A
Preparation process, be all made of plural serial stage rectifying column be made PODE3~4For target product, unreacted formaldehyde (or metaformaldehyde)
With PODE2Fraction is recycled directly to point that reaction member has exempted from formaldehyde (or metaformaldehyde) as recycle stock after passing through rectifying
From.However, PODE2It is a kind of potential high-quality solvent with good dissolubility energy, when fraction needs are separately separated out
Or when being not suitable for directly returning to synthesis unit, it is necessary to be related to the separation of formaldehyde.
We carry out the hair that studies for a long period of time of rectifying separation to the reaction mixture obtained with dimethoxym ethane and polyformaldehyde reaction
It is existing, separate PODE2Distillation process in, formaldehyde be easy to be gathered on condenser white solid and with device operation accumulate
It is tired, cause the blocking of return pipe and discharge nozzle to cause parking maintenance, it is difficult to long-term continuous production operating.Chinese patent
CN103333060B discloses a kind of method refined and purify polymethoxy dialkyl ether, and this method to reaction balance by producing
It adds the sodium hydrate aqueous solution that concentration is 40-50wt% in object to be condensed back, to reach the mesh for eliminating formaldehyde reaction
's.However this method need to be condensed back 2h, the processing time is longer, is unfavorable for expanding production.
Therefore, the separation problem of formaldehyde is the technology bottle for influencing polymethoxy dimethyl ether separating technology continuous and steady operation
Neck.
Summary of the invention
The technical problem to be solved by the present invention is to formaldehyde separation in the purifying technique of rectification method purification polymethoxy dimethyl ether
The problem of, provide a kind of refining methd of polymethoxy dimethyl ether, the influence of the simple and quick elimination formaldehyde of this method, cost
It is cheap, be conducive to production and continuously run for a long time.
In order to solve the problems, such as the isolation technics of formaldehyde, technical scheme is as follows: for purifying polymethoxy diformazan
The method of ether, comprising:
(a) the reaction equilibrium mixture that reaction synthesis unit obtains removes dimethoxym ethane fraction in the first knockout tower first, obtains
To the first tower bottoms；
(b) the first tower bottoms enters purification kettle, contacts with the chemical pretreatment solution being added to purification kettle, and chemistry is discharged from bottom
It disposes waste liquid, obtains comprising PODE2~8Purification feed liquid；
(c) purification feed liquid enters Second distillation column, isolates the second fraction comprising PODE2, first alcohol and water from top, obtains
To the second tower bottoms；
(d) the second fraction enters third distillation column, isolates the third comprising first alcohol and water by third distillation column tower top and evaporates
Point, and obtain third tower bottoms；
(e) the second tower bottoms enters the 4th rectifying column, and the 4th rectifying column product cut is isolated in the 4th the top of the distillation column；
The chemical pretreatment solution includes the aqueous dispersions selected from alkali compounds；The third tower bottoms is high-purity
PODE2 product；The 4th rectifying column product cut is PODE3~4Or PODE3~5。
In the case where disclosing above-mentioned technical proposal, those skilled in the art can be according to market demand situation, rationally
The process conditions such as operating pressure and the tower top temperature of the 4th rectifying column are adjusted, selecting the 4th rectifying column product cut is PODE3~4Also
It is PODE3~5。
In above-mentioned technical proposal, the alkali compounds preferably is selected from metal hydroxides or metal sulphite, the gold
Belong to more preferable alkali or alkaline earth metal.
In the above technical solution, the alkali compounds preferably comprises Ca (OH)2、KOH、NaOH、Mg(OH)2、
Na2SO3And K2SO3At least one of compound.
In the above technical solution, the alkali compounds preferably comprises Ca (OH)2、KOH、NaOH、Mg(OH)2、
Na2SO3And K2SO3In at least two compounds.
As one of most preferred technical solution, in above-mentioned technical proposal, the alkali compounds includes simultaneously metallic hydrogen
Oxide and metal sulphite, it has been surprisingly found that metal hydroxides and metal sulphite are improving PODE3~4With/
Or PODE3~5There is synergistic effect in terms of purity and the purity of PODE2 fraction.As non limiting example, such as, but not limited to
Ca(OH)2With Na2SO3, NaOH and Na2SO3, KOH and K2SO3.Further preferred metal hydroxides and metal sulphite
Mass ratio be 0.1~10, such as, but not limited to 0.5,0.6,0.7,0.8,0.9,1.0,1.1,1.2,1.3,1.4,1.5,2,3,
4,5,6,7,8,9 etc., much further preferably from 0.5~8.
As second of preferred technical solution, the alkali compounds includes simultaneously the first metal hydroxides and second
Metal hydroxides, first metal hydroxides are preferably NaOH, and the second metal hydroxides is preferably KOH or Ca
(OH)2, the first metal hydroxides and the second hydroxide are improving PODE at this time3~4And/or PODE3~5Purity and PODE2
There is synergistic effect in terms of the purity of fraction.As non limiting example, such as, but not limited to the first metal hydroxides and
The group of two metal hydroxides is combined into NaOH and KOH, NaOH and Ca (OH)2Etc..Further preferred first metal hydroxides
Be 0.1~10, such as, but not limited to 0.5 with the mass ratio of the second hydroxide, 0.6,0.7,0.8,0.9,1.0,1.1,1.2,
1.3,1.4,1.5,2,3,4,5,6,7,8,9 etc., much further preferably from 0.5~8.
In the above technical solution, reaction synthesis unit described in step (a) is preferably to include formaldehyde or solid formaldehyde
The compound of (metaformaldehyde or paraformaldehyde) is starting material, most preferably paraformaldehyde.
In the above technical solution, reaction equilibrium mixture described in step (a) includes preferably dimethoxym ethane, formaldehyde, first
Alcohol, water and PODE2~8, most preferred content of formaldehyde is 0.1~6%, and the content of water is preferably 0.1~5%.
In the above technical solution, the first knockout tower described in step (a) be preferably atmospheric distillation tower, vacuum rectification tower or
Flash column.
In the above technical solution, the first tower bottoms includes preferably PODE2-8With the mixture of formaldehyde.
In above-mentioned technical proposal, the mass percent of water is preferably 30~70% in chemical pretreatment solution described in step (b),
More preferably 40~60%.
In the above technical solution, chemical pretreatment solution dosage described in step (b) be preferably the first tower bottoms 5~
20%.
In the above technical solution, it will be appreciated by those skilled in the art that the purification kettle described in step (b) is liquid liquid mixing dress
It sets, can select those of commonly used in the art, such as, but not limited to the equipment can be stirred tank, column for counter-currently contacting, extraction tower
Etc..
In the above technical solution, the operating pressure that kettle is purified described in step (b) is not particularly limited, but preferably normal
Pressure, the operation temperature for purifying kettle is preferably 30~90 DEG C；Residence time of the material in purification kettle is preferably 5~60min, more excellent
Turn to 10~30min.
In the above technical solution, Second distillation column described in step (c) is preferably atmospheric tower.
In the above technical solution, the second tower bottoms described in step (c) includes preferably PODE3~8Mixed liquor, wherein
PODE2 content is no more than 0.5%.
In the above technical solution, third distillation column operating pressure described in step (d) is 0.1~0.5MPa, tower top temperature
Degree is 70~130 DEG C, and reflux ratio is 1~10, and more optimized is 2~6.
In the above technical solution, PODE in third tower bottoms described in step (d)2Content is preferably 98~99.9%.
In the above technical solution, product cut PODE described in step (e)3~4Or PODE3~5Purity is preferably 98~
99.9%.
Unless stated otherwise, heretofore described % refers both to weight percent or weight percentage.
We have surprisingly found that the technique is based on rectifying, after isolating dimethoxym ethane, are carrying out polymethoxy diformazan
It, can be by first using the waste heat of first rectifying column by being contacted with the alkaline matter containing catalytic action before the rectifying of ether dimer
Aldehyde reaction removes, and easy to operate and efficiency is higher, thus greatly reduces influence of the formaldehyde to distillation process, improves rectifying
Efficiency, time of contact is short, reaction thoroughly be conducive to expanding production.PODE in the product cut that this method process obtains3~4/
PODE3~5Purity reaches 98% or more, while obtaining the PODE that purity is greater than 98%2Product, it is ensured that the separation of paraformaldehyde and
Continuous rectification is gone on smoothly.
Detailed description of the invention
Fig. 1 is the process flow chart of embodiment of the present invention.
The reaction equilibrium mixture 1 of polymethoxy dimethyl ether is obtained in reaction synthesis unit, first passes around first rectifying column
2, tower top steams the first fraction 5 comprising methanol and unreacted dimethoxym ethane, and the first tower bottoms 4 enters purification kettle by thermo-insulating pipe line
After 6 contact with chemical pretreatment solution 5, isolates chemical treatment waste liquid 7 and be purified feed liquid 8 into Second distillation column 9, adopted from top
The fraction 10 comprising PODE2, first alcohol and water, tower bottom obtain the second tower bottoms 11 comprising PODE3~8 out；Second fraction 10
Into third distillation column 12, the third fraction 13 comprising first alcohol and water is isolated by tower top, obtains third tower bottoms 14；Second tower
Kettle liquid 11 enters the 4th rectifying column 15, isolates high-purity PODE from tower top3~4Or PODE3~5Product cut 16.First fraction 3
It can be used as recycle stock with the 4th tower bottoms 17 and return to synthesis unit participation synthetic reaction.Third tower bottoms 14 can be used as conduct
Recycle stock returns to synthesis unit or produces as high-purity PODE2 product.
Specific embodiment
[embodiment 1]
It is normal through first rectifying column first using the reaction mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction
It presses rectifying to remove the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.First tower bottoms enters purification kettle and chemical pretreatment solution
Haptoreaction；NaOH the and KOH solid mixture that chemical pretreatment solution is mass ratio 1:1 and 40% buck that water is configured to are molten
Liquid；Dosage is the 10% of the first tower bottoms.The reaction temperature for purifying kettle is 90 DEG C, and being stirred to react the time is 20min, is then separated
It is obtained after chemical pretreatment solution out comprising PODE2-5Purification feed liquid.Purification feed liquid enters Second distillation column, rectifying under normal pressure, tower
Kettle temperature degree is 155 DEG C, the second fraction from top extraction comprising PODE2, first alcohol and water.Second fraction enters third distillation column,
It is 0.2MPa in operating pressure, reflux ratio 6, tower top temperature is rectifying under the conditions of 92.5 DEG C, after isolating light component by tower top,
Obtaining third tower bottoms is PODE2 product.Second tower bottoms enters the 4th rectifying column, isolates high-purity PODE by tower top3~4
Or PODE3~5Product cut.First fraction and the 4th tower bottoms are used as recycle stock to return to synthesis unit and participate in reaction.Each object
Material is through gas chromatographic analysis, and the results are shown in Table 1.
[comparative example 1]
It is normal through first rectifying column first using the reaction mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction
It presses rectifying to remove the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.The not purified kettle of first tower bottoms is directly entered second
Rectifying column, directly progress rectifying；As a result, it has been found that: occur a large amount of white solids after about 2h in rectifying tower top condenser and is adhered to condensation
Tube wall, overhead condensation liquid is muddy, and continuous rectification can not continue, and tower is washed in parking.
[embodiment 2]
It is normal through first rectifying column first using the reaction mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction
It presses rectifying to remove the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.First tower bottoms enters purification kettle and chemical pretreatment solution
Reaction；Chemical pretreatment solution used is the NaOH aqueous solution that concentration is 40%, and dosage is the 10% of the first tower bottoms.Purify the anti-of kettle
Answering temperature is 90 DEG C, and being stirred to react the time is 20min, is obtained after chemical pretreatment solution is then demultiplex out comprising PODE2-5Purification material
Liquid.Purification feed liquid enters Second distillation column, rectifying under normal pressure, as a result, it has been found that Second distillation column tower top has white solid after about 4h
It is precipitated.Component analysis finds that content of formaldehyde is higher in purification feed liquid, is as a result listed in table 1c.
[embodiment 3]
It is normal through first rectifying column first using the reaction mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction
It presses rectifying to remove the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.First tower bottoms enters purification kettle and chemical pretreatment solution
Reaction；Chemical pretreatment solution used is the KOH aqueous solution that concentration is 40%, and dosage is the 10% of the first tower bottoms.Purify the anti-of kettle
Answering temperature is 90 DEG C, and being stirred to react the time is 20min, is obtained after chemical pretreatment solution is then demultiplex out comprising PODE2-5Purification material
Liquid.Purification feed liquid enters Second distillation column, rectifying under normal pressure, as a result, it has been found that Second distillation column tower top has white solid after about 3h
It is precipitated.Component analysis finds that content of formaldehyde is higher in purification feed liquid, is as a result listed in table 1c.
[embodiment 4]
It is normal through first rectifying column first using the reaction mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction
It presses rectifying to remove the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.First tower bottoms enters purification kettle and chemical pretreatment solution
Reaction；Chemical pretreatment solution is the Ca (OH) of mass ratio 2:12And Na2SO330% buck that solid mixture and water are configured to is mixed
Close liquid；Dosage is the 5% of the first tower bottoms.The reaction temperature for purifying kettle is 80 DEG C, and being stirred to react the time is 30min, is then divided
It obtains after separating out chemical pretreatment solution comprising PODE2-5Purification feed liquid.Purification feed liquid enters Second distillation column, rectifying under normal pressure,
Bottom temperature is 155 DEG C, the second fraction from top extraction comprising PODE2, first alcohol and water.Second fraction enters third rectifying
Tower is 0.1MPa in operating pressure, and reflux ratio 10, tower top temperature is rectifying under the conditions of 73 DEG C, isolates light component by tower top
Afterwards, obtaining third tower bottoms is PODE2 product.Second tower bottoms enters the 4th rectifying column, isolates high-purity by tower top
PODE3~4Or PODE3~5Product cut.First fraction and the 4th tower bottoms are used as recycle stock to return to synthesis unit and participate in instead
It answers.Each material is through gas chromatographic analysis, and the results are shown in Table 2.
[embodiment 5]
The first tower bottoms is obtained with embodiment 4, the first tower bottoms enters purification kettle and reacts with chemical pretreatment solution；Chemical treatment
Liquid is Ca (OH)230% suspension being configured to water；Dosage is the 5% of the first tower bottoms.Purification kettle reaction temperature be
80 DEG C, being stirred to react the time is 30min, is obtained after chemical pretreatment solution is then demultiplex out comprising PODE2-5Purification feed liquid.Purification
Feed liquid enters Second distillation column, under normal pressure rectifying, finds that Second distillation column tower top has white solid precipitation in distillation process.Group
Analysis is divided to find, content of formaldehyde is higher in purification feed liquid, is as a result listed in table 1c.
[embodiment 6]
The first tower bottoms is obtained with embodiment 4, the first tower bottoms enters purification kettle and reacts with chemical pretreatment solution；Chemistry used
Treatment fluid is the Na that concentration is 30%2SO3Aqueous solution；Dosage is the 5% of the first tower bottoms.The reaction temperature for purifying kettle is 80 DEG C,
Being stirred to react the time is 30min, is obtained after chemical pretreatment solution is then demultiplex out comprising PODE2-5Purification feed liquid.Purify feed liquid into
Enter Second distillation column, under normal pressure rectifying, finds that Second distillation column tower top has white solid precipitation in distillation process.Component analysis
It was found that content of formaldehyde is higher in purification feed liquid, it is as a result listed in table 1c.
[embodiment 7]
The first tower bottoms is obtained with embodiment 1, the first tower bottoms enters purification kettle and reacts with chemical pretreatment solution；Chemical treatment
2 solid mixture of NaOH and Ca (OH) that liquid is mass ratio 4:1 and 50% aqueous alkali that water is configured to；Dosage is the first tower
The 15% of kettle liquid.The reaction temperature for purifying kettle is 70 DEG C, and being stirred to react the time is 10min, after chemical pretreatment solution is then demultiplex out
It obtains comprising PODE2-5Purification feed liquid.Purification feed liquid enters Second distillation column, rectifying under normal pressure, and bottom temperature is 155 DEG C,
The second fraction from top extraction comprising PODE2, first alcohol and water.Second fraction enters third distillation column, is in operating pressure
0.4MPa, reflux ratio 3, tower top temperature are rectifying under the conditions of 114.8 DEG C, after isolating light component by tower top, obtain third tower
Kettle liquid is PODE2 product.Second tower bottoms enters the 4th rectifying column, isolates high-purity PODE by tower top3~4Or PODE3~5
Product cut.First fraction and the 4th tower bottoms are used as recycle stock to return to synthesis unit and participate in reaction.Each material is through gas phase
Chromatography, the results are shown in Table 3.
[embodiment 8]
The first tower bottoms is obtained with embodiment 1, the first tower bottoms enters purification kettle and reacts with chemical pretreatment solution；Chemical treatment
Liquid is the NaOH and Na of mass ratio 6:12SO360% aqueous alkali that solid mixture and water are configured to；Dosage is the first tower reactor
The 20% of liquid.The reaction temperature for purifying kettle is 60 DEG C, and being stirred to react the time is 40min, is obtained after chemical pretreatment solution is then demultiplex out
To including PODE2-5Purification feed liquid.Purification feed liquid enters Second distillation column, rectifying under normal pressure, and bottom temperature is 155 DEG C, from
Second fraction of the top extraction comprising PODE2, first alcohol and water.Second fraction enters third distillation column, is in operating pressure
0.3MPa, reflux ratio 4, tower top temperature are rectifying under the conditions of 105 DEG C, after isolating light component by tower top, obtain third tower reactor
Liquid is PODE2 product.Second tower bottoms enters the 4th rectifying column, isolates high-purity PODE by tower top3~4Or PODE3~5It produces
Product fraction.First fraction and the 4th tower bottoms are used as recycle stock to return to synthesis unit and participate in reaction.Each material is through gas phase color
Spectrum analysis, the results are shown in Table 4.
[embodiment 9]
The first tower bottoms is obtained with embodiment 1, the first tower bottoms enters purification kettle and reacts with chemical pretreatment solution；Chemical treatment
Liquid is the KOH and K of mass ratio 8:12SO350% aqueous alkali that solid mixture and water are configured to；Dosage is the first tower bottoms
8%.The reaction temperature for purifying kettle is 40 DEG C, and being stirred to react the time is 60min, is wrapped after chemical pretreatment solution is then demultiplex out
Containing PODE2-5Purification feed liquid.Purification feed liquid enters Second distillation column, rectifying under normal pressure, and bottom temperature is 155 DEG C, from top
Second fraction of the extraction comprising PODE2, first alcohol and water.Second fraction enters third distillation column, is 0.5MPa in operating pressure, returns
Stream is than being 2.1, and tower top temperature is rectifying under the conditions of 123 DEG C, and after isolating light component by tower top, obtaining third tower bottoms is
PODE2 product.Second tower bottoms enters the 4th rectifying column, isolates high-purity PODE by tower top3~4Or PODE3~5Product cut.
First fraction and the 4th tower bottoms are used as recycle stock to return to synthesis unit and participate in reaction.Each material through gas chromatographic analysis,
The results are shown in Table 5.
Table 1
Table 1c
Table 2
Table 3
Table 4
Table 5
Claims (10)
1. the method for purifying polymethoxy dimethyl ether, comprising:
(a) the reaction equilibrium mixture (1) obtained in reaction synthesis unit removes dimethoxym ethane in the first knockout tower (2) first and evaporates
Divide (3), obtains the first tower bottoms (4)；
(b) the first tower bottoms enters purification kettle (6), is contacted with the chemical pretreatment solution (5) being added to purification kettle, separation chemistry
Dispose waste liquid (7), obtains comprising PODE2~8Purification feed liquid (8)；
(c) purification feed liquid (8) enters Second distillation column (9), and the second fraction comprising PODE2, first alcohol and water is isolated from top
(10), the second tower bottoms (11) are obtained；
(d) the second fraction (10) enters third distillation column (12), is isolated by third distillation column (12) tower top comprising first alcohol and water
Third fraction (13), and obtain third tower bottoms (14)；
(e) the second tower bottoms (11) enters the 4th rectifying column (15), and the 4th the top of the distillation column is isolated the 4th rectifying column product and evaporated
Divide (16)；
The chemical pretreatment solution (5) includes the aqueous dispersions selected from alkali compounds；The third tower bottoms (14) is high-purity
The PODE2 product of degree；The 4th rectifying column product cut (16) is PODE3~4Or PODE3~5。
2. the method according to claim 1 for purifying polymethoxy dimethyl ether, it is characterized in that described in step (a)
One knockout tower is atmospheric distillation tower, vacuum rectification tower or flash column.
3. the method according to claim 1 for purifying polymethoxy dimethyl ether, it is characterized in that the first tower bottoms is packet
Containing methanol, water, PODE2-8With the mixture of formaldehyde.
4. the method according to claim 3 for purifying polymethoxy dimethyl ether, it is characterized in that change described in step (b)
The mass percentage for learning water in treatment fluid is 30~70%.
5. the method according to claim 1 for purifying polymethoxy dimethyl ether, it is characterized in that change described in step (b)
Learn 5~20% that treatment fluid dosage is the first tower bottoms.
6. the method according to claim 1 for purifying polymethoxy dimethyl ether, it is characterized in that net described in step (b)
Changing kettle is stirred tank or column for counter-currently contacting, and operation temperature is 30~90 DEG C.
7. the method according to claim 1 for purifying polymethoxy dimethyl ether, it is characterized in that described in step (c)
Two rectifying columns are atmospheric tower.
8. the method according to claim 1 for purifying polymethoxy dimethyl ether, it is characterized in that described in step (d)
Three rectifying column operating pressures are 0.1~0.5MPa, and tower top temperature is 70~130 DEG C, and reflux ratio is 1~10.
9. the method according to claim 1 for purifying polymethoxy dimethyl ether, it is characterized in that described in step (d)
PODE in third tower bottoms2Content is 98~99.9%.
10. the method according to claim 1 for purifying polymethoxy dimethyl ether, it is characterized in that step (e) is described
Product cut PODE3~4Or PODE3~5Purity is 98~99.9%.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776289A (en) * | 2019-01-31 | 2019-05-21 | 北洋国家精馏技术工程发展有限公司 | A kind of method and apparatus of separation and purification polymethoxy dimethyl ether |
| CN110031569A (en) * | 2019-05-17 | 2019-07-19 | 四川省产品质量监督检验检测院 | A kind of separation and measuring method of polymethoxy dimethyl ether |
| CN110642687A (en) * | 2019-11-11 | 2020-01-03 | 无锡赫利邦化工科技有限公司 | Synthesis device and synthesis process for polymethoxy dimethyl ether |
| EP3714691A1 (en) * | 2019-03-28 | 2020-09-30 | Arkema France | Aqueous composition made of polyoxymethylene dialkyl ethers (pom) and use thereof for conservation and/or embalming of the human or animal body |
| CN112225651A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Method for refining polymethoxy dimethyl ether |
| CN112225648A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Formaldehyde removal method in polymethoxy dimethyl ether separation process |
| CN112225649A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Method for preparing high-purity poly methoxy dimethyl ether |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333061A (en) * | 2013-06-21 | 2013-10-02 | 北京东方红升新能源应用技术研究院有限公司 | Method for refining and purifying polyformaldehyde dialkyl ether |
| CN103333060A (en) * | 2013-06-21 | 2013-10-02 | 北京东方红升新能源应用技术研究院有限公司 | Method for refining and purifying polyformaldehyde dialkyl ether |
| CN106588598A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether refinement method |
| CN106588590A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Refinement method for polyoxymethylene dimethyl ether |
| CN106588596A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Method for purifying polyoxymethylene dimethyl ether |
-
2017
- 2017-06-21 CN CN201710473507.2A patent/CN109096062B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333061A (en) * | 2013-06-21 | 2013-10-02 | 北京东方红升新能源应用技术研究院有限公司 | Method for refining and purifying polyformaldehyde dialkyl ether |
| CN103333060A (en) * | 2013-06-21 | 2013-10-02 | 北京东方红升新能源应用技术研究院有限公司 | Method for refining and purifying polyformaldehyde dialkyl ether |
| CN106588598A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether refinement method |
| CN106588590A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Refinement method for polyoxymethylene dimethyl ether |
| CN106588596A (en) * | 2015-10-16 | 2017-04-26 | 中国石油化工股份有限公司 | Method for purifying polyoxymethylene dimethyl ether |
Non-Patent Citations (1)
| Title |
|---|
| 张晓宇等: "聚甲氧基二甲醚的精制及应用研究进展", 《现代化工》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776289A (en) * | 2019-01-31 | 2019-05-21 | 北洋国家精馏技术工程发展有限公司 | A kind of method and apparatus of separation and purification polymethoxy dimethyl ether |
| CN109776289B (en) * | 2019-01-31 | 2022-07-19 | 北洋国家精馏技术工程发展有限公司 | Method and device for separating and refining polymethoxy dimethyl ether |
| EP3714691A1 (en) * | 2019-03-28 | 2020-09-30 | Arkema France | Aqueous composition made of polyoxymethylene dialkyl ethers (pom) and use thereof for conservation and/or embalming of the human or animal body |
| US11903380B2 (en) | 2019-03-28 | 2024-02-20 | Arkema France | Aqueous composition based on polyoxymethylene dialkyl ethers (POM) and their use for the preservation and/or embalming of the human or animal body |
| CN110031569A (en) * | 2019-05-17 | 2019-07-19 | 四川省产品质量监督检验检测院 | A kind of separation and measuring method of polymethoxy dimethyl ether |
| CN112225651A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Method for refining polymethoxy dimethyl ether |
| CN112225648A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Formaldehyde removal method in polymethoxy dimethyl ether separation process |
| CN112225649A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Method for preparing high-purity poly methoxy dimethyl ether |
| CN112225649B (en) * | 2019-07-15 | 2023-05-02 | 中国石油化工股份有限公司 | Method for preparing high-purity polymethoxy dimethyl ether |
| CN112225648B (en) * | 2019-07-15 | 2023-05-02 | 中国石油化工股份有限公司 | Aldehyde removing method in polymethoxy dimethyl ether separation process |
| CN112225651B (en) * | 2019-07-15 | 2023-11-28 | 中国石油化工股份有限公司 | Method for refining polymethoxy dimethyl ether |
| CN110642687A (en) * | 2019-11-11 | 2020-01-03 | 无锡赫利邦化工科技有限公司 | Synthesis device and synthesis process for polymethoxy dimethyl ether |
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