CN106588590B - The refining methd of polyoxymethylene dimethyl ethers - Google Patents
The refining methd of polyoxymethylene dimethyl ethers Download PDFInfo
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- CN106588590B CN106588590B CN201510673650.7A CN201510673650A CN106588590B CN 106588590 B CN106588590 B CN 106588590B CN 201510673650 A CN201510673650 A CN 201510673650A CN 106588590 B CN106588590 B CN 106588590B
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- dimethyl ethers
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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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- 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
Abstract
Feed blocking the top of the distillation column is difficult to the problem of long-term continuous production operates during purifying polyoxymethylene dimethyl ethers the technical problem to be solved by the present invention is to rectification method, using the technical solution included the following steps: (a) reacting the reaction mixture that synthesis unit obtains, initially enter first rectifying column, it is separated off main the first fraction comprising dimethoxym ethane, obtains the first tower bottoms；(b) the first tower bottoms enters extraction cells, is extracted with the two-phase extractant comprising organic solvent and water phase, and the extraction phase comprising n=2-8 polyoxymethylene dimethyl ethers and organic solvent is obtained, and raffinate phase is the water phase comprising formaldehyde；(c) extraction phase sequentially enters Second distillation column, third distillation column and the 4th rectifying column rectifying, respectively obtains the 4th fraction of the second fraction comprising organic solvent, the third fraction comprising high-purity n=2 polyoxymethylene dimethyl ethers and the polyoxymethylene dimethyl ethers comprising n=3-4.
Description
Technical field
The present invention relates to the processes of purification polyoxymethylene dimethyl ethers, more particularly to are the reaction of raw material from paraformaldehyde
Obtained in prepare in reaction mixture containing polyoxymethylene dimethyl ethers high-purity n=3-4 polyoxymethylene dimethyl ethers method.
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.
Polyoxymethylene dimethyl ethers (PODE) are 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).Polyoxymethylene dimethyl ethers, especially n
=2~5 condensate oxygen content with higher (45%~49%) and Cetane number (63~100), can improve diesel oil and exist
Combustion position in engine improves the thermal efficiency, reduces pollutant emission.Therefore, PODE3~4It is the diesel oil of great application prospect
Machine fuel additive ideal composition may be used as part and replace diesel oil, improves the efficiency of combustion of diesel 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 polyoxymethylene dimethyl ethers is caused to hydrolyze to form hemiacetal, and hemiacetal is difficult to from polyformaldehyde diformazan
It is removed in base ether, so that the separating-purifying of polyoxymethylene dimethyl ethers 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
Formaldehyde 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
Paraformaldehyde (or formalin of concentration) method of synthesizing polyoxymethylene dimethyl ethers 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 polyoxymethylene dimethyl ethers
Method, the conversion ratio of dimethoxym ethane are that the yield of the polyoxymethylene dimethyl ethers of 54%, n=2~5 is 51.2%.CN103664549A and
It is raw material using solid super-strong acid as catalyst synthesizing polyoxymethylene dimethyl ethers that CN103880614A, which uses paraformaldehyde, in product
Comprising unreacted raw material dimethoxym ethane and paraformaldehyde, in the composition of reaction mixture, dimethoxym ethane, polyoxymethylene dimethyl ethers are removed
Outside, also include 8.3% unreacted paraformaldehyde.
For in the preparation method of polyoxymethylene dimethyl ethers, 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 polyoxymethylene dimethyl ethers introduced in CN101048357A and CN102786397A
Preparation process, be all made of multi-stage series connection rectifying column be made PODE3-4For target product, unreacted formaldehyde (or metaformaldehyde)
With n=2 polyoxymethylene dimethyl ethers fraction by be recycled directly to after rectifying reaction member as recycle stock exempted from formaldehyde (or
Metaformaldehyde) separation.However, the polyoxymethylene dimethyl ethers fraction needs of n=2 are separately separated out or are not suitable for directly returning
When returning 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, in the distillation process for separating the polyoxymethylene dimethyl ethers of n=2, in rectifying tower top and condenser (especially on condenser) easily
There is white solid and accumulated as device is run, the blocking of return pipe and discharge nozzle is caused to cause parking maintenance, it is difficult to
Long-term continuous production operating.This problem is the bottleneck for influencing the separating technology continuous operation.
Summary of the invention
The technical problem to be solved by the present invention is to feed blockings in the purifying technique of rectification method purification polyoxymethylene dimethyl ethers
The top of the distillation column is difficult to the problem of long-term continuous production operating, provides a kind of refining methd of polyoxymethylene dimethyl ethers, the party
Method overcomes the shortcomings that accumulation at the top of rectifying column, is conducive to production and continuously runs for a long time.
In order to solve the above-mentioned technical problem, technical scheme is as follows: the refining methd of polyoxymethylene dimethyl ethers, packet
It includes:
(a) reaction mixture that reaction synthesis unit obtains, initially enters first rectifying column, is separated off mainly comprising first
First fraction of acetal, obtains the first tower bottoms；
(b) the first tower bottoms enters extraction cells, is extracted, is obtained with the two-phase extractant comprising organic solvent and water phase
To the extraction phase comprising n=2-8 polyoxymethylene dimethyl ethers and organic solvent, raffinate phase is the water phase comprising formaldehyde；
(c) extraction phase sequentially enters Second distillation column, third distillation column and the 4th rectifying column rectifying, respectively obtains and includes
Second fraction of solvent, the third fraction comprising high-purity n=2 polyoxymethylene dimethyl ethers and the polyformaldehyde two comprising n=3-4
4th fraction of methyl ether.
In above-mentioned technical proposal, reaction mixture described in step (a) include n=1-8 polyoxymethylene dimethyl ethers and
Formaldehyde；The by-products such as water and methanol can also be further included.
In above-mentioned technical proposal, first rectifying column operating pressure described in step (a) is preferably 0~0.2MPa, tower reactor temperature
Preferably 50~200 DEG C of degree, reflux ratio is preferably 0.5-10, and dimethoxym ethane content is preferably no greater than 0.5% in the first tower bottoms.
In above-mentioned technical proposal, organic solvent boiling point described in step (b) is preferably 50~100 DEG C.
In above-mentioned technical proposal, the organic solvent is preferably the hydrocarbon or halogenated hydrocarbons of C1~C8.Such as can be selected from but
It is not limited at least one of n-hexane, hexamethylene, normal heptane, dichloroethanes, dichloropropane, chloroform and carbon tetrachloride.
In above-mentioned technical proposal, water phase preferably is selected from water, sodium hydrate aqueous solution, potassium hydroxide aqueous solution, sodium sulfite water
At least one of solution, potassium sulfite aqueous solution.
In above-mentioned technical proposal, the mass ratio of the water phase and organic solvent is preferably 0.05~5, more preferably
0.5~3；The dosage of two-phase extractant is preferably 0.1~10 times of the first tower bottoms quality, more preferably 0.5~4 times.
In above-mentioned technical proposal, the extraction cells can for single-stage, two-stage, or more grade extraction equipment；Described
Extraction equipment includes at least one of extraction tower, extraction centrifuge.
In above-mentioned technical proposal, Second distillation column operating pressure described in step (c) is preferably 0.05~0.1MPa, tower reactor
Temperature is preferably 50~120 DEG C, and reflux ratio is preferably 0.5-10.
In above-mentioned technical proposal, the second tower bottoms described in step (c) preferably comprises the poly- first that reaction product is n=2-8
Aldehyde dimethyl ether, content are preferably not less than 99%, and water content is preferably more than 0.5%, and content of formaldehyde is preferably more than 0.5%.
In above-mentioned technical proposal, step (c) third distillation column operating pressure is preferably 0~0.08MPa, and bottom temperature is preferred
It is 50~150 DEG C, reflux ratio is preferably 0.5-10.
In above-mentioned technical proposal, the 4th rectifying column operating pressure of step (c) is preferably 0~0.05MPa, and tower top temperature is preferred
It is 20~150 DEG C, reflux ratio is preferably 0.5-10.
In above-mentioned technical proposal, purity > 99% of n=2 polyoxymethylene dimethyl ethers, preferably water content preferably in third fraction
< 0.5%；It is preferred that in the 4th fraction the polyoxymethylene dimethyl ethers of n=3~4 purity>99%, preferred water content<0.1%.
In above-mentioned technical proposal, the 4th tower bottoms of the first fraction and the polyoxymethylene dimethyl ethers high polymer comprising n >=5 can
It is recycled back to synthesis unit；Second fraction can enter water process list back to recycling in step (b), raffinate phase
Member.
Unless stated otherwise, heretofore described % refers both to weight percent or weight percentage.
The technique is based on rectifying, to guarantee going on smoothly for rectifying, handles rectifying intermediate product using two-phase extractant,
The by-products such as formaldehyde, water and methanol can be removed simultaneously, and easy to operate and efficiency is higher, thus greatly reduces these by-products
Influence to distillation process reduces the possibility of rectifying column blocking, improves the efficiency of rectifying.This method process can guarantee poly
The separation and recovery of formaldehyde and going on smoothly for rectifying, the polyoxymethylene dimethyl ethers purity of n=3-4 reaches in obtained product cut
99% or more, while obtaining the n=2 polyoxymethylene dimethyl ethers of purity > 99%.
Detailed description of the invention
Fig. 1 is the process flow chart of embodiment of the present invention.
Catalysis reaction is carried out in synthesis unit 2 by the feed stream 1 that dimethoxym ethane and paraformaldehyde and catalyst form,
Obtain the neutral reaction mixing containing the polyoxymethylene dimethyl ethers that formaldehyde, dimethoxym ethane, methanol, water and reaction product are n=2-8
Object 3.First rectifying column 4 is first passed around, tower top steams the first fraction 5 comprising methanol and unreacted dimethoxym ethane, the first tower bottoms 6
Enter extraction cells 8 jointly with two-phase extractant 7, obtain extraction phase 9 and raffinate phase 10, extraction phase 9 enters Second distillation column 11
Middle rectifying obtains the fraction 12 containing organic solvent phase, and the second tower bottoms 13 of the polyoxymethylene dimethyl ethers comprising n=2-8；
Second tower bottoms 13 sequentially enters third distillation column 14 and the 4th rectifying column rectification under vacuum, obtains the polyformaldehyde diformazan comprising n=2
The fraction 15 of base ether；With the product 18 of the polyoxymethylene dimethyl ethers main component comprising n=3-4, remaining is to include by-product and n
4th tower bottoms 19 of >=5 polyoxymethylene dimethyl ethers high polymer.Fraction 12 is used as to return and be recycled in two-phase extractant；It evaporates
Points 10 go waste water treatment system to separate organic phase after be recycled；First fraction 5 and the 4th tower bottoms 19 are returned as recycle stock
It returns synthesis unit 2 and participates in reaction.
Specific embodiment
[embodiment 1]
Using the reaction mixture that paraformaldehyde and dimethoxym ethane obtain after acid catalysis as raw material, first through first rectifying column,
In 0.1MPa, reflux ratio 1, rectifying removes the first fraction DMM under the conditions of 105 DEG C of bottom temperature；Water and hexamethylene press the ratio of 1:1
The two-phase extractant of example composition, enters extraction tower with the first tower bottoms with the ratio of 2:1, obtains extraction phase into the second rectifying
Tower, in normal pressure, reflux ratio is rectifying under conditions of 2, and tower top obtains the second fraction mainly comprising cyclohexane solvent, returns to two-phase
In extractant；Second tower bottoms of the polyoxymethylene dimethyl ethers comprising n=2-8 sequentially enters third distillation column and the 4th rectifying column
Rectification under vacuum is obtained the polyoxymethylene dimethyl ethers of n=2 and the polyoxymethylene dimethyl ethers product of n=3-4 by tower top respectively, wherein
Third distillation column operating condition is 0.08MPa, reflux ratio 8,150 DEG C of bottom temperature；4th rectifying column operating condition is
0.04MPa, reflux ratio 0.5,118 DEG C of tower top temperature；First fraction and the 4th tower bottoms, which can return to reaction member circulation, to be made
With.Each material is through gas chromatographic analysis, and the results are shown in Table 1.
[comparative example 1]
With embodiment 1, the first tower bottoms without two-phase extractant handle be directly entered third distillation column 0.08MPa, return
Stream carries out rectification under vacuum under the conditions of 150 DEG C of bottom temperature than being 8；It is solid to occur a large amount of whites after rectifying about 3h in overhead condenser
Body is adhered to condensation tube wall, and overhead condensation liquid is muddy, and continuous rectification can not continue, and tower is washed in parking.
[embodiment 2]
Using the reaction mixture that paraformaldehyde and dimethoxym ethane obtain after acid catalysis as raw material, first through first rectifying column,
In 0.05MPa, reflux ratio 3, rectifying removes the first fraction DMM under the conditions of 88 DEG C of bottom temperature；Aqueous solution containing NaOH and just
The two-phase extractant that hexane is formed with the ratio of 0.2:1 enters extraction tower with the first tower bottoms with the ratio of 1:5, is extracted
Mutually enter Second distillation column, in 0.1MPa, reflux ratio is rectifying under conditions of 5, and tower top obtains mainly including n-hexane solvent
Second fraction returns in two-phase extractant；Second tower bottoms of the polyoxymethylene dimethyl ethers comprising n=2-8 sequentially enters third
Rectifying column and the 4th rectifying column rectification under vacuum are obtained the polyoxymethylene dimethyl ethers of n=2 and the polyformaldehyde of n=3-4 by tower top respectively
Dimethyl ether product, wherein third distillation column operating condition be 0.05Mpa, reflux ratio 4,130 DEG C of bottom temperature；4th rectifying
Tower operating condition is 0.02MPa, reflux ratio 2,90 DEG C of tower top temperature；First fraction and the 4th tower bottoms return to reaction member
It is recycled.Each material is through gas chromatographic analysis, and the results are shown in Table 2.
[embodiment 3]
Using the reaction mixture that paraformaldehyde and dimethoxym ethane obtain after acid catalysis as raw material, first through first rectifying column,
In 0.15MPa, reflux ratio 0.5, rectifying removes the first fraction DMM under the conditions of 125 DEG C of bottom temperature；Water and normal heptane are with 3:1
Ratio composition two-phase extractant, extraction and separation pump is entered with the ratio of 4:1 with the first tower bottoms, extraction phase is obtained and enters the
Two rectifying columns, in 0.05MPa, reflux ratio is rectifying under conditions of 8, and tower top obtains main second comprising normal heptane solvent and evaporates
Point, it returns in two-phase extractant；Second tower bottoms of the polyoxymethylene dimethyl ethers comprising n=2-8 sequentially enters third distillation column
With the 4th rectifying column rectification under vacuum, the polyoxymethylene dimethyl ethers of n=2 and the polyformaldehyde dimethyl of n=3-4 are obtained by tower top respectively
Ether product, wherein third distillation column operating condition be 0.03MPa, reflux ratio 1,116 DEG C of bottom temperature；The operation of 4th rectifying column
Condition is 0.01MPa, reflux ratio 1,74 DEG C of tower top temperature；First fraction and the 4th tower bottoms can return to reaction member circulation
It uses.Each material is through gas chromatographic analysis, and the results are shown in Table 3.
[embodiment 4]
Using the reaction mixture that paraformaldehyde and dimethoxym ethane obtain after acid catalysis as raw material, first through first rectifying column,
In 0.1MPa, reflux ratio 5, rectifying removes the first fraction DMM under the conditions of 105 DEG C of bottom temperature；Water phase and hexamethylene containing KOH
The two-phase extractant formed with the ratio of 1:10 is entered extraction and separation pump with the first tower bottoms with the ratio of 1:1, obtains extraction phase
Into Second distillation column, in 0.08MPa, reflux ratio is rectifying under conditions of 1, tower top obtain mainly comprising cyclohexane solvent the
Two fractions return in two-phase extractant；Second tower bottoms of the polyoxymethylene dimethyl ethers comprising n=2-8 sequentially enters third essence
Tower and the 4th rectifying column rectification under vacuum are evaporated, obtains the polyoxymethylene dimethyl ethers of n=2 and the polyformaldehyde two of n=3-4 by tower top respectively
Methyl ether product, wherein third distillation column operating condition be 0.01MPa, reflux ratio 0.5,65 DEG C of bottom temperature；4th rectifying
Tower operating condition is 0.004MPa, reflux ratio 5,50 DEG C of tower top temperature；First fraction and the 4th tower bottoms can return to reaction
Unit is recycled.Each material is through gas chromatographic analysis, and the results are shown in Table 4.
Table 1
Table 2
Table 3
Table 4
Claims (10)
1. the refining methd of polyoxymethylene dimethyl ethers, comprising:
(a) reaction mixture that reaction synthesis unit obtains, initially enters first rectifying column, is separated off mainly comprising dimethoxym ethane
The first fraction, obtain the first tower bottoms；
(b) the first tower bottoms enters extraction cells, is extracted, is wrapped with the two-phase extractant comprising organic solvent and water phase
Extraction phase containing n=2-8 polyoxymethylene dimethyl ethers and organic solvent, raffinate phase are the water phase comprising formaldehyde；
(c) extraction phase sequentially enters Second distillation column, third distillation column and the 4th rectifying column rectifying, respectively obtains comprising organic
Second fraction of solvent, the third fraction comprising the polyoxymethylene dimethyl ethers of high-purity n=2 and the polyformaldehyde dimethyl comprising n=3-4
4th fraction of ether.
2. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that reaction described in step (a) is mixed
Close the polyoxymethylene dimethyl ethers and formaldehyde that object includes n=1-8.
3. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that the first essence described in step (a)
Evaporating tower operating pressure is 0 ~ 0.2MPa, and bottom temperature is 50 ~ 200 DEG C, reflux ratio 0.5-10, and dimethoxym ethane contains in the first tower bottoms
Amount is not higher than 0.5%.
4. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that organic molten described in step (b)
Agent boiling point is 50 ~ 100 DEG C.
5. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that the organic solvent be C1 ~
The hydrocarbon or halogenated hydrocarbons of C8.
6. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that water phase is selected from water, sodium hydroxide
At least one of aqueous solution, potassium hydroxide aqueous solution, sodium sulfite aqueous solution, potassium sulfite aqueous solution.
7. according to claim 1 or the refining methd of polyoxymethylene dimethyl ethers as claimed in claim 3, it is characterized in that step (b)
The mass ratio of the water phase and organic solvent is 0.05 ~ 5.
8. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that the second essence described in step (c)
Evaporating tower operating pressure is 0.05 ~ 0.1MPa, and bottom temperature is 50 ~ 120 DEG C, reflux ratio 0.5-10.
9. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that step (c) third distillation column is grasped
It is 0 ~ 0.08MPa as pressure, bottom temperature is 50 ~ 150 DEG C, reflux ratio 0.5-10.
10. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that the 4th rectifying column of step (c)
Operating pressure is 0 ~ 0.05MPa, and tower top temperature is 20 ~ 150 DEG C, reflux ratio 0.5-10.
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| CN109096064B (en) * | 2017-06-21 | 2021-09-03 | 中国石油化工股份有限公司 | Refining method of polyoxymethylene dimethyl ether |
| CN109096065B (en) * | 2017-06-21 | 2021-07-30 | 中国石油化工股份有限公司 | Purification method of polyoxymethylene dimethyl ether |
| CN109096062B (en) * | 2017-06-21 | 2021-09-03 | 中国石油化工股份有限公司 | Method for purifying polymethoxy dimethyl ether |
| CN110372477B (en) * | 2018-04-13 | 2022-07-15 | 中国科学院大连化学物理研究所 | Continuous catalytic extraction method for preparing poly-methoxy-dimethyl ether |
| FR3094178B1 (en) | 2019-03-28 | 2021-05-14 | Arkema France | AQUEOUS COMPOSITION BASED ON POLYOXYMETHYLENES DIALKYL ETHERS (POM) AND ITS USE FOR THE CONSERVATION AND / OR BIRTH OF THE HUMAN OR ANIMAL BODY |
| 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 |
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| CN103626640A (en) * | 2013-12-13 | 2014-03-12 | 江苏凯茂石化科技有限公司 | Process unit and method for preparing polymethoxy dimethyl ether |
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