CN107793300A - A kind of reaction solution separating technology of polymethoxy dimethyl ether - Google Patents
A kind of reaction solution separating technology of polymethoxy dimethyl ether Download PDFInfo
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- CN107793300A CN107793300A CN201711091422.4A CN201711091422A CN107793300A CN 107793300 A CN107793300 A CN 107793300A CN 201711091422 A CN201711091422 A CN 201711091422A CN 107793300 A CN107793300 A CN 107793300A
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- tower
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- dimethyl ether
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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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Abstract
The invention discloses a kind of reaction solution separating technology of polymethoxy dimethyl ether, first separate the formic acid and water in reaction solution, the reaction that acid is disproportionated into follow-up formaldehyde serves inhibitory action well, then plate column dealdehyder tower is used, by setting circulating pump to produce the material of dealdehyder tower inside points column plate, back-mixing is to top plate after superheater overheats, increase the high temperature section column plate quantity of dealdehyder tower, be advantageous to the vaporization separation of thermal sensitivity formaldehyde, superheater heating can accelerate the hemiacetal of unstable state to be thermally decomposed, the formaldehyde for solving to occur during conventional simple distillation is generated a large amount of formic acid by Heat disproportionation reaction, and the problem of separation can not be carried out caused by formic acid analytical product.Coordinate leading portion separating technology, realize selective acquisition dmmn, n=2 8 component.And ensure that tower reactor content of formaldehyde, formic acid content are nearly no detectable, obtain the product of high quality.This invented technology is simply efficient, and cost of investment is greatly reduced.
Description
Technical field
The present invention relates to the production of polymethoxy dimethyl ether, the reaction solution separation work of specially a kind of polymethoxy dimethyl ether
Skill.
Background technology
At present, polymethoxy dimethyl ether is that (formaldehyde may be from formalin/tri- with formaldehyde with dimethoxym ethane/methanol mostly
Polyformaldehyde/paraformaldehyde) generation is reacted under the catalytic action of acidic catalyst.For remaining unreacted formaldehyde in reaction solution
Separation, typically use alkali neutralization reaction, be hydrogenated to carry out conventional rectification separation after alcohols material again.Due to alkali neutralization reaction
Formaldehyde in liquid, big content of starting materials is consumed, and produce substantial amounts of sewage.Industrialized production is uneconomical.Then power consumption is high for hydrogenation, hydrogen into
This height.If not handling formaldehyde directly to distill, temperature is high, and in the heated vaporization engineering of reaction solution, formaldehyde is easy to disproportionated reaction generation
Formic acid.Formic acid analytical product generation dimethoxym ethane and formaldehyde in separation process.This process low separation efficiency, product are further divided
Take off.
The content of the invention
The technical problem to be solved in the present invention is to overcome polymethoxy dimethyl ether remaining unreacted in reaction solution in producing
A kind of the defects of separation of formaldehyde, existing isolation technics are undesirable, there is provided the reaction solution separating technology of polymethoxy dimethyl ether.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
A kind of reaction solution separating technology of polymethoxy dimethyl ether, comprises the following steps：
Dimethoxym ethane and high-concentration formaldehyde react in solid acid cation resin catalyzing agent, obtain reaction solution through lightness-removing column,
Separation obtains dmmn (n=2-8 product) after dehydrating tower, piptonychia aldehyde tower.
1), the reaction solution from reaction system enters lightness-removing column, and the dimethoxym ethane and methanol of reaction will be not participated in tower,
Reactor is sent back to by overhead extraction and continues to participate in reaction, the material of tower reactor is pumped into the middle part of dehydrating tower tower, lightness-removing column be packed tower or
Plate column, number of theoretical plate are 20~50 pieces；The tower operating pressure is 0.1~0.2Mpa, and operation temperature is 40~130 DEG C；Backflow
Than for 0.5~4；
2), depart from the moisture and the moisture brought into of raw material of reaction system generation in dehydrating tower, dehydrating tower be packed tower or
Plate column, number of theoretical plate are 10~40 pieces；The tower operating pressure is 0.01~0.2MPa, and operation temperature is 80~110 DEG C；
3), the preheated device of reaction solution of removing dimethoxym ethane and water enters dealdehyder tower after being preheated to 140~160 DEG C, described de-
Aldehyde tower is plate column, sets circulating pump to produce the material of tower inside points column plate, after superheater overheats back-mixing to top plate,
In piptonychia aldehyde tower acquisition dmmn, n=2-8 product are separated after removing formaldehyde and formic acid.
Further, described dealdehyder tower number of theoretical plate is 40~60 pieces；Reflux ratio is 0.8~8.
Further, tower pressure interior force by the voltage-controlled valve regulation of tower top in 0.5-1Mpa, 170~200 DEG C of tower reactor operation temperature, tower
It is 100~140 DEG C to push up operation temperature.Dealdehyder tower uses the operator scheme of Stress control, improves the boiling point of material, temperature is raised
To more than threshold methanol temperature (140 DEG C), the formaldehyde for being can not liquefy.
Further, by the material back-mixing of the descending trays more than at 2 to top plate.
Further, the material at tower inner panel 19 is produced after platen superheater overheats through circulating pump, delivers to tower inner panel
At 17, the material at tower inner panel 25 is produced after platen superheater overheats through circulating pump, delivered at tower inner panel 23, by tower inner panel
Material at 32 is produced after platen superheater overheats through circulating pump, is delivered at tower inner panel 30.
Further, described superheater is platen superheater, and heat exchange area is 10~25 ㎡, heating medium be 0.5~
1.0Mpa steam.
Further, described dealdehyder tower bottom is provided with reboiler.Reboiler uses the pattern of forced circulation, if local
Temperature is too high, and formaldehyde is easy to disproportionated reaction generation formic acid.Forced circulation can effectively reduce material and stop in thermal extremes area
Stay the time.
The present invention first separates formic acid and water in reaction solution, and the reaction that acid is disproportionated into follow-up formaldehyde serves well
Inhibitory action, dealdehyder tower are plate column, set circulating pump to produce the material of tower inside points column plate, the back-mixing after superheater overheats
To top plate, that is, the high temperature section column plate quantity of tower is added, is advantageous to the vaporization separation of thermal sensitivity formaldehyde, superheater heating can add
The hemiacetal (hemiacetal is the unstable existence form of formaldehyde) of fast unstable state is thermally decomposed, during solving conventional simple distillation
The problem of formaldehyde of appearance is generated a large amount of formic acid by Heat disproportionation reaction, and separation can not be carried out caused by formic acid analytical product.Match somebody with somebody
Leading portion separating technology is closed, realizes selective acquisition dmmn, n=2-8 component.And ensure tower reactor content of formaldehyde, formic acid content
It is nearly no detectable.Obtain the product of high quality.This invented technology is simply efficient, and cost of investment is greatly reduced.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and a part for constitution instruction, the reality with the present invention
Apply example to be used to explain the present invention together, be not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the structural representation of dealdehyder tower in the embodiment of the present invention, wherein 1 tower top voltage-controlled valve, 2 preheaters, 3 superheaters
4 circulating pumps, 5 tower reactor discharging pumps, 6 reboilers.
Embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that described herein preferred real
Apply example to be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment
A kind of reaction solution separating technology of polymethoxy dimethyl ether, comprises the following steps：
Dimethoxym ethane and high-concentration formaldehyde react in solid acid cation resin catalyzing agent, obtain reaction solution through lightness-removing column,
Separation obtains dmmn (n=2-8 product) after dehydrating tower, piptonychia aldehyde tower.
1), the reaction solution from reaction system enters lightness-removing column, and the dimethoxym ethane and methanol of reaction will be not participated in tower,
Reactor is sent back to by overhead extraction and continues to participate in reaction, the material of tower reactor is pumped into the middle part of dehydrating tower tower, lightness-removing column be packed tower or
Plate column, number of theoretical plate are 20~50 pieces；The tower operating pressure is 0.1~0.2Mpa, and operation temperature is 40~130 DEG C；Backflow
Than for 0.5~4；The charging of lightness-removing column reaction solution (dimethoxym ethane 40-60%, methanol 2-15%, formaldehyde 5-8%, water 1-3% its
Remaining is product dmm2-8), the boiling point of dimethoxym ethane is minimum during this is formed, and only 42 DEG C, the dimethoxym ethane in composition is steamed from tower top, after
It is continuous to participate in reaction；
2), depart from the moisture and the moisture brought into of raw material of reaction system generation in dehydrating tower, dehydrating tower be packed tower or
Plate column, number of theoretical plate are 10~40 pieces；The tower operating pressure is 0.01~0.2MPa, and operation temperature is 80~110 DEG C；It is de- light
Tower kettle material is pumped into the middle part of dehydrating tower tower, realizes the moisture that the moisture for departing from reaction system generation and raw material are brought into.Lightness-removing column
A small amount of moisture (2-4%) that tower reactor contains depressurizes in dehydrating tower departs from residual water (0.2-1%).
3), the preheated device 2 of reaction solution of removing dimethoxym ethane and water enters dealdehyder tower, dealdehyder tower after being preheated to 140~160 DEG C
For plate column, circulating pump is set to produce the material of tower inside points column plate, back-mixing is to top plate after superheater overheats, in piptonychia
In aldehyde tower acquisition dmmn, n=2-8 product are separated after removing formaldehyde and formic acid.Overhead reflux (logistics 2) is 90-99% contents
Dimethoxym ethane.Qualified product is produced by bottom of towe discharging pump.Light component dimethoxym ethane, formaldehyde are from overhead extraction dereaction system.
Dealdehyder tower number of theoretical plate is 40~60 pieces；Reflux ratio is 0.8~8.Tower pressure interior force is adjusted by tower top voltage-controlled valve 1
0.5-1Mpa, 170~200 DEG C of tower reactor operation temperature, tower top operation temperature are 100~140 DEG C.Dealdehyder tower is using Stress control
Operator scheme, the boiling point of material is improved, temperature is increased to more than threshold methanol temperature (140 DEG C) so that formaldehyde can not liquefy.
Tower top is not condensed using dimethoxym ethane backflow, is further reacted with gas phase and formaldehyde Returning reactor.
Material at tower inner panel 19 is produced after platen superheater 3 overheats through circulating pump 4, delivered at tower inner panel 17, will
Material at tower inner panel 25 is produced after the overheat of platen superheater 3 through circulating pump 4, is delivered at tower inner panel 23, at tower inner panel 32
Material through circulating pump 4 produce through platen superheater 3 overheat after, deliver at tower inner panel 30.The back-mixing of partial material is realized to carry
The temperature of high tower upper semisection.So as to promote formaldehyde to be separated within the scope of a reasonable temperature totally.Simultaneously because board-like overheat
Device crosses heat effect, accelerates the Formaldehyde decomposition vaporization dissolved in logistics.
Superheater 3 uses platen superheater, and heat exchange area is 10~25 ㎡, and heating medium is 0.5~1.0Mpa steam.
Dealdehyder tower bottom is provided with reboiler 6.Reboiler 6 uses the pattern of forced circulation, if local temperature is too high, formaldehyde
It is easy to disproportionated reaction generation formic acid.Forced circulation can effectively reduce residence time of the material in thermal extremes area.
It is as follows to circulating-pump outlet sample examination content of formaldehyde：
| Plate 19 | Plate 17 | Plate 25 | Plate 23 | Plate 32 | Plate 30 | |
| Formaldehyde w% | 1-3 | --- | 0.5-1 | --- | 0.01-0.05 | --- |
| Temperature DEG C | 120-160 | 110-150 | 140-180 | 130-170 | 160-200 | 150-190 |
When tower reactor obtains dmmn (n=3-8) product.Operating pressure 0.1-0.3Mpa, 140-200 DEG C of operation temperature.
Now a large amount of M2 steam back reactor from tower top and continue to participate in reaction.
It is as follows to circulating-pump outlet sample examination content of formaldehyde：
| Plate 19 | Plate 17 | Plate 25 | Plate 23 | Plate 32 | Plate 30 | |
| Formaldehyde w% | 1-3 | --- | 0.5-1 | --- | 0.01-0.05 | --- |
| Temperature DEG C | 105-145 | 100-140 | 125-165 | 120-160 | 145-185 | 140-180 |
This tower effectively removes formaldehyde, leaves product dmmn (n=2-8), and will not produce formic acid analytical product phenomenon.Can
Freely to change operating parameter by tower top regulating valve to realize the product form of needs.Selected according to market and enterprise itself
Whether dmm2 is taken out as product.Or dmm2 is continued into Returning reactor as reaction intermediate and reacted.
Under this technique, it is as follows that tower reactor discharging pump 5 measures content of formaldehyde：
| Obtain m2-8 | Obtain m3-8 | Normal mode | |
| Content of formaldehyde | <10ppm | It can't detect | 100-1000ppm |
Product dmmn (n2-8) or product dmmn (n=3-8) that pump comes are subjected to decompression separation in this tower.According to
Need, the separation of selectivity is carried out to product.Different separation conditions is selected according to separation requirement.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (7)
1. the reaction solution separating technology of a kind of polymethoxy dimethyl ether, it is characterised in that comprise the following steps：
1), the reaction solution from reaction system enters lightness-removing column, by the dimethoxym ethane and methanol in reaction solution in tower, is adopted by tower top
Go out to send back to reactor and continue to participate in reaction, the material of tower reactor is pumped into the middle part of dehydrating tower tower, and lightness-removing column is packed tower or plate column, is managed
It it is 20~50 pieces by plate number；The tower operating pressure is 0.1~0.2Mpa, and operation temperature is 40~130 DEG C；Reflux ratio be 0.5~
4；
2) moisture that the moisture of reaction system generation and raw material are brought into, is departed from dehydrating tower, dehydrating tower is packed tower or board-like
Tower, number of theoretical plate are 10~40 pieces；The tower operating pressure is 0.01~0.2MPa, and operation temperature is 80~110 DEG C；
3), the preheated device of reaction solution of removing dimethoxym ethane and water enters dealdehyder tower, the dealdehyder tower after being preheated to 140~160 DEG C
For plate column, circulating pump is set to produce the material of tower inside points column plate, back-mixing is to top plate after superheater overheats, in piptonychia
In aldehyde tower acquisition dmmn, n=2-8 product are separated after removing formaldehyde and formic acid.
2. the reaction solution separating technology of polymethoxy dimethyl ether as claimed in claim 1, it is characterised in that described dealdehyder tower
Number of theoretical plate is 40~60 pieces；Reflux ratio is 0.8~8.
3. the reaction solution separating technology of polymethoxy dimethyl ether as claimed in claim 1 or 2, it is characterised in that tower pressure interior force
By the voltage-controlled valve regulation of tower top in 0.5-1Mpa, 170~200 DEG C of tower reactor operation temperature, tower top operation temperature is 100~140 DEG C.
4. the reaction solution separating technology of polymethoxy dimethyl ether as claimed in claim 2, it is characterised in that more than at 2
The material back-mixing of descending trays is to top plate.
5. the reaction solution separating technology of polymethoxy dimethyl ether as claimed in claim 4, it is characterised in that at tower inner panel 19
Material through circulating pump produce after platen superheater overheats, deliver at tower inner panel 17, by the material at tower inner panel 25 through circulation
Pump is produced after platen superheater overheats, and is delivered at tower inner panel 23, and the material at tower inner panel 32 is produced through board-like through circulating pump
After superheater overheat, deliver at tower inner panel 30.
6. the reaction solution separating technology of polymethoxy dimethyl ether as claimed in claim 3, it is characterised in that described superheater
For platen superheater, heat exchange area is 10~25 ㎡, and heating medium is 0.5~1.0Mpa steam.
7. the reaction solution separating technology of polymethoxy dimethyl ether as claimed in claim 1, it is characterised in that described dealdehyder tower
Bottom is provided with reboiler.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711091422.4A CN107793300B (en) | 2017-11-08 | 2017-11-08 | Separation process of reaction liquid of polymethoxy dimethyl ether |
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|---|---|---|---|
| CN201711091422.4A CN107793300B (en) | 2017-11-08 | 2017-11-08 | Separation process of reaction liquid of polymethoxy dimethyl ether |
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| CN107793300A true CN107793300A (en) | 2018-03-13 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015067610A (en) * | 2013-09-29 | 2015-04-13 | 蘇州奥索特新材料有限公司Ｓｕｚｈｏｕ ＯＳＴ Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． | Reaction system and method for producing polymethoxy dimethyl ether |
| CN105693479A (en) * | 2016-03-15 | 2016-06-22 | 江苏凯茂石化科技有限公司 | Process device special for preparing polyoxymethylene dimethyl ethers through formaldehyde gas |
| CN106365960A (en) * | 2016-10-12 | 2017-02-01 | 江苏凯茂石化科技有限公司 | Device and method for removing formaldehyde in polyoxymethylene dimethyl ethers |
-
2017
- 2017-11-08 CN CN201711091422.4A patent/CN107793300B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015067610A (en) * | 2013-09-29 | 2015-04-13 | 蘇州奥索特新材料有限公司Ｓｕｚｈｏｕ ＯＳＴ Ａｄｖａｎｃｅｄ Ｍａｔｅｒｉａｌｓ Ｃｏ．， Ｌｔｄ． | Reaction system and method for producing polymethoxy dimethyl ether |
| CN105693479A (en) * | 2016-03-15 | 2016-06-22 | 江苏凯茂石化科技有限公司 | Process device special for preparing polyoxymethylene dimethyl ethers through formaldehyde gas |
| CN106365960A (en) * | 2016-10-12 | 2017-02-01 | 江苏凯茂石化科技有限公司 | Device and method for removing formaldehyde in polyoxymethylene dimethyl ethers |
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Effective date of registration: 20190325 Address after: 214000 K-park Service Center Building 402, No. 50 Xiuxi Road, Binhu District, Wuxi City, Jiangsu Province Applicant after: Wuxi Helibang Chemical Technology Co., Ltd. Address before: 214000 southeast 4 floor, 3 K-PARK service center, 50 embroidery Road, Binhu District, Wuxi, Jiangsu. Applicant before: Jiangsu Dalton Petrochemical Technology Co., Ltd. |
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