CN106397144B - A method of moisture in removal dimethoxym ethane raw material - Google Patents
A method of moisture in removal dimethoxym ethane raw material Download PDFInfo
- Publication number
- CN106397144B CN106397144B CN201610801293.2A CN201610801293A CN106397144B CN 106397144 B CN106397144 B CN 106397144B CN 201610801293 A CN201610801293 A CN 201610801293A CN 106397144 B CN106397144 B CN 106397144B
- Authority
- CN
- China
- Prior art keywords
- dmm
- mpa
- molecular sieve
- kettle
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method of moisture in removal dimethoxym ethane raw material, it is related to a kind of method for handling industrial chemicals, this method is using DMM as raw material, in the case where 25-45 DEG C of temperature, pressure are 1.0-5.0 MPa, using molecular sieve 3a, 4A, 5A and molecular sieve mixing with the one or more topological structures of MWW, FEB, MFI, MOR, FAU, BEA, as deicer, reactor fills stirring of inert gas, can remove the moisture in DMM.The present invention is not related to chemically reacting, it is only to be removed water using the wettability power of molecular sieve, it is pollution-free, it is DMM liquid and molecular sieve solid-liquid two-phase after water removal, there is no product separation problem, other impurity will not be introduced, and energy consumption of the present invention is smaller, water removal effect is good, the water content in DMM can be down to 10 ppm.Oxonation is carried out using the DMM after water removal, obtains preferable carbonylation effect.
Description
Technical field
The present invention relates to it is a kind of handle industrial chemicals method, more particularly to moisture in a kind of removal dimethoxym ethane raw material
Method.
Background technique
DMM(CH3OCH2OCH3), Chinese name dimethoxym ethane also known as dimethoxymethane, methylal, achromaticity and clarification is easy
Volatilize flammable liquid, there is chloroform smell and a pungent taste, and 42 DEG C of boiling point.DMM has good physicochemical property, i.e., good water-soluble
Property, it is non-toxic, it is important chemical intermediate, is widely used as the production such as cosmetics, auto industry articles, drug, cleaning supplies
In product.Just because of dimethoxym ethane is widely used, it has excellent performance, therefore continuous always to the research of its synthesis technology in recent decades
Carry out.
Consulting literatures are it is found that the method for synthesis DMM mainly has following four: methanol and formaldehyde acetal reaction method；Methanol one
Walk oxidizing process；Dimethyl ether oxidizing process；Methanol and polyformaldehyde reaction method.But these method majorities are not able to achieve commercial scale life
It produces.Really realize that the method for industrialized production only has methanol and formaldehyde acetal reaction method.As shown in equation (1):
HCHO+2CH3OH → CH3OCH2OCH3+H2O..................................(1)
Methanol and formaldehyde acetal reaction method are divided into three kinds of techniques: batch technology, half-continuous process and continuous processing.
Batch technology is disposably to put into reaction raw materials methanol, formaldehyde, catalyst in reaction kettle by a certain percentage, is added
Thermal response, cooling is discharged to distillation system after reaction, and rectifying is up to dimethoxym ethane product.The process flow and equipment are simple,
But the disadvantage is that feed stock conversion less than 50%, has a large amount of methanol and formaldehyde remaining after reaction in system, while having in system big
Measure water residual.
Half-continuous process is that a certain amount of formaldehyde, methanol, catalyst conduct are put into the reaction kettle with rectifying column first
The formaldehyde centainly matched, methanol is continuously added when tower top starts reflux (85-95 DEG C) in bottom material, heating into reaction kettle,
It controls suitable reflux ratio extraction dimethoxym ethane product and stops acquisition when bottom temperature is more than 95 DEG C.It is brought into due to raw material
The water that water and reaction generate, so that there is a large amount of water to remain in the technological reaction kettle.
Continuous processing is the reactor that one or more filled solid acid catalysts are connected on single rectifying column, and reaction is former
Material formaldehyde, methanol carry out solid-liquid with solid acid catalyst in the reactor and contact, and reaction generates dimethoxym ethane.Reactor cycles go out
The solution containing methanol, formaldehyde, water and dimethoxym ethane contacted with the steam that rectifying column rises, the steam after contact again with it is advanced anti-
The solution for answering device to recycle contacts, such gradual reaction, and the concentration of dimethoxym ethane is gradually increased in gas phase.Although the technique dimethoxym ethane
Yield it is higher (being calculated as 90% with formaldehyde charging), but contain a large amount of water in the dimethoxym ethane product produced, product quality is poor.
The processing disadvantages of above-mentioned three productions DMM are that have a large amount of first alcohol and waters remaining after reacting.It is exhausted in dimethoxym ethane raw material
Although most of water can be removed by distillation, remaining minor amount of water remains in DMM in raw material, it is difficult to remove.It can using DMM
To prepare DMMn(n=3-8), as shown in equation (2), DMMnIt is excellent diesel fuel additives；It is raw that disproportionated reaction occurs for DMM itself
Formic acid methyl esters (MF) and dimethyl ether (DME) can prepare DME and MF using this reaction as shown in equation (3)；DMM and CO
Direct oxonation can prepare the methoxy menthyl acetate (MMAc) of high added value, and as shown in equation (4), MMAc is very
Useful intermediate, can be used for the Kinetic Resolution of chiral aminated compounds, and it is phonetic to can be used for synthesizing vitamin B6, sulfanilamide (SN) -5-
Pyridine etc., in addition, MMAc also is used as the catalyst etc. of polymerization reaction.And the presence of minor amount of water by the carbonylation of extreme influence DMM and
The efficiency of other reactions.
CH3OCH2OCH3+nHCHO→CH3O(CH2O)nCH3(DMMn) ... ... ... ... .. (2)
2CH3OCH2OCH3→2CH3OCH3(DME)+HCOOCH3(MF) ... ... ... ... (3)
CH3OCH2OCH3+CO→CH3OCH2COOCH3(MMAc) ... ... ... ... (4) ...
Summary of the invention
The purpose of the present invention is to provide a kind of method of moisture in removal dimethoxym ethane raw material, this method utilizes 3A, 4A, 5A
The molecular sieve (MWW, FEB, MFI, MOR, FAU, BEA) of molecular sieve and other topological structures water removal, to solve due to water
There are problems that and cause DMM carbonylation efficiency reduction.
The purpose of the present invention is what is be achieved through the following technical solutions:
A method of moisture in removal dimethoxym ethane raw material, the method includes following procedure: using DMM as raw material, in temperature
Degree 25-45 DEG C, pressure be 1.0-5.0 MPa under, with molecular sieve 3a, 4A, 5A and have MWW, FEB, MFI, MOR, FAU,
The molecular sieve of the one or more topological structures of BEA mixes, as deicer, and reactor is filled stirring of inert gas, can be removed
Moisture in DMM.
The method of moisture in a kind of removal dimethoxym ethane raw material, the molecular sieve still more preferably 4A molecular sieve.
The method of moisture in a kind of removal dimethoxym ethane raw material, the inert gas are argon gas, carbon monoxide, hydrogen
One of gas, nitrogen or gaseous mixture.
The method of moisture in a kind of removal dimethoxym ethane raw material, the reactor are fixed bed or still reaction
Device.
The advantages and effects of the present invention are:
The present invention can effectively remove the micro-moisture in DMM, mainly utilize 3A, 4A, 5A molecular sieve and other
The molecular sieve (MWW, FEB, MFI, MOR, FAU, BEA) of topological structure removes water, to solve the presence due to water and lead to DMM
The problem of carbonylation efficiency reduces it is an advantage of the invention that not being related to chemically reacting is removed water using the wettability power of molecular sieve,
It is pollution-free, it is DMM liquid and molecular sieve solid two-phase after water removal, product separation problem is not present, other impurity will not be introduced,
And energy consumption of the present invention is smaller, water removal effect is good, the water content in DMM can be down to 10 ppm.Carbonyl is carried out using the DMM after water removal
Change reaction, obtains preferable carbonylation effect.
Detailed description of the invention
Fig. 1 is the change curve of DMM conversion ratio and MMAc selectivity with DMM water content.
Specific embodiment
The following describes the present invention in detail with reference to examples.
Raw material of the present invention is DMM liquid, CO gas, N2Gas, Ar gas, H2Gas, 3A, 4A, 5A molecular sieve and other
The molecular sieve (MWW, FEB, MFI, MOR, FAU, BEA) of topological structure, all molecular sieves are using preceding in advance in 500 DEG C of dryings
6 h are roasted in air.Used equipment are as follows: slurry bed system pressure autoclave type reactor, karl Fischer with stirring with temperature programming
Micro-water analyzer (SF101 type, 0.1 ug H of sensitivity2O, measurement range: 0.1 ug-200 mg H2O) etc..Using karr
Taking water content in not micro-moisture analyzer analysis experimental day experimental raw DMM is 1100 ppm.
Embodiment 1
(50 mL) DMM, 12g 4A molecular sieve of certain volume is added separately to the reaction kettle of tape program heat riser
In, the air in kettle is then replaced under the conditions of 1.0 MPa three times with CO at room temperature, makes remaining air content in kettle
Lower than 0.1%, and it is passed through 2.0 MPa CO again, stands 30 min, leak hunting for reaction kettle, it is ensured that emptying after device is air tight
Gas reactor.500 revs/min of reaction kettle mixing speed, 5.0 MPa CO are passed through, distinguish (25 DEG C) stirrings 8 h, 12 at room temperature
H, 16 h, 20 h, 24 h, the results are shown in Table 1 after water removal.
Influence of the different mixings time of table 1 to DMM water removal effect
As shown in table 1, under mutually synthermal, pressure, with the increase of mixing time, residual water content gradually subtracts in DMM
Few, when mixing time is 24 h, residual water content is 25 ppm in DMM.
Embodiment 2
By (50 mL) DMM of certain volume, 12 g 4A molecular sieves are added separately to the reaction kettle of tape program heat riser
In, the air in kettle is then replaced under the conditions of 1.0 MPa three times with CO at room temperature, makes remaining air content in kettle
Lower than 0.1%, and it is passed through 2.0 MPa CO again, stands 30 min, leak hunting for reaction kettle, it is ensured that emptying after device is air tight
Gas reactor.500 revs/min of reaction kettle mixing speed, each lead into 1.0 MPa, 2.0 MPa, 3.0 MPa, 4.0 MPa, 5.0
The CO of MPa, at room temperature (25 DEG C) 24 h of stirring, the results are shown in Table 2 after water removal.
Influence of the 2 difference CO pressure of table to DMM water removal effect
As shown in table 2, when temperature is 25 DEG C, mixing time is 24 h, when to be passed through CO gas pressure be 1.0 MPa, in DMM
Residual water content is 68 ppm, and with the increase for being passed through CO gas pressure, residual water content is gradually reduced in DMM, when CO gas
When to be passed through pressure be 5.0 MPa, residual water content is 25 ppm in DMM.
Embodiment 3
By (50 mL) DMM of certain volume, 12 g 4A molecular sieves are added separately to the reaction kettle of tape program heat riser
In, the air in kettle is then replaced under the conditions of 1.0 MPa three times with CO at room temperature, makes remaining air content in kettle
Lower than 0.1%, and it is passed through 2.0 MPa CO again, stands 30 min, leak hunting for reaction kettle, it is ensured that emptying after device is air tight
Gas reactor.500 revs/min of reaction kettle mixing speed, it is passed through the CO of 5.0 MPa, respectively at 25 DEG C, 30 DEG C, 35 DEG C, 40
DEG C, 45 DEG C of 24 h of stirring, the results are shown in Table 3 after water removal.
Influence of 3 different temperatures of table to DMM water removal effect
As shown in table 3, upon agitation between it is identical, CO pressure is also under the same conditions, remaining in DMM when temperature is 25 DEG C
Water content is 25 ppm, and as the temperature rises, residual water content is gradually reduced in DMM, when temperature reaches 45 DEG C, in DMM
Minimum 10 ppm of residual water content.
Embodiment 4
By (50 mL) DMM of certain volume, 12 g 4A molecular sieves are added separately to the reaction kettle of tape program heat riser
In, N is then used at room temperature2Air under the conditions of 1.0 MPa in displacement kettle makes remaining air content in kettle three times
Lower than 0.1%, and it is passed through 2.0 MPa N again2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that emptying after device is air tight
Gas reactor.500 revs/min of reaction kettle mixing speed, it is passed through the N of 5.0 MPa2, in 45 DEG C of 24 h of stirring, respectively with CO gas
Body, Ar gas, H2Gas repeats aforesaid operations, and the results are shown in Table 4 after water removal.
Influence of 4 gas with various of table to DMM water removal effect
As shown in table 4, mutually synthermal, under conditions of identical mixing time, it is passed through 5.0 MPa's into reaction kettle respectively
N2Gas, CO gas, Ar gas, H2Gas, residual water content is substantially suitable in DMM, illustrates the type that gas is passed through in reaction kettle
DMM water removal effect is influenced and little.
Embodiment 5
By (50 mL) DMM of certain volume, 12 g topological structures are that the molecular sieve of MWW is added to tape program heat riser
Reaction kettle in, then replace the air in kettle under the conditions of 1.0 MPa three times with CO at room temperature, make remaining in kettle
Air content is lower than 0.1%, and is passed through 2.0 MPa CO again, stands 30 min, leaks hunting for reaction kettle, it is ensured that device does not leak
Gas reactor is emptied after gas.500 revs/min of reaction kettle mixing speed, it is passed through the CO of 5.0 MPa, in 45 DEG C of 24 h of stirring, respectively
Aforesaid operations are repeated with the molecular sieve (FEB, MFI, MOR, FAU, BEA) of other topological structures, result such as 5 institute of table after water removal
Show.
Influence of the 5 molecular sieve different topology structure of table to DMM water removal effect
As shown in table 5, mutually synthermal, under conditions of identical mixing time, the molecular sieve that topological structure is MFI removes water effect
Fruit is preferable, and residual water content is 21 ppm in DMM after water removal；The molecular sieve water removal that topological structure is MWW and topological structure is MOR
Effect is substantially suitable；Topological structure is that the molecular sieve water removal effect of BEA is poor.
Embodiment 6
By (50 mL) DMM of certain volume, 12 g 4A molecular sieves are added in the reaction kettle of tape program heat riser, and
The air in kettle is replaced under the conditions of 1.0 MPa three times with CO at room temperature afterwards, is lower than remaining air content in kettle
0.1%, and it is passed through 2.0 MPa CO again, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that after device is air tight in emptying kettle
Gas.500 revs/min of reaction kettle mixing speed, it is passed through the CO of 5.0 MPa, in 45 DEG C of 24 h of stirring, respectively with different pore size
Molecular sieve (3A, 5A) repeats aforesaid operations, and the results are shown in Table 6 after water removal.
Influence of the 6 molecular sieve different pore size of table to DMM water removal effect
As shown in table 6, mutually synthermal, under conditions of identical mixing time, the water removal effect of 4A molecular sieve be better than 3A,
5A molecular sieve, minimum 10 ppm of the residual water content of DMM after water removal.
Embodiment 7
Solvent, D-009B(vinylbenzenesulfonic acid and divinylbenzene copolymer are done with sulfolane) it is catalyst, by different water
The DMM of content is applied to oxonation, and reaction temperature is 110 DEG C, and reaction pressure is 5.0 MPa, and the reaction time is 6 h, reaction
The results are shown in Table 7 afterwards.
The DMM oxonation result of the different water contents of table 7
As shown in table 7, in identical reaction temperature, reaction pressure, under conditions of the reaction time, the conversion ratio of DMM with
The selectivity of MMAc is all dramatically increased with the reduction of DMM water content, and the above results absolutely prove, remove to raw material DMM
Water, carbonylation efficiency significantly improve.Oxonation is carried out using the DMM after water removal, more MMAc can be received.
Claims (2)
1. a kind of method of moisture in removal dimethoxym ethane raw material, which is characterized in that the method includes following procedure: being by volume
50 mL DMM, 12 g 4A molecular sieves are added separately in the reaction kettle of tape program heat riser, then use at room temperature
CO replaces the air in kettle three times under the conditions of 1.0 Mpa, so that remaining air content in kettle is lower than 0.1%, and be passed through again
2.0 Mpa CO stand 30 min, leak hunting for reaction kettle, it is ensured that gas reactor, reaction kettle stirring are emptied after device is air tight
500 revs/min of speed, be passed through the CO of 5.0 Mpa, in 45 DEG C of 24 h of stirring to get into DMM residual water content be 10ppm.
2. a kind of method of moisture in removal dimethoxym ethane raw material, which is characterized in that the method includes following procedure: being by volume
50 mL DMM, 12 g 4A molecular sieves are added separately in the reaction kettle of tape program heat riser, then use at room temperature
Ar replaces the air in kettle three times under the conditions of 1.0 Mpa, so that remaining air content in kettle is lower than 0.1%, and be passed through again
2.0 Mpa Ar stand 30 min, leak hunting for reaction kettle, it is ensured that gas reactor, reaction kettle stirring are emptied after device is air tight
500 revs/min of speed, be passed through the Ar of 5.0 Mpa, in 45 DEG C of 24 h of stirring to get into DMM residual water content be 10ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610801293.2A CN106397144B (en) | 2016-09-05 | 2016-09-05 | A method of moisture in removal dimethoxym ethane raw material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610801293.2A CN106397144B (en) | 2016-09-05 | 2016-09-05 | A method of moisture in removal dimethoxym ethane raw material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106397144A CN106397144A (en) | 2017-02-15 |
| CN106397144B true CN106397144B (en) | 2019-04-05 |
Family
ID=57999537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610801293.2A Active CN106397144B (en) | 2016-09-05 | 2016-09-05 | A method of moisture in removal dimethoxym ethane raw material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106397144B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110054550B (en) * | 2019-04-09 | 2022-03-29 | 天津大学 | Process system and method for producing polymethoxy dimethyl ether by gas-phase formaldehyde method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320940A (en) * | 2011-06-20 | 2012-01-18 | 印海平 | Method for purifying methylal |
| CN104447240A (en) * | 2014-11-10 | 2015-03-25 | 中国海洋石油总公司 | Method for preparing high-purity methylal |
| CN104961631A (en) * | 2015-05-26 | 2015-10-07 | 海门市明阳实业有限公司 | Methylal purifying method |
-
2016
- 2016-09-05 CN CN201610801293.2A patent/CN106397144B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320940A (en) * | 2011-06-20 | 2012-01-18 | 印海平 | Method for purifying methylal |
| CN104447240A (en) * | 2014-11-10 | 2015-03-25 | 中国海洋石油总公司 | Method for preparing high-purity methylal |
| CN104961631A (en) * | 2015-05-26 | 2015-10-07 | 海门市明阳实业有限公司 | Methylal purifying method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106397144A (en) | 2017-02-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100344596C (en) | Method for preparing methylal using combined continuous distillation and liquid-liquid extraction | |
| KR100830083B1 (en) | Organometallic building materials and method for producing the same | |
| CN104892423B (en) | The technique that a kind of methanol oxidative carbonylation prepares dimethyl carbonate | |
| AU2003298422B2 (en) | Continuous method for preparing ethyl lactate | |
| CN100355712C (en) | Process for the preparation of methanol | |
| KR20190065949A (en) | Method for obtaining alcohols from aldehydes | |
| CN106397144B (en) | A method of moisture in removal dimethoxym ethane raw material | |
| RU2203264C2 (en) | Method of synthesis of acetic acid | |
| FR2848209A1 (en) | Continuous production of ethyl lactate by esterifying lactic acid with ethanol, comprises using a flash column and distillation column for product recovery | |
| CN103665366B (en) | A kind of method of continuous synthesis polyethers | |
| EP0129459B1 (en) | Process for the purification of a water-c1-c2-alcohol mixture, produced by the industrial manufacture of ethanol, by means of an extraction agent | |
| CN102976897A (en) | Method for purifying tetrafluoro propanol | |
| CN110172013B (en) | Process for synthesizing tertiary amyl alcohol based on catalytic distillation solvent method | |
| JP5661761B2 (en) | Production method of low odor n-butane | |
| CN114409541A (en) | System for preparing propionate through ethylene carbonylation | |
| FR2947264A1 (en) | PROCEDURE FOR THE PREPARATION OF DIFLUOROACETIC ACID | |
| CN106397145B (en) | A kind of industry dimethoxym ethane raw material dewatering process method | |
| Chen et al. | A highly efficient sulfonic acid resin for liquid-phase carbonylation of dimethoxymethane | |
| US5250156A (en) | Method of separating ethyl tertiobutyl ether from mixtures with ethanol | |
| JP6836745B2 (en) | Method for producing hydroxypivalaldehyde | |
| CN101155770B (en) | Process for producing alpha,beta-unsaturated carboxylic acid | |
| CA2439571A1 (en) | Method and apparatus for the preparation of triptane and/or triptene | |
| CN105793227B (en) | Oxidation of aldehydes method | |
| JP2015527990A (en) | Vinyl ester of isononanoic acid derived from 2-ethylhexanol, process for its production and use thereof | |
| CN107746369A (en) | A kind of butyl glycol ether synthetic method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |