CN109096064A - The refining methd of polyoxymethylene dimethyl ethers - Google Patents
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- 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
Long-term continuous production operating is difficult to caused by there are problems that the technical problem to be solved by the present invention is to formaldehyde during fractional distillation refining polyoxymethylene dimethyl ethers, using the technical solution included the following steps: the reaction equilibrium mixture that synthesizing polyoxymethylene dimethyl ethers unit obtains, it is separated off main the first fraction comprising dimethoxym ethane first, obtain the first tower bottoms, the material enters purifying column from bottom, obtains from tower top comprising methanol and PODE2‑8Purifying column feed liquid；Purifying column feed liquid sequentially enters dehydrating tower, Second distillation column and third distillation column, obtains methanol-water fraction, PODE by tower top respectively2Product and PODE3~4/PODE3~5Product.
Description
Technical field
The present invention relates to the refining methds of polyoxymethylene dimethyl ethers, more particularly to from the reaction that paraformaldehyde is raw material
To reaction mixture containing polyoxymethylene dimethyl ethers in prepare high-purity PODE3~4/PODE3~5Method.
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
=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.Meanwhile PODE2It is a kind of potential high-quality solvent with good dissolubility energy.
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 separation and purification 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 separation and purification 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 54%, PODE2~5Yield be 51.2%.CN103664549A and CN103880614A is used
Paraformaldehyde is raw material using solid super-strong acid as catalyst synthesizing polyoxymethylene dimethyl ethers, includes unreacted raw material in product
Dimethoxym ethane and paraformaldehyde, in the composition of reaction mixture, in addition to dimethoxym ethane, polyoxymethylene dimethyl ethers, also not comprising 8.3%
The paraformaldehyde of reaction.
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 separation and purification to reaction mixture.The polyoxymethylene dimethyl ethers 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 green solvent, when fraction needs are separately separated out or are not suitable for directly returning
When 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 refine 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 polyoxymethylene dimethyl ethers separating technology continuous and steady operation
Neck.
Summary of the invention
The technical problem to be solved by the present invention is to formaldehyde in the process for refining of fractional distillation refining polyoxymethylene dimethyl ethers to separate
The problem of, provide a kind of refining methd of polyoxymethylene dimethyl ethers, 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: the purification of polyoxymethylene dimethyl ethers
Method, comprising:
(a) the reaction equilibrium mixture that synthesizing polyoxymethylene dimethyl ethers unit obtains, initially enters first rectifying column, separation
The first fraction mainly comprising dimethoxym ethane is removed, the first tower bottoms is obtained；
(b) the first tower bottoms enters purifying column from bottom, obtains from tower top comprising methanol and PODE2~8Purifying column feed liquid；
(c) purifying column feed liquid enters dehydrating tower from middle part, from the dehydration overhead fraction of top extraction by-product carbinol and water；
(d) dehydrating tower kettle liquid enters Second distillation column, isolates PODE in Second distillation column tower top2Product cut；
(e) Second distillation column kettle liquid enters third distillation column, isolates third distillation column product in third distillation column tower top
Fraction；
Wherein the third distillation 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 third distillation column are adjusted, select third distillation column product cut for PODE3~4Also
It is PODE3~5。
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, first rectifying column described in step (a) is preferably atmospheric distillation or rectification under vacuum；Tower reactor
Temperature is preferably 70~105 DEG C；First tower bottoms preferably comprises methanol, water, PODE2-8And formaldehyde.
In the above technical solution, the first tower bottoms described in step (a) includes preferably methanol, water, PODE2-8And first
The mixture of aldehyde.
In the above technical solution, it includes preferably Ca (OH) that purifying column described in step (b), which includes filler,2。
In the above technical solution, purification tower packing, which removes, includes Ca (OH)2First group is especially, preferably also comprising KOH,
NaOH、Mg(OH)2, sodium sulfite, sodium sulphate, at least one of magnesium sulfate and calcium chloride the second component when, we are surprised
Ground discovery is improving PODE between the first component and the second component3~4And/or PODE3~5The purity of purity and PODE2 fraction
Aspect has synergistic effect.
In the above technical solution, Ca (OH) in tower packing is purified2The percentage for accounting for the first component and the second component total amount contains
Amount is preferably not lower than 5% to less than 100%.As non limiting example, for example, the numerical value can be 10%, 20%, 30%,
40%, 50%, 60%, 70%, 80%, 90% etc..
In the above technical solution, the operating pressure of step (b) purifying column is not particularly limited, but preferably normal
Pressure, operation temperature is preferably 50~100 DEG C；The residence time of material is preferably 10~60min.
In the above technical solution, dehydrating tower operating pressure described in step (c) is preferably 0.1~0.5MPa, reflux ratio
Preferably 0.1-10；Methanol content is preferably 0~0.1% in dehydrating tower kettle liquid.
In the above technical solution, PODE described in step (d)2PODE in product cut2Content is preferably 99~
99.9%；Water content is preferably 0~0.5%；
In the above technical solution, third distillation column product cut (15) PODE described in step (d)3~4Or
PODE3~5Purity is preferably 98~99.9%.
It is that purifying column includes Ca (OH) as most preferred technical solution in above-mentioned technical proposal2, NaOH and sodium sulfite
Mixture be filler.
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 polyformaldehyde dimethyl
By contacting with the alkaline filler in purifying column before the rectifying of ether dimer, it is higher that formaldehyde is removed into easy to operate and efficiency,
Thus greatly reduce influence of the by-products such as formaldehyde and water to distillation process, improve the efficiency of rectifying, time of contact it is short and
It can be carried out continuously.PODE in the product cut that this method process obtains3~4/PODE3~5Purity reaches 98% or more, obtains simultaneously
Purity is greater than 99% PODE2, it is ensured that the separation of paraformaldehyde and going on smoothly for continuous rectification.
Detailed description of the invention
Fig. 1 is the process flow chart of embodiment of the present invention.
The reaction equilibrium mixture 1 to be come by synthesizing polyoxymethylene dimethyl ethers unit, first passes around first rectifying column 2, tower
Top steams the first fraction 3 comprising unreacted dimethoxym ethane, and the first tower bottoms 4, which enters by thermo-insulating pipe line from bottom, includes upper and lower two
The purifying column 5 of section, obtains the purifying column material 7 comprising methanol and PODE2-8 from tower top；Purifying column feed liquid 7 enters dehydration from middle part
Tower 8 produces by-product carbinol fraction 9 from top；Dehydrating tower kettle liquid 10 enters Second distillation column 11, isolates PODE by tower top2
Product cut 12, the second obtained tower bottoms 13 enter third distillation column 14, isolate PODE by tower top respectively2Product cut 12
And PODE3~4/PODE3~5Product cut 15；16 be third distillation column kettle material.
Specific embodiment
[embodiment 1]
Using the reaction equilibrium mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction, first through the first rectifying
Tower atmospheric distillation removes the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.The warm pipeline of first tower bottoms from bottom into
Enter with Ca (OH)2For the purifying column of filler, purifying column temperature is 100 DEG C, residence time 10min, and tower top is obtained comprising methanol
And PODE2-5Purifying column material.Purifying column discharging enters dehydrating tower, is normal pressure, reflux ratio 8 in operating pressure, bottom temperature is
Rectifying is carried out under the conditions of 110 DEG C, includes the fraction of first alcohol and water from overhead extraction.Dehydrating tower kettle liquid sequentially enters Second distillation column
And third distillation column, PODE is isolated by tower top respectively2Product cut and PODE3~4Product cut.Each material is through gas-chromatography point
Analysis, the results are shown in Table 1.
[comparative example 1]
Using the reaction equilibrium mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction, first through the first rectifying
Tower atmospheric distillation removes the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.The warm pipeline of first tower bottoms from bottom into
Enter the purifying column using anhydrous calcium chloride as filler, purifying column temperature is 100 DEG C, residence time 10min, and tower top is obtained comprising first
Pure and mild PODE2-5Purifying column material.Purifying column discharging enters dehydrating tower, is normal pressure, reflux ratio 8, bottom temperature in operating pressure
Rectifying is carried out under the conditions of being 110 DEG C, white solid occurs in overhead condenser discharge nozzle, and rectifying experiment stops.Each material is through gas phase
As a result chromatography is listed in table 1c.
[embodiment 2]
Using the reaction equilibrium mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction, first through the first rectifying
Tower atmospheric distillation removes the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.The warm pipeline of first tower bottoms from bottom into
Enter the purifying column using NaOH as filler, purifying column temperature is 100 DEG C, residence time 10min, tower top obtain comprising methanol and
PODE2-5Purifying column material.Purifying column discharging enters dehydrating tower, is normal pressure, reflux ratio 8 in operating pressure, bottom temperature is
Rectifying is carried out under the conditions of 110 DEG C, includes the fraction of first alcohol and water from overhead extraction.Dehydrating tower kettle liquid sequentially enters Second distillation column
And third distillation column, PODE is isolated by tower top respectively2Product cut and PODE3~4Product cut.Each material is through gas-chromatography point
Analysis, the results are shown in Table 2.
[embodiment 3]
Using the reaction equilibrium mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction, first through the first rectifying
Tower atmospheric distillation removes the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.The warm pipeline of first tower bottoms from bottom into
Enter the Ca (OH) with weight ratio for 1:12It is the purifying column of filler with NaOH mixture, purifying column temperature is 100 DEG C, the residence time
For 10min, tower top is obtained comprising methanol and PODE2-5Purifying column material.Purifying column discharging enters dehydrating tower, is in operating pressure
0.2Mpa, reflux ratio 8, bottom temperature carry out rectifying under the conditions of being 110 DEG C, include the fraction of first alcohol and water from overhead extraction.
Dehydrating tower kettle liquid sequentially enters Second distillation column and third distillation column, isolates PODE by tower top respectively2Product cut and
PODE3~4Product cut.Each material is through gas chromatographic analysis, and the results are shown in Table 3.
[embodiment 4]
Using the reaction equilibrium mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction, first through the first rectifying
Tower atmospheric distillation removes the first fraction, obtains 105 DEG C of temperature of the first tower bottoms.The warm pipeline of first tower bottoms from bottom into
Enter the Ca (OH) with weight ratio for 1:12It is the purifying column of filler with NaOH mixture, purifying column temperature is 100 DEG C, the residence time
For 10min, tower top is obtained comprising methanol and PODE2-5Purifying column material.Purifying column discharging enters dehydrating tower, is in operating pressure
Normal pressure, reflux ratio 8, bottom temperature carry out rectifying under the conditions of being 110 DEG C, include the fraction of methanol from overhead extraction.Dehydrating tower
Kettle liquid sequentially enters Second distillation column and third distillation column, isolates PODE by tower top respectively2Product cut and PODE3~4Product
Fraction.Each material is through gas chromatographic analysis, and the results are shown in Table 4.
[embodiment 5]
Using the reaction equilibrium mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction, first through the first rectifying
Tower atmospheric distillation removes the first fraction, obtains 102 DEG C of temperature of the first tower bottoms.The warm pipeline of first tower bottoms from bottom into
Enter the Ca (OH) with weight ratio for 1:22Mixture with KOH is the purifying column of filler, and purifying column temperature is 85 DEG C, the residence time
For 20min, tower top is obtained comprising methanol and PODE2-5Purifying column material.Purifying column discharging enters dehydrating tower, is in operating pressure
0.2MPa, reflux ratio 4, bottom temperature carry out rectifying under the conditions of being 140 DEG C, include the fraction of first alcohol and water from overhead extraction.
Dehydrating tower kettle liquid sequentially enters Second distillation column and third distillation column, isolates PODE by tower top respectively2Product cut and
PODE3~5Product cut.Each material is through gas chromatographic analysis, and the results are shown in Table 5.
[embodiment 6]
Using the reaction equilibrium mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction, first through the first rectifying
Tower atmospheric distillation removes the first fraction, obtains 100 DEG C of temperature of the first tower bottoms.The warm pipeline of first tower bottoms from bottom into
Enter the Ca (OH) with weight ratio for 2:2:12It is the purifying column of filler, purifying column temperature with the mixture of NaOH and sodium sulfite
It is 70 DEG C, residence time 30min, tower top is obtained comprising methanol and PODE2-5Purifying column material.Purifying column discharging enters dehydration
Tower, operating pressure be 0.3MPa, reflux ratio 2, bottom temperature be 158 DEG C under the conditions of carry out rectifying, include from overhead extraction
The fraction of first alcohol and water.Dehydrating tower kettle liquid sequentially enters Second distillation column and third distillation column, isolates PODE by tower top respectively2
Product cut and PODE3~4Product cut.Each material is through gas chromatographic analysis, and the results are shown in Table 6.
[embodiment 7]
Using the reaction equilibrium mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction, first through the first rectifying
Tower rectification under vacuum at pressure 0.08MPa removes the first fraction, obtains 95 DEG C of temperature of the first tower bottoms.First tower bottoms is through protecting
Warm pipeline enters purifying column from bottom, and purifying column is the Ca (OH) of 2:1 with weight ratio2With Mg (OH)2Mixture be filler, only
Changing tower temperature degree is 60 DEG C, residence time 45min, and tower top is obtained comprising methanol and PODE2-5Purifying column material.Purifying column discharging
Into dehydrating tower, operating pressure be 0.3MPa, reflux ratio 1, bottom temperature carries out rectifying under the conditions of being 158 DEG C, from tower top
Extraction includes the fraction of first alcohol and water.Dehydrating tower kettle liquid sequentially enters Second distillation column and third distillation column, respectively by tower top point
Separate out PODE2Product cut and PODE3~4Product cut.Each material is through gas chromatographic analysis, and the results are shown in Table 7.
[embodiment 8]
Using the reaction equilibrium mixture that paraformaldehyde and dimethoxym ethane are obtained as raw material through catalysis reaction, first through the first rectifying
Tower atmospheric distillation removes the first fraction, obtains the first tower bottoms.The warm pipeline of first tower bottoms enters purifying column from bottom, only
Changing tower using weight ratio is Ca (OH) 2, the NaOH of 1:1:1 and the mixture of sodium sulphate as filler, and purifying column temperature is 50 DEG C, lower section
Residence time is 60min, and tower top obtains the purifying column material comprising methanol and PODE2-5.Purifying column discharging enters dehydrating tower, is grasping
As pressure be 0.5MPa, reflux ratio 0.5, it includes methanol from overhead extraction that bottom temperature, which carries out rectifying under the conditions of being 175 DEG C,
Fraction.Dehydrating tower kettle liquid sequentially enters Second distillation column and third distillation column, respectively by tower top isolate PODE2 product cut and
The product cut of PODE3~4.Each material is through gas chromatographic analysis, and the results are shown in Table 8.
From embodiment 3 and embodiment 1 and embodiment 2 it is year-on-year in can intuitively find out, when purification tower packing is except including Ca
(OH) 2 first groups especially, preferably also comprising in KOH, NaOH, Mg (OH) 2, sodium sulfite, sodium sulphate, magnesium sulfate and calcium chloride
When at least one second component, it has been surprisingly found that between the first component and the second component improve PODE3~4 and/or
There is synergistic effect in terms of the purity of PODE3~5 and the purity of PODE2 fraction.
Table 1
Table 1c
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
Table 8
Claims (9)
1. the refining methd of polyoxymethylene dimethyl ethers, comprising:
(a) the reaction equilibrium mixture (1) that synthesizing polyoxymethylene dimethyl ethers unit obtains, initially enters first rectifying column (2), point
From the first fraction (3) removed mainly comprising dimethoxym ethane, the first tower bottoms (4) are obtained；
(b) the first tower bottoms enters purifying column (5) from bottom, obtains from tower top comprising PODE2-8Purifying column feed liquid (7)；
(c) purifying column feed liquid (7) enters dehydrating tower (8) from middle part, and from top, extraction includes the dehydrating tower of by-product carbinol and water
Tops (9)；
(d) dehydrating tower kettle liquid (10) enters Second distillation column (11), and in Second distillation column (11), tower top isolates PODE2Product evaporates
Divide (12)；
(e) Second distillation column kettle liquid (13) enters third distillation column (14), isolates third essence in third distillation column (14) tower top
Evaporate tower product cut (15)；
Wherein the third distillation column product cut (15) is PODE3~4Or PODE3~5。
2. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that reaction described in step (a) is flat
Weighing apparatus mixture (1) includes dimethoxym ethane, formaldehyde, methanol, water and PODE2~8。
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 (2) is normal pressure or rectification under vacuum.
4. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that purifying column described in step (b)
(5) filler includes Ca (OH)2。
5. the refining methd of polyoxymethylene dimethyl ethers according to claim 4, it is characterized in that purifying column described in step (b)
Filler, which removes, includes Ca (OH)2Outside also comprising being selected from KOH, NaOH, Mg (OH)2, sodium sulfite, sodium sulphate, in magnesium sulfate and calcium chloride
At least one.
6. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that purifying column described in step (b)
(5) operating pressure is normal pressure.
7. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that dehydration described in step (c)
Tower (8) operating pressure is 0.1~0.5MPa, reflux ratio 0.1-10；In dehydrating tower kettle liquid methanol quality percentage composition be 0~
0.1%.
8. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that with weight,
PODE described in step (d)2PODE in product cut (12)2Content is preferably 99~99.9%.
9. the refining methd of polyoxymethylene dimethyl ethers according to claim 1, it is characterized in that with weight,
Step (e) third distillation column product cut (15) PODE3~4Or PODE3~5Purity is preferably 98~99.9%.
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| CN112707800A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Method for pretreating polymethoxy dimethyl ether and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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| CN112707800A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Method for pretreating polymethoxy dimethyl ether and application |
| CN112707800B (en) * | 2019-10-25 | 2023-04-07 | 中国石油化工股份有限公司 | Method for pretreating polymethoxy dimethyl ether and application |
| CN113087602A (en) * | 2020-01-09 | 2021-07-09 | 中国石油化工股份有限公司 | Production and refining method of polymethoxy dimethyl ether |
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