CN102372614A - Production method of polyoxymethylene dimethylether - Google Patents
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Abstract
The invention relates to a production method of polyoxymethylene dimethylether and mainly solves the problems of low selectivity of polyoxymethylene dimethylether, complex technology and high energy consumption during the present production process of polyoxymethylene dimethylether. The production method provided by the invention comprises the following steps of: carrying out a reaction between methylal and trioxane in a catalytic distillation column while separating ingredients, condensing steam on the top of the column, followed by reflux, allowing a first part of the materials on the bottom of the column to return to the catalytic distillation column after vaporizing the first part through a reboiler while a second part is used as a production stream I and the weight ratio of the first part materials to the second part materials is 1-10: 1; allowing the production stream I to enter into a divided wall distillation column for separation, and collecting polyoxymethylene dimethylether DMM3-8 from the produced central part in the divided wall distillation column. The technical scheme provided by the invention greatly solves the problems and can be used in the industrial production of polyoxymethylene dimethylether.
Description
Technical field
The present invention relates to a kind of working method of polyoxymethylene dimethyl ether.
Background technology
In recent years, international community increases the diesel oil demand day by day, and limited diesel oil resource reduces day by day, has occurred that diesel oil is under-supply, the trend of price increase.Because the alkane molecule amount of diesel component is bigger, and rate of combustion is not high enough, and combustionproperty is good inadequately, this has not only increased oil consumption, and has deepened the pollution level of exhaust to environment in addition.In order to reach energy-conservation and purpose environmental protection, the numerous and confused increasing of fuel oil scientific and technological industry circle both at home and abroad is to the research and development dynamics of diesel-dope.(skeleton symbol is CH to polyoxymethylene dimethyl ether
3O (CH
2O)
nCH
3), abbreviate DMM as
n, have very high cetane value and oxygen level, in diesel oil, add 10%～20%, can improve the combustioncharacteristics of diesel oil significantly, effectively improve thermo-efficiency, significantly reduce NO
xDischarging with particulate matter.Consider its vp, boiling point and the solubleness in oil product, the suitable polyoxymethylene dimethyl ether (DMM that is generally 3≤n≤8 that does the oil product interpolation
n).
In the laboratory, polyoxymethylene dimethyl ether can through trace sulfuric acid or hydrochloric acid in the presence of under 150～180 ℃, heat low polymerization degree Paraformaldehyde 96 or paraformaldehyde and methyl alcohol and prepare, the reaction times is 12～15 hours.Cause forming carbonic acid gas and the decomposition reaction that forms dme like this.Ratio at paraformaldehyde or low polymerization degree Paraformaldehyde 96 and methyl alcohol is 6: 1 o'clock, obtains wherein n＞100, usually the polymkeric substance of n=300～500.Product is used the sodium sulphite solution washing, separates through fractional crystallization then.US2449469 has described the method that a kind of wherein methylal and paraformaldehyde or concentrated methylal solution heat in the presence of sulfuric acid.This method provides per molecule to have the polyoxymethylene dimethyl ether of 2～4 formaldehyde units.US5746785 has described molar mass to be 80～350 and to be equivalent to the preparation method of the polyoxymethylene dimethyl ether of n=1～10; This method exists fourth 150～240 ℃ of reactions down through 1 part of methylal and 5 parts of paraformaldehydes at 0.1 weight % formic acid, perhaps reacts down at 150～240 ℃ through 1 part of methyl alcohol and 3 parts of paraformaldehydes.The polyoxymethylene dimethyl ether that is obtained adds in the diesel-fuel with the amount of 5～30 weight %.WO2006/045506A1 has introduced BASF AG and has used sulfuric acid, trifluoromethanesulfonic acid as catalyzer, is the series product that raw material has obtained n=1～10 with methylal, paraformaldehyde, trioxymethylene.Above several method all adopts protonic acid as catalyzer, and this catalyzer is cheap and easy to get, but corrodibility is strong, is difficult to separate, and environmental pollution is big, to the demanding shortcoming of equipment.
CN101665414A has introduced the employing acidic ion liquid as catalyzer; Through methylal and trioxymethylene is the method for reactant synthesizing polyoxymethylene dme; But this method exists the catalyzer cost higher; To equipment corrosion, the catalyzer its separate reclaims and purifies, and reaction conversion ratio and the low problem of selectivity.It is raw material that patent US6160174 and US62655284 have introduced BP company employing methyl alcohol, formaldehyde, dme and methylal; Adopt anionite-exchange resin as catalyzer,, help advantages such as circulation though this method has the catalyzer separate easily; Help advantages such as circulation; Gas-solid phase reaction obtains polyoxymethylene dimethyl ether, though this method has the catalyzer separate easily, has the low and low problem of selectivity of transformation efficiency.In addition, patent US20070260094A1 has introduced a kind of method for preparing polyoxymethylene dimethyl ether, and adopting trioxymethylene and methylal is raw material; With heterogeneous an acidic catalyst contact reacts, and realized the separation of product, thereby obtained the polyoxymethylene dimethyl ether product through three distillation towers; This method has trioxymethylene transformation efficiency height; The segregative advantage of product, but exist the polyoxymethylene dimethyl ether selectivity low, the shortcoming that complex process and energy consumption are high.
Summary of the invention
Technical problem to be solved by this invention is that the polyoxymethylene dimethyl ether selectivity is low in the present polyoxymethylene dimethyl ether production process, and the problem that complex process and energy consumption are high provides a kind of working method of new polyoxymethylene dimethyl ether.This method has polyoxymethylene dimethyl ether selectivity height, technology is simple and characteristic of low energy consumption.
For solving the problems of the technologies described above, the technical scheme that the present invention adopts is following, a kind of working method of polyoxymethylene dimethyl ether; May further comprise the steps: a) methylal and trioxymethylene react in catalytic distillation tower; Carry out component in the time of reaction and separate, overhead vapours refluxes after condensation, and the first part of bottoms material turns back to catalytic distillation tower after the reboiler vaporization; Second section is as extraction liquid stream I; The weight ratio of first part and second section material is 1～10: 1, and wherein the mixture of trioxymethylene gets into from cat head, and methylal can get into from stripping section top to the cat head optional position; B) stream I gets into the middle part of bulkhead rectifying tower feeding side, cat head extraction light constituent, and light constituent turns back to the cat head of catalytic distillation tower, bulkhead rectifying tower extraction middle side part extraction polyoxymethylene dimethyl ether DMM
3～8, the tower still obtains heavy constituent, and heavy constituent turn back to the cat head of catalytic distillation tower.Wherein, the catalyzer in the catalytic distillation tower is a heterogeneous acid catalyst, and the mass ratio of trioxymethylene and methylal is 0.1～10: 1.
In technique scheme; The stripping section number of theoretical plate of described catalytic distillation tower is 5～50, and it is 5～50 that conversion zone is equivalent to number of theoretical plate, and the working pressure of catalytic distillation tower is 0.1～4MPa; Total reflux after the overhead vapours condensation, the controlled temperature of conversion zone are 50～200 ℃; The public theoretical number of plates of rectifying section of bulkhead rectifying tower is 5～50, and public stripping section number of theoretical plate is 5～50, and the number of theoretical plate of feeding side and extraction side is 5～70, and the cat head and the tower still of control bulkhead rectifying tower do not contain polyoxymethylene dimethyl ether DMM
3～8The stripping section number of theoretical plate of described catalytic distillation tower is preferably 10～30, and conversion zone is equivalent to number of theoretical plate and is preferably 10～30, and the controlled temperature of conversion zone is preferably 90～150 ℃; Heterogeneous acid catalyst is selected from least a in acidic ion exchange resin, zeolite, silico-aluminate, aluminum oxide, titanium oxide or the Indian red, and the mass ratio of trioxymethylene and methylal is preferably 0.5～5: 1; The public theoretical number of plates of rectifying section of bulkhead rectifying tower is preferably 10～30, and public stripping section number of theoretical plate is preferably 10～30, and the number of theoretical plate of feeding side and extraction side is preferably 20～40.
The present invention has given full play to the advantage of catalytic distillation and bulkhead rectifying; On the one hand, because distillment makes tower internal reaction section temperature be difficult for fluctuation, it is wayward to have overcome on-catalytic distil process temperature in the catalytic distillation tower; The shortcoming that catalyst life is short; The more important thing is that separate while reactant reacts in catalytic distillation tower with reaction product, the polyoxymethylene dimethyl ether of generation constantly shifts out from conversion zone; Reach the purpose that promotes reaction through isolating effect, thereby improved the selectivity of polyoxymethylene dimethyl ether; On the other hand, because reaction product comprises light constituent, polyoxymethylene dimethyl ether DMM
3～8With three types of heavy constituent; If adopt conventional rectification, need two rectifying tower could realize separating, adopt the bulkhead rectifying tower to reach the effect of two towers unification at present; Promptly separate to adopt and only adopt the bulkhead rectifying tower just can obtain to separate, thereby have the simple and characteristic of low energy consumption of technology.Use the inventive method to adopt catalytic distillation tower and bulkhead rectifying tower two tower process flow processs, optimize processing condition, under the situation of identical separation effect, compare with existing technology, separation process scheme is simple, DMM
3～8Selectivity reaches 58.6%, and total energy consumption reduces by 31.2%, has obtained better technical effect.
Description of drawings
The schematic flow sheet that Fig. 1 produces for polyoxymethylene dimethyl ether.
Fig. 2 is the schematic flow sheet that traditional polyoxymethylene dimethyl ether is produced.
Among Fig. 1, I is a catalytic distillation tower, and II is the bulkhead rectifying tower, and 1 is methylal, and 2 is trioxymethylene, and 3 is light constituent, and 4 is polyoxymethylene dimethyl ether DMM
3～8, 5 are heavy constituent.
Among Fig. 2, I is a reactor drum, and II is an adsorption bed, and III is first distillation tower, and IV is a second column; V is the 3rd distillation tower, and 1 is methylal, and 2 is trioxymethylene, and 3 is reaction product; 4 reaction product for deacidification, 5 is light constituent, and 6 for removing the reaction product of light constituent, and 7 is polyoxymethylene dimethyl ether DMM
2, 8 is the polyoxymethylene dimethyl ether of n＞2,9 is polyoxymethylene dimethyl ether DMM
3～8, 10 are heavy constituent.
As shown in Figure 1, methylal 1 gets into catalytic distillation tower I with trioxymethylene 2 and reacts, and reaction product gets into the middle part of bulkhead rectifying tower II feeding side, and cat head extraction light constituent 3, light constituent 3 return in the catalytic distillation tower I, extraction side extraction polyoxymethylene dimethyl ether DMM
3～8, the tower still obtains heavy constituent 5, and heavy constituent 5 also turn back in the catalytic distillation tower I.
As shown in Figure 2, methylal 1 gets into reactor drum I with trioxymethylene 2, contacts with heterogeneous an acidic catalyst to react; Reaction product 3 gets into adsorption bed II, removes an acidic catalyst, the reaction product 4 that obtains deacidifying; Continue to get into the first distillation tower III, cat head extraction light constituent 5, light constituent 5 turns back to reactor drum I; The tower still obtains removing the reaction product 6 of light constituent, gets into second column IV then, cat head extraction polyoxymethylene dimethyl ether DMM
27, turn back to reactor drum I, the tower still obtains the polyoxymethylene dimethyl ether 8 of n＞2, gets into the 3rd distillation tower V at last, cat head extraction polyoxymethylene dimethyl ether DMM
3～89, the tower still obtains heavy constituent 10, heavy constituent 10 Returning reactor I.
Through specific embodiment the present invention is further described below, still, scope of the present invention has more than and is limited to the scope that embodiment covers.
Embodiment
[embodiment 1]
By shown in Figure 1, catalytic distillation tower working pressure 0.5MPa, wherein the stripping section number of theoretical plate is 20; It is 25 that the catalyst reaction section separation efficiency is equivalent to number of theoretical plate, and catalyzer is the SAPO-34 molecular sieve, and trioxymethylene gets into the 1st theoretical stage with 2 gram/minute flows and (counts from top to bottom; As follows), methylal gets into the cat head total reflux with 1 gram/minute flow from the catalyst reaction section bottom; First and second part logistics ratio of tower still is 3: 1, and the catalyst reaction section temperature is 100～110 ℃, at the bottom of the tower with 3 gram/minute flow extraction; Reaction product gets into the middle part of bulkhead rectifying tower feeding side, and wherein public theoretical number of plates of rectifying section is 20, and public stripping section number of theoretical plate is 20; The number of theoretical plate of feeding side and extraction side is 30, and the cat head of control and tower still do not contain polyoxymethylene dimethyl ether DMM
3～8, polyoxymethylene dimethyl ether DMM in the reaction
3～8The one way selectivity be 58.6%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8Be benchmark, the cat head of two towers and tower still total energy consumption are seen table 1 in the technology.
[embodiment 2～5]
Other conditions are identical with embodiment 1, just change the kind of catalyzer, and catalyzer is respectively Su Qing board 001 * semi-finals acidic resins, ZSM-5, SO
4 -2/ Fe
2O
3, Cl
-1/ TiO
2And SO
4 -2/ Fe
2O
3, polyoxymethylene dimethyl ether DMM in the reaction
3～8The one way selectivity be respectively 52.5%, 53.4%, 55.7% and 58.2%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～ 8Be benchmark, the cat head of two towers and tower still total energy consumption are seen table 1 in the technology.
[embodiment 6]
By shown in Figure 1, catalytic distillation tower working pressure 4.0MPa, wherein the stripping section number of theoretical plate is 5; It is 5 that the catalyst reaction section separation efficiency is equivalent to number of theoretical plate, and catalyzer is the MCM-22 molecular sieve, and trioxymethylene gets into the 1st theoretical stage with 1 gram/minute flow and methylal with 10 gram/minute flows; The cat head total reflux, first and second part logistics ratio of tower still is 10: 1, the catalyst reaction section temperature is 180～200 ℃; At the bottom of the tower with 11 gram/minute flow extraction; Reaction product gets into the middle part of bulkhead rectifying tower feeding side, and wherein public theoretical number of plates of rectifying section is 5, and public stripping section number of theoretical plate is 5; The number of theoretical plate of feeding side and extraction side is 5, and the cat head of control and tower still do not contain polyoxymethylene dimethyl ether DMM
3～8, polyoxymethylene dimethyl ether DMM in the reaction
3～8The one way selectivity be 48.2%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8Be benchmark, the cat head of two towers and tower still total energy consumption are seen table 1 in the technology.
[embodiment 7]
By shown in Figure 1, catalytic distillation tower working pressure normal pressure, wherein the stripping section number of theoretical plate is 50; It is 50 that the catalyst reaction section separation efficiency is equivalent to number of theoretical plate, and catalyzer is an X type zeolite, and trioxymethylene gets into the 1st theoretical stage with 1 gram/minute flow; Methylal gets into from the catalyst reaction section bottom with 3 gram/minute flows, the cat head total reflux, and first and second part logistics ratio of tower still is 1: 1; The catalyst reaction section temperature is 50～70 ℃, and with 4 gram/minute flow extraction, reaction product gets into the middle part of bulkhead rectifying tower feeding side at the bottom of the tower; Wherein public theoretical number of plates of rectifying section is 50; Public stripping section number of theoretical plate is 50, and the number of theoretical plate of feeding side and extraction side is 70, and the cat head of control and tower still do not contain polyoxymethylene dimethyl ether DMM
3～8, polyoxymethylene dimethyl ether DMM in the reaction
3～8The one way selectivity be 51.7%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8Be benchmark, the cat head of two towers and tower still total energy consumption are seen table 1 in the technology.
[embodiment 8]
By shown in Figure 1, catalytic distillation tower working pressure 1.0MPa, wherein the stripping section number of theoretical plate is 25; It is 30 that the catalyst reaction section separation efficiency is equivalent to number of theoretical plate, and catalyzer is the ZSM-5 molecular sieve, and trioxymethylene gets into the 1st theoretical stage with 3 gram/minute flows; Methylal gets into from the catalyst reaction section bottom with 1 gram/minute flow, the cat head total reflux, and first and second part logistics ratio of tower still is 4: 1; The catalyst reaction section temperature is 140～150 ℃, and with 4 gram/minute flow extraction, reaction product gets into the middle part of bulkhead rectifying tower feeding side at the bottom of the tower; Wherein public theoretical number of plates of rectifying section is 30; Public stripping section number of theoretical plate is 30, and the number of theoretical plate of feeding side and extraction side is 50, and the cat head of control and tower still do not contain polyoxymethylene dimethyl ether DMM
3～ 8, polyoxymethylene dimethyl ether DMM in the reaction
3～8The one way selectivity be 60.5%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8Be benchmark, the cat head of two towers and tower still total energy consumption are seen table 1 in the technology.
[embodiment 9]
Other conditions are identical with embodiment 8; Trioxymethylene gets into the 1st theoretical stage with 10 gram/minute flows, and methylal gets into the cat head total reflux with 1 gram/minute flow from the catalyst reaction section bottom; First and second part logistics ratio of tower still is 2: 1; The catalyst reaction section temperature is 120～130 ℃, at the bottom of the tower with 11 gram/minute flow extraction, polyoxymethylene dimethyl ether DMM in the reaction
3～ 8The one way selectivity be 62.7%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8Be benchmark, the cat head of two towers and tower still total energy consumption are seen table 1 in the technology.
[comparative example 1]
By flow process shown in Figure 2, according to the method that patent US20070260094A1 introduces, feed conditions is identical with embodiment 1 with separating effect; Adopting trifluoromethanesulfonic acid in the reaction is catalyzer; Temperature of reaction is 100 ℃, and the reaction times is 12 hours, polyoxymethylene dimethyl ether DMM in the reaction
3～8The one way selectivity be 42.3%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8Be benchmark, ignore the needed energy consumption of reactor drum and adsorption bed, the cat head of three towers and tower still total energy consumption are seen table 1 in the technology.
Table 1 catalytic distillation result
| Embodiment | Cat head total energy consumption/kilojoule/hour | Tower still total energy consumption/kilojoule/hour |
| Embodiment 1 | -3.60 | 6.10 |
| Embodiment 2 | -3.84 | 6.53 |
| Embodiment 3 | -3.77 | 6.42 |
| Embodiment 4 | -3.71 | 6.32 |
| Embodiment 5 | -3.65 | 6.24 |
| Embodiment 6 | -4.86 | 7.53 |
| Embodiment 7 | -4.26 | 6.35 |
| Embodiment 8 | -4.54 | 7.48 |
| Embodiment 9 | -3.72 | 6.47 |
| Comparative example 1 | -5.63 | 8.47 |
Claims (6)
1. the working method of a polyoxymethylene dimethyl ether may further comprise the steps:
A. methylal and trioxymethylene react in catalytic distillation tower; Carry out component in the time of reaction and separate, overhead vapours refluxes after condensation, and the first part of bottoms material turns back to catalytic distillation tower after the reboiler vaporization; Second section is as extraction liquid stream I; The weight ratio of first part and second section material is 1～10: 1, and wherein the mixture of trioxymethylene gets into from cat head, and methylal can get into from stripping section top to the cat head optional position;
B. stream I gets into the middle part of bulkhead rectifying tower feeding side, cat head extraction light constituent, and light constituent turns back to the cat head of catalytic distillation tower, bulkhead rectifying tower extraction middle side part extraction polyoxymethylene dimethyl ether DMM
3～8, the tower still obtains heavy constituent, and heavy constituent turn back to the cat head of catalytic distillation tower.
Wherein, the catalyzer in the catalytic distillation tower is a heterogeneous acid catalyst, and the mass ratio of trioxymethylene and methylal is 0.1～10: 1.
2. according to the working method of the said polyoxymethylene dimethyl ether of claim 1; The stripping section number of theoretical plate that it is characterized in that described catalytic distillation tower is 5～50; It is 5～50 that conversion zone is equivalent to number of theoretical plate; The working pressure of catalytic distillation tower is 0.1～4MPa, total reflux after the overhead vapours condensation, and the controlled temperature of conversion zone is 50～200 ℃.
3. according to the working method of the said polyoxymethylene dimethyl ether of claim 1; The public theoretical number of plates of rectifying section that it is characterized in that the bulkhead rectifying tower is 5～50; Public stripping section number of theoretical plate is 5～50; The number of theoretical plate of feeding side and extraction side is 5～70, and the cat head and the tower still of control bulkhead rectifying tower do not contain polyoxymethylene dimethyl ether DMM
3～8
4. according to the working method of the said polyoxymethylene dimethyl ether of claim 1; It is characterized in that heterogeneous acid catalyst is selected from least a in acidic ion exchange resin, zeolite, silico-aluminate, aluminum oxide, titanium oxide or the Indian red, the mass ratio of trioxymethylene and methylal is 0.5～5: 1.
5. according to the working method of the said polyoxymethylene dimethyl ether of claim 2, the stripping section number of theoretical plate that it is characterized in that described catalytic distillation tower is 10～30, and it is 10～30 that conversion zone is equivalent to number of theoretical plate, and the controlled temperature of conversion zone is 90～150 ℃.
6. according to the working method of the said polyoxymethylene dimethyl ether of claim 3, the public theoretical number of plates of rectifying section that it is characterized in that the bulkhead rectifying tower is 10～30, and public stripping section number of theoretical plate is 10～30, and the number of theoretical plate of feeding side and extraction side is 20～40.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104447221A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Refining method of polyoxymethylene dimethyl ether |
| CN104557484A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for refining polyoxymethylene dimethyl ether (PODE) |
| CN106957221A (en) * | 2017-05-05 | 2017-07-18 | 凯瑞环保科技股份有限公司 | The device and method of polymethoxy dimethyl ether is produced in a kind of methanol oxidation |
| CN108299167A (en) * | 2018-01-31 | 2018-07-20 | 天津大学 | The method and apparatus for detaching polymethoxy dimethyl ether using next door tower |
| CN110559678A (en) * | 2019-10-21 | 2019-12-13 | 无锡赫利邦化工科技有限公司 | rectifying tower for synthesizing and separating polymethoxy dimethyl ether and use method thereof |
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| CN104447221A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Refining method of polyoxymethylene dimethyl ether |
| CN104447221B (en) * | 2013-09-24 | 2016-04-13 | 中国石油化工股份有限公司 | The process for purification of polyoxymethylene dimethyl ethers |
| CN104557484A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for refining polyoxymethylene dimethyl ether (PODE) |
| CN106957221A (en) * | 2017-05-05 | 2017-07-18 | 凯瑞环保科技股份有限公司 | The device and method of polymethoxy dimethyl ether is produced in a kind of methanol oxidation |
| CN108299167A (en) * | 2018-01-31 | 2018-07-20 | 天津大学 | The method and apparatus for detaching polymethoxy dimethyl ether using next door tower |
| CN108299167B (en) * | 2018-01-31 | 2021-10-22 | 天津大学 | Method and device for separating polymethoxy dimethyl ether by using partition column |
| CN110559678A (en) * | 2019-10-21 | 2019-12-13 | 无锡赫利邦化工科技有限公司 | rectifying tower for synthesizing and separating polymethoxy dimethyl ether and use method thereof |
| CN110559678B (en) * | 2019-10-21 | 2024-02-27 | 无锡赫利邦化工科技有限公司 | Rectifying tower for synthesizing and separating polymethoxy dimethyl ether and application method thereof |
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