CN102372614B - 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 production method of polyoxymethylene dimethyl ether.
Background technology
In recent years, international community increases day by day to diesel oil demand, 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 larger, rate of combustion is not high enough in addition, and combustionproperty is good not, and this has not only increased oil consumption, and has deepened the pollution level of exhaust to environment.In order to reach energy-conservation and object environmental protection, fuel oil scientific and technological industry circle strengthens the research and development dynamics to diesel-dope one after another both at home and abroad.(skeleton symbol is CH to polyoxymethylene dimethyl ether
3o (CH
2o)
ncH
3), referred to as DMM
n, there is very high cetane value and oxygen level, in diesel oil, add 10%～20%, can improve significantly the combustioncharacteristics of diesel oil, effectively improve thermo-efficiency, significantly reduce NO
xdischarge with particulate matter.Consider its vapour pressure, boiling point and the solubleness in oil product, the suitable polyoxymethylene dimethyl ether (DMM that is generally 3≤n≤8 that does oil product interpolation
n).
In laboratory, polyoxymethylene dimethyl ether can by under existing at trace sulfuric acid or hydrochloric acid at 150～180 ℃, heating low polymerization degree paraformaldehyde or paraformaldehyde and Methanol are standby, the reaction times is 12～15 hours.The decomposition reaction that causes like this forming carbonic acid gas and form dme.At paraformaldehyde or low polymerization degree paraformaldehyde, be 6: 1 o'clock with the ratio of methyl alcohol, obtain wherein n > 100, conventionally the polymkeric substance of n=300～500.Product sodium sulphite solution washing, then separated by fractional crystallization.US2449469 has described the method for a kind of wherein methylal and paraformaldehyde or concentrated methylal solution heating under sulfuric acid exists.The 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, the method exists fourth 150～240 ℃ to react with 5 parts of paraformaldehydes at 0.1 % by weight formic acid by 1 part of methylal, or at 150～240 ℃, reacts with 3 parts of paraformaldehydes by 1 part of methyl alcohol.The polyoxymethylene dimethyl ether obtaining adds in diesel-fuel with the amount of 5～30 % by weight.WO2006/045506A1 has introduced BASF AG and has used sulfuric acid, trifluoromethanesulfonic acid as catalyzer, take methylal, paraformaldehyde, trioxymethylene to have obtained the series product of n=1～10 as raw material.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 separation, and environmental pollution is large, the high shortcoming that requires to equipment.
CN101665414A has introduced employing acidic ion liquid as catalyzer, by methylal and trioxymethylene, it is the method for reactant synthesizing polyoxymethylene dme, but the method exists catalyzer cost higher, to equipment corrosion, the Separation and Recovery of catalyzer self and purification, and reaction conversion ratio and the low problem of selectivity.It is raw material that patent US6160174 and US62655284 introduce LiaoBP company employing methyl alcohol, formaldehyde, dme and methylal, adopt anionite-exchange resin as catalyzer, although but this method has easily separation of catalyzer, be conducive to the advantages such as circulation, be conducive to the advantages such as circulation, gas-solid phase reaction obtains polyoxymethylene dimethyl ether, although this method has easily separation of catalyzer, has the problem that low conversion rate and selectivity are low.In addition, patent US20070260094A1 has introduced a kind of method of preparing polyoxymethylene dimethyl ether, adopting trioxymethylene and methylal is raw material, with heterogeneous an acidic catalyst contact reacts, and realize the separation of product by three distillation towers, thereby obtained polyoxymethylene dimethyl ether product, it is high that the method has trioxymethylene transformation efficiency, the segregative advantage of product, but exist 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 in current polyoxymethylene dimethyl ether production process, polyoxymethylene dimethyl ether selectivity is low, and the problem that complex process and energy consumption are high provides a kind of production method of new polyoxymethylene dimethyl ether.The method has the advantages that polyoxymethylene dimethyl ether selectivity is high, technique is simple and energy consumption is low.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows, a kind of production method of polyoxymethylene dimethyl ether, comprise the following steps: a) methylal and trioxymethylene react in catalytic distillation tower, in the time of reaction, carry out component separation, overhead vapours refluxes after condensation, the first part of materials at bottom of tower turns back to catalytic distillation tower after reboiler vaporization, second section is as Produced Liquid stream I, the weight ratio of first part and second section material is 1～10: 1, wherein the mixture of trioxymethylene enters from tower top, methylal can enter to tower top optional position from stripping section top, b) stream I enters the middle part of rectifying tower with bulkhead feeding side, overhead extraction light constituent, and light constituent turns back to the tower top of catalytic distillation tower, rectifying tower with bulkhead extraction middle side part extraction polyoxymethylene dimethyl ether DMM
3～8, tower reactor obtains heavy constituent, and heavy constituent turns back to the tower top of catalytic distillation tower.Wherein, the catalyzer in catalytic distillation tower is 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 overhead vapours condensation, the control temperature of conversion zone is 50～200 ℃; The public theoretical number of plates of rectifying section of rectifying tower with bulkhead 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 tower top and the tower reactor of controlling rectifying tower with bulkhead do not contain polyoxymethylene dimethyl ether DMM
3～8; The 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 control temperature of conversion zone is preferably 90～150 ℃; Heterogeneous acid catalyst is selected from least one in acidic ion exchange resin, zeolite, silico-aluminate, aluminum oxide, titanium dioxide or 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 rectifying tower with bulkhead 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, in catalytic distillation tower, because making conversion zone temperature in tower, distillment is difficult for fluctuation, overcome on-catalytic distil process temperature wayward, the shortcoming that catalyst life is short, the more important thing is, reactant and reaction product in catalytic distillation tower while reacting separated, the polyoxymethylene dimethyl ether generating constantly shifts out from conversion zone, by separated effect, reach the object that promotes reaction, thereby improved the selectivity of polyoxymethylene dimethyl ether; On the other hand, because reaction product comprises light constituent, polyoxymethylene dimethyl ether DMM
3～8with heavy constituent three classes, if adopt conventional rectification, need two rectifying tower to realize separated, now adopt rectifying tower with bulkhead to reach the effect of two tower unifications, separated employing only adopts rectifying tower with bulkhead just can obtain separation, thereby has technique simply and the low feature of energy consumption.Use the inventive method to adopt catalytic distillation tower and rectifying tower with bulkhead two tower process flow processs, Optimizing Technical, the in the situation that of identical separation effect, compared with the prior art, separation process scheme is simple, DMM
3～8selectivity reaches 58.6%, and total energy consumption reduces by 31.2%, has obtained good technique effect.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that polyoxymethylene dimethyl ether is produced.
Fig. 2 is the schematic flow sheet that traditional polyoxymethylene dimethyl ether is produced.
In Fig. 1, I is catalytic distillation tower, and II is rectifying tower with bulkhead, and 1 is methylal, and 2 is trioxymethylene, and 3 is light constituent, and 4 is polyoxymethylene dimethyl ether DMM
3～8, 5 is heavy constituent.
In Fig. 2, I is reactor, and II is adsorption bed, and III is the first distillation tower, and IV is 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 is the reaction product except 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 is heavy constituent.
As shown in Figure 1, methylal 1 and trioxymethylene 2 enter catalytic distillation tower I and react, and reaction product enters the middle part of rectifying tower with bulkhead II feeding side, overhead extraction light constituent 3, and light constituent 3 returns in catalytic distillation tower I, extraction side extraction polyoxymethylene dimethyl ether DMM
3～8, tower reactor obtains heavy constituent 5, and heavy constituent 5 also turns back in catalytic distillation tower I.
As shown in Figure 2, methylal 1 and trioxymethylene 2 enter reactor I, contact and react with heterogeneous an acidic catalyst, and reaction product 3 enters adsorption bed II, remove an acidic catalyst, the reaction product 4 that obtains deacidification, continues to enter the first distillation tower III, overhead extraction light constituent 5, light constituent 5 turns back to reactor I, tower reactor obtains the reaction product 6 except light constituent, then enters second column IV, overhead extraction polyoxymethylene dimethyl ether DMM
27, turn back to reactor I, tower reactor obtains the polyoxymethylene dimethyl ether 8 of n > 2, finally enters the 3rd distillation tower V, overhead extraction polyoxymethylene dimethyl ether DMM
3～89, tower reactor obtains heavy constituent 10, heavy constituent 10 Returning reactor I.
Below by specific embodiment, the present invention is further illustrated, and still, scope of the present invention has more than and is limited to the scope that embodiment covers.
Embodiment
[embodiment 1]
Press shown in Fig. 1, catalytic distillation tower working pressure 0.5MPa, wherein stripping section number of theoretical plate is 20, it is 25 that catalyst reaction section separation efficiency is equivalent to number of theoretical plate, catalyzer is SAPO-34 molecular sieve, trioxymethylene enters the 1st theoretical stage with 2 gram/minute flows and (counts from top to bottom, as follows), methylal enters from catalyst reaction section bottom with 1 gram/minute flow, tower top total reflux, first and second part logistics ratio of tower reactor is 3: 1, catalyst reaction section temperature is 100～110 ℃, at the bottom of tower with 3 gram/minute flow extraction, reaction product enters the middle part of rectifying tower with bulkhead feeding side, wherein public theoretical number of plates of rectifying section is 20, public stripping section number of theoretical plate is 20, the number of theoretical plate of feeding side and extraction side is 30, the tower top of controlling and tower reactor be not containing polyoxymethylene dimethyl ether DMM
3～8, polyoxymethylene dimethyl ether DMM in reaction
3～8one way selectivity be 58.6%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8for benchmark, in technique, the tower top of two towers and tower reactor total energy consumption are in Table 1.
[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 reaction
3～8one way selectivity be respectively 52.5%, 53.4%, 55.7% and 58.2%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～ 8for benchmark, in technique, the tower top of two towers and tower reactor total energy consumption are in Table 1.
[embodiment 6]
Press shown in Fig. 1, catalytic distillation tower working pressure 4.0MPa, wherein stripping section number of theoretical plate is 5, it is 5 that catalyst reaction section separation efficiency is equivalent to number of theoretical plate, catalyzer is MCM-22 molecular sieve, trioxymethylene enters the 1st theoretical stage with 1 gram/minute flow and methylal with 10 gram/minute flows, tower top total reflux, first and second part logistics ratio of tower reactor is 10: 1, catalyst reaction section temperature is 180～200 ℃, at the bottom of tower with 11 gram/minute flow extraction, reaction product enters the middle part of rectifying tower with bulkhead feeding side, wherein public theoretical number of plates of rectifying section is 5, public stripping section number of theoretical plate is 5, the number of theoretical plate of feeding side and extraction side is 5, the tower top of controlling and tower reactor be not containing polyoxymethylene dimethyl ether DMM
3～8, polyoxymethylene dimethyl ether DMM in reaction
3～8one way selectivity be 48.2%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8for benchmark, in technique, the tower top of two towers and tower reactor total energy consumption are in Table 1.
[embodiment 7]
Press shown in Fig. 1, catalytic distillation tower working pressure normal pressure, wherein stripping section number of theoretical plate is 50, it is 50 that catalyst reaction section separation efficiency is equivalent to number of theoretical plate, catalyzer is X-type zeolite, trioxymethylene enters the 1st theoretical stage with 1 gram/minute flow, methylal enters from catalyst reaction section bottom with 3 gram/minute flows, tower top total reflux, first and second part logistics ratio of tower reactor is 1: 1, catalyst reaction section temperature is 50～70 ℃, at the bottom of tower with 4 gram/minute flow extraction, reaction product enters the middle part of rectifying tower with bulkhead feeding side, wherein public theoretical number of plates of rectifying section is 50, public stripping section number of theoretical plate is 50, the number of theoretical plate of feeding side and extraction side is 70, the tower top of controlling and tower reactor be not containing polyoxymethylene dimethyl ether DMM
3～8, polyoxymethylene dimethyl ether DMM in reaction
3～8one way selectivity be 51.7%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8for benchmark, in technique, the tower top of two towers and tower reactor total energy consumption are in Table 1.
[embodiment 8]
Press shown in Fig. 1, catalytic distillation tower working pressure 1.0MPa, wherein stripping section number of theoretical plate is 25, it is 30 that catalyst reaction section separation efficiency is equivalent to number of theoretical plate, catalyzer is ZSM-5 molecular sieve, trioxymethylene enters the 1st theoretical stage with 3 gram/minute flows, methylal enters from catalyst reaction section bottom with 1 gram/minute flow, tower top total reflux, first and second part logistics ratio of tower reactor is 4: 1, catalyst reaction section temperature is 140～150 ℃, at the bottom of tower with 4 gram/minute flow extraction, reaction product enters the middle part of rectifying tower with bulkhead feeding side, wherein public theoretical number of plates of rectifying section is 30, public stripping section number of theoretical plate is 30, the number of theoretical plate of feeding side and extraction side is 50, the tower top of controlling and tower reactor be not containing polyoxymethylene dimethyl ether DMM
3～ 8, polyoxymethylene dimethyl ether DMM in reaction
3～8one way selectivity be 60.5%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8for benchmark, in technique, the tower top of two towers and tower reactor total energy consumption are in Table 1.
[embodiment 9]
Other conditions are identical with embodiment 8, trioxymethylene enters the 1st theoretical stage with 10 gram/minute flows, methylal enters from catalyst reaction section bottom with 1 gram/minute flow, tower top total reflux, first and second part logistics ratio of tower reactor is 2: 1, catalyst reaction section temperature is 120～130 ℃, at the bottom of tower with 11 gram/minute flow extraction, polyoxymethylene dimethyl ether DMM in reaction
3～ 8one way selectivity be 62.7%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8for benchmark, in technique, the tower top of two towers and tower reactor total energy consumption are in Table 1.
[comparative example 1]
Press flow process shown in Fig. 2, the method for introducing according to patent US20070260094A1, feed conditions and separating effect are identical with embodiment 1, in reaction, adopting trifluoromethanesulfonic acid is catalyzer, temperature of reaction is 100 ℃, and the reaction times is 12 hours, polyoxymethylene dimethyl ether DMM in reaction
3～8one way selectivity be 42.3%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8for benchmark, ignore the needed energy consumption of reactor and adsorption bed, in technique, the tower top of three towers and tower reactor total energy consumption are in Table 1.
Table 1 catalytic distillation result
| Embodiment | Tower top total energy consumption/kilojoule/hour | Tower reactor 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 (1)
1. a production method for polyoxymethylene dimethyl ether, comprises the following steps:
A. methylal and trioxymethylene react in catalytic distillation tower, in the time of reaction, carry out component separation, overhead vapours refluxes after condensation, the first part of materials at bottom of tower turns back to catalytic distillation tower after reboiler vaporization, second section is as Produced Liquid stream I, and the weight ratio of first part and second section material is 3: 1, and wherein trioxymethylene enters the 1st theoretical stage with 2 gram/minute flows from tower top, methylal enters from catalyst reaction section bottom with 1 gram/minute flow, tower top total reflux; Catalytic distillation tower working pressure 0.5MPa, wherein stripping section number of theoretical plate is 20, and it is 25 that catalyst reaction section separation efficiency is equivalent to number of theoretical plate, and catalyst reaction section temperature is 100～110 ℃,
B. materials at bottom of tower is with 3 gram/minute flow extraction, enter the middle part of rectifying tower with bulkhead feeding side, wherein public theoretical number of plates of rectifying section is 20, public stripping section number of theoretical plate is 20, the number of theoretical plate of feeding side and extraction side is 30, overhead extraction light constituent, light constituent turns back to the tower top of catalytic distillation tower, and the tower top of control and tower reactor be not containing polyoxymethylene dimethyl ether DMM
3～8, rectifying tower with bulkhead extraction middle side part extraction polyoxymethylene dimethyl ether DMM
3～8, tower reactor obtains heavy constituent, and heavy constituent turns back to the tower top of catalytic distillation tower; Polyoxymethylene dimethyl ether DMM in reaction
3～8one way selectivity be 58.6%, to produce 10 gram/minute polyoxymethylene dimethyl ether DMM
3～8for benchmark, in technique the tower top total energy consumption of two towers be-3.60 kilojoules/hour and tower reactor total energy consumption 6.10 kilojoules/hour;
Wherein, the catalyzer in catalytic distillation tower is SAPO-34 molecular sieve.
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| 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 |
| CN104557484B (en) * | 2013-10-28 | 2016-08-17 | 中国石油化工股份有限公司 | The method of refined polyoxymethylene dimethyl ethers |
| 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 |
| CN108299167B (en) * | 2018-01-31 | 2021-10-22 | 天津大学 | Method and device for separating polymethoxy dimethyl ether by using partition column |
| 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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