CN107118083A - A kind of apparatus and method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde - Google Patents
A kind of apparatus and method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde Download PDFInfo
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- CN107118083A CN107118083A CN201710410666.8A CN201710410666A CN107118083A CN 107118083 A CN107118083 A CN 107118083A CN 201710410666 A CN201710410666 A CN 201710410666A CN 107118083 A CN107118083 A CN 107118083A
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Abstract
It is main to include mainly including piece-rate system and elution condensation cycle system the present invention relates to a kind of apparatus and method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde.The piece-rate system is mainly made up of reaction member (I), deacidifying device (II), the first atmospheric fractional tower (III), the second atmospheric fractional tower (IV), vacuum distillation tower (Ⅸ), vacuum rectification tower (Ⅹ), dehydration device (VII)；The elution condensation cycle system main device includes the first leaching absorption tower (V), the second leaching absorption tower (VI) and elution liquid storage tank (VIII) and associated pipe is constituted.Combination of the invention by separating elution circuit, efficiently solve the problem of oxymethylene polymerization blocks condenser and pipeline during separating the product of polymethoxy dimethyl ether containing aldehyde, formaldehyde 100% is recycled in separation product, realize the continuous separation process for the product of polymethoxy dimethyl ether containing formaldehyde of product, energy-conserving and environment-protective with DMM3 6.
Description
Technical field
The present invention relates to a kind of apparatus and method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde, more particularly to life
Production is suitable as diesel fuel additives DMM3-6 process.
Background technology
Polymethoxy dimethyl ether (polyoxymethylene dimethyl ethers, abbreviation DMMn), also known as polyformaldehyde
Dimethyl ether.Molecular formula is CH3O (CH2O) nCH3 (n >=1), is novel environment friendly diesel oil addO-on therapy generally acknowledged at present.In diesel oil
The polyoxymethylene dimethyl ether of addition 5%~30%, can be greatly lowered the discharge of NOx and particulate pollutant in tail gas, 20%
PODE3-8 mixture oil sample properties meet the GB standard of 0# diesel oil, while condensation point of diesel oil is down into -6 DEG C, diesel oil 16 from 0 DEG C
Alkane value is improved to 53.6 from 46, and 55 DEG C of close flash point is increased to 57 DEG C, is a kind of extraordinary diesel fuel additives.Therefore,
Development polymethoxy dimethyl ether not only contributes to alleviate China's methanol production overstock problem as diesel oil blending component, while can
Further alleviate Environmental Pollution, with high economic potential and environmental benefit, by the extensive concern of domestic and foreign scholars.
The reaction of synthesizing polyoxymethylene dimethyl ether is reversible balanced reaction, product be comprising DMMn (n >=1), methanol, formaldehyde,
The mixture of the materials such as metaformaldehyde, formic acid, methyl formate and water, simply may be used although directly being seemed with conventional separation methods purification
OK, but in actual mechanical process always it is difficult to the DMMn products for obtaining desired purity.A wherein topmost reason is exactly first
The autohemagglutination problem of aldehyde.Due to certain density formaldehyde gas to the cold when easily occur self-polymeric reaction generation solid polyformaldehyde,
The self-polymeric reaction of formaldehyde is easily triggered to cause a large amount of paraformaldehydes of adhesion in equipment inner wall and pipeline in the condensation process of rectifying separation
Solid blocks pipeline, has a strong impact on the continuity of production.
Current researcher mainly removes the formaldehyde in reaction product using chemical method, respectively by being thrown into reaction product
Enter sodium hydroxide solution (CN103333060), solid sulphite (CN103333061), solid SODIUM PERCARBONATE
(CN103319319), ammonia (CN104276067) etc. reacts with formaldehyde, the formaldehyde in product is reacted away, so as to avoid essence
Oxymethylene polymerization problem during evaporating.Although but being carried out by adding the method for other chemical substances into product except formaldehyde is refined
It can produce a desired effect, but will also result in the loss of a certain amount of reaction product, reactant formaldehyde by complete or partial wave
Take, it is impossible to reclaim.Other materials are put into system so that later stage rectifying product processing process becomes more complicated simultaneously, increase
Uncertain factor.Formaldehyde recovery utilization rate is low in reaction product, while adding equipment energy consumption, generates a large amount of pollutant effluents.
CN104447236 provides a kind of DMMn methods of purification for reducing oxymethylene polymerization in distillation process, first by acid
Reaction product with after obtains light component DMM1 and the first tower bottoms by distillation, and the first kettle liquid rectifying is obtained containing methanol, many
The DMM2 overhead components and tower bottoms of polyformaldehyde, are gone out the paraformaldehyde solid that the second kettle liquid is separated out by the method cooled
Fall, so as to obtain the material of low formaldehyde content, then carry out rectifying and obtain DMM3-5.But pass through the side of condensation paraformaldehyde
Formula reduction content of formaldehyde can only reduce influence of the paraformaldehyde to rectifying, and the possibility blocked, with certain limitation,
The problem of oxymethylene polymerization thoroughly can not being solved.
The content of the invention
In order to eliminate in the product purification separation process of polymethoxy dimethyl ether containing formaldehyde formaldehyde in condenser inner wall and condensation
The problem of pipeline polymerize occluding device, patent of the present invention provides a kind of dress for the refining spearation of polymethoxy dimethyl ether containing formaldehyde
Put, solve the problem of conventional rectification separation process of polymethoxy dimethyl ether containing aldehyde is difficult to continuous operation.
The technical solution adopted for the present invention to solve the technical problems is：One kind is used for the essence of polymethoxy dimethyl ether containing formaldehyde
The process unit of separation is made, mainly includes piece-rate system and elution condensation cycle system.The piece-rate system is main by reacting
Unit (I), deacidifying device (II), the first atmospheric fractional tower (III), the second atmospheric fractional tower (IV), vacuum distillation tower (Ⅸ), subtract
Rectifying column (Ⅹ), dehydration device (VII) is pressed to constitute；The elution condensation cycle system main device includes the first leaching absorption tower
(V), the second leaching absorption tower (VI) and elution liquid storage tank (VIII).
Reaction member (I) discharging opening is connected with deacidifying device (II) charging aperture, and deacidifying device (II) discharging opening leads to
The charging aperture that the first atmospheric fractional tower feed pipe 1 is crossed with the first atmospheric fractional tower (III) is connected, first atmospheric fractional tower
(III) tower top frozen-free equipment, its top gaseous phase material flow export is drenched by the first top gaseous phase material stream delivery pipe 2 and first
Wash absorption tower (V) gaseous phase materials inflow entrance to be connected, the first atmospheric fractional tower (III) tower reactor discharging opening passes through the second atmospheric fractional tower
Feed pipe 6 is connected with the charging aperture of the second atmospheric fractional tower (IV), the second atmospheric fractional tower (IV) tower top frozen-free equipment,
Its top gaseous phase material flow export passes through the second top gaseous phase material stream delivery pipe 7 and the gas gas-phase objects of the second leaching absorption tower (VI)
Stream entrance is connected, and the tower reactor discharging opening of the second atmospheric fractional tower (IV) passes through vacuum distillation tower feed pipe 13 and vacuum distillation
The charging aperture of tower (Ⅸ) is connected.The tower top discharging opening of vacuum distillation tower (Ⅸ) ejects expects pipe 14 and dehydration by vacuum distillation tower
Device (VII) is connected, and the tower reactor discharging opening of vacuum distillation tower (Ⅸ) passes through vacuum rectification tower feed pipe 15 and vacuum rectification tower (Ⅹ)
It is connected.The dehydration device (VII) is connected with reaction member.
Packing layer built in first leaching absorption tower (V), tower top is provided with sprinkling equipment, and enters provided with tower top leacheate
Mouth, the outlet of tower top discharging opening, tower reactor leacheate and tower reactor gaseous phase materials inflow entrance.The tower top discharging opening is connected with condensing unit
Connect, and expects pipe 16 is ejected by leaching absorption tower and be connected to dehydration device entrance.The tower reactor leacheate outlet and the first elution
Absorb tower reactor constant temperature leacheate delivery pipe 3 to be connected, 3 points of the first leaching absorption tower kettle constant temperature leacheate delivery pipe is first
Constant temperature leacheate delivery pipe 4 and leacheate extraction pipe 5 two.Wherein the first constant temperature leacheate delivery pipe 4 is drenched by the first constant temperature
Washing lotion feed pipe 12 is connected to form loop with tower top leacheate entrance.The leacheate extraction pipe 5 is connected to dehydration device entrance.
Packing layer built in second leaching absorption tower (VI), tower top is provided with sprinkling equipment, and enters provided with tower top leacheate
Mouth, the outlet of tower reactor leacheate and tower reactor gaseous phase materials inflow entrance；The tower top leacheate entrance and the second constant temperature leacheate are fed
Pipe 10 is connected, and the tower reactor leacheate outlet passes through the second leaching absorption tower kettle constant temperature leacheate delivery pipe 8 and elution liquid storage tank
(VIII) leacheate import is connected.The elution liquid storage tank (VIII) is provided with leacheate import, leacheate outlet and side elution
Liquid supply port.The leacheate outlet of the elution liquid storage tank (VIII) is connected with constant temperature elution liquid storage tank delivery pipe 9, the constant temperature
Elution liquid storage tank delivery pipe 9 is divided into the second constant temperature leacheate feed pipe 10 and the second 11 liang of constant temperature leacheate delivery pipe in end
Bar, wherein pipeline 10 are connected to form circulation loop with tower top leacheate entrance.The second constant temperature leacheate delivery pipe 11 is then
The first constant temperature leacheate feed pipe 12 is incorporated to the first constant temperature leacheate delivery pipe 4.
The elution liquid storage tank (VIII) is provided with the new leacheate entrance of side.
Preferably, the leacheate is in raw material to be separated itself the thing systems such as DMMn (n >=1), methanol, water, formalin
Material in one or more combination.Second leaching absorption tower (VI), elution liquid storage tank (VIII) and constant temperature leacheate are defeated
Send pipe 8-10 to constitute first and elute condensation cycle system, first leaching absorption tower (V) constitutes second with pipeline 3,4,12 and drenched
Condensation cycle system is washed, both are connected in series the whole elution condensation cycle system of composition by the second constant temperature leacheate delivery pipe 11
System.
Concrete technology method is as follows：
The material of polymethoxy dimethyl ether containing formaldehyde obtained in reaction member, handles by simple filtration, removes solid and urge
The paraformaldehyde of agent and residual, obtains clarifying material.Due to material acid number it is higher in the case of easily cause production in separation process
Thing is decomposed and tower reactor aggregation problem, therefore material first passes around depickling unit II and carries out depickling processing, and the material after depickling leads to
Cross the first atmospheric fractional tower feed pipe 1 and enter the de- light work of the first atmospheric fractional tower III progress, 30-60 DEG C obtains first contracting in tower top
The stream of gas gas-phase objects containing formaldehyde based on aldehyde, the gaseous phase materials stream enters first by the first top gaseous phase material stream delivery pipe 2 and drenched
Wash the progress elution condensation full gear of absorption tower V to operate, a small amount of formaldehyde, which is absorbed, in material stream is distributed in leacheate, so that effectively
Avoid to the cold aggregation problem of the gaseous formaldehyde in direct condensation process.Elution is caused by the temperature of Non-leaching liquid simultaneously
The temperature control of absorption tower V a large amount of dimethoxym ethanes in 40-80 DEG C, gas gas-phase objects stream remain in that gas phase by this temperature
One leaching absorption tower V, is condensed through overhead condenser and obtains the dimethoxym ethane product without formaldehyde, and the dimethoxym ethane is absorbed by eluting
Tower top discharge nozzle 16 is recycled to return reaction member I after dehydration device VII is handled and re-used as raw material.
The tower reactor of first atmospheric fractional tower III obtains predominantly DMM2-8 containing aldehyde products, and into the second atmospheric fractional tower IV,
The gas gas-phase objects stream of predominantly DMM2 and water containing a large amount of formaldehyde is obtained in 70-110 DEG C of tower top, the gaseous phase materials flow through second
Top gaseous phase material stream delivery pipe 7 enters the second leaching absorption tower VI and carries out elution condensation operation, passes through the temperature of Non-leaching liquid
Spend all to absorb the formaldehyde in gas gas-phase objects stream and be distributed in leacheate, thus it is possible to prevente effectively from high-concentration formaldehyde gas
Aggregation problem to the cold.All DMM2, water cooling are congealed into liquid phase simultaneously, because DMM2 and water have the energy of higher dissolving formaldehyde
Power, therefore isolated DMM2 and water can participate in whole elute in cyclic process as leacheate.
The tower reactor of second atmospheric fractional tower IV obtains light containing a small amount of DMM2, water, metaformaldehyde, formaldehyde and micro formic acid etc.
The DMM3-8 crude products of component, the tower reactor product enters vacuum distillation tower Ⅸ through vacuum distillation tower feed pipe 13, quick in tower top
The light components such as remnants DMM2, metaformaldehyde, water, formaldehyde, formic acid are isolated, vacuum distillation is passed through after the overhead components are condensed
Tower top discharge nozzle 14 enters return reaction member after dehydration device VII is handled and re-used as raw material.
The tower reactor of vacuum distillation tower Ⅸ obtains the DMM3-8 crude products without formaldehyde, and is entered by vacuum rectification tower feed pipe 15
Enter vacuum rectification tower Ⅹ further to be separated, obtain pure DMM3-6 products at 70-150 DEG C of tower top, tower reactor obtains DMMn>6
Product.The tower reactor product is also recycled into reaction member recycling.
In the refining spearation scheme, it should be controlled by material acid number after deacidifying device within 0-0.2mgKOH/g.
In the refining spearation scheme, the first atmospheric fractional tower III is packed tower, theoretical cam curve 20-40, packed height
10-30 meters.Second atmospheric fractional tower III is packed tower, theoretical cam curve 20-40,10-30 meters of packed height.
In the refining spearation scheme, filler built in vacuum distillation tower Ⅸ, operating pressure preferred 0-30Kp, number of theoretical plate 5-
20,5-20 meters of packed height.The operating pressure of vacuum rectification tower Ⅹ preferred 0-15Kp, number of theoretical plate 5-30, packed height 10-30
Rice.
In the refining spearation scheme, the cycling elution liquid used is DMMn (n >=1), methanol, water, formalin, formic acid
One or more combination in methyl esters.
In the refining spearation scheme, packing layer built in the first leaching absorption tower V, 5-30 meters of bed stuffing height, second drenches
Wash packing layer built in absorption tower V, 5-30 meters of bed stuffing height.
In the refining spearation scheme, the leacheate temperature into the first leaching absorption tower should be controlled at 40-80 DEG C, entered
The leacheate temperature of second leaching absorption tower should be controlled at 50-80 DEG C.
In above-mentioned refining spearation scheme, into the cycling elution liquid and the matter of the stream of gas gas-phase objects containing aldehyde of the first leaching absorption tower
Amount is than being 0.2-10.The mass ratio of cycling elution liquid and the stream of gas gas-phase objects containing aldehyde into the second leaching absorption tower is 1-10.
In the refining spearation scheme, the cycling elution liquid aldehyde into the first leaching absorption tower and the second leaching absorption tower contains
Amount should be controlled in 0.1wt%-40wt%.
In above-mentioned refining spearation scheme, the dehydrating agent that dewatering unit (VII) is used uses molecular sieve, Silica hydrogel, water-absorbing resin
One or more combination in.
Technical scheme having the beneficial effect that compared with prior art：
1. the present invention efficiently solves the oxymethylene polymerization during the separation product of polymethoxy dimethyl ether containing aldehyde and blocks condensation
The problem of device and pipeline, realize the continuous separation process of the product of polymethoxy dimethyl ether containing formaldehyde using DMM3-6 as product.
2. the present invention is by two of the first leaching absorption tower (V), the second leaching absorption tower (VI) and associated pipe composition
Elution condensation cycle system is organically combined by way of series connection, and the secondary cycle for realizing leacheate is fully recycled, significantly
Reduce the consumption of leacheate.
3. the leacheate that the present invention is used is material in polymethoxy dimethyl ether product itself system, what is so produced contains aldehyde
The higher leacheate of amount can return reaction member through subsequent treatment Posterior circle and be re-used as raw material, and normal pressure is fractionated what is obtained
The azeotropic mixture of DMM2 and water can be used as new leacheate, realized the combination of separation-lessivation, not only solved first
Aldehyde aggregation problem, and whole system is without the introducing of other materials, energy saving economy.
4. apparatus of the present invention system process is simple, the side that rectifying is separated again after aldehyde is removed with the current conventional alkali cleaning deacidification used
Method is compared, and realize formaldehyde in product 100% is recycled, and greatly reduces alkali cleaning industrial wastewater discharge, energy-conserving and environment-protective.
5. the present invention is used for point of the reaction product of polymethoxy dimethyl ether containing aldehyde of any reaction formation under heterogeneous catalysis
From applied widely.
Brief description of the drawings
Fig. 1 is the described process for refining apparatus structure schematic diagram of polymethoxy dimethyl ether containing aldehyde；Specific equipment and pipeline are such as
Shown in lower:
I-reaction member, II-deacidifying device, the III-the first atmospheric fractional tower, the IV-the second atmospheric fractional tower, V-the
One leaching absorption tower, the VI-the second leaching absorption tower, VII-dehydration device, VIII-elution liquid storage tank, Ⅸ-vacuum distillation tower,
Ⅹ-vacuum rectification tower
1-the first atmospheric fractional tower feed pipe, the 2-the first top gaseous phase material stream delivery pipe, the 3-the first leaching absorption tower
Kettle constant temperature leacheate delivery pipe, the 4-the first constant temperature leacheate delivery pipe, 5-leacheate extraction pipe, the 6-the second atmospheric fractional tower
Feed pipe, the 7-the second top gaseous phase material stream delivery pipe, the 8-the second leaching absorption tower kettle constant temperature leacheate delivery pipe, 9-perseverance
Temperature elution liquid storage tank delivery pipe, the 10-the second constant temperature leacheate feed pipe, the 11-the second constant temperature leacheate delivery pipe, 12-the first
Constant temperature leacheate feed pipe, 13-vacuum distillation tower feed pipe, 14-vacuum distillation tower ejection expects pipe, 15-vacuum rectification tower are entered
Expects pipe, 16-leaching absorption tower ejection expects pipe.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate
The present invention, rather than limitation the scope of the present invention, after the present invention has been read, those skilled in the art are for the present invention's
The modification of the various equivalent form of values falls within the application appended claims limited range.
In the synthetic product of polymethoxy dimethyl ether, a certain amount of formaldehyde is always there is, and the gaseous phase materials containing aldehyde
Formaldehyde self-polymeric reaction easily occurs in normal pressure condensation process and generates paraformaldehyde solids adhering in equipment and pipeline inner wall for stream, blocks up
Pipeline is filled in, forces distillation process not to be carried out continuously.For the higher material of aldehyde contenting amount, its separation process first step piptonychia acetal
Process is that a little oxymethylene polymerization phenomenon occurs.The present invention is predominantly used for the refining spearation of the polymethoxy dimethyl ether containing formaldehyde
Process unit, the separation of the material of polymethoxy dimethyl ether containing aldehyde is carried out using the process unit, is thoroughly solved in separation process
The problem of oxymethylene polymerization.And it can obtain being entirely free of the pure DMM3-6 products of formaldehyde.
As shown in figure 1, reaction member (I) discharging opening is connected with deacidifying device (II) charging aperture, the deacidifying device
(II) discharging opening is connected by the first atmospheric fractional tower feed pipe 1 with the charging aperture of the first atmospheric fractional tower (III), and described
One atmospheric fractional tower (III) tower top frozen-free equipment, its top gaseous phase material flow export is defeated by the first top gaseous phase material stream
Pipe 2 is sent to be connected with the first leaching absorption tower (V) gaseous phase materials inflow entrance, the first atmospheric fractional tower (III) tower reactor discharging opening passes through
Second atmospheric fractional tower feed pipe 6 is connected with the charging aperture of the second atmospheric fractional tower (IV), second atmospheric fractional tower (IV)
Tower top frozen-free equipment, its top gaseous phase material flow export is inhaled by the second top gaseous phase material stream delivery pipe 7 and the second elution
The gaseous phase materials inflow entrance for receiving tower (VI) is connected, and the tower reactor discharging opening of the second atmospheric fractional tower (IV) is fed by vacuum distillation tower
Pipe 13 is connected with the charging aperture of vacuum distillation tower (Ⅸ).The tower top discharging opening of vacuum distillation tower (Ⅸ) passes through vacuum distillation tower top
Discharge nozzle 14 is connected with dehydration device (VII), and the tower reactor discharging opening of vacuum distillation tower (Ⅸ) passes through vacuum rectification tower feed pipe 15
It is connected with vacuum rectification tower (Ⅹ).The dehydration device (VII) is connected with reaction member.
Packing layer built in first leaching absorption tower (V), tower top is provided with sprinkling equipment, and enters provided with tower top leacheate
Mouth, the outlet of tower top discharging opening, tower reactor leacheate and tower reactor gaseous phase materials inflow entrance.The tower top discharging opening is connected with condensing unit
Connect, and expects pipe 16 is ejected by leaching absorption tower and be connected to dehydration device entrance.The tower reactor leacheate outlet and the first elution
Absorb tower reactor constant temperature leacheate delivery pipe 3 to be connected, 3 points of the first leaching absorption tower kettle constant temperature leacheate delivery pipe is first
Constant temperature leacheate delivery pipe 4 and leacheate extraction pipe 5 two.Wherein the first constant temperature leacheate delivery pipe 4 is drenched by the first constant temperature
Washing lotion feed pipe 12 is connected to form loop with tower top leacheate entrance.The leacheate extraction pipe 5 is connected to dehydration device entrance.
Packing layer built in second leaching absorption tower (VI), tower top is provided with sprinkling equipment, and enters provided with tower top leacheate
Mouth, the outlet of tower reactor leacheate and tower reactor gaseous phase materials inflow entrance.The tower top leacheate entrance and the second constant temperature leacheate are fed
Pipe 10 is connected.The tower reactor leacheate outlet passes through the second leaching absorption tower kettle constant temperature leacheate delivery pipe 8 and elution liquid storage tank
(VIII) leacheate import is connected.The elution liquid storage tank (VIII) is provided with leacheate import, leacheate outlet and side elution
Liquid supply port.The leacheate outlet of the elution liquid storage tank (VIII) is connected with constant temperature elution liquid storage tank delivery pipe 9, the constant temperature
Elution liquid storage tank delivery pipe 9 is divided into the second constant temperature leacheate feed pipe 10 and the second 11 liang of constant temperature leacheate delivery pipe in end
Bar, wherein pipeline 10 are connected to form circulation loop with tower top leacheate entrance.The second constant temperature leacheate delivery pipe 11 is then
The first constant temperature leacheate feed pipe 12 is incorporated to the first constant temperature leacheate delivery pipe 4.
The material of polymethoxy dimethyl ether containing formaldehyde obtained in reaction member, handles by simple filtration, removes solid and urge
The paraformaldehyde of agent and residual, obtains clarifying material.Due to material acid number it is higher in the case of easily cause production in separation process
Thing is decomposed and tower reactor aggregation problem, therefore material first passes around depickling unit II and carries out depickling processing, and material acid number is controlled
Within 0-0.2mgKOH/g, the material after depickling enters the first atmospheric fractional tower III by the first atmospheric fractional tower feed pipe 1
(theoretical cam curve 20-40,10-30 meters of packed height) carries out de- light work, is obtained in 30-60 DEG C of tower top based on dimethoxym ethane
The stream of gas gas-phase objects containing formaldehyde, the gaseous phase materials stream enters the first leaching absorption tower by the first top gaseous phase material stream delivery pipe 2
V (5-30 meters of bed stuffing height), carries out elution condensation full gear and operates, a small amount of formaldehyde, which is absorbed, in material stream is distributed to leacheate
In, so as to effectively prevent to the cold aggregation problem of the gaseous formaldehyde in direct condensation process.Pass through Non-leaching liquid simultaneously
Temperature causes the temperature control of leaching absorption tower V a large amount of dimethoxym ethanes in 40-80 DEG C, gas gas-phase objects stream still to protect at this temperature
Gas phase is held by the first leaching absorption tower V, is condensed through overhead condenser and obtains the dimethoxym ethane product without formaldehyde, the dimethoxym ethane
Expects pipe 16 is ejected by leaching absorption tower be recycled to after dehydration device VII is handled and return to reaction member I to be used as raw material again sharp
With.The tower reactor of first atmospheric fractional tower III obtains predominantly DMM2-8 containing aldehyde products, and enters the (theoretical plate of the second atmospheric fractional tower IV
Number 10-40,10-30 meter of packed height), 70-110 DEG C of tower top obtain containing a large amount of formaldehyde be mainly DMM2 and water gas gas-phase objects
Stream, the gaseous phase materials flow through the second top gaseous phase material stream delivery pipe 7 and enter (the bed stuffing height 5- of the second leaching absorption tower VI
Elution condensation operation 30m) is carried out, the formaldehyde in gas gas-phase objects stream is all absorbed by the temperature of Non-leaching liquid and is distributed to pouring
In washing lotion, thus it is possible to prevente effectively from high-concentration formaldehyde gas aggregation problem to the cold.All DMM2, water cooling are congealed into simultaneously
Liquid phase, because DMM2 and water have the ability of higher dissolving formaldehyde, therefore isolated DMM2 and water can be used as leacheate
Participate in whole elution cyclic process.The tower reactor of the second atmospheric fractional tower IV obtain containing a small amount of DMM2, water, metaformaldehyde,
The DMM3-8 crude products of the light component such as formaldehyde and micro formic acid, the tower reactor product enters through vacuum distillation tower feed pipe 13 to depressurize
Destilling tower Ⅸ (number of theoretical plate 5-20,5-20 meters of packed height) tower top quick separating under operating pressure 0-30Kp goes out remnants'
The light components such as DMM2, metaformaldehyde, water, formaldehyde, formic acid, expects pipe 14 is ejected after the overhead components are condensed by vacuum distillation tower
Reaction member is returned to after into the processing of dehydration device VII to re-use as raw material.The tower reactor of vacuum distillation tower Ⅸ obtains being free of formaldehyde
DMM3-8 crude products, and pass through vacuum rectification tower feed pipe 15 and enter vacuum rectification tower Ⅹ (number of theoretical plate 5-30, packed height
10-30 meters), further separated under operating pressure 0-15Kp, pure DMM3-6 products are obtained at 70-150 DEG C of tower top,
Tower reactor obtains DMMn>6 products.The tower reactor product is also recycled into reaction member recycling.
Elute condensation cycle system main by leacheate transfer pipeline 3-5,8-12 and the first leaching absorption tower V, second
Leaching absorption tower VI, elution liquid storage tank VIII are constituted.Wherein the second leaching absorption tower VI, elution liquid storage tank VIII and leacheate conveying
Pipeline 8-10 constitutes first and elutes condensation cycle system, and the first leaching absorption tower V and leacheate transfer pipeline 3,4,12 constitute the
Two elution condensation cycle systems, both are connected by the second constant temperature leacheate delivery pipe 11.Pass through the second top gaseous phase material stream
Delivery pipe 7 enters first and eluted after the DMM2 of fluid circulation, water condensation as the utilization of new leacheate, the first elution condensation cycle
System is entered by the second constant temperature leacheate delivery pipe 11 extraction part leacheate and reused in second circulation system, and most
Return reaction member after pipe 5 handles the final feeding of leacheate containing aldehyde dehydration device VII is produced by leacheate eventually and makees raw material profit
With.Increase new leacheate to the elution side leacheate supply port of liquid storage tank VIII simultaneously to keep whole elution condensation cycle system
It is stable.Whole elution condensation cycle system efficiently solves in continuous separation process formaldehyde in the stream of gas gas-phase objects containing aldehyde condensation process
The problem of polymerizeing blocking pipeline.The continuous operation of whole production process is ensure that, while using polymethoxy dimethyl ether itself thing
Material in system is used as leacheate so that final leacheate containing aldehyde can return to reaction member as raw material and utilize.Realize simultaneously
The combination of separation-elution circuit, is introduced without other materials, and the formaldehyde 100% in product is recycled, energy saving economy.
Claims (9)
1. a kind of device for the refining spearation of polymethoxy dimethyl ether containing formaldehyde, including piece-rate system and elution condensation cycle
System；It is characterized in that piece-rate system it is main by reaction member (I), it is deacidifying device (II), the first atmospheric fractional tower (III), second normal
Pressure fractionating tower (IV), vacuum distillation tower (Ⅸ), vacuum rectification tower (Ⅹ), dehydration device (VII) are constituted；The elution condensation cycle
System main device includes the first leaching absorption tower (V), the second leaching absorption tower (VI) and elution liquid storage tank (VIII)；Reaction
Unit (I) discharging opening is connected with deacidifying device (II) charging aperture, and deacidifying device (II) discharging opening passes through the first normal pressure point
The charging aperture for evaporating tower feed pipe (1) with the first atmospheric fractional tower (III) is connected, the first atmospheric fractional tower (III) tower top without
Condensing plant, its top gaseous phase material flow export passes through the first top gaseous phase material stream delivery pipe (2) and the first leaching absorption tower
(V) gaseous phase materials inflow entrance is connected, and the first atmospheric fractional tower (III) tower reactor discharging opening passes through the second atmospheric fractional tower feed pipe
(6) charging aperture with the second atmospheric fractional tower (IV) is connected, the second atmospheric fractional tower (IV) tower top frozen-free equipment, its tower
Top gas phase materials flow export passes through the second top gaseous phase material stream delivery pipe (7) and the gaseous phase materials of the second leaching absorption tower (VI)
Inflow entrance is connected, and the tower reactor discharging opening of the second atmospheric fractional tower (IV) passes through vacuum distillation tower feed pipe (13) and vacuum distillation tower
(Ⅸ) charging aperture is connected；The tower top discharging opening of vacuum distillation tower (Ⅸ) ejects expects pipe (14) and dehydration by vacuum distillation tower
Device (VII) is connected, and the tower reactor discharging opening of vacuum distillation tower (Ⅸ) passes through vacuum rectification tower feed pipe (15) and vacuum rectification tower
(Ⅹ) it is connected；The dehydration device (VII) is connected with reaction member.
2. device as claimed in claim 1, it is characterized in that packing layer built in first leaching absorption tower (V), tower top is provided with
Sprinkling equipment, and provided with tower top leacheate entrance, tower top discharging opening, the outlet of tower reactor leacheate and tower reactor gaseous phase materials inflow entrance；
The tower top discharging opening is connected with condensing unit, and ejects expects pipe (16) by leaching absorption tower and be connected to dehydration device and enter
Mouthful；The outlet of tower reactor leacheate is connected with the first leaching absorption tower kettle constant temperature leacheate delivery pipe (3), first leaching absorption tower
Kettle constant temperature leacheate delivery pipe (3) is divided into the first constant temperature leacheate delivery pipe (4) and leacheate extraction pipe (5) two；Wherein
One constant temperature leacheate delivery pipe (4) is connected to form back by the first constant temperature leacheate feed pipe (12) and tower top leacheate entrance
Road；The leacheate extraction pipe (5) is connected to dehydration device entrance.
3. device as claimed in claim 1, it is characterized in that packing layer built in second leaching absorption tower (VI), tower top is provided with
Sprinkling equipment, and provided with tower top leacheate entrance, the outlet of tower reactor leacheate and tower reactor gaseous phase materials inflow entrance；The tower top elution
Liquid entrance is connected with the second constant temperature leacheate feed pipe (10), and the tower reactor leacheate outlet is permanent by the second leaching absorption tower kettle
Warm leacheate delivery pipe (8) is connected with the leacheate import of elution liquid storage tank (VIII)；The elution liquid storage tank (VIII) is provided with pouring
Washing lotion import, leacheate outlet and side leacheate supply port；The leacheate outlet connection of the elution liquid storage tank (VIII) is persevering
Temperature elution liquid storage tank delivery pipe (9), the constant temperature elution liquid storage tank delivery pipe (9) is divided into the charging of the second constant temperature leacheate in end
(10) and the second constant temperature leacheate delivery pipe (11) two are managed, wherein pipeline (10) is connected to be formed and followed with tower top leacheate entrance
Loop back path；The second constant temperature leacheate delivery pipe (11) is then incorporated to the pouring of the first constant temperature with the first constant temperature leacheate delivery pipe (4)
Washing lotion feed pipe (12).
4. device as claimed in claim 1, it is characterized in that elution liquid storage tank (VIII) is provided with the new leacheate entrance of side.
5. the device of claim 1 is used for the method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde, it is characterized in that into first
The leacheate temperature of leaching absorption tower is at 40-80 DEG C, and the leacheate temperature into the second leaching absorption tower should be controlled in 50-80
℃。
6. the device of claim 1 is used for the method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde, it is characterized in that into first
The cycling elution liquid of leaching absorption tower is 0.2-10 with the mass ratio of the stream of gas gas-phase objects containing aldehyde；Into following for the second leaching absorption tower
Ring leacheate and the mass ratio of the stream of gas gas-phase objects containing aldehyde are 1-10.
7. the device of claim 1 is used for the method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde, it is characterized in that the first normal pressure
Fractionating column III carries out de- light work, 30-60 DEG C of tower top；The temperature control of leaching absorption tower V is at 40-80 DEG C；Second atmospheric fractional tower
IV 70-110 DEG C of tower top.
8. the device of claim 1 is used for the method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde, it is characterized in that vacuum distillation
70-150 DEG C of Ⅸ tower top of tower, operating pressure 0-30Kp；The operating pressure 0-15Kp of vacuum rectification tower Ⅹ.
9. the device of claim 1 is used for the method for the refining spearation of polymethoxy dimethyl ether containing formaldehyde, it is characterized in that passing through depickling
Material acid number should be controlled within 0-0.2mgKOH/g after device.
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN109776289A (en) * | 2019-01-31 | 2019-05-21 | 北洋国家精馏技术工程发展有限公司 | A kind of method and apparatus of separation and purification polymethoxy dimethyl ether |
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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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| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725203A (en) * | 2015-03-24 | 2015-06-24 | 江苏凯茂石化科技有限公司 | Process device and method for synthesizing polymethoxyl dimethyl ether and deacidifying by formaldehyde gas |
| CN104817440A (en) * | 2015-05-14 | 2015-08-05 | 江苏凯茂石化科技有限公司 | Process unit and method for absorbing formaldehyde in polymethoxy dimethyl ether synthesis |
| CN204644230U (en) * | 2015-05-14 | 2015-09-16 | 江苏凯茂石化科技有限公司 | Formaldehyde absorption process unit in a kind of polymethoxy dimethyl ether synthesis |
-
2017
- 2017-06-03 CN CN201710410666.8A patent/CN107118083B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104725203A (en) * | 2015-03-24 | 2015-06-24 | 江苏凯茂石化科技有限公司 | Process device and method for synthesizing polymethoxyl dimethyl ether and deacidifying by formaldehyde gas |
| CN104817440A (en) * | 2015-05-14 | 2015-08-05 | 江苏凯茂石化科技有限公司 | Process unit and method for absorbing formaldehyde in polymethoxy dimethyl ether synthesis |
| CN204644230U (en) * | 2015-05-14 | 2015-09-16 | 江苏凯茂石化科技有限公司 | Formaldehyde absorption process unit in a kind of polymethoxy dimethyl ether synthesis |
| WO2016180085A1 (en) * | 2015-05-14 | 2016-11-17 | 江苏凯茂石化科技有限公司 | Formaldehyde absorption process device and method in polyoxymethylene dimethyl ether synthesis |
Non-Patent Citations (1)
| Title |
|---|
| 张晓宇等: "聚甲氧基二甲醚的精制及应用研究进展", 现代化工, no. 03, pages 63 - 66 * |
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