CN102675154A - Separation and purification device and method for preparing methylene diphenyl diisocyanate (MDI) complex product by utilizing pyrolysis of carbamate - Google Patents
Separation and purification device and method for preparing methylene diphenyl diisocyanate (MDI) complex product by utilizing pyrolysis of carbamate Download PDFInfo
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Abstract
The invention relates to a separation and purification device and a method for preparing an MDI complex product by utilizing pyrolysis of carbamate. The separation and purification device comprises a solvent dehydration tower (2), a cooling and crystallization system (4), a heat filter (5) and a de-heavy fractionator (6), reboilers (3) are arranged at the bottoms of the solvent dehydration tower (2) and the de-heavy fractionator (6) respectively, and condensers (1) are arranged at the tops of the solvent dehydration tower (2) and the de-heavy fractionator (6) respectively. The method includes adding a mixing material containing solvents, raw materials, by-products and the MDI product to the solvent dehydration tower (2) for rectification and separation so as to achieve recycling of the solvents, adding the obtained liquid containing the MDI product to the cooling and crystallization system (4) for cooling and crystallization, obtaining a part of the raw materials, by-product solid and filtrate containing the MDI product after the filtration of the heat filter (5), and adding the filtrate to the de-heavy fractionator (6) for separation to obtain the MDI product. The separation and purification device and the method for preparing the MDI complex product by utilizing the pyrolysis of carbamate have the advantages of being simple in process, easy to operate and capable of achieving continuous operation.
Description
Technical field
The present invention relates to the separation field of MDI, particularly, the present invention relates to the separation and purification device and method that a kind of carbamate pyrolysis prepares the complicated product of MDI.
Background technology
Diphenylmethanediisocyanate (being called for short MDI) is the main basic material of polyurethane industrial.Different according to the position of two-NCO group on phenyl ring, can have 2,2 '-MDI, 2,4 '-MDI and 4,4 '-three kinds of isomerss of MDI.
At present, produce MDI both at home and abroad and mainly adopt phosgenation, prepare the diamines and the polyamines of diphenylmethane, again vulcabond (MDI) and the POLYMETHYLENE POLYPHENYLISOCYANATE through phosgenation prepared in reaction diphenylmethane series through the condensation reaction of aniline and formaldehyde.Owing to introduce phosgene, in its product system chlorine-containing compound is arranged, comprise three kinds of isomerss, POLYMETHYLENE POLYPHENYLISOCYANATE and the light naphthas etc. of MDI in addition.
Because phosgenation technology is used hypertoxic raw material phosgene; And the strong hydrochloric acid of by-product macro-corrosion property; Exist environmental pollution, severe reaction conditions, equipment corrosion and residual chlorine to influence problems such as quality product, the friendly non-phosgene of development environment prepares MDI technology and receives much attention.
At present to concentrate on the Urethylane be raw material to the more non-phosgene technology of report, thermolysis or directly aspect the gas phase high temperature pyrolysis synthesizing isocyanate under the liquid phase solvent system.Because being the reaction mechanism of isocyanic ester, the Urethylane pyrolysis belongs to the reversible thermo-negative reaction of consecutive, at two-NHCOOCH
3All pyrolysis generates in two purpose product group-NCO processes, and will inevitably generate intermediate product is that an end contains-NHCOOCH
3Group, an end contain-material of NCO group; Simultaneously; Active-NCO the group that contains among the MDI; Under comparatively high temps, be prone to make two MDI that polycondensation takes place and generate dimer, rough sledding such as coking further occur, so the pyrolytic reaction time can not be oversize; Thereby limited the transformation efficiency of carbamate, often contained some unconverted intact raw material in the product system.Therefore; Prepare in the MDI technology in the carbamate pyrolysis; The product system of its product system and existing phosgenation technology is completely different, except three kinds of isomerss that contain MDI equally, also contains intermediate product, the unconverted component of raw material, solvent carrier etc. completely.Develop a kind of brand-new product system separation and refining method; To remove intermediate product, unconverted raw material completely etc.; Obtain the mixture of highly purified MDI isomers; The further refining product that obtains the different isomerss of MDI is the important factor that the pyrolysis of decision carbamate prepares this technological feasibility of MDI and ripening degree.
The carbamate pyrolysis prepare MDI technology not only product form very complicatedly, and its two contained components are that intermediate product also has following singularity with the carbamate raw material that unreacted finishes, and have increased the difficulty of separating technology.
First; The intact carbamate of intermediate product and unreacted is heat-sensitive substance, when temperature is too high, is prone to take place decomposition reaction and generates MDI and methyl alcohol, if their too high levels; The methyl alcohol that perhaps generates can not in time be discharged in separation system, all can influence the purity of purpose product MDI.
Second; All contain active-NCO group among intermediate product and the MDI; Be easy to make between two MDI, MDI and intermediate products or two intermediate products polycondensation generation dimer takes place, rough sledding such as coking further occur, therefore; The separation system temperature can not be too high, and the isolating residence time can not be oversize under the hot environment.
At present, produce MDI technology by the carbamate pyrolysis, more about the report of its preparation aspect, and to the separation of its complicated product system and refining, all do not hear with the report and the research that obtain high-purity MDI isomers product.
Summary of the invention
To the objective of the invention is in order addressing the above problem, to provide a kind of carbamate pyrolysis to prepare the separation and purification device of the complicated product of MDI.
A purpose more of the present invention has been to provide a kind of carbamate pyrolysis to prepare the separation and refining method of the complicated product of MDI.
In order to address the above problem; The separation and purification device that carbamate pyrolysis provided by the present invention prepares the complicated product of MDI comprises: desolventizing tower 2, crystallisation by cooling system 4, hot filter 5 and weight-removing column 6; Bottom at desolventizing tower 2 and weight-removing column 6 is provided with reboiler 3 respectively, at the top of desolventizing tower 2 and weight-removing column 6 condensing surface 1 is set respectively;
The mixture that will contain solvent, raw material, by product and product MDI adds desolventizing tower 2 and carries out rectifying separation, and solvent at the condensing surface 1 at reboiler 3 effect gasified entering desolventizing towers 2 tops, reclaims, utilizes solvent in desolventizing tower 2; The raw material that the tower still of desolventizing tower 2 obtains, by product and product MDI get into crystallisation by cooling system 4 and cool off and crystallization; Separate out part material and by product, filter the filter cake that obtains raw material and by product through hot filter 5, the filtrating of containing the MDI product gets into weight-removing column 6 and separates; The MDI gasification gets into weight-removing column 6 evaporator overhead condensers 1 under the effect of reboiler 3; Condensation obtains product, and raw material, by product are discharged at the tower still with liquid form, realize the separation of the complicated product of MDI.
As a kind of improvement of such scheme, described condensing surface 1 is a shell-and tube condenser; Described reboiler 3 is a falling film evaporator.
Another improvement as such scheme; Described mixture is a carbamate pyrolysis products therefrom system, and wherein raw material is ditan diamino-methyl formate (being called for short MDC), and by product is 4-Urethylane-4-isocyanic ester ditan (being called for short MMI); Product is 2; 2 '-MDI, 2,4 '-MDI, 4,4 '-MDI.
The inventive system comprises: desolventizing tower 2, crystallisation by cooling system 4, hot filter 5, weight-removing column 6 etc.Incoming mixture rectifying separation in desolventizing tower 2 such as MDI, MMI, MDC, the cat head gained is high-purity light naphtha, can get back to the reuse of carbamate pyrolytic reaction systemic circulation; Tower still material entering crystallisation by cooling system 4 and hot filter 5 are removed the crystal of part MMI and MDC; Filtrating gets into weight-removing column 6, and weight-removing column cat head gained is high-purity MDI isomer mixt, can further utilize the refining product that obtains the different isomerss of MDI of existing technology; The tower still is MMI and MDC; Can with the filter cake of heat filtering system get back to together carbamate pyrolytic reaction system once more pyrolysis prepare MDI, thereby obtain cyclically utilizing, improve the yield of MDI product.
In the crystallisation by cooling system 4 and hot filter 5 that the present invention adopts, crystallization and filtration temperature are 40～200 ℃, and the mold residence time is 5～240min; Before weight-removing column separates MDI and MMI, MDC; Crystallisation by cooling system and hot filter are set remove the MMI and the MDC of part thermo-sensitivity; Reduce the MMI and the MDC content that get in the weight-removing column, the amount that makes MMI and MDC pyrolysis generate methyl alcohol reduces, thereby guarantees the purity of product MDI; Simultaneously, realized partial condensation through being provided with of temperature, made the methyl alcohol of generation in time discharge system with gaseous phase at the condensing surface of weight-removing column cat head, more than two aspects guarantee to obtain highly purified MDI isomers product.
In order to realize another object of the present invention, the present invention also provides a kind of carbamate pyrolysis to prepare the separation and refining method of the complicated product of MDI, and this method may further comprise the steps:
1) will contain in the mixture adding desolventizing tower 2 of solvent, raw material, by product and product MDI; Control tower still temperature is lower than 250 ℃; Tower top pressure is that 0.2～50KPa separates; Solvent obtains liquid solvent at the condensing surface 1 at effect gasified entering desolventizing tower 2 tops of reboiler 3, obtains the mixing liquid of raw material, by product and product MDI simultaneously at the tower still;
2) solvent in the step 1) is for recycling and reuse; The mixing liquid of raw material in the step 1), by product and product MDI gets into crystallisation by cooling system 4 and carries out crystallization; Obtain the crystal of part material, by product; Filter through hot filter 5, obtain the filter cake and the filtrating of containing product MDI of raw material and by product;
3) filtrating of containing product MDI step 2) gets into weight-removing column 6; Tower still temperature is lower than 250 ℃ in the control weight-removing column 6, and tower top pressure is 0.2～10KPa, separates; The condensing surface 1 at product MDI gasification entering weight-removing column 6 tops carries out condensation under reboiler 3 effects; Obtain product, raw material, by product are discharged from the tower still with liquid form, realize the separation of the complicated product of MDI.
As a kind of improvement of such scheme, in described step 2) in, described mixture is a carbamate pyrolysis products therefrom system; Wherein solvent comprises one or more in chlorobenzene, orthodichlorobenzene or its isomers, and raw material is MDC, and by product is MMI; Product is 2; 2 '-MDI, 2,4 '-MDI, 4,4 '-MDI.
As another improvement of such scheme, described step 2) in crystallization and filtering temperature be 40～150 ℃, crystallization time is 5～120min.
Another improvement as such scheme; Condensing surface is a shell-and tube condenser in the described step 3); Controlling its temperature is 40～150 ℃; Wherein gaseous product MDI is converted into liquid state and collects behind condensing surface 1, and the methyl alcohol of generation is in time discharged with gaseous phase behind condensing surface 1 and realized the partial condensation of gas in the condensing surface.
In the method for the present invention, the raw material feeding liquid is sloughed light naphtha earlier in the desolventizing tower, and wherein, light naphtha comprises the mixture of chlorobenzene, orthodichlorobenzene or its isomers; Get into crystallisation by cooling then and part MMI and MDC remove in the hot filter system, the thick MDI mixture of gained gets into weight-removing column and further removes MMI and MDC, promptly obtains highly purified MDI isomer mixt.
The invention has the advantages that; Carbamate pyrolysis of the present invention prepares the separation and purification apparatus and method of the complicated product of MDI; Realized that the carbamate pyrolysis prepares the separation of complicated product system in the MDI process and refining; And said device and method adopts industry to go up sophisticated technology and technology, advantage such as have that technology is simple, ripe, reliable, easy to operate, device and facility investment are little, and can realize that the technology serialization moves.
Description of drawings
Fig. 1 prepares the separation and purification schematic representation of apparatus of the complicated product of MDI for carbamate pyrolysis of the present invention.
The accompanying drawing sign
1, condensing surface 2, desolventizing tower 3, reboiler
4, crystallisation by cooling system 5, hot filter 6, weight-removing column
Embodiment
Below in conjunction with accompanying drawing device and method of the present invention is carried out detailed explanation.
As shown in Figure 1, the inventive system comprises: desolventizing tower 2, crystallisation by cooling system 4, hot filter 5, the reboiler 3 that the bottom of weight-removing column 6 and the condensing surface 1, desolventizing tower 2 and the weight-removing column 6 that are provided with respectively at the top of desolventizing tower 2 and weight-removing column 6 is provided with respectively.Mixture rectifying separation in desolventizing tower 2 such as solvent, MDI, MMI, MDC; 1 condensation obtains high-purity light naphtha to overhead gas through condensing surface; Can get back to the reuse of carbamate pyrolytic reaction systemic circulation, tower still material entering crystallisation by cooling system 4 and hot filter 5 are removed the crystal of part MMI and MDC, and filtrating gets into weight-removing column 6; Weight-removing column cat head gained is high-purity MDI isomer mixt; Can further utilize the refining product that obtains the different isomerss of MDI of existing technology, the tower still is MMI and MDC liquid, can with the filter cake of hot filter 5 get back to together carbamate pyrolytic reaction system once more pyrolysis prepare MDI; Thereby obtain cyclically utilizing, improve the yield of MDI product.
The desolventizing tower 2 tower still temperature that the present invention adopts are controlled at and are no more than 250 ℃, and tower top pressure is controlled at 0.2～50KPa, and reboiler is that falling film evaporator is rapidly heated with realization, and condensing surface is a shell-and tube condenser; Crystallisation by cooling system 4 and hot filter, crystallization and filtration temperature are 40～150 ℃, and the mold residence time is 5～120min; Can remove part MMI and MDC; The MMI and the MDC content that get into weight-removing column are reduced, decompose the amount minimizing that generates methyl alcohol, thereby guarantee the purity of product MDI; Weight-removing column tower still temperature is controlled at and is no more than 250 ℃; Tower top pressure is controlled at 0.2～10KPa; Reboiler is that falling film evaporator is rapidly heated with realization, and tower top condensing system adopts the partial condensation mode, and the methyl alcohol of generation is in time discharged with gaseous phase; Guarantee that the gained phlegma is highly purified MDI isomer mixt, condenser temperature is controlled at 40～150 ℃.
In the method for the present invention, a stream gang a is the raw material incoming flow, comprise 2,2 at least '-MDI, 2; 4 '-MDI, 4,4 '-MDI, MMI, MDC, light naphtha, a stream gang b is desolventizing tower 2 overhead condensate, is high-purity light naphtha; Stream gang c extracts out at the tower still, and main ingredient is 2,2 '-MDI, 2,4 '-MDI, 4; 4 '-MDI, MMI, MDC, stream gang d is filtrating, is thick MDI isomer mixt, and part MMI and MDC; A stream gang e is a filter cake, and main ingredient is MMI and MDC solid, and a stream gang f is that condenser system is discharged gas, and main ingredient is a methyl alcohol; A stream gang g is the phlegma of condenser system, promptly high-purity MDI isomer mixt, and a stream gang h is a tower bottoms, main ingredient is MMI and MDC liquid.
Embodiment 1
In embodiment 1, take by weighing 664g form comprise 2,2 '-MDI, 2; 4 '-the stream thigh a of MDI, 4,4 '-MDI, MMI, MDC, chlorobenzene, reduce to 3.16% through chlorobenzene content among the stream gang c behind the desolventizing tower; Stream gang c is through crystallisation by cooling and heat filtering system, and MMI and MDC content reduce to 13.7%, 4.97% respectively among the gained stream gang d, and stream gang d is through behind the weight-removing column; A gained stream gang f consists of chlorobenzene, methyl alcohol does not detect, and stream gang g is the mixture that purity reaches high-purity MDI isomers of 97%.
Embodiment 2
In embodiment 2, take by weighing 616.8g form comprise 2,2 '-MDI, 2; 4 '-the stream thigh a of MDI, 4,4 '-MDI, MMI, MDC, chlorobenzene, reduce to 2.79% through chlorobenzene content among the stream gang c behind the desolventizing tower; Stream gang c is through crystallisation by cooling and heat filtering system, and MMI and MDC content reduce to 9.07%, 0.57% respectively among the gained stream gang d, and stream gang d is through behind the weight-removing column; A gained stream gang f consists of chlorobenzene, methyl alcohol does not detect, and stream gang g is the mixture that purity reaches high-purity MDI isomers of 96.8%.
The invention provides the separation and purification apparatus and method that a kind of carbamate pyrolysis prepares the complicated product of MDI; Realized that the carbamate pyrolysis prepares the separation of complicated product system in the MDI process and refining; The various drawbacks that previous methods prepares MDI have been solved; And can find out that through embodiment 1 and 2 apparatus and method of the present invention have good effect, all reach more than 96% through the mixture purity of separating the MDI isomers that obtains.
Claims (9)
1. a carbamate pyrolysis prepares the separation and purification device of the complicated product of MDI; It is characterized in that; Described separation and purification device comprises: desolventizing tower (2), crystallisation by cooling system (4), hot filter (5) and weight-removing column (6); The bottom of described desolventizing tower (2) and weight-removing column (6) is provided with reboiler (3) respectively, and the top of described desolventizing tower (2) and weight-removing column (6) is provided with condensing surface (1) respectively;
The mixture that will contain solvent, raw material, by product and product MDI adds desolventizing tower (2) and carries out rectifying separation; Solvent acts on the condensing surface (1) that gasified gets into desolventizing tower (2) top at reboiler (3) in desolventizing tower (2); Condensation obtains liquid solvent, and solvent is reclaimed, utilizes; The liquid that contains raw material, by product and product MDI that the tower still of desolventizing tower (2) obtains gets into crystallisation by cooling system (4) and cools off and crystallization; Separate out part solid material and by product; Filter the filtrating that obtains the filter cake of raw material and by product and contain product MDI through hot filter (5); Filtrating gets into weight-removing column (6) separates, and the MDI gasification gets into the condensing surface (1) at weight-removing column (6) top under the effect of reboiler (3), and condensation obtains product MDI; Raw material, by product are discharged with liquid form at the tower still, realize the separation of the complicated product of MDI.
2. carbamate pyrolysis according to claim 1 prepares the separation and purification device of the complicated product of MDI, it is characterized in that described condensing surface (1) is a shell-and tube condenser.
3. carbamate pyrolysis according to claim 1 prepares the separation and purification device of the complicated product of MDI, it is characterized in that described reboiler (3) is a falling film evaporator.
4. carbamate pyrolysis according to claim 1 prepares the separation and purification device of the complicated product of MDI, it is characterized in that described mixture is a carbamate pyrolysis products therefrom system; Wherein raw material is the ditan diamino-methyl formate; By product is 4-Urethylane-4-isocyanic ester ditan, product is 2,2 '-MDI, 2; 4 '-MDI, 4,4 '-MDI.
5. a carbamate pyrolysis prepares the separation and refining method of the complicated product of MDI, and this method may further comprise the steps:
1) will contain in the mixture adding desolventizing tower (2) of solvent, raw material, by product and product MDI; Control tower still temperature is lower than 250 ℃; Tower top pressure is that 0.2～50KPa separates; Solvent obtains liquid solvent at the condensing surface (1) at effect gasified entering desolventizing tower (2) top of reboiler (3), obtains the mixing liquid of raw material, by product and product MDI simultaneously at the tower still;
2) solvent in the step 1) is for recycling and reuse; The mixing liquid of raw material in the step 1), by product and product MDI gets into crystallisation by cooling system (4) and cools off and crystallization, obtains the crystal of part material, by product, filters through hot filter (5); Remove the filter cake of raw material and by product; Thereby reduce the amount of the methanol gas of raw material and by product generation, obtained containing the filtrating of product MDI simultaneously;
3) filtrating of containing product MDI step 2) gets into weight-removing column (6); The interior tower still of control weight-removing column (6) temperature is lower than 250 ℃, and tower top pressure is 0.2～10KPa, separates; The condensing surface (1) at product MDI gasification entering weight-removing column (6) top carries out condensation under reboiler (3) effect; Obtain product, raw material, by product are discharged from the tower still with liquid form, realize the separation of the complicated product of MDI.
6. carbamate pyrolysis according to claim 5 prepares the separation and refining method of the complicated product of MDI, it is characterized in that, in described step 1); Described mixture is a carbamate pyrolysis products therefrom system; Wherein solvent comprises one or more in chlorobenzene, orthodichlorobenzene or its isomers, and raw material is the ditan diamino-methyl formate, and by product is 4-Urethylane-4-isocyanic ester ditan; Product is 2; 2 '-MDI, 2,4 '-MDI, 4,4 '-MDI.
7. carbamate pyrolysis according to claim 5 prepares the separation and refining method of the complicated product of MDI, it is characterized in that described step 2) in crystallization and filtering temperature be 40～150 ℃, crystallization time is 5～120min.
8. carbamate pyrolysis according to claim 5 prepares the separation and refining method of the complicated product of MDI; It is characterized in that; Condensing surface is a shell-and tube condenser in the described step 3), and controlling its temperature is 40～150 ℃, and wherein gaseous product MDI is converted into liquid state and collects behind condensing surface (1); Methyl alcohol is still discharged with gas form through condensing surface (1), has realized the partial condensation of gas in the condensing surface.
9. carbamate pyrolysis according to claim 5 prepares the separation and refining method of the complicated product of MDI; It is characterized in that described method also comprises step 4): with step 2) in obtain in filter cake and the step 3) of raw material and by product discharging the pyrolysis that raw material, by product be further used for carbamate and prepare MDI from the tower still.
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| CN110483337A (en) * | 2018-05-14 | 2019-11-22 | 中国科学院过程工程研究所 | A kind of separation and purification system and method for benzene dimethylene diisocyanate product |
| CN114984601A (en) * | 2022-07-05 | 2022-09-02 | 中国科学院过程工程研究所 | Device system and method for separating and refining 1, 5-pentamethylene diisocyanate by non-phosgene method |
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| CN105837471A (en) * | 2015-01-16 | 2016-08-10 | 中国科学院过程工程研究所 | Two-stage pyrolysis device for preparation of polymethylene polyphenyl polyisocyanate by liquid phase pressurization thermal decomposition method and pyrolysis method |
| CN105837471B (en) * | 2015-01-16 | 2018-01-12 | 中国科学院过程工程研究所 | A kind of liquid phase pressurization thermal decomposition method prepares the two level pyrolysis installation and method for pyrolysis of poly methylene poly phenyl poly isocyanate |
| CN110483337A (en) * | 2018-05-14 | 2019-11-22 | 中国科学院过程工程研究所 | A kind of separation and purification system and method for benzene dimethylene diisocyanate product |
| CN110483337B (en) * | 2018-05-14 | 2020-08-28 | 中国科学院过程工程研究所 | System and method for separating and refining xylylene diisocyanate product |
| CN114984601A (en) * | 2022-07-05 | 2022-09-02 | 中国科学院过程工程研究所 | Device system and method for separating and refining 1, 5-pentamethylene diisocyanate by non-phosgene method |
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