CN1246472A - Method for decomposing solid leavings - Google Patents
Method for decomposing solid leavings Download PDFInfo
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- CN1246472A CN1246472A CN99111081A CN99111081A CN1246472A CN 1246472 A CN1246472 A CN 1246472A CN 99111081 A CN99111081 A CN 99111081A CN 99111081 A CN99111081 A CN 99111081A CN 1246472 A CN1246472 A CN 1246472A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Processing Of Solid Wastes (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The present invention provides a process for converting a solid residue which has been by-produced in the production of an isocyanate and hitherto disposed into the corresponding amine which can be reused, without using any hydrolyzation promoter such as an alkaline material and the like. In the invention, a solid residue by-produced in the production of an isocyanate is heated in the presence of water which is in gaseous, liquid or super critical state, or of a mixed solution of wafer and an alcohol, whereby a component compound of the solid residue is converted into an amine corresponding to said component compound.
Description
The present invention relates to will be when producing isocyanic ester the solid residue of by-product under the mixture existence condition of the water of gas, liquid or supercritical state or alcohol and water, be hydrolyzed, be transformed into decomposition method with the solid residue of the corresponding amine of composition compound of solid residue.
Reclaim isocyanic ester the distillation residue of by-product when the invention still further relates to, make solid residue, as mentioned above the method for this solid residue of hydrolysis from the production isocyanic ester.
Isocyanic ester is general by following method production, will react the distillation reaction resultant with corresponding amine of isocyanic ester and carbonyl chloride, remove by product and tar composition respectively, make thick isocyanic ester, should carry out rectifying by thick isocyanic ester, obtain the purified isocyanic ester.This tar composition that obtains as distillation residue is to generate by side reaction in the phosphinylidyne chloride process and the thermal polycondensation in the distillation process etc., can think the mixture of the polycondensate that urea, biuret, carbodiimide, chlorinated isocyanurates etc. are complicated.These distillation residue normally further reclaim wherein contained isocyanic ester, and its residue is disposed as trade waste, perhaps distillation residue are directly handled as trade waste.
As mentioned above, though at present when producing isocyanic ester the isocyanic ester distillation residue of by-product can be used as trade waste and dispose, the while is also studied its effective utilization.In recent years from reducing the viewpoint of carrying capacity of environment and resource recovery, stepped up to carry out about the research of effective utilization of trade waste.
Existing research about the isocyanic ester distillation residue can be enumerated the technical scheme below having put down in writing in No. 79690/1993 communique of patent announcement: add monohydroxy-alcohol in the tolylene diisocyanate distillation residue, generate after the carbamate, make and add the mixture that polyvalent alcohol forms, toward wherein adding whipping agent etc., make the polyurethane foam.This method just becomes distillation residue more effective useful matter.
On the other hand, as the method that begins from isocyanates production process, carried out by further reclaim isocyanic ester from existing distillation residue, perhaps destructive distillation residue reclaims the trial that the method for corresponding amine reduces production costs.
For example, in No. 142501/1975 communique of patent disclosure, No. 130525/1979 communique of patent disclosure and No. 201751/1983 communique of patent disclosure, put down in writing by there are hydrolysis isocyanic ester distillation residue under the situation at alkaline aqueous solution, the solid part of separating in the decomposed liq assigns to obtain corresponding amine.In more detail, No. 142501/1975 communique of patent disclosure put down in writing the isocyanic ester distillation residue existed under the situation with 100～200 ℃ saturated solution form heating 30 minutes～5 hours oxyhydroxide, oxide compound and the amine of at least a and alkali of water, pure and mild amine or alkaline-earth metal at least a, separate the solid of separating out, obtain corresponding amine.But, because any one of these methods all will adopt alkali to promote hydrolysis, and separate out complex procedures such as solid separation, therefore increase cost inevitably, can not be called is the method for economy.
Recently, as modification method, No. 151270/1997 communique of patent disclosure put down in writing the waste of fused or liquid state decomposed the objectification compound with near the hydromining the stagnation point with the unpredictable short period of time in so-called 10 minutes the prior art, generates corresponding starting compound or its derivative reclaims.This technology does not adopt existing hydrolysis promotor with the waste of fusion or liquid state, only adopts water to decompose, and decomposes under near the condition the stagnation point of water, because the time is short, construction cost is so not high.
But, in the method, the waste of fusion or liquid state for example since in its production process, contain can round-robin useful material such as isocyanic ester, its hydrolysis is transformed into and the corresponding amine of isocyanic ester, in the production process of isocyanic ester, in order to utilize again, must react with carbonyl chloride once more, be uneconomic from this respect.
As mentioned above, these existing methods are not with solid waste, and promptly solid residue is an object, and the result is that solid residue left behind, and have at last dispose as industrial waste.
The purpose of this invention is to provide a kind of hydrolysis promotor such as alkali that when the isocyanic ester that only carries out waste disposal is so far produced, do not add in the solid residue of by-product, be transformed into the method for the corresponding amine that can utilize again.
The distillation residue that a present purpose of the present invention provides by-product when producing isocyanic ester are separating isocyanate effectively, does not add alkali, and the resulting solid residue of hydrolysis effectively is transformed into the method for recycling corresponding amine.
Present inventors have carried out making great efforts research for solving above-mentioned problem, the result is that the solid residue of by-product when find producing isocyanic ester exists under the situation by the mixture at the water of gas, liquid or supercritical state or alcohol and water and heats, be transformed into the corresponding amine of composition compound with solid residue, and necessary for this reason conditions suitable, thereby finish the present invention.
That is, the present invention relates to the solid residue decomposition method of record in following (1)～(12).
(1) decomposition method of solid residue, the solid residue of by-product existed under the situation at the water of gas, liquid or supercritical state or the mixture of alcohol and water when it will produce isocyanic ester, under the pressure under the temperature more than 100 ℃, more than the 0.1MPa, heat, be transformed into this solid residue in the corresponding amine of composition compound.
(2) decomposition method of solid residue of record in above-mentioned (1), when 20 holders, 180 ℃ kept 1 hour, the weight of this solid residue was reduced to below 3% with aforementioned solid residue.
(3) decomposition method of the solid residue of record in above-mentioned (1), water is more than 0.1 for the weight ratio of aforementioned solid residue.
(4) decomposition method of the solid residue of record in above-mentioned (1) or (3), alcohol is below 5 with respect to the mol ratio of aforementioned water.
(5) decomposition method of the solid residue of above-mentioned (1) record, aforementioned pressure is that 0.5～40MPa, aforementioned temperature are 150～450 ℃.
(6) decomposition method of solid residue, it separates the composition that volatilizees distillation residue by-product, that contain the composition that volatilize when producing isocyanic ester, the solid residue that obtains is existed under the situation at the water of gas, liquid or supercritical state or the mixture of alcohol and water, under the pressure under the temperature more than 100 ℃, more than the 0.1MPa, heat, be transformed into this solid residue in the corresponding amine compound of composition compound.
(7) separation method of the solid residue of record in above-mentioned (6), the separation of aforementioned volatilization composition is to carry out in having the two-phase flow pattern evaporation unit of piston sliding.
(8) separation method of the solid residue of record in above-mentioned (7), aforementioned two-phase flow pattern evaporation unit is the dual pipe type evaporation unit.
(9) separation method of the solid residue of record in above-mentioned (7) or (8), the separation of aforementioned volatilization composition is to be 120～350 ℃ in temperature, pressure is 1～200 mmhg, and the gas flow rate that exports at two-phase flow pattern evaporation unit is that 100～700 meter per seconds carry out.
(10) decomposition method of the solid residue of record in above-mentioned (6), water is more than 0.1 for the weight ratio of aforementioned solid residue.
(11) decomposition method of the solid residue of record in above-mentioned (6) or (10), alcohol is below 5 with respect to the mol ratio of aforementioned water.
(12) treatment process of distillation residue, distillation residue by-product, that contain isocyanic ester heated in having the two-phase flow pattern evaporation unit of piston sliding when it will produce isocyanic ester, separating isocyanate from these distillation residue, the solid residue that obtains is existed under the situation at the water of gas, liquid or supercritical state or the mixture of alcohol and water, under the temperature more than 100 ℃, pressure more than the 0.1MPa, contact, be transformed into this solid residue in the corresponding amine of composition compound.
The simple declaration of accompanying drawing
Fig. 1 is a synoptic diagram of removing the technology of volatilization composition by the dual pipe type heat exchanger from distillation residue.
Fig. 2 is the synoptic diagram of the technology of hydrolysis solid residue.
Below the solid residue of by-product referred to when in the present invention, what is called was produced isocyanates One isocyanates, vulcabond of record etc. are at least a a NCO base The residue that produces when compound is produced.
One isocyanates for example can be enumerated, and general formula is that (R is aliphatic group to R-NCO Perhaps aromatic group) represented aliphatic one isocyanates, aromatic series one isocyanic acid Ester etc.
The object lesson of aliphatic one isocyanates can be enumerated methyl isocyanate, positive fourth Base isocyanates etc. And that the object lesson of aromatic series one isocyanates can be enumerated phenyl is different Cyanate etc.
Vulcabond can enumerate general formula OCN-R-NCO (R be above-mentioned group or Person's alcyl) aliphatic diisocyanate, aromatic diisocyanate, the alicyclic ring of expression Vulcabond etc.
The object lesson of aliphatic diisocyanate can be enumerated HDI Deng. Aromatic diisocyanate can be enumerated xyxylene vulcabond, toluene support two Isocyanates, naphthylene vulcabond, benzhydryl vulcabond etc. Ester ring type two Isocyanates can be enumerated IPDI, norbornene alkyl diisocyanate Deng. Except above-mentioned isocyanates, can also adopt such as triisocyanate etc. to have More than three-solid of by-product was residual when the isocyanates compound of NCO group was produced Slag. The present invention decompose the solid residue adopt if when producing isocyanates by-product Solid residue, then can adopt any technology to produce. Specifically, be at amine The reaction operation of production technology, amine and phosgene, the refining operation of isocyanates or recovery The solid residue of by-product in any one technologies such as the operation of isocyanates. These solids are residual Slag can be melting, dissolving in each technology. Be applicable to solid residue of the present invention Be not limited to adopt the isocyanates of phosgene production, in the situation of producing with non-phosgene method Lower, also can decompose the solid residue of by-product in any one of these each operations.
Solid residue can adopt any, but normally consolidating that each operation is produced The body residue is adopted with liquid composition after separating by solid-liquid separation process, distillation process etc. With. Preferably make with extra care the solid residue of operation through isocyanates. Particularly passing through distillation In the situation of refining isocyanates, its bottoms (being the refining distillation process of isocyanates) Be preferred, from these bottoms, reclaim the volatilization composition until in fact do not contain and wave It is particularly preferred sending out composition.
The said solid that does not in fact contain the composition that volatilizees refer to 20 the holder, 180 ℃ Keep that weight reduces in 3% weight with interior solid after one hour.
The solid residue of these by-products when producing isocyanates is that Main Ingredients and Appearance is amine, different The mixture that the pyrocondensation polymers such as cyanate consist of. The pyrocondensation polymers for example have urea (urethane), Group or the ring of biuret, carbodiimides, chlorinated isocyanurates etc. Particularly comprise Many compounds with labyrinth of a plurality of such groups or ring. Above-mentioned solid The water of residue and gas, liquid or supercriticality or the mixture of pure and mild water are at height Contact under temperature, the high pressure, be hydrolyzed into the amine corresponding with the composition compound of solid residue.
Decomposition process to this solid residue describes with reference to Fig. 1. Solid residue is logical Crossing pipeline 101 joins in the slurrying rotary drum 102. Water adds by pipeline 103. Water can To contain as required quantitative alcohol. The slurry of preparation heat exchanger 104 in 102 Heat up, add in the reactor 105, analyte is extracted out with 106, and is as required refining, Circulation is as isocyanates raw material etc.
Discharging the gas that is decomposed by-product by solid residue from pipeline 107, mainly is two oxidations Carbon.
Used solid residue is according to preamble, can be that any one produces isocyanic acid The solid residue that produces during ester. Wherein, especially preferably adopt by having the piston sliding Two-phase flow pattern vaporising device separated the solid residue of volatilization composition. In fact do not contain and wave The solid residue of sending out composition (that is, from remaining isocyanates monomer number is 10% tar Further reclaim the above-mentioned by-product of isocyanates monomer to the limit in the shape bottoms The residue that the mixture of the pyrocondensation polymers that thing consists of etc. forms) be especially preferred.
These solid residues decompose by contacting with water under HTHP. The high temperature height Press and specifically refer to temperature more than 100 ℃, pressure is more than 0.1MPa. At this moment, Water can have gas, liquid, postcritical any one state according to temperature, pressure. Water can be independent water, or contains the water of alcohol etc.
Solid residue is contacted with water under HTHP when decomposing, in order to increase it The interface of contact, solid residue is the micro mist shape preferably, and is in the situation that is bulk, preferred Be ground in advance suitable size.
In order to decompose solid residue, preferred temperature and pressure condition be 150 ℃ with On, more than the 0.5MPa. Particularly temperature and pressure does not have the upper limit, preferred 45 ℃ with Lower, below the 40MPa.
The resolving time of solid residue, there is no particular limitation, reach given temperature after, At 1 minute～300 minutes, carry out in preferred 1 minute～30 minutes scope.
The mixing heating of water and solid residue can be adopted following any method, and is excellent Select 3).
1) water and solid residue mix under temperature given in advance.
When 2) water being mixed with solid residue, be heated to given temperature, mix, reach decomposition temperature by water and solid residue with heating.
3) water and solid residue are mixed with given concentration in slurrying cylinder etc. in advance, make slurry, be heated to decomposition temperature then.
Weight ratio (water/solid residue) with respect to the water of solid residue is preferred more than 1/10, more preferably more than 1/2.Water for the weight ratio of solid residue less than 1/10 situation under, decomposition product not only major part has become pitch shape residue, the yield rate of corresponding amine also has the trend of reduction, is not so good therefore.
In the present invention, alcohol with respect to the mol ratio (alcohol/water) of water preferably below 5, more preferably below 3.If alcohol has surpassed 5 with respect to the mol ratio of water, the yield rate of amine reduces easily, because the trend of generation from the pure by product that comes of carbamate body and other is arranged greatly, so be not so good.In the present invention, by coexistence in reaction system alcohol is arranged, the aqueous solution that the resultant after the decomposition can be used as homogeneous reclaims.Make the aqueous solution of homogeneous by the resultant after will decomposing, can reclaim amine easily from resolvent.
The alcohol of Shi Yonging has no particular limits in the present invention, can enumerate for example monohydroxy-alcohols such as methyl alcohol, ethanol, Virahol, propyl carbinol, the trimethyl carbinol, 1-octanol particularly, dibasic alcohol, trihydroxymethyl propanes, 1 such as ethylene glycol, propylene glycol, di-alcohol, 2, tetravalent alcohol such as trivalent alcohol such as 6-hexanetriol and tetramethylolmethane.These alcohol can independent or two or more mixing and water mixing use.
In these alcohol, with high methyl alcohol, ethanol, Virahol, ethylene glycol, the propylene glycol of the solvability of water be that the alcohol of representative is more preferred.In the present invention, by these alcohol are used simultaneously with water, the pitch shape residue that solid residue is decomposed in the regenerant afterwards dissolves.
The mixing solutions of these solid residues and water or alcohol and water can be separately respectively or make slurry and join in the reactor.
In decomposing the aqueous solution that above-mentioned solid residue obtains, except water or alcohol and water, much less also contain as major ingredient with the corresponding amine of isocyanic ester, corresponding amine is adopted methods such as common distillation or extraction can easily reclaim.The amine that reclaims can react with carbonyl chloride as the raw material circulation in the isocyanic ester production process after further making with extra care as required.
Dissolving is the lower boiling composition of major ingredient with the carbonic acid gas in the aqueous solution of separation of amine, and it is not perhaps removed after stripping etc. removes by carrying out, and adds after the alcohol water of using as hydrolysis and recycling as required.Perhaps, draining after common wastewater treatment.
Distillation residue when in the present invention, producing isocyanic ester can be the distillation residue that produce by distillation in any one operation in the production unit of isocyanic ester.Usually, by mainly being amine production process or amine and carbonyl source, for example the reaction solution distillation that obtains of the operation of carbonyl chloride reaction generates.
The by-product amount of these distillation residue is according to the preparation method and in general difference, is about 10% weight with respect to the isocyanic ester of partly extracting out from the cat head of refining and distilling tower.These distillation residue are liquid normally, contain several 10%, the volatilization composition of 50～10% weight for example.
In the present invention, from above-mentioned distillation residue, reclaim until the device of the state that does not in fact contain the composition that volatilize and to enumerate thin-film evaporator, mixing and blending machine or have used device in the volatilization recovery process that the device etc. of heater block uses always.Wherein, particularly preferably be the two-phase flow pattern evaporation unit that employing has piston lubrication.
Evaporation unit with piston lubrication is meant the upper reaches defluent certain orientation mobile equipment of body from device that is evaporated.Two-phase flow pattern evaporation unit is any one the evaporation unit of two phase flow that has gas-liquid, gas-solid at least, also can the gas-liquid-solid three-phase coexistence.
Its typical example can be enumerated mixing and blending machine or dual pipe type heat exchanger etc.Wherein especially preferably can form the cast evaporation unit of at least a flow state of wavy flow, scoriform stream, annular-flow, spray flow.Most preferably above-mentioned flow state is the device that forms by at the inner gas that produces of evaporation unit, and for example dual pipe type heat exchanger etc. is to be fit to adopt.
Referring to Fig. 2, to being applicable to that the evaporation unit with piston sliding of the present invention is that example describes with the dual pipe type heat exchanger.
The distillation residue that come out from distillation tower join the dual pipe type heat exchanger 202 by pump 201.Distillation residue can adopt other heat exchanger (not shown) to carry out preheating in advance.At the inlet of dual pipe type heat exchanger, as required pressure control valve 203 can be set.The distillation residue that join in the dual pipe type heat exchanger adopt steam heating such as (STM).According to the temperature that joins the distillation residue in the dual pipe type heat exchanger, volatilization composition, pressure etc. and different, has following flow state in the flow state of dual pipe type heat exchanger inside.
1) under the low situation of volatilization composition temperature many, distillation residue
Distillation residue are preheated near the dual pipe type heat exchanger entrance, all liquefy.By the heating of thermal mediums such as steam, the volatilization composition forms wavy flow, scoriform stream, annular-flow, spray flow through evaporation, through bubble flow by this pre-heated flow.
2) few at the volatilization composition, under the high situation of the temperature of distillation residue such as preheating
Usually, there is gas phase from the material inlet of dual pipe type heat exchanger, forms bubble flow, wavy flow, scoriform stream, then by it is heated with thermal mediums such as steam, the volatilization composition forms wavy flow, scoriform stream, annular-flow, spray flow through evaporation, through bubble flow.Particularly under the situation of carrying out preheating, what suppress bubble in preheat exchanger is preferred, therefore preferably at the dual pipe type heat exchanger entrance valve is set.
In having the two-phase flow pattern evaporation unit of piston lubrication, these flow states are by evaporation volatilization composition, volumetric expansion, and it is that fluid by accelerated evaporation device inside moves and produces.Thus, even volatilization composition evaporation, viscosity rises, and the kinergety that keeps its gas phase can inaccessible heat exchanger, can reach the separation of volatilization composition.Particularly, if at the inner spray flow that forms of two-phase flow pattern evaporation unit, the solid residue that obtains has formed the micro mist shape in the outlet of two-phase flow pattern evaporation unit, is preferred therefore.The solid residue that obtains can be pulverized as required.
In having the evaporation unit of piston lubrication, institute adds heat and is evaporated latent heat immediately and consumes, and has suppressed the evaporation unit temperature inside and has risen, and can keep evaporating the low temperature of required thermal source.As mentioned above, keep the low temperature of thermal medium, not only reduced the cost of unit energy, can also suppress raw-material loss.That is,, can suppress its polycondensation speed, suppress the generation of oligopolymer by keeping the low temperature of thermal medium because the thermal polycondensation speed of isocyanic ester etc. is relevant with its temperature and concentration.Heat by other adding evaporates the volatilization composition successively, can keep the lower concentration of pyrocondensation polymers such as isocyanic ester, and then suppresses the speed of thermal polycondensation.
Can carry out boiling heat transfer by evaporating the volatilization composition successively, keep its state for a long time.And then by aforesaid volumetric expansion, the fluidic linear velocity of evaporation equipment inside sharply raises, and promotes the Surface Renewal on the heat transfer interface.The promotion of Surface Renewal, the utilization of boiling heat transfer have further improved heat transfer efficiency, can suppress the pyrocondensation polymers that by-product is difficult to decompose recovery, according to circumstances in fact also can not make its generation.There is no particular limitation to the temperature in the above-mentioned evaporation equipment, pressure etc., and temperature is generally 120～350 ℃, more preferably 180～230 ℃.Pressure changes along with the boiling point of volatilization composition, and for preferred 1～200 mmhg of decompression, more preferably absolute pressure is 5～15 mmhg.Gas line speed 100～700m/s normally with two-phase flow pattern evaporation unit of piston lubrication, preferred 200～600m/s.The linear velocity that is gas gradually changes in two-phase flow pattern evaporation unit, and the gas line speed that therefore is used in the outlet of two-phase flow pattern evaporation unit is stipulated.
Thermal medium with two-phase flow pattern evaporation unit of piston sliding can be any one of steam, electric heating device, deep fat etc., preferred steam.
In above-mentioned dual pipe type heat exchanger 202, the distillation residue that separated the volatilization composition are added in the funnel 204, be separated into gas phase and solid residue, gas phase is extracted out from pipeline 205, solid residue is transported to decomposition process 207 (for example slurrying rotary drum 102 of Fig. 1) through solid discharger 206, carry out the said hydrolyzed reaction, be transformed into amine.Powder trap (not shown)s such as bag filter can be set in funnel 204 as required.Condensation is refining as required for the gas phase that will extract out by pipeline 205, reclaims as isocyanic ester composition or isocyanic ester production raw material.There is no particular limitation to the solid discharger, can adopt spiral powder charging machine commonly used, air-flowing type powder conveying device etc.
The present invention is illustrated further that the following examples are not any limitation of the invention by following embodiment.
Embodiment 1
The distillation residue that will contain 50% the tolylene diisocyanate of having an appointment, adopt the dual pipe type evaporation unit, the temperature of residue on evaporation in the pipe is 200 ℃, and absolute pressure is to separate after the volatilization composition under the condition of 10 mmhg, obtains containing the solid residue of 0.5% tolylene diisocyanate.At this moment, in the outlet of dual pipe type evaporation unit, gas line speed is 400 meter per seconds.4.0 these solid residues of gram are filled in the reactor, and the water after the adding 25.4 gram vacuum outgass 380 ℃ of heating, decomposes solid residue under this temperature.At this moment, pressure is 27MPa.After 10 minutes, be cooled fast to room temperature, when taking out content, recovering liquid 24.6 grams.The viscous bitumen shape remnant that on the inwall of reaction tubes, adheres to black.In this pitch shape remnant, add methyl alcohol, reclaim pitch shape remnant fully.
Consequently from the pitch shape remnant that reclaims liquid and adding methyl alcohol, can obtain respectively to be respectively 16.7% and 5.8% by weight with respect to the tolylene diamine of filling solid residue, the two adds is 22.5% yield rate together altogether, can determine solid residue is transformed into and wherein the corresponding amine of composition compound.
Embodiment 2
Water keeps the ratio identical with embodiment 1 for the solid weight ratio, is heating 10 minutes under the 19MPa condition at 380 ℃, pressure, reclaims the resultant of decomposition similarly to Example 1.
Consequently from the pitch shape remnant that reclaims liquid and adding methyl alcohol, can obtain respectively to be respectively 15.6% and 5.7% by weight with respect to the tolylene diamine of filling solid residue, the two adds is 21.4% yield rate together altogether, can determine solid residue is transformed into and wherein the corresponding amine of composition compound.
Embodiment 3
Water keeps the ratio identical with embodiment 1 for the solid weight ratio, is heating 10 minutes under the 23MPa condition at 300 ℃, pressure, reclaims the resultant of decomposition similarly to Example 1.
Consequently from the pitch shape remnant that reclaims liquid and adding methyl alcohol, can obtain respectively to be respectively 29.6% and 6.8% by weight with respect to the tolylene diamine of filling solid residue, the two adds is 36.4% yield rate together altogether, can determine solid residue is transformed into and wherein the corresponding amine of composition compound.
Embodiment 4
Water is 3 times for the solid weight ratio, is heating 10 minutes under the 8.8MPa condition at 300 ℃, pressure, reclaims the resultant that decomposes similarly to Example 1.
Consequently from the pitch shape remnant that reclaims liquid and adding methyl alcohol, can obtain respectively to be respectively 39.6% and 5.6% by weight with respect to the tolylene diamine of filling solid residue, the two adds is 45.2% yield rate together altogether, can determine solid residue is transformed into and wherein the corresponding amine of composition compound.
Embodiment 5
Water keeps the ratio identical with embodiment 4 for the solid weight ratio, is heating 60 minutes under the 2.4MPa condition at 220 ℃, pressure, reclaims the resultant of decomposition similarly to Example 1.
Consequently from the pitch shape remnant that reclaims liquid and adding methyl alcohol, can obtain respectively to be respectively 30.3% and 5.2% by weight with respect to the tolylene diamine of filling solid residue, the two adds is 35.5% yield rate together altogether, can determine solid residue is transformed into and wherein the corresponding amine of composition compound.
Embodiment 6
The solid residue that 4.0 grams are further reclaimed from the tolylene diisocyanate distillation residue behind the isocyanic ester joins in the reactor, adds the mixed solution of 33.0 gram water and methyl alcohol, makes that the solid weight ratio is 3 times after water and the vacuum outgas.At this moment the molar ratio of methyl alcohol and water is 1 times.Then reaction tubes is heated to decomposition temperature at 300 ℃.At this moment, pressure is 15MPa.After 10 minutes, be cooled fast to room temperature, when taking out content, recovering liquid 36.5 grams.What is not found outside in reaction tubes, dewatering.
Analyzing the result who reclaims liquid is that the yield rate that obtains is to count 35.8% with tolylene diamine with respect to the weight of filling solid residue, confirms to be transformed into and the corresponding amine of solid residue.
Comparative Examples 1
Water is 3 times for the solid weight ratio, outside the heating 60 minutes, carries out processing similarly to Example 1 under 90 ℃, the condition of 0.2MPa.Form when consequently solid is filled with maintenance is remaining, is not pitch shape residue.Do not detect tolylene diamine the liquid after solid-liquid separation.
The method according to this invention, the solid residue of the isocyanic ester that will dispose as existing trade waste does not add additives such as alkali, can be transformed into effectively and the corresponding amine of solid residue.Have the two-phase flow pattern evaporation unit of piston lubrication by employing, suppress the thermal polycondensation of the composition of thermal polycondensation easily such as isocyanic ester, reclaim isocyanic ester effectively, further preparation is suitable for the solid residue of hydrolysis.
Claims (12)
1. the decomposition method of a solid residue, the solid residue that it is characterized in that by-product when producing isocyanic ester is under the mixture existence condition of the water of gas, liquid or supercritical state or alcohol and water, under the temperature more than 100 ℃, pressure more than the 0.1MPa, heat, be transformed into this solid residue in the corresponding amine of composition compound.
2. the decomposition method of the solid residue of claim 1 record is characterized in that, when 20 holders, 180 ℃ kept 1 hour down, the weight of this solid residue was reduced to below 3% with aforementioned solid residue.
3. the decomposition method of the solid residue of claim 1 record is characterized in that water is more than 0.1 for the weight ratio of aforementioned solid residue.
4. the decomposition method of the solid residue of claim 1 or 3 records is characterized in that, alcohol is below 5 with respect to the mol ratio of aforementioned water.
5. the decomposition method of the solid residue of claim 1 record is characterized in that aforementioned pressure is that 0.5～40MPa, aforementioned temperature are 150～450 ℃.
6. the decomposition method of a solid residue, separate the volatilization composition distillation residue by-product, that contain the composition that volatilizees when it is characterized in that from the production isocyanic ester, with the solid residue that obtains under the mixture existence condition of the water of gas, liquid or supercritical state or alcohol and water, under the temperature more than 100 ℃, pressure more than the 0.1MPa, heat, be transformed into this solid residue in the corresponding amine of composition compound.
7. the decomposition method of the solid residue of claim 6 record is characterized in that the separation of aforementioned volatilization composition is to carry out in having the two-phase flow pattern evaporation unit of piston sliding.
8. the decomposition method of the solid residue of claim 7 record is characterized in that aforementioned two-phase flow pattern evaporation unit is double cast evaporation unit.
9. the decomposition method of solid residues of claim 7 or 8 records, it is characterized in that, the separation of aforementioned volatilization composition is to be 120～350 ℃ in temperature, and pressure is 1～200 mmhg, is to carry out under 100～700 meter per seconds at two-phase flow pattern evaporation unit exit gas flow velocity.
10. the decomposition method of the solid residue of claim 6 record is characterized in that water is more than 0.1 for the weight ratio of aforementioned solid residue.
11. the decomposition method of the solid residue of claim 6 or 10 records is characterized in that, alcohol is below 5 with respect to the mol ratio of aforementioned water.
12. the treatment process of distillation residue, distillation residue by-product, that contain isocyanic ester heat in having the two-phase flow pattern evaporation unit of piston sliding when it is characterized in that the production isocyanic ester, separating isocyanate from this residue on evaporation, the solid residue that obtains is existed under the situation at the water of gas, liquid or supercritical state or the mixture of alcohol and water, under the temperature more than 100 ℃, pressure more than the 0.1MPa, contact, be transformed into this solid residue in the corresponding amine of composition compound.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24216798 | 1998-08-27 | ||
| JP242167/1998 | 1998-08-27 | ||
| JP19181099A JP4112750B2 (en) | 1998-08-27 | 1999-07-06 | Solid residue decomposition method |
| JP191810/1999 | 1999-07-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1246472A true CN1246472A (en) | 2000-03-08 |
| CN1127475C CN1127475C (en) | 2003-11-12 |
Family
ID=26506906
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99111081A Expired - Fee Related CN1127475C (en) | 1998-08-27 | 1999-08-02 | Method for decomposing solid leavings |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4112750B2 (en) |
| KR (1) | KR100369455B1 (en) |
| CN (1) | CN1127475C (en) |
| TW (1) | TW445250B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104411681A (en) * | 2012-07-11 | 2015-03-11 | 拜耳材料科技股份有限公司 | Method for working up distillation residues from isocyanate production |
| CN106496631A (en) * | 2016-11-03 | 2017-03-15 | 南京工程学院 | The method that overcritical fluid-mixing reclaims carbon fiber enhancement resin base composite material |
| CN114605288A (en) * | 2020-12-03 | 2022-06-10 | 万华化学集团股份有限公司 | High-efficiency separation and recovery process and device for isocyanate polymer |
| CN115819285A (en) * | 2022-10-28 | 2023-03-21 | 宁夏瑞泰科技股份有限公司 | Method for treating distillation still residues containing 1,5-naphthalene diisocyanate |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002340487A (en) * | 2001-05-18 | 2002-11-27 | Noritake Co Ltd | Circulation type heat exchanging method and heat exchanger |
| JP2010053055A (en) * | 2008-08-27 | 2010-03-11 | Nippon Polyurethane Ind Co Ltd | Method for decomposing hexamethylene diisocyanate-based polyurea compound |
| JP2010215519A (en) * | 2009-03-13 | 2010-09-30 | Nippon Polyurethane Ind Co Ltd | Method of decomposing tolylene diisocyanate-based polyurea compound |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3659717B2 (en) * | 1995-11-30 | 2005-06-15 | 株式会社神戸製鋼所 | Chemical plant waste decomposition method and apparatus |
-
1999
- 1999-07-06 JP JP19181099A patent/JP4112750B2/en not_active Expired - Lifetime
- 1999-07-28 TW TW88112765A patent/TW445250B/en active
- 1999-08-02 CN CN99111081A patent/CN1127475C/en not_active Expired - Fee Related
- 1999-08-27 KR KR10-1999-0036026A patent/KR100369455B1/en not_active IP Right Cessation
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104411681A (en) * | 2012-07-11 | 2015-03-11 | 拜耳材料科技股份有限公司 | Method for working up distillation residues from isocyanate production |
| CN104411681B (en) * | 2012-07-11 | 2017-03-29 | 科思创德国股份有限公司 | Method of the post processing by the bottoms for preparing isocyanates generation |
| CN106496631A (en) * | 2016-11-03 | 2017-03-15 | 南京工程学院 | The method that overcritical fluid-mixing reclaims carbon fiber enhancement resin base composite material |
| CN114605288A (en) * | 2020-12-03 | 2022-06-10 | 万华化学集团股份有限公司 | High-efficiency separation and recovery process and device for isocyanate polymer |
| CN114605288B (en) * | 2020-12-03 | 2024-02-02 | 万华化学集团股份有限公司 | Efficient separation and recovery process and device for isocyanate polymer |
| CN115819285A (en) * | 2022-10-28 | 2023-03-21 | 宁夏瑞泰科技股份有限公司 | Method for treating distillation still residues containing 1,5-naphthalene diisocyanate |
Also Published As
| Publication number | Publication date |
|---|---|
| KR100369455B1 (en) | 2003-01-24 |
| KR20000017605A (en) | 2000-03-25 |
| TW445250B (en) | 2001-07-11 |
| JP4112750B2 (en) | 2008-07-02 |
| CN1127475C (en) | 2003-11-12 |
| JP2000136264A (en) | 2000-05-16 |
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