CN114539072B - Method for co-production of diaminotoluene and ethylene urea derivatives by aminolysis of tar residues - Google Patents
Method for co-production of diaminotoluene and ethylene urea derivatives by aminolysis of tar residues Download PDFInfo
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- CN114539072B CN114539072B CN202210211220.3A CN202210211220A CN114539072B CN 114539072 B CN114539072 B CN 114539072B CN 202210211220 A CN202210211220 A CN 202210211220A CN 114539072 B CN114539072 B CN 114539072B
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- ethylene urea
- aminolysis
- ethylenediamine
- tdi tar
- diaminotoluene
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- 239000011273 tar residue Substances 0.000 title claims abstract description 60
- 238000007098 aminolysis reaction Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 26
- DYFXGORUJGZJCA-UHFFFAOYSA-N phenylmethanediamine Chemical compound NC(N)C1=CC=CC=C1 DYFXGORUJGZJCA-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title abstract description 5
- MGPYDQFQAJEDIG-UHFFFAOYSA-N ethene;urea Chemical class C=C.NC(N)=O MGPYDQFQAJEDIG-UHFFFAOYSA-N 0.000 title abstract 2
- YAMHXTCMCPHKLN-UHFFFAOYSA-N imidazolidin-2-one Chemical compound O=C1NCCN1 YAMHXTCMCPHKLN-UHFFFAOYSA-N 0.000 claims abstract description 50
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000005185 salting out Methods 0.000 claims abstract description 12
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000012071 phase Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000012043 crude product Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 6
- 238000005915 ammonolysis reaction Methods 0.000 claims description 5
- 238000011033 desalting Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 239000011269 tar Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 18
- 238000000746 purification Methods 0.000 abstract description 6
- 239000000543 intermediate Substances 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract 1
- 239000004202 carbamide Substances 0.000 abstract 1
- 238000000638 solvent extraction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 238000009835 boiling Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- FAFWKDXOUWXCDP-UHFFFAOYSA-N ethenylurea Chemical class NC(=O)NC=C FAFWKDXOUWXCDP-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/62—Preparation of compounds containing amino groups bound to a carbon skeleton by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/32—One oxygen atom
- C07D233/34—Ethylene-urea
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of TDI tar residue recycling, and particularly relates to a method for co-producing diaminotoluene and ethylene urea derivatives by using tar residue aminolysis, which is characterized in that urea substances in TDI tar residue and ethylenediamine are subjected to aminolysis reaction to obtain diaminotoluene and ethylene urea organic chemical intermediates. According to the invention, through stepwise feeding, ethylenediamine is utilized to hydrolyze TDI tar residues, and the aminolysis product is subjected to salting out by saturated saline solution, solvent extraction by an organic solvent, hydrazine hydrate reduction, recrystallization, separation and purification, and the purity can reach more than 97%. The invention has mild process condition, low equipment investment cost and high product purity, and can realize industrialized mass production.
Description
Technical Field
The invention belongs to the technical field of toluene diisocyanate tar residue recycling, and particularly relates to a method for co-producing diaminotoluene and ethylene urea derivatives by aminolysis of tar residues.
Background
Patent CN105985247a mentions a high-temperature high-pressure hydrolysis method of TDI tar residue, by raising the pressure of the reaction system, raising the reaction temperature of hydrolysis, and adding a catalyst to hydrolyze the tar residue into TDA. The method can realize the resource utilization of tar residues, but needs high-temperature and high-pressure reaction conditions, which puts higher requirements on the reactor, and meanwhile, the hydrolysis reaction time is long, a large amount of alkali catalyst and solvent are required to be consumed, the separation energy consumption is high, the solid waste is much, and the investment is large.
Patent CN102633651A, CN103787894a mentions an atmospheric hydrolysis method of TDI tar residue, which increases the boiling point of the system by introducing a high boiling point polyol solvent, so that the hydrolysis reaction of the tar residue can still reach a very high reaction temperature under normal pressure or low pressure, and the tar residue is depolymerized into TDA under normal pressure. However, the tar residue is introduced with a large amount of high boiling point solvent, so that the subsequent separation difficulty is improved, and meanwhile, the problems of low hydrolysis reaction rate, large catalyst consumption, large solid waste and the like still exist.
Patent CN113480435a mentions a method for aminolysis of TDI tar residue by introducing polyamine as a reactant, a solvent so that the tar residue is depolymerized to TDA at normal pressure. The method can achieve higher TDA yield and selectivity, can completely react within 15-30 min without introducing other alkali catalysts, solvents and water, greatly reduces the dosage of the solvents and the alkali catalysts, and can produce the imidazolidone substances with high added value as byproducts. However, when ethylenediamine is used as a solvent, the boiling point of ethylenediamine is 116 ℃, the consumption of TDI tar residue and ethylenediamine is 1:3, and excessive ethylenediamine can limit the reaction temperature, so that the reaction temperature of aminolysis is limited by the boiling point of ethylenediamine, the yield of the TDA is only 36.98%, the subsequent separation of the product adopts a method of crude distillation followed by rectification, and the purity of the TDA and ethylene urea is relatively low (95%).
According to the TDI tar residue aminolysis co-production diaminotoluene (TDA) and ethylene urea and product separation and purification process, ethylenediamine is simultaneously used as a reactant, a solvent and a catalyst, the aminolysis reaction temperature is improved under normal pressure conditions through optimization of the aminolysis process, the TDA yield is remarkably improved, the aminolysis products diaminotoluene and ethylene urea are separated and purified through salting-out, filtering, extraction, concentration, crystallization, reduction and recrystallization processes of an aminolysis solution, a high-quality product with the purity of more than 97% is obtained, large-scale high-temperature rectification separation equipment is not needed in the separation process, and the separation energy consumption and the equipment investment are low.
Disclosure of Invention
In order to overcome the defects and shortcomings of the existing TDI tar residue ammonolysis process, the invention aims to provide a method for producing diaminotoluene and ethylene urea derivatives by ammonolysis of tar residues, which improves the degradation rate by feeding materials step by step and separates TDI tar residue ammonolysis products by adopting salting-out, filtering, extracting, concentrating, crystallizing, reducing and recrystallizing processes.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for co-producing diaminotoluene and ethylene urea derivatives by aminolysis of tar residues uses ethylenediamine as a reactant, a solvent and a catalyst to aminolysis of TDI tar residues to prepare diaminotoluene and ethylene urea derivatives as an organic chemical intermediate; the reaction formula involved is:
。
the method for co-producing the diaminotoluene and the ethylene urea derivatives by the ammonolysis of the tar residues specifically comprises the following steps:
(1) Adding TDI tar slag powder and ethylenediamine in a certain proportion into a reaction kettle in batches, heating to a specified temperature under normal pressure, and reacting for a period of time under mechanical stirring to obtain aminolysis solution;
(2) After the amine solution obtained in the step (1) is cooled to room temperature, adding a certain amount of saturated saline solution for salting out, filtering to remove the tar residues which are not reacted, and collecting filtrate;
(3) Extracting the filtrate obtained in the step (2) with a certain amount of organic solvent for 3 times, and separating an organic phase and a water phase; concentrating the organic phase, and then cooling and crystallizing to obtain diaminotoluene; concentrating and desalting the water phase, recrystallizing with methanol to obtain a crude product of the ethylene urea derivatives, reducing and decoloring the crude product of the ethylene urea derivatives with 80wt% hydrazine hydrate, and recrystallizing with a mixed solution of acetone and ethyl acetate to obtain the ethylene urea derivatives.
The mass ratio of the TDI tar residue powder to the ethylenediamine in the step (1) is 3:1.
The batch feeding reaction mode in the step (1) is specifically as follows: adding TDI tar residue powder into a reaction kettle, adding 50% of the total feeding mass of ethylenediamine under mechanical stirring, heating and refluxing at 140 ℃ for 30min, dropwise adding the rest ethylenediamine into the reaction kettle, and reacting at 200 ℃ for 30min.
The mass ratio of the saturated saline solution to the aminolysis solution in the step (2) is 2:1.
The organic solvent in the step (3) is one or more of ethyl acetate, dichloromethane and chloroform; the dosage of the organic solvent is 3 times of the mass of the filtrate.
The amount of the hydrazine hydrate of 80wt% in the step (3) is 5% of the mass of the crude product of the ethylene urea derivative.
And (3) the mass ratio of the acetone to the ethyl acetate in the mixed solution of the acetone and the ethyl acetate in the step (3) is 10:1.
The invention has the beneficial effects that:
according to the invention, through two-step feeding and two-step heating, the reaction temperature of ethylenediamine as an aminolysis TDI tar residue reactant and a solvent is increased, the limit of low boiling point of ethylenediamine is broken through, the original reaction which needs to be carried out under pressure can be carried out, the high-temperature reaction can be carried out under normal pressure, the reaction condition is greatly reduced, and the aminolysis rate, namely the TDA yield, is increased; the salting-out, filtering, extracting, concentrating, crystallizing, reducing, recrystallizing, separating and purifying technology developed by the invention can realize the separation, purification and decoloration of TDA and ethylene urea high boiling point products on the basis of not needing large-scale high-temperature rectifying equipment for the TDI tar residue aminolysis product, and lays a foundation for the industrialization of the TDI tar residue resource utilization.
Drawings
FIG. 1 is a flow chart of a process for co-producing TDA and ethylene urea and separating and purifying products by using ethylenediamine aminolysis TDI tar residues.
Detailed description of the preferred embodiments
The invention discloses a process flow chart for co-producing TDA and ethylene urea and separating and purifying products by using ethylenediamine aminolysis TDI tar residues, which is shown in figure 1.
The invention is further illustrated by the following specific examples. The scope of the invention is not limited to the following examples.
Example 1
(1) Ethylenediamine aminolysis of TDI tar residue: crushing TDI tar residue, sieving with a 100-mesh sieve to obtain TDI tar residue powder, weighing 60 g TDI tar residue powder, adding 10g of ethylenediamine into a reaction kettle under mechanical stirring, heating and refluxing at 140 ℃ for 30min, then dropwise adding 10g of ethylenediamine into the reaction kettle, and reacting at 200 ℃ for 30min to obtain an ethylenediamine aminolysis solution; detecting the contents of TDA and ethylene urea derivatives in ethylenediamine aminolysis solution by liquid chromatography, calculating to obtain the reaction yield of TDA as 52.42% and ethylene urea derivatives as 97.22%, detecting ethylene urea derivatives by gas chromatography-mass spectrometry, determining it as 2-imidazolidone, CAS:120-93-4.
(2) Salting out and filtering ethylenediamine aminolysis solution: after the aminolysis solution of ethylenediamine obtained in (1) is cooled to room temperature, adding saturated saline water twice the mass of the aminolysis solution into the aminolysis solution for salting out, filtering to remove unreacted TDI tar residues, and collecting filtrate.
(3) Separation and purification of TDA and ethylene urea derivatives: extracting the filtrate obtained in the step (2) with ethyl acetate 3 times of the mass of the filtrate for 3 times, and separating an ethyl acetate phase and a water phase; concentrating ethyl acetate phase by rotary evaporation at 55deg.C under 0.1 MPa, cooling to-4deg.C, cooling and crystallizing to obtain TDA with purity of 98.40% and separation yield of 70.25%; evaporating and concentrating the water phase under reduced pressure, filtering and desalting, recrystallizing methanol to obtain a crude product of the ethylene urea derivatives, adding 80wt% of hydrazine hydrate with the mass of 5% of the crude product of the ethylene urea derivatives as a reducing agent into the crude product of the ethylene urea derivatives, adding Pd/C with the mass of 0.5% of the crude product of the ethylene urea derivatives as a catalyst, adding distilled water with the mass of 10 times of the crude product of the ethylene urea derivatives as a solvent, reducing and decoloring at 80 ℃ for 3 h, filtering while the product is hot, and using acetone as a solid with the mass ratio: recrystallizing the mixed solution of ethyl acetate=10:1 to obtain the ethylene urea derivative with the purity of 97.20 percent and the separation yield of 69.78 percent.
Example 2
(1) Ethylenediamine aminolysis of TDI tar residue: the TDI tar residue is crushed, then the TDI tar residue powder is obtained through a 100-mesh sieve, 60 g of the TDI tar residue powder is weighed and added into a reaction kettle, 10g of ethylenediamine is added under mechanical stirring, heating reflux is carried out for 30min at 140 ℃, then 10g of ethylenediamine is added into the reaction kettle dropwise, and reaction is carried out for 30min at 200 ℃ to obtain an ethylenediamine aminolysis solution.
(2) Salting out and filtering ethylenediamine aminolysis solution: after the aminolysis solution of ethylenediamine obtained in (1) is cooled to room temperature, adding saturated saline water twice the mass of the aminolysis solution into the aminolysis solution for salting out, filtering to remove unreacted TDI tar residues, and collecting filtrate.
(3) Separation and purification of TDA and ethylene urea derivatives: extracting the filtrate obtained in the step (2) with dichloromethane 3 times of the filtrate by mass for 3 times, and separating a dichloromethane phase and a water phase; concentrating dichloromethane phase by rotary evaporation under vacuum degree of 50 deg.C and 0.1 MPa, cooling to-4deg.C, cooling and crystallizing to obtain TDA with purity of 95.20% and separation yield of 86.33%; concentrating the water phase by reduced pressure evaporation, filtering, desalting, recrystallizing the methanol to obtain a crude product of the ethylene urea derivative; adding 80wt% hydrazine hydrate with the mass of 5% of the raw product of the ethylene urea derivatives as a reducing agent into the raw product of the ethylene urea derivatives, adding Pd/C with the mass of 0.5% of the raw product of the ethylene urea derivatives as a catalyst, adding distilled water with the mass of 10 times of the raw product of the ethylene urea derivatives as a solvent, reducing and decoloring at 80 ℃ for 3 h, filtering while the mixture is hot, and using acetone with the mass ratio of the obtained solid: recrystallizing the mixed solution of ethyl acetate=10:1 to obtain the ethylene urea derivative with the purity of 90.22 percent and the separation yield of 80.35 percent.
Example 3
(1) Ethylenediamine aminolysis of TDI tar residue: the TDI tar residue is crushed, then the TDI tar residue powder is obtained through a 100-mesh sieve, 60 g of the TDI tar residue powder is weighed and added into a reaction kettle, 10g of ethylenediamine is added under mechanical stirring, heating reflux is carried out for 30min at 140 ℃, then 10g of ethylenediamine is added into the reaction kettle dropwise, and reaction is carried out for 30min at 200 ℃ to obtain an ethylenediamine aminolysis solution.
(2) Salting out and filtering ethylenediamine aminolysis solution: after the aminolysis solution of ethylenediamine obtained in (1) is cooled to room temperature, adding saturated saline water twice the mass of the aminolysis solution into the aminolysis solution for salting out, filtering to remove unreacted TDI tar residues, and collecting filtrate.
(3) Separation and purification of TDA and ethylene urea derivatives: extracting the filtrate obtained in the step (2) with 3 times of chloroform for 3 times, and separating a chloroform phase and a water phase; concentrating chloroform phase by rotary evaporation at 55deg.C under 0.1 MPa, cooling to-4deg.C, cooling and crystallizing to obtain TDA with purity of 94.97% and separation yield of 85.71%; concentrating the water phase by reduced pressure evaporation, filtering, desalting, recrystallizing the methanol to obtain a crude product of the ethylene urea derivative; adding 80wt% hydrazine hydrate with the mass of 5% of the raw product of the ethylene urea derivatives as a reducing agent into the raw product of the ethylene urea derivatives, adding Pd/C with the mass of 0.5% of the raw product of the ethylene urea derivatives as a catalyst, adding distilled water with the mass of 10 times of the raw product of the ethylene urea derivatives as a solvent, reducing and decoloring at 80 ℃ for 3 h, filtering while the mixture is hot, and using acetone with the mass ratio of the obtained solid: recrystallizing the mixed solution of ethyl acetate=10:1 to obtain the ethylene urea derivative with the purity of 89.32 percent and the separation yield of 79.07 percent.
Example 4
Crushing TDI tar residue, sieving with a 100-mesh sieve to obtain TDI tar residue powder, weighing 60 g TDI tar residue powder, adding into a reaction kettle, adding 20g of ethylenediamine under mechanical stirring, and heating and refluxing at 140 ℃ for 1h; after the completion of the reaction, the contents of TDA and vinylurea derivative in the reaction solution were measured by liquid chromatography, and the reaction yield of TDA was calculated to be 0% and the reaction yield of vinylurea derivative was calculated to be 0%.
Example 5
Crushing TDI tar residue, sieving with a 100-mesh sieve to obtain TDI tar residue powder, weighing 60 g TDI tar residue powder, adding the TDI tar residue powder into a reaction kettle, pressurizing to 1.5 MPa by introducing nitrogen, adding 20g of ethylenediamine, and reacting for 1h at 200 ℃; after the completion of the reaction, the contents of TDA and vinylurea derivative in the reaction solution were measured by liquid chromatography, and the reaction yield of TDA was 52.21% and that of vinylurea derivative was 100%.
Claims (6)
1. A method for co-producing diaminotoluene and ethylene urea by the ammonolysis of TDI tar residues is characterized by comprising the following steps: using ethylenediamine as a reactant, a solvent and a catalyst to aminolysis TDI tar residues to prepare diaminotoluene and ethylene urea as an organic chemical intermediate;
the method specifically comprises the following steps:
(1) Adding TDI tar slag powder and ethylenediamine in a certain proportion into a reaction kettle in batches, heating to a specified temperature under normal pressure, and reacting for a period of time under mechanical stirring to obtain aminolysis solution;
(2) After the amine solution obtained in the step (1) is cooled to room temperature, adding a certain amount of saturated saline solution for salting out, filtering to remove unreacted TDI tar residues, and collecting filtrate;
(3) Extracting the filtrate obtained in the step (2) with a certain amount of organic solvent for 3 times, and separating an organic phase and a water phase; concentrating the organic phase, and then cooling and crystallizing to obtain diaminotoluene; concentrating and desalting the water phase, recrystallizing with methanol to obtain a crude product of ethylene urea, reducing and decoloring the crude product of ethylene urea with 80wt% hydrazine hydrate, and recrystallizing with a mixed solution of acetone and ethyl acetate to obtain ethylene urea;
the batch feeding reaction mode in the step (1) is specifically as follows: adding TDI tar residue powder into a reaction kettle, adding 50% of the total feeding mass of ethylenediamine under mechanical stirring, heating and refluxing at 140 ℃ for 30min, dropwise adding the rest ethylenediamine into the reaction kettle, and reacting at 200 ℃ for 30min.
2. The method according to claim 1, characterized in that: the mass ratio of the TDI tar residue powder to the ethylenediamine in the step (1) is 3:1.
3. the method according to claim 1, characterized in that: the mass ratio of the saturated saline solution to the aminolysis solution in the step (2) is 2:1.
4. the method according to claim 1, characterized in that: the organic solvent in the step (3) is one or more of ethyl acetate, dichloromethane and chloroform; the dosage of the organic solvent is 3 times of the mass of the filtrate.
5. The method according to claim 1, characterized in that: the amount of the 80wt% hydrazine hydrate in the step (3) is 5% of the mass of the ethylene urea crude product.
6. The method according to claim 1, characterized in that: the mass ratio of the acetone to the ethyl acetate in the mixed solution of the acetone and the ethyl acetate in the step (3) is 10:1.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4506040A (en) * | 1983-08-01 | 1985-03-19 | Olin Corporation | Preparation of a stable dispersion from TDI residue and its use in the production of polyurethane compositions |
| US5902459A (en) * | 1996-06-10 | 1999-05-11 | Basf Corporation | Recovery of products from toluenediisocyanate residues |
| KR20010001488A (en) * | 1999-06-04 | 2001-01-05 | 김충섭 | A process for toluenediamine recovery |
| CN110000193A (en) * | 2019-04-16 | 2019-07-12 | 福建工程学院 | A method of for disposing TDI tar residue |
| CN113480435A (en) * | 2021-08-06 | 2021-10-08 | 福州大学 | Method for aminolysis of tar residues and recovery of organic resources |
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| WO2009127591A2 (en) * | 2008-04-14 | 2009-10-22 | Basf Se | Method for treating residues from the production of isocyanates |
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