CN113996280A - Solid base catalyst for hydrolyzing TDI tar residue and application thereof - Google Patents

Solid base catalyst for hydrolyzing TDI tar residue and application thereof Download PDF

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CN113996280A
CN113996280A CN202111243303.2A CN202111243303A CN113996280A CN 113996280 A CN113996280 A CN 113996280A CN 202111243303 A CN202111243303 A CN 202111243303A CN 113996280 A CN113996280 A CN 113996280A
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base catalyst
solid base
solid
tdi
tdi tar
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CN113996280B (en
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孙道华
何旺
齐丽雪
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Xiamen University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • 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
    • 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 Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a solid base catalyst for hydrolyzing TDI tar residue and application thereof. The solid base catalyst is prepared by combining an impregnation method and an ultrasonic technology, and the general formula of the solid base catalyst is M2O3CaO, wherein M is lanthanum, cerium or zirconium. The method for recovering Toluenediamine (TDA) by hydrolyzing Toluenediisocyanate (TDI) tar residues by adopting the solid alkali catalyst comprises the following steps: after the TDI tar residue is ground, glycol is used as a solvent, a solid base catalyst is adopted for hydrolysis under normal pressure, and the TDI tar residue can be hydrolyzed and important industrial raw material TDA can be recycled without any additional high pressure, so that more effective comprehensive recycling treatment is achieved, and the reduction and harmless treatment targets are achieved.

Description

Solid base catalyst for hydrolyzing TDI tar residue and application thereof
Technical Field
The invention belongs to the technical field of TDI tar residue treatment, and particularly relates to a solid base catalyst for hydrolyzing TDI tar residue and application of the solid base catalyst as an atmospheric hydrolysis catalyst in treatment and recovery of TDI tar residue.
Background
Toluene Diisocyanate (TDI) is one of the main raw materials in the polyurethane industry, and is mainly used for preparing polyurethane soft foams, hard foams, adhesives, coatings and elastomers, and is also used for surface processing of natural rubber, textile processing and the like. It is mainly prepared by a Toluenediamine (TDA) phosgene method. The isonitrile ester functional group of TDI has high reactivity and can react with various substances (such as water, alcohol, amine and the like) containing active hydrogen, so that a large amount of tar residue by-products are generated. The TDI tar residue has complex by-product components, mainly comprises polyurea and polydiurea, contains a small amount of TDI and tar, and also contains a small amount of substances such as carbodiimide, allophanate and the like.
The simple method for treating TDI tar slag comprises burying treatment and incineration treatment, but the two methods do not meet the requirements of current green environmental protection, the burying treatment needs to occupy land, and the incineration treatment can generate a large amount of CO2And nitrogen oxides, which cause secondary pollution to the environment.
The distillation treatment of TDI residues to recover some chemical raw materials is a widely applied method for solving the residues. It is reported that methyl o-phenylenediamine is extracted from TDI hydrogenated organic residue by dissolving TDI organic residue and vacuum purifying and rectifying, then the methyl o-phenylenediamine is reacted with excessive sodium nitrite solution, and then the obtained product is acidified, rinsed, vacuum dewatered, rectified and purified to obtain the methyl benzotriazole product. Also, TDI tar residues are efficiently treated by mixing them with diphenylmethane diisocyanate and partially converting them into polyurethane by distillation. However, the distillation process has high requirements on equipment, temperature and pressure.
The hydrolysis treatment of TDI residues is the current leading-edge method. Reports show that the TDI residue is hydrolyzed under normal pressure to obtain a 2, 4-diaminotoluene product by adding a high-boiling point solvent under the condition of catalytic hydrolysis by caustic soda; or hydrolyzing the diethyl isophthalate (DEIP) in the residue by sodium hydroxide solution to obtain isophthalic acid (IPA) product.
Most of the existing technologies for preparing TDA by hydrolyzing TDI tar residues adopt liquid alkali catalysts and are carried out under the conditions of high temperature and high pressure, a pressure-resistant closed reactor is needed, the production equipment cost is high, a large amount of soluble inorganic alkali is consumed, the production equipment is easy to corrode, a large amount of wastewater is generated, the separation and recovery are difficult in the later period, and the hydrolytic industrial treatment cannot be realized so far, so that most of the TDI tar residues are still buried deeply.
Therefore, how to solve the problems that the prior hydrolysis needs to adopt a high-temperature and high-pressure condition, the mass transfer resistance of the hydrolysis is large under a normal pressure condition, a large amount of waste water is generated, the catalyst is difficult to recycle and the like according to the characteristics of the main components of the TDI tar residue becomes the key of the hydrolysis industrial treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the solid base catalyst for hydrolyzing TDI tar residue and the application thereof, solves the problem of harsh conditions of the method for treating the TDI tar residue in the background technology, also solves the problem of the application of the liquid base catalyst, and realizes the industrial hydrolysis treatment of the TDI tar residue.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: provides a solid base catalyst for hydrolyzing TDI tar residue, wherein the general formula of the solid base catalyst is M2O3CaO, wherein M is lanthanum, cerium or zirconium.
In a preferred embodiment of the present invention, the preparation method comprises the following steps:
(1) placing CaO in a conical flask, adding deionized water and stirring;
(2) preparing a nitrate aqueous solution of M, pouring the nitrate aqueous solution into the conical flask filled with CaO in the step (1), and stirring to obtain a mixed liquid; wherein, M: the molar weight ratio of Ca is 0.05-0.5;
(3) placing the mixed liquid obtained in the step (2) in an ultrasonic cleaning instrument for 20-30 min;
(4) putting the mixture into an oven at 80 ℃ for drying overnight, then putting the mixture into a constant temperature muffle furnace for calcining for 3 hours at the calcining temperature of 700-950 ℃, and collecting a product, namely M2O3CaO solid base catalyst.
In a preferred embodiment of the present invention, in the step (2), M: the molar weight ratio of Ca is 0.1-0.25.
In a preferred embodiment of the present invention, the calcination temperature in the step (4) is 800-900 ℃.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the application of the solid base catalyst is provided, which is used for hydrolyzing TDI tar residues under normal pressure to recover TDA. The method specifically comprises the following steps:
(1) grinding the TDI tar residue raw material into powder, weighing the TDI tar residue powder, placing the powder into an oil bath pan with a stirring device, and mixing the powder with the TDI tar residue powder according to a solid-to-liquid ratio of 1: adding 1-20 kg/L of glycol solvent, and condensing and refluxing for 70min at 180 ℃ to obtain a solid-liquid mixture A containing TDI tar residues;
(2) cooling the solid-liquid mixture A to 80-140 ℃, adding a solid base catalyst for hydrolysis reaction for 3-11 h to obtain a hydrolyzed solid-liquid mixture B, and cooling to normal temperature;
(3) and (3) performing solid-liquid separation on the hydrolysis solid-liquid mixture B to respectively obtain hydrolysis filtrate and a solid alkali catalyst, washing the solid alkali catalyst for a plurality of times by using absolute ethyl alcohol, and drying and recovering.
In a preferred embodiment of the present invention, in the step (2), the temperature of the solid-liquid mixture a is reduced to 100 to 120 ℃.
In a preferred embodiment of the present invention, the solid base catalyst is in a powder form, and the amount of the solid base catalyst is 10 to 90% of the TDI tar residue powder.
In a preferred embodiment of the present invention, the amount of the solid base catalyst is 30-70% of the TDI tar residue powder.
In a preferred embodiment of the present invention, in the step (2), the hydrolysis reaction time is 5 to 9 hours.
Compared with the background technology, the technical scheme has the following advantages:
1. based on the alkaline hydrolysis principle of TDI tar residues, namely the nucleophilic addition reaction of oxoanions (hydroxide ions or alkoxy anions) to specific functional groups (carbamido groups or ester groups), the invention adopts a heterogeneous solid alkaline catalyst to replace the traditional homogeneous soluble alkaline catalyst, optimizes the hydrolysis process, and overcomes the defects of harsh conditions, high cost, complex working procedures, secondary pollution caused by the treatment process and the like in the conventional method for treating the TDI tar residues.
2. The solid base catalyst is easy to separate from the product, does not generate a large amount of wastewater in the treatment process, can be recycled for multiple times, has obvious advantages for continuous industrial production, realizes the recycling of the catalyst while the TDI tar residue is effectively hydrolyzed and converted into TDA, and reduces the process difficulty and the cost.
3. The method can realize the low-cost, rapid, mild and effective hydrolysis of the TDI tar residue, and can realize the environmental protection concepts of no wastewater discharge and catalyst recycling.
Detailed Description
Example 1
This example is a La2O3The preparation method of the CaO solid base catalyst comprises the following steps:
2g of CaO is weighed and placed in a conical flask, and deionized water is added and stirred; configuration La (NO)3)3An aqueous solution satisfying La: ca in a molar ratio of 0.2, adding La (NO)3)3Pouring the aqueous solution into the conical flask filled with CaO, and stirring at normal temperature; placing the obtained white turbid liquid in a 100w power ultrasonic cleaning instrument for 30 min; drying in 80 deg.C oven overnight, calcining in 850 deg.C constant temperature muffle furnace for 3 hr, and collecting product, i.e. La2O3the/CaO solid base catalyst is ground into powder and stored in a closed container.
The solid base catalyst of the embodiment is adopted to hydrolyze TDI tar residues to recover TDA, and the method comprises the following specific steps:
the TDI tar residue was ground to a powder of 80 mesh size. Weighing 1g of TDI powder, placing the TDI powder in an oil bath pan with a reflux device, and mixing the TDI powder and the TDI powder according to a solid-to-liquid ratio of 1: 20(kg/L) of ethylene glycol solvent is added, and the mixture is condensed and refluxed for 70min at 180 ℃ to obtain a mixture A containing TDI tar residue. The oil bath pan is cooled to 110 ℃, and 0.5g (50 percent, mass fraction) of La is added2O3CaO solid base catalyst, and carrying out hydrolysis reaction for 7 hours to obtain a hydrolysis mixture B. After the reaction is finished, the reaction product is cooled to room temperature, and is centrifuged to obtain hydrolysis filtrate and a catalyst, and the yield of the toluenediamine is 31.02% through liquid chromatography detection. Washing the catalyst for 3-5 times by using a small amount of absolute ethyl alcohol, and drying for later use. The TDA yield obtained after the catalyst is recycled for three times still keeps the initial 86%, and the catalyst has good recycling performance.
Example 2
This example describes the preparation of a solid base catalyst with La (NO)3)3By conversion to Ce (NO)3)3Preparation of Ce under otherwise the same conditions as in example 12O3CaO solid base catalyst. The TDI tar residue was hydrolyzed under the same conditions as in example 1, and the yield of p-toluenediamine was quantitatively determined to be 21.78%.
Example 3
This example describes the preparation of a solid base catalyst with La (NO)3)3By conversion to Zr (NO)3)3Zr preparation in the same manner as in example 12O3CaO solid base catalyst. The TDI tar residue was hydrolyzed under the same conditions as in example 1, and the yield of p-toluenediamine was quantitatively measured to be 20.79%.
Example 4
This example prepared the solid base catalyst by mixing La: the Ca molar ratio was changed to 0.15, and the other preparation conditions were the same as in example 1. The hydrolysis conditions were the same as in example 1, and the yield of p-tolylenediamine was quantitatively determined to be 25.52%.
Example 5
This example prepared the solid base catalyst by mixing La: the Ca molar ratio was changed to 0.25, and the other preparation conditions were the same as in example 1. The hydrolysis conditions were the same as in example 1, and the yield of p-tolylenediamine was quantitatively determined to be 26.75%.
Example 6
In this example, the calcination temperature was changed to 800 ℃ in the preparation of the solid base catalyst, and other preparation conditions were the same as in example 1. The hydrolysis conditions were the same as in example 1, and the yield of p-tolylenediamine was quantitatively determined to be 30.44%.
Example 7
In this example, the calcination temperature was changed to 900 ℃ in the preparation of the solid base catalyst, and other preparation conditions were the same as in example 1. The hydrolysis conditions were the same as in example 1, and the yield of p-tolylenediamine was quantitatively determined to be 30.51%.
Example 8
In this example, the solid base catalyst of example 1 was used, and the temperature of the oil bath was changed to 90 ℃ for the hydrolysis of TDI tar residue, and the yield of p-tolylenediamine was quantitatively determined to be 22.46% under the same conditions as in example 1.
Example 9
In this example, the solid base catalyst of example 1 was used, and the temperature of the oil bath was changed to 130 ℃ during the hydrolysis of TDI tar residue, and the yield of p-tolylenediamine was quantitatively determined to be 28.01% under the same conditions as in example 1.
Example 10
In this example, the solid base catalyst of example 1 was used, and the amount of the catalyst added was changed to 0.3g in the hydrolysis of TDI tar residue, and the yield of p-tolylenediamine was quantitatively determined to be 28.65% under the same conditions as in example 1.
Example 11
In this example, the solid base catalyst of example 1 was used, and the amount of the catalyst added was changed to 0.7g in the hydrolysis of TDI tar residue, and the yield of p-tolylenediamine was quantitatively determined to be 29.84% under the same conditions as in example 1.
Example 12
In this example, the solid base catalyst of example 1 was used, and the holding time was changed to 5 hours for the hydrolysis of TDI tar residue, and the yield of p-tolylenediamine was quantitatively determined to be 26.46% under the same conditions as in example 1.
Example 13
In this example, the solid base catalyst of example 1 was used, and the holding time was changed to 9 hours for the hydrolysis of TDI tar residue, and the yield of p-tolylenediamine was quantitatively determined to be 28.20% under the same conditions as in example 1.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A solid base catalyst for hydrolyzing TDI tar residue is characterized in that: the general formula of the solid base catalyst is M2O3CaO, wherein M is lanthanum, cerium or zirconium.
2. The solid base catalyst for hydrolyzing TDI tar residues as claimed in claim 1, wherein: the preparation method comprises the following steps:
(1) placing CaO in a conical flask, adding deionized water and stirring;
(2) preparing a nitrate aqueous solution of M, pouring the nitrate aqueous solution into the conical flask filled with CaO in the step (1), and stirring to obtain a mixed liquid; wherein, M: the molar weight ratio of Ca is 0.05-0.5;
(3) placing the mixed liquid obtained in the step (2) in an ultrasonic cleaning instrument for 20-30 min;
(4) putting the mixture into an oven at 80 ℃ for drying overnight, then putting the mixture into a constant temperature muffle furnace for calcining for 3 hours at the calcining temperature of 700-950 ℃, and collecting a product, namely M2O3CaO solid base catalyst.
3. The solid base catalyst for hydrolyzing TDI tar residues as claimed in claim 2, wherein: m in the step (2): the molar weight ratio of Ca is 0.1-0.25.
4. The solid base catalyst for hydrolyzing TDI tar residues as claimed in claim 2, wherein: the calcination temperature in the step (4) is 800-900 ℃.
5. The use of a solid base catalyst according to any one of claims 1 to 4, wherein: the method is used for hydrolyzing TDI tar residues under normal pressure to recover TDA.
6. The use of a solid base catalyst according to claim 5, wherein: the method comprises the following steps:
(1) grinding the TDI tar residue raw material into powder, weighing the TDI tar residue powder, placing the powder into an oil bath pan with a stirring device, and mixing the powder with the TDI tar residue powder according to a solid-to-liquid ratio of 1: adding 1-20 kg/L of glycol solvent, and condensing and refluxing for 70min at 180 ℃ to obtain a solid-liquid mixture A containing TDI tar residues;
(2) cooling the solid-liquid mixture A to 80-140 ℃, adding a solid base catalyst for hydrolysis reaction for 3-11 h to obtain a hydrolyzed solid-liquid mixture B, and cooling to normal temperature;
(3) and (3) performing solid-liquid separation on the hydrolysis solid-liquid mixture B to respectively obtain hydrolysis filtrate and a solid alkali catalyst, washing the solid alkali catalyst for a plurality of times by using absolute ethyl alcohol, and drying and recovering.
7. The use of a solid base catalyst according to claim 6, wherein: in the step (2), the temperature of the solid-liquid mixture A is reduced to 100-120 ℃.
8. The use of a solid base catalyst according to claim 6, wherein: the solid base catalyst is powdery, and the using amount of the solid base catalyst is 10-90% of that of TDI tar residue powder.
9. The use of a solid base catalyst according to claim 6, wherein: the dosage of the solid base catalyst is 30-70% of TDI tar residue powder.
10. The use of a solid base catalyst according to claim 6, wherein: in the step (2), the hydrolysis reaction time is 5-9 h.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004108656A1 (en) * 2003-06-09 2004-12-16 Hanwha Chemical Corporation Method for recovering toluene diamine from high boiling tar residue discharged from toluene diisocyanate preparation process
CN102264466A (en) * 2008-11-05 2011-11-30 韦恩州立大学 Calcium and lanthanum solid base catalysts for transesterification
US20130041182A1 (en) * 2011-01-27 2013-02-14 Cangzhou Fengyuan Environmental Protection Science And Technology Co., Ltd. Recovery of toluene diamine from tar waste residue discharged from synthesis process of toluene diisocyanate
CN105294406A (en) * 2015-11-18 2016-02-03 常州大学 Method for catalyzed synthesis of polyformaldehyde dimethyl ether by solid alkali CaO/ZrO2 catalyst
CN107876037A (en) * 2017-12-08 2018-04-06 湖南长岭石化科技开发有限公司 Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis
CN110000193A (en) * 2019-04-16 2019-07-12 福建工程学院 A method of for disposing TDI tar residue
CN110511132A (en) * 2019-09-20 2019-11-29 兰州理工大学 A kind of TDI residue method for hydrolysis for using dolomite as catalyst

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004108656A1 (en) * 2003-06-09 2004-12-16 Hanwha Chemical Corporation Method for recovering toluene diamine from high boiling tar residue discharged from toluene diisocyanate preparation process
CN102264466A (en) * 2008-11-05 2011-11-30 韦恩州立大学 Calcium and lanthanum solid base catalysts for transesterification
US20130041182A1 (en) * 2011-01-27 2013-02-14 Cangzhou Fengyuan Environmental Protection Science And Technology Co., Ltd. Recovery of toluene diamine from tar waste residue discharged from synthesis process of toluene diisocyanate
CN105294406A (en) * 2015-11-18 2016-02-03 常州大学 Method for catalyzed synthesis of polyformaldehyde dimethyl ether by solid alkali CaO/ZrO2 catalyst
CN107876037A (en) * 2017-12-08 2018-04-06 湖南长岭石化科技开发有限公司 Solid base catalyst, its preparation method, application and the method that dihydric alcohol diacetate is prepared using its catalysis
CN110000193A (en) * 2019-04-16 2019-07-12 福建工程学院 A method of for disposing TDI tar residue
CN110511132A (en) * 2019-09-20 2019-11-29 兰州理工大学 A kind of TDI residue method for hydrolysis for using dolomite as catalyst

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