CN110511132A - A kind of TDI residue method for hydrolysis for using dolomite as catalyst - Google Patents
A kind of TDI residue method for hydrolysis for using dolomite as catalyst Download PDFInfo
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- CN110511132A CN110511132A CN201910890181.2A CN201910890181A CN110511132A CN 110511132 A CN110511132 A CN 110511132A CN 201910890181 A CN201910890181 A CN 201910890181A CN 110511132 A CN110511132 A CN 110511132A
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- tdi
- residue
- dolomite
- ethylene glycol
- tdi residue
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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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
Abstract
The present invention provides a kind of TDI residue method for hydrolysis for using dolomite as catalyst, comprising the following steps: S1, crushes the solid residue of TDI；S2, using ethylene glycol as reaction medium, TDI residue is added, wherein the mass ratio of TDI residue and ethylene glycol be 1:20~1:25, then it is heated to reflux, wherein reflux temperature is 180-200 DEG C, and return time is that 0.5~2h dissolves TDI residue, obtains TDI residue ethylene glycol mixture；S3, into TDI residue ethylene glycol mixture, reaction is hydrolyzed in addition dolomite and sodium hydroxide solution；S4, reaction product is filtered, dry and is weighed, calculated its and hydrolyze yield.The condition that the present invention is decomposed relative to traditional residue of TDI in the supercritical state, the reaction that TDI residue decomposes in the present invention can be completed under mild conditions, it reduces the loss to equipment while also improving the safety of equipment, the catalyst of this method is low in cost and easily common simultaneously, yield is hydrolyzed also relative to traditional height, convenient for the environmentally friendly hydrolysis process of TDI residue.
Description
Technical field
The invention belongs to TDI residue technology for hydrolyzing fields, and in particular to a kind of TDI residue for using dolomite as catalyst
Method for hydrolysis.
Background technique
TDI is the abbreviation of toluene di-isocyanate(TDI), and TDI is the important foundation chemical materials for manufacturing polyurethane, since TDI is raw
Produce and investment be big, scientific and technological level is high, therefore is also " two big one is high " product generally acknowledged in the world, product be widely used in family,
Building, automobile, coating.Polyurethane is the world six greatly with one of the synthetic material of development prospect, is had wear-resisting, low temperature resistant, resistance to
The functions such as oily and resistance to ozone, achieve fast development in China in recent years.Toluene di-isocyanate(TDI) (TDI) is used as polyurethane industrial
One of primary raw material, the excellent properties and extensive use having due to itself, it has also become using wide in isocyanate compound
One of general kind.
M-phthalic acid is mainly used in the application fields such as unsaturated polyester resin, PET copolymer resins, alkyd resin.I
For the consumption figure of state's unsaturated polyester resin up to 440,000 tons, in-between terephthalate-type unsaturated polyester (UP) is about 50,000 tons, about needs isophthalic
10,000 tons of dioctyl phthalate.
Synthesis TDI reaction process in TDI easily occurs polymerization reaction generate one kind be mainly made of carbamide compounds
Tar.This tar there is certain thermal sensitivity, the especially TDI contained in the tar to be steamed net moment be easier to send out
Raw extruding phenomenon, i.e. moment become the solid with honeycomb gap.Currently, using rectifying column by product in TDI production process
It is steamed from tower top, the bottom product containing a certain amount of TDI and tar is discharged from rectifying column bottom.Rectifying column tower bottom also due to
The reasons such as operation temperature height and residence time are long further generate new tar.In order to guarantee the continuous steady of rectifying tower bottom reboiler
Fixed operation, it is necessary at least retain 50%TDI in the tar of bottom, otherwise reboiler is easy to coking and blocking, and cause the accident parking.
But in toluene di-isocyanate(TDI) manufacturing process, tar waste is generated as by-product, and in the past, it will
It fills or puts into ocean, so as to cause soil pollution and water pollution.In addition, the processing method of dislocation waste has burning
Method, and cause to be only second to fill or put into the environment of ocean to ask because generating nitrogen oxides, oxysulfide, dioxin etc. when burning
Topic, influences the resolution process of TDI residue.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of white clouds masonry
For the TDI residue method for hydrolysis of catalyst, environmental pollution will cause to solve TD residue treatment mentioned above in the background art
The problem of.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of TDI using dolomite as catalyst
Residue method for hydrolysis, comprising the following steps:
S1, the solid residue of TDI is crushed；
S2, using ethylene glycol as reaction medium, TDI residue is added, wherein the mass ratio of TDI residue and ethylene glycol be 1:20
~1:25, is then heated to reflux, and wherein reflux temperature is 180-200 DEG C, and return time is that 0.5~2h dissolves TDI residue, obtains
TDI residue ethylene glycol mixture；
S3, into TDI residue ethylene glycol mixture, reaction is hydrolyzed in addition dolomite and sodium hydroxide solution；
S4, reaction product is filtered, dry and is weighed, calculated its and hydrolyze yield.
Preferably, the dolomite described in S3 is specially to pass through 3h calcination processing at a temperature of 800 DEG C.
Preferably, the sodium hydroxide solution described in S3 is specially that 5g sodium hydroxide is dissolved in 20ml distilled water and being made.
Preferably, the reaction temperature in S3 is 90~100 DEG C, and the reaction time is 5~7h.
Compared with the prior art, the present invention has the following advantages:
The condition that the present invention is decomposed relative to the traditional residue of TDI in the supercritical state, TDI residue decomposes in the present invention
Reaction can complete under mild conditions, reduce to equipment loss and meanwhile also improve the safety of equipment, together
When this method catalyst it is low in cost and easily common, also relative to traditional height, hydrolyze yield can reach hydrolysis yield
69%, there are also the raw material of this high industrial value of TDI in hydrolysate.It can greatly realize refuse reclamation again
Recycling, convenient for the environmental protection hydrolysis of TDI residue.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1, the present invention provide a kind of technical solution: a kind of TDI residue hydrolysis side using dolomite as catalyst
Method, comprising the following steps:
S1, smashed 5gTDI bottoms are weighed and 100g ethylene glycol is spare；
S2, using ethylene glycol as reaction medium, TDI residue is added to equipped with blender, reflux condensing tube and thermometer
Capacity is in the reactor of 250mL and to be heated to reflux, and is boiled wherein reflux mid-term temperature is 180 DEG C to system, and flow back 1.5h, returns
Temperature is down to 90 DEG C after stream, obtains TDI residue ethylene glycol mixture；
S3, into TDI residue ethylene glycol mixture, reaction is hydrolyzed in addition dolomite and sodium hydroxide solution, wherein
Reaction temperature is 90 DEG C, reaction time 7h, and dolomite is specially at a temperature of 800 DEG C by 3h calcination processing, hydroxide
Sodium solution is specially that 5g sodium hydroxide is dissolved in 20ml distilled water and being made；
S4, reaction product is filtered, dry and is weighed, calculating it and hydrolyzing yield is 64%.
Tri- second tetramine of 3g is added unlike the first embodiment in comparative example 1 in S3 into TDI residue ethylene glycol mixture
With 20ml sodium hydroxide solution, then similarly by reaction product filtering, drying and weighing, calculating it and hydrolyzing yield is 60%.
It is molten that sodium hydroxide is added unlike the first embodiment in comparative example 2 in S3 into TDI residue ethylene glycol mixture
Liquid, similarly by reaction product filtering, drying and weighing, calculating it and hydrolyzing yield is 30%.
The last hydrolysis yield of comparative example 1 can be obtained compared with embodiment 1, traditional Triethylamine catalyst and hydroxide
Sodium mixed catalyst, although hydrolysis yield can reach 60%, triethylamine than the cost of dolomite it is expensive very much, use three
Ethamine catalyst increases the cost input of hydrolytic process, it has not been convenient to a large amount of to use；By the last hydrolysis yield of comparative example 1 and reality
It applies example 1 and compares the hydrolysis yield that individual sodium hydroxide catalyst can be obtained and there was only 30%, hydrolysis efficiency is lower, is unfavorable for TDI
The hydrolysis process of residue.
Embodiment 2, the present invention provide a kind of technical solution: a kind of TDI residue hydrolysis side using dolomite as catalyst
Method, comprising the following steps:
S1, smashed 5gTDI bottoms are weighed and 110g ethylene glycol is spare；
S2, using ethylene glycol as reaction medium, TDI residue is added to equipped with blender, reflux condensing tube and thermometer
Capacity is in the reactor of 250mL and to be heated to reflux, and is boiled wherein reflux mid-term temperature is 180 DEG C to system, and flow back 1.5h, returns
Temperature is down to 90 DEG C after stream, obtains TDI residue ethylene glycol mixture；
S3, into TDI residue ethylene glycol mixture, reaction is hydrolyzed in addition dolomite and sodium hydroxide solution, wherein
Reaction temperature is 100 DEG C, reaction time 7h, and dolomite is specially at a temperature of 800 DEG C by 3h calcination processing, hydroxide
Sodium solution is specially that 5g sodium hydroxide is dissolved in 20ml distilled water and being made；
S4, reaction product is filtered, dry and is weighed, calculating it and hydrolyzing yield is 69%.
Embodiment 3, the present invention provide a kind of technical solution: a kind of TDI residue hydrolysis side using dolomite as catalyst
Method, comprising the following steps:
S1, smashed 5gTDI bottoms are weighed and 120g ethylene glycol is spare；
S2, using ethylene glycol as reaction medium, TDI residue is added to equipped with blender, reflux condensing tube and thermometer
Capacity is in the reactor of 250mL and to be heated to reflux, and is boiled wherein reflux mid-term temperature is 180 DEG C to system, and flow back 1.5h, returns
Temperature is down to 90 DEG C after stream, obtains TDI residue ethylene glycol mixture；
S3, into TDI residue ethylene glycol mixture, reaction is hydrolyzed in addition dolomite and sodium hydroxide solution, wherein
Reaction temperature is 100 DEG C, reaction time 5h, and dolomite is specially at a temperature of 800 DEG C by 3h calcination processing, hydroxide
Sodium solution is specially that 5g sodium hydroxide is dissolved in 20ml distilled water and being made；
S4, reaction product is filtered, dry and is weighed, calculating it and hydrolyzing yield is 62%.
Embodiment 4, the present invention provide a kind of technical solution: a kind of TDI residue hydrolysis side using dolomite as catalyst
Method, comprising the following steps:
S1, smashed 5gTDI bottoms are weighed and 125g ethylene glycol is spare；
S2, using ethylene glycol as reaction medium, TDI residue is added to equipped with blender, reflux condensing tube and thermometer
Capacity is in the reactor of 250mL and to be heated to reflux, and is boiled wherein reflux mid-term temperature is 180 DEG C to system, and flow back 1.5h, returns
Temperature is down to 90 DEG C after stream, obtains TDI residue ethylene glycol mixture；
S3, into TDI residue ethylene glycol mixture, reaction is hydrolyzed in addition dolomite and sodium hydroxide solution, wherein
Reaction temperature is 90 DEG C, reaction time 5h, and dolomite is specially at a temperature of 800 DEG C by 3h calcination processing, hydroxide
Sodium solution is specially that 5g sodium hydroxide is dissolved in 20ml distilled water and being made；
S4, reaction product is filtered, dry and is weighed, calculating it and hydrolyzing yield is 59%.
It 1,2,3 and 4 can obtain in conjunction with the embodiments, carry out process in hydrolysis, reaction temperature is 100 DEG C, and the reaction time is
The hydrolysis yield highest of TDI residue, reaches 69% under the conditions of the hydrolysis of 7h, is optimal implementation condition.
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (4)
1. a kind of TDI residue method for hydrolysis for using dolomite as catalyst, is characterized in that: the following steps are included:
S1, the solid residue of TDI is crushed；
S2, using ethylene glycol as reaction medium, TDI residue is added, wherein the mass ratio of TDI residue and ethylene glycol be 1:20~1:
25, it is then heated to reflux, wherein reflux temperature is 180-200 DEG C, and return time is that 0.5~2h dissolves TDI residue, and it is residual to obtain TDI
Slag ethylene glycol mixture；
S3, into TDI residue ethylene glycol mixture, reaction is hydrolyzed in addition dolomite and sodium hydroxide solution under normal pressure；
S4, reaction product is filtered, dry and is weighed, calculated its and hydrolyze yield.
2. a kind of TDI residue method for hydrolysis for using dolomite as catalyst according to claim 1, which is characterized in that
The dolomite described in S3 is specially to pass through 3h calcination processing at a temperature of 800 DEG C.
3. a kind of TDI residue method for hydrolysis for using dolomite as catalyst according to claim 1, which is characterized in that
The sodium hydroxide solution described in S3 is specially that 5g sodium hydroxide is dissolved in 20ml distilled water and being made.
4. a kind of TDI residue method for hydrolysis for using dolomite as catalyst according to claim 2, which is characterized in that
Reaction temperature in S3 is 90~100 DEG C, and the reaction time is 5~7h.
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| CN201910890181.2A CN110511132A (en) | 2019-09-20 | 2019-09-20 | A kind of TDI residue method for hydrolysis for using dolomite as catalyst |
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| CN201910890181.2A CN110511132A (en) | 2019-09-20 | 2019-09-20 | A kind of TDI residue method for hydrolysis for using dolomite as catalyst |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387814A (en) * | 2021-06-11 | 2021-09-14 | 兰州理工大学 | Method for hydrolyzing TDI residues by taking magnesite and sodium hydroxide as mixed treating agent |
| CN113996280A (en) * | 2021-10-25 | 2022-02-01 | 厦门大学 | Solid base catalyst for hydrolyzing TDI tar residue and application thereof |
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|---|---|---|---|---|
| JPS50142501A (en) * | 1974-05-09 | 1975-11-17 | ||
| JPS54130525A (en) * | 1978-03-31 | 1979-10-09 | Mitsui Toatsu Chem Inc | Recovery of amine |
| JPS58201751A (en) * | 1982-05-17 | 1983-11-24 | Mitsui Toatsu Chem Inc | Recovery of amine |
| CN1305456A (en) * | 1998-06-18 | 2001-07-25 | 巴斯福股份公司 | Method for treating distillation residues from synthesis of toluene diisocyanate |
| 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 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113387814A (en) * | 2021-06-11 | 2021-09-14 | 兰州理工大学 | Method for hydrolyzing TDI residues by taking magnesite and sodium hydroxide as mixed treating agent |
| CN113387814B (en) * | 2021-06-11 | 2023-06-13 | 兰州理工大学 | TDI residue hydrolysis method using magnesite and sodium hydroxide as mixed treating agents |
| CN113996280A (en) * | 2021-10-25 | 2022-02-01 | 厦门大学 | Solid base catalyst for hydrolyzing TDI tar residue and application thereof |
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Application publication date: 20191129 |