CN101671275A - Method for continuously manufacturing toluene di-isocyanate - Google Patents
Method for continuously manufacturing toluene di-isocyanate Download PDFInfo
- Publication number
- CN101671275A CN101671275A CN200910070489A CN200910070489A CN101671275A CN 101671275 A CN101671275 A CN 101671275A CN 200910070489 A CN200910070489 A CN 200910070489A CN 200910070489 A CN200910070489 A CN 200910070489A CN 101671275 A CN101671275 A CN 101671275A
- Authority
- CN
- China
- Prior art keywords
- phosgene
- tolylene
- inert solvent
- reaction
- tolylene diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for continuously manufacturing toluene di-dsocyanate, comprising the following steps: (1) premixing a toluenediamine inert solvent solution with a phosgene inert solvent solution containing a hydrogen chloride with a mass fraction lower than 0.1 percent by a premixer and generating reaction; (2) importing the reacted mixture into a high shear reactor and refillingthe phosgene inert solvent solution containing the hydrogen chloride with the mass fraction lower than 0.5 percent to continue mixing and generating reaction; (3) leading materials in an outlet of thehigh shear reactor into detention equipment, continuing reacting at a temperature of 90-200 DEG C and an absolute pressure of 0.3-1.8 MPa until the solution turns transparent and a crude toluene di-isocyanatel is generated. The method for continuously manufacturing toluene di-dsocyanate is realized by mixing the phosgene with hydrogen chlorides in different contents with the toluenediamine step by step, thereby reducing the generation amount of low amine hydrochloride, improving the yield of the product toluene di-isocyanate and avoiding the addition of the energy consumption in refining phosgene recovering.
Description
Technical field
The present invention relates to a kind of method for continuous production of tolylene diisocyanate.
Background technology
Polyurethane material has characteristics such as modification is convenient, easily machine-shaping, easy construction, extremely is widely used in fields such as various thermal insulation, shockproof, sound insulation, pad material, packing and slight structure.Isocyanic ester is the important monomer raw material of polyurethane industrial, the method that is prepared isocyanic ester by the primary amine phosgenation reaction is repeatedly reported in patent, and carried out on a large scale industrial, especially aromatic isocyanate TDI (tolylene diisocyanate), contingent reaction is as follows in its preparation process:
TDI+ urea → TDI biuret (7)
TDI+TDI biuret → polyureas (8)
Reaction (1), (2) are the main reactions that generates isocyanic ester, and all the other are some side reactions in the reaction system.Wherein, it is a quick strong exothermal reaction that organic primary amine and phosgene reaction generate urea chloride, and the reaction process quality depends on mixed effect largely.Reaction mass wants short mix even, prevents the local superfluous side reaction that takes place of organic amine.Simultaneously, the urea chloride that reaction produces and the hydrochloride of amine can be separated out with solid form, may stop up reactor.Generate urea and be regarded as the major cause that the isocyanic ester yield reduces and react the reaction of (6) urea chloride and organic amine.
Minimum for the formation of by product and solid is reduced to, generally organic primary amine and excessive phosgene are dissolved in the inert organic solvents separately, in mixing equipment, carry out short mix.Mixing equipment can be divided into dynamic mixer and static mixer substantially.Known mixing equipment especially comprises nozzle, as annular space nozzle (DE 1792660), annular distance nozzle (DE 3744001), Venturi mixing nozzle (DE-B 1175666) etc.
For increasing effective meltage of phosgene in the solvent, reduce the excessive degree of phosgene, a kind of possible technology approach is to carry out phosgenation reaction under pressure.But more economical in order to guarantee to produce output, generally all under elevated temperature, operate by the large-scale production process of primary amine phosgenation production organic isocyanate.High service temperature causes active phosgene amount to reduce, and the effect that reactor pressure increases is cancelled.In addition, the device of withstand voltage operation is very expensive in the scale operation, and phosgene leaks easily under the high pressure.Add and depress when carrying out the phosgenation operation,, finally can cause the growing amount of amine hydrochlorate to increase because the hydrogenchloride meltage also increases.
DE-A 1768439 has described a kind of continuous method for preparing organic isocyanate, and this method use surpasses 180 ℃ high temperature and the high pressure of 20～150atm, and adopts the high density phosgene in reaction zone.The phosgene that uses is stoichiometric 2.5～5.5 times, and preferred solvent is a chlorobenzene.Because high pressure and very high temperature can realize acceptable space-time yield.Reactant residence time in reaction zone is 5～60 seconds.The shortcoming of this method is that productive rate and quality product reduce, by product especially urea formation Yin Gaowen and increase.
Cold and hot light phosgenation claims two-step approach again, is meant the first step of carrying out the primary amine phosgenation reaction at low temperatures, mainly generates urea chloride and amine hydrochlorate, and temperature of reaction is generally 0 ℃ or room temperature, 80 ℃ at the most.For reducing the generation of amine hydrochlorate, need the hydrolyzable chlorine content in the strict control raw material phosgene.Cold light gasification reaction mixture is transferred under the comparatively high temps, normally 90～200 ℃, continues reaction with the preparation organic isocyanate.Hot phosgenation stop equipment is generally a kind of in stirring tank, tubular reactor, phosgenation tower or the static mixer or combination that certain is several.
In US 3381025, the organic primary amine phosgenation prepares isocyanic ester and divides two sections to carry out, and first section temperature of reaction is lower than 60 ℃, and second section temperature of reaction is 100～190 ℃.Isolate the mixture of the hydrogenchloride of inert solvent, excess phosgene and formation from second conversion zone, isolate hydrogenchloride by this mixture being cooled to-20 ℃.With the cold liquid circulation of gained phosgene and solvent to first conversion zone.But in this technology, the cooling reactant is to extremely low temperature separating hydrogen chloride component, and reacting by heating thing again is irrational from the energy utilization subsequently.
For the higher yields that guarantees isocyanic ester and less by product production rate, existing processes is still mostly tended to use very big phosgene overrate, operates under not too high temperature and absolute pressure.These excessive phosgene need be separated in thick product treatment process, turn back to phosgenation reaction workshop section with the fresh phosgene that replenishes again.But hydrogen chloride content is higher usually in the phosgene that reclaims, and reaches about 0.5% (massfractions), if be directly used in phosgenation reaction, can produce more organic amine salt hydrochlorate.This continuous and stable production to isocyanic ester is disadvantageous: on the one hand, the amine hydrochlorate quality is hard, can cause abrasion to equipment; On the other hand, it is slow that amine hydrochlorate continues reaction generation isocyanic ester speed, needs elevated temperature to accelerate speed of reaction, and this has increased the degree that side reaction takes place.If be reduced to lower scope to reduce the growing amount of organic amine salt hydrochlorate by hydrogen cloride concentration in the phosgene that will be reclaimed, can increase the energy consumption of phosgene recovery system again.
Summary of the invention
The objective of the invention is to overcome deficiency of the prior art, a kind of method for continuous production of tolylene diisocyanate is provided.
Technical scheme of the present invention is summarized as follows:
A kind of method for continuous production of tolylene diisocyanate comprises the steps:
(1) be that the inert solvent solution of 5%～50% tolylene diamine and temperature are that 40～50 ℃ the mass concentration that massfraction is lower than 0.1% hydrogenchloride that contains is 5%～85% phosgene inert solvent solution pre-mixing and reacts with mass concentration with premixer, temperature of reaction is 50～80 ℃, the reaction absolute pressure is 0.5～2MPa, and the mean residence time of material in premixer is no more than 10s; The mol ratio of contained amino of tolylene diamine and phosgene is 1: 1～5 in described premixer;
(2) post reaction mixture is imported high-shear reactor, in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 80～160 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 5%～85% phosgene inert solvent solution continuation mixes and reacts for 1: 1～5 ratio, control reaction temperature is 80～140 ℃, the reaction absolute pressure is 0.5～2MPa, and the material mean residence time is no more than 10s;
(3) material of high-shear reactor outlet is introduced in the stop equipment,, continued to react under absolute pressure 0.3～1.8MPa, generate the tolylene diisocyanate crude product to the solution becomes clarification at 90～200 ℃;
Solvent in the described tolylene diamine inert solvent solution is identical solvent with solvent in the described phosgene inert solvent solution.
A kind of method for continuous production of tolylene diisocyanate also comprises: the tolylene diisocyanate crude product through the degassing, hydrogenchloride stripping, solvent removal and refining, is obtained highly purified tolylene diisocyanate.
Described premixer is any one or its combination of jet mixer or percussion flow mixing tank.
Described tolylene diamine is 2,4-tolylene diamine, mass ratio be 80: 20 2,4-tolylene diamine and 2, the mixture of 6-tolylene diamine or mass ratio be 65: 35 2,4-tolylene diamine and 2, the mixture of 6-tolylene diamine.
The mass concentration of the inert solvent solution of described tolylene diamine selects 10%～40% preferably, and preferably 15%～25%.
Described phosgene inert solvent solution mass concentration selects 10%～60% preferably, and preferably 20%～50%.
The mol ratio of contained amino of tolylene diamine and phosgene is 1: 1.5～3 preferably in premixer.
Described step (2) is: post reaction mixture is imported high-shear reactor, in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 100～130 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 20%～50% phosgene inert solvent solution continuation mixes and reacts for 1: 1.5～3 ratio, 80～140 ℃ of control reaction temperature, reaction absolute pressure 0.5～2MPa, the material mean residence time is no more than 10s.
Described stop equipment is stirring tank, tubular reactor, phosgenation tower, flasher or static mixer.
Described inert solvent is selected from chlorobenzene, orthodichlorobenzene, santochlor, trichlorobenzene, chlorotoluene, xylene monochloride, chloro ethylbenzene, a chlordiphenyl, α-Lv Huanai, β-chlorinated naphthalene, and is at least a in dimethyl terephthalate ester or the diethyl phthalate.Preferred chlorobenzene or orthodichlorobenzene.
The method for continuous production of a kind of tolylene diisocyanate of the present invention phosgene that hydrogen chloride content is different mixes step by step with tolylene diamine, both reduced the amine hydrochlorate growing amount, alleviated abrasion to equipment, improved product tolylene diisocyanate yield, avoided increasing phosgene again and reclaim the purified energy consumption.
Description of drawings
Fig. 1 is a kind of continuously manufacturing schematic flow sheet of tolylene diisocyanate.
Being described as follows of major parts and details in the Figure of description of the present invention:
1 premixer;
2 high-shear reactors;
3 stop equipment;
4 stop equipment circulation loop well heater;
The solution of a tolylene diamine/inert solvent;
B hydrogenchloride mass content is lower than phosgene/inert solvent solution of 0.1%;
C hydrogenchloride mass content is lower than phosgene/inert solvent solution of 0.5%;
D stops the discharging of environment division liquid phase, goes to the workshop section that outgases;
E stops the discharging of equipment gas phase, and the gas recycle section delusters.
Embodiment
Embodiment 1
This embodiment is the continuous production processes of the tolylene diisocyanate (TDI) before improving, and specifically is meant, tolylene diamine only mixes through a step with phosgene, adopts injection reactor as phosgenation reactor.
After organic inert solvent orthodichlorobenzene (ODCB) heating, dilution toluylenediamine (m-TDA) to mass concentration is 20%, and control adds heat makes the temperature of toluylenediamine solution about 100～140 ℃.Equally, with fresh phosgene with reclaim phosgene to be made into mass concentration be 40% solution, control its temperature, contain massfraction in the phosgene solution and be 0.44% hydrogenchloride at 80～100 ℃ with the orthodichlorobenzene after the heating.The mol ratio that contains amino photoreactive gas in the control tolylene diamine is 1: 3, and adjusting temperature of reaction is 100～110 ℃, and the reaction absolute pressure is 1.5～1.8MPa.The phosgenation reaction crude product, continues to react under absolute pressure 0.6～0.7MPa to the solution becomes clarification at 140～160 ℃ through in the phosgenation reaction tower, obtains the thick product of TDI.Through the degassing, hydrogenchloride stripping, solvent removal and refining, final TDI yield is 95.4% with thick product.
Embodiment 2
A kind of method for continuous production of tolylene diisocyanate comprises the steps:
(1) with after organic inert solvent orthodichlorobenzene (ODCB) heating, dilution toluylenediamine (m-TDA) to mass concentration is 20%, and control adds heat makes the dissolving of toluylenediamine solution.In the phosgene treating tower, with the orthodichlorobenzene after the heating non-condensable gas of fresh phosgene photoreactive gas reacting coarse product flasher and degassing tower cat head is absorbed into 35%～40% phosgene o-dichlorobenzene solution, wherein contain the hydrogenchloride massfraction less than 0.1%, control its temperature at 40～50 ℃, according to the mol ratio that contains amino photoreactive gas in the toluylenediamine is 1: 2, the o-dichlorobenzene solution of toluylenediamine and hydrogenchloride mass content are lower than 0.1% phosgene o-dichlorobenzene solution mixes in jet mixer and reacts, temperature of reaction is 50～60 ℃, and absolute pressure is 1.5～1.6MPa; The mean residence time of material in premixer is no more than 10s;
(2) post reaction mixture is imported high-shear reactor, in containing amino mol ratio with phosgene in the raw materials used toluylenediamine is that to continue to add temperature be that 110～130 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is 40%～45% phosgene o-dichlorobenzene solution (the phosgene o-dichlorobenzene solution that massfraction is lower than 0.5% hydrogenchloride obtains for the condensable gases from phosgenation reaction crude product flasher and degassing tower absorbs through orthodichlorobenzene) for 1: 5 ratio, mix and reaction, control reaction temperature is 100～110 ℃, absolute pressure is 1.4～1.5Mpa, and the mean residence time of material is no more than 10s;
(3) material of high-shear reactor outlet is introduced in the phosgenation reaction crude product flasher, Control Circulation loop Heating temperature continues to react under absolute pressure 0.6～0.7MPa to the solution becomes clarification at 140～160 ℃, obtains the thick product of TDI;
(4) with the degassing of the thick product process of TDI, hydrogenchloride stripping, solvent removal and refining, obtain highly purified tolylene diisocyanate, yield is 98.2%.
Embodiment 3
A kind of method for continuous production of tolylene diisocyanate comprises the steps:
(1) be that the chlorobenzene solution of 5% tolylene diamine and temperature are that 40～50 ℃ the mass concentration that massfraction is lower than 0.1% hydrogenchloride that contains is 5%～10% phosgene chlorobenzene solution pre-mixing and reacts with mass concentration with the percussion flow mixing tank, temperature of reaction is 70～80 ℃, the reaction absolute pressure is 0.5～0.7MPa, and the mean residence time of material in the percussion flow mixing tank is no more than 10s; The mol ratio of contained amino of tolylene diamine and phosgene is 1: 1.5 in the percussion flow mixing tank;
(2) post reaction mixture is imported high-shear reactor, in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 140～160 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 40%～45% phosgene chlorobenzene solution continuation mixes and reacts for 1: 1 ratio, control reaction temperature is 130～140 ℃, the reaction absolute pressure is 0.5～0.7MPa, and the material mean residence time is no more than 10s;
(3) material of high-shear reactor outlet is introduced in the phosgenation tower,, continued to react under absolute pressure 0.3～0.5MPa, generate the crude product of tolylene diisocyanate to the solution becomes clarification at 180～200 ℃.
(4) with the degassing of the thick product process of tolylene diisocyanate, hydrogenchloride stripping, solvent removal and refining, obtain highly purified tolylene diisocyanate, yield is 97.6%.
Embodiment 4
A kind of method for continuous production of tolylene diisocyanate comprises the steps:
(1) be that the santochlor solution of 10% tolylene diamine and temperature are that 40～50 ℃ the mass concentration that massfraction is lower than 0.1% hydrogenchloride that contains is 40%～45% phosgene santochlor solution pre-mixing and reacts with mass concentration with premixer, temperature of reaction is 60～70 ℃, the reaction absolute pressure is 1.0～1.2MPa, and the mean residence time of material in premixer is no more than 10s; The mol ratio of contained amino of tolylene diamine and phosgene is 1: 1 in described premixer; Described premixer is that jet mixer and percussion flow mixing tank are used in combination;
(2) post reaction mixture is imported high-shear reactor, in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 80～100 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 20%～25% phosgene santochlor solution continuation mixes and reacts for 1: 5 ratio, control reaction temperature is 80～90 ℃, the reaction absolute pressure is 1.1～1.2MPa, and the material mean residence time is no more than 10s;
(3) material of high-shear reactor outlet is introduced in the stirring tank,, continued to react under absolute pressure 0.5～0.7MPa, generate the crude product of tolylene diisocyanate to the solution becomes clarification at 90～120 ℃;
(4) with the degassing of the thick product process of tolylene diisocyanate, hydrogenchloride stripping, solvent removal and refining, obtain highly purified tolylene diisocyanate, yield is 96.4%.
Embodiment 5
A kind of method for continuous production of tolylene diisocyanate comprises the steps:
(1) be that the chlorotoluene solution of 15% tolylene diamine and temperature are that 40～50 ℃ the mass concentration that massfraction is lower than 0.1% hydrogenchloride that contains is 40%～45% phosgene chlorotoluene solution pre-mixing and reacts with mass concentration with jet mixer, temperature of reaction is 60～70 ℃, the reaction absolute pressure is 1.4～1.5MPa, and the mean residence time of material in jet mixer is no more than 10s; The mol ratio of contained amino of tolylene diamine and phosgene is 1: 3 in jet mixer;
(2) post reaction mixture is imported high-shear reactor, in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 110～120 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 55%～60% phosgene chlorotoluene solution continuation mixes and reacts for 1: 3 ratio, control reaction temperature is 110～120 ℃, the reaction absolute pressure is 1.2～1.4MPa, and the material mean residence time is no more than 10s;
(3) material of high-shear reactor outlet is introduced in the tubular reactor,, continued to react under absolute pressure 0.8～1.0MPa, generate the crude product of tolylene diisocyanate to the solution becomes clarification at 170～180 ℃;
(4) with the degassing of the thick product process of tolylene diisocyanate, hydrogenchloride stripping, solvent removal and refining, obtain highly purified tolylene diisocyanate, yield is 98.0%.
Embodiment 6
A kind of method for continuous production of tolylene diisocyanate comprises the steps:
(1) be that the trichlorobenzene solution of 25% tolylene diamine and temperature are that 40～50 ℃ the mass concentration that massfraction is lower than 0.1% hydrogenchloride that contains is 35%～40% phosgene trichlorobenzene solution pre-mixing and reacts with mass concentration with the percussion flow mixing tank, temperature of reaction is 70～80 ℃, the reaction absolute pressure is 1.6～1.7MPa, and the mean residence time of material in the percussion flow mixing tank is no more than 10s; The mol ratio of contained amino of tolylene diamine and phosgene is 1: 4 in the percussion flow mixing tank;
(2) post reaction mixture is imported high-shear reactor, in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 110～120 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 80%～85% phosgene trichlorobenzene solution continuation mixes and reacts for 1: 2 ratio, control reaction temperature is 120～130 ℃, the reaction absolute pressure is 1.5～1.6MPa, and the material mean residence time is no more than 10s;
(3) material of high-shear reactor outlet is introduced in the static mixer,, continued to react under absolute pressure 0.5～0.6MPa, generate the crude product of tolylene diisocyanate to the solution becomes clarification at 140～160 ℃;
(4) with the degassing of the thick product process of tolylene diisocyanate, hydrogenchloride stripping, solvent removal and refining, obtain highly purified tolylene diisocyanate, yield is 97.6%.
Embodiment 7
A kind of method for continuous production of tolylene diisocyanate comprises the steps:
(1) be that the chloro ethylbenzene solution of 40% tolylene diamine and temperature are that 40～50 ℃ the mass concentration that massfraction is lower than 0.1% hydrogenchloride that contains is 20%～25% phosgene chloro ethylbenzene solution pre-mixing and reacts with mass concentration with jet mixer, temperature of reaction is 60～70 ℃, the reaction absolute pressure is 1.8～2.0MPa, and the mean residence time of material in jet mixer is no more than 10s; The mol ratio of contained amino of tolylene diamine and phosgene is 1: 5 in jet mixer;
(2) post reaction mixture is imported high-shear reactor, in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 90～110 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 40%～45% phosgene chloro ethylbenzene solution continuation mixes and reacts for 1: 3 ratio, control reaction temperature is 80～90 ℃, the reaction absolute pressure is 1.8～2.0MPa, and the material mean residence time is no more than 10s;
(3) material of high-shear reactor outlet is introduced in the phosgenation tower,, continued to react under absolute pressure 1.6～1.8MPa, generate the crude product of tolylene diisocyanate to the solution becomes clarification at 140～160 ℃;
(4) with the degassing of the thick product process of tolylene diisocyanate, hydrogenchloride stripping, solvent removal and refining, obtain highly purified tolylene diisocyanate, yield is 97.4%.
Can also use xylene monochloride, a chlordiphenyl, α-Lv Huanai, β-chlorinated naphthalene, dimethyl terephthalate ester or diethyl phthalate substitute the chloro ethylbenzene in the present embodiment, form new embodiment.
Embodiment 8
A kind of method for continuous production of tolylene diisocyanate comprises the steps:
(1) be that the inert solvent solution of 50% tolylene diamine and temperature are that 40～50 ℃ the mass concentration that massfraction is lower than 0.1% hydrogenchloride that contains is 60%～65% phosgene inert solvent solution pre-mixing and reacts with mass concentration with the percussion flow mixing tank, temperature of reaction is 60～70 ℃, the reaction absolute pressure is 1.4～1.5MPa, and the mean residence time of material in the percussion flow mixing tank is no more than 10s; The mol ratio of contained amino of tolylene diamine and phosgene is 1: 2 in the percussion flow mixing tank;
(2) post reaction mixture is imported high-shear reactor, in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 110～120 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 50%～55% phosgene inert solvent solution continuation mixes and reacts for 1: 1.5 ratio, control reaction temperature is 120～130 ℃, the reaction absolute pressure is 1.4～1.5MPa, and the material mean residence time is no more than 10s;
(3) material of high-shear reactor outlet is introduced in the phosgenation tower,, continued to react under absolute pressure 0.7～0.8MPa, generate the crude product of tolylene diisocyanate to the solution becomes clarification at 140～150 ℃;
Solvent in the described tolylene diamine inert solvent solution is identical solvent with solvent in the described phosgene inert solvent solution, and this solvent is that mass ratio is 1: 1 santochlor and an orthodichlorobenzene;
(4) with the degassing of the thick product process of tolylene diisocyanate, hydrogenchloride stripping, solvent removal and refining, obtain highly purified tolylene diisocyanate, yield is 97.5%.
Claims (10)
1. the method for continuous production of a tolylene diisocyanate is characterized in that comprising the steps:
(1) be that the inert solvent solution of 5%～50% tolylene diamine and temperature are that 40～50 ℃ the mass concentration that massfraction is lower than 0.1% hydrogenchloride that contains is 5%～85% phosgene inert solvent solution pre-mixing and reacts with mass concentration with premixer, temperature of reaction is 50～80 ℃, the reaction absolute pressure is 0.5～2MPa, and the mean residence time of material in premixer is no more than 10s; The mol ratio of contained amino of tolylene diamine and phosgene is 1: 1～5 in described premixer;
(2) post reaction mixture is imported high-shear reactor, in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 80～160 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 5%～85% phosgene inert solvent solution continuation mixes and reacts for 1: 1～5 ratio, control reaction temperature is 80～140 ℃, the reaction absolute pressure is 0.5～2MPa, and the material mean residence time is no more than 10s;
(3) material of high-shear reactor outlet is introduced in the stop equipment,, continued to react under absolute pressure 0.3～1.8MPa, generate the tolylene diisocyanate crude product to the solution becomes clarification at 90～200 ℃;
Solvent in the described tolylene diamine inert solvent solution is identical solvent with solvent in the described phosgene inert solvent solution.
2. the method for continuous production of a kind of tolylene diisocyanate according to claim 1, its feature also comprises: described tolylene diisocyanate crude product through the degassing, hydrogenchloride stripping, solvent removal with make with extra care, is obtained highly purified tolylene diisocyanate.
3. the method for continuous production of a kind of tolylene diisocyanate according to claim 1 is characterized in that described premixer is any one or its combination of jet mixer or percussion flow mixing tank.
4. the method for continuous production of a kind of tolylene diisocyanate according to claim 1, it is characterized in that described tolylene diamine is 2,4-tolylene diamine, mass ratio be 80: 20 2,4-tolylene diamine and 2, the mixture of 6-tolylene diamine or mass ratio be 65: 35 2,4-tolylene diamine and 2, the mixture of 6-tolylene diamine.
5. according to the method for continuous production of claim 1 or 4 described a kind of tolylene diisocyanates, the mass concentration that it is characterized in that the inert solvent solution of described tolylene diamine is 10%～40%.
6. the method for continuous production of a kind of tolylene diisocyanate according to claim 1 is characterized in that described phosgene inert solvent solution mass concentration is 10%～60%.
7. the method for continuous production of a kind of tolylene diisocyanate according to claim 1 is characterized in that the mol ratio of the contained amino of tolylene diamine and phosgene is 1: 1.5～3 in premixer.
8. the method for continuous production of a kind of tolylene diisocyanate according to claim 1, it is characterized in that being: post reaction mixture is imported high-shear reactor in described step (2), in containing amino and the mol ratio of phosgene in the raw materials used tolylene diamine is that to continue to add temperature be that 100～130 ℃ the mass concentration that massfraction is lower than 0.5% hydrogenchloride of containing is that 20%～50% phosgene inert solvent solution continuation mixes and reacts for 1: 1.5～3 ratio, 80～140 ℃ of control reaction temperature, reaction absolute pressure 0.5～2MPa, the material mean residence time is no more than 10s.
9. the method for continuous production of a kind of tolylene diisocyanate according to claim 1 is characterized in that at described stop equipment be stirring tank, tubular reactor, phosgenation tower, flasher or static mixer.
10. according to the method for continuous production of claim 1,5 or 6 described a kind of tolylene diisocyanates, it is characterized in that described inert solvent is selected from chlorobenzene, orthodichlorobenzene, santochlor, trichlorobenzene, chlorotoluene, xylene monochloride, chloro ethylbenzene, a chlordiphenyl, α-Lv Huanai, β-chlorinated naphthalene, at least a in dimethyl terephthalate ester or the diethyl phthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910070489A CN101671275A (en) | 2009-09-18 | 2009-09-18 | Method for continuously manufacturing toluene di-isocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910070489A CN101671275A (en) | 2009-09-18 | 2009-09-18 | Method for continuously manufacturing toluene di-isocyanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101671275A true CN101671275A (en) | 2010-03-17 |
Family
ID=42018723
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910070489A Pending CN101671275A (en) | 2009-09-18 | 2009-09-18 | Method for continuously manufacturing toluene di-isocyanate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101671275A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206160A (en) * | 2011-04-06 | 2011-10-05 | 罗梅 | Preparation and synthesis method for 2-aminophenylamine hydrochloride |
| CN102276478A (en) * | 2011-06-15 | 2011-12-14 | 罗梅 | Preparation and synthesizing method of 3-aminoaniline hydrochloride |
| CN103492364A (en) * | 2011-05-18 | 2014-01-01 | 三井化学株式会社 | Method for manufacturing tolylene diisocyanate |
| CN107473198A (en) * | 2017-07-21 | 2017-12-15 | 淄博飞源化工有限公司 | It is a kind of to utilize the method that carbonyl fluoride is manufactured to trichloromethyl phenylisocyanate |
| CN109305930A (en) * | 2018-05-28 | 2019-02-05 | 江阴市万丰化工物资有限公司 | The synthetic method of 3,3 '--4,4 '-biphenyl diisocyanates of dimethyl |
| CN109810024A (en) * | 2019-03-28 | 2019-05-28 | 南京工业大学 | A kind of spray circuits reactor being used to prepare penta diisocyanate and its application method |
| CN112062679A (en) * | 2019-06-11 | 2020-12-11 | 科思创知识产权两合公司 | Process for preparing amine hydrochloride suspensions |
| CN114749116A (en) * | 2021-01-11 | 2022-07-15 | 万华化学集团股份有限公司 | Method and reaction device for preparing polyisocyanate |
| CN116239502A (en) * | 2022-12-14 | 2023-06-09 | 上海奕朗化工有限公司 | Method for synthesizing 1, 5-pentanediol by 1, 5-pentanediamine |
| CN116239501A (en) * | 2022-12-14 | 2023-06-09 | 上海奕朗化工有限公司 | Method for preparing low-chlorine 1, 5-pentanediisocyanate by high-temperature gas phase |
| CN117820171A (en) * | 2024-01-09 | 2024-04-05 | 中国融通资源开发集团有限公司 | Process method for synthesizing toluene triisocyanate by using triamino toluene phosgene |
| CN116239502B (en) * | 2022-12-14 | 2024-06-07 | 上海奕朗化工有限公司 | Method for synthesizing 1, 5-pentanediol by 1, 5-pentanediamine |
-
2009
- 2009-09-18 CN CN200910070489A patent/CN101671275A/en active Pending
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206160A (en) * | 2011-04-06 | 2011-10-05 | 罗梅 | Preparation and synthesis method for 2-aminophenylamine hydrochloride |
| CN102206160B (en) * | 2011-04-06 | 2013-04-24 | 罗梅 | Preparation and synthesis method for 2-aminophenylamine hydrochloride |
| CN103492364A (en) * | 2011-05-18 | 2014-01-01 | 三井化学株式会社 | Method for manufacturing tolylene diisocyanate |
| CN103492364B (en) * | 2011-05-18 | 2015-03-18 | 三井化学株式会社 | Method for manufacturing tolylene diisocyanate |
| CN102276478A (en) * | 2011-06-15 | 2011-12-14 | 罗梅 | Preparation and synthesizing method of 3-aminoaniline hydrochloride |
| CN102276478B (en) * | 2011-06-15 | 2013-10-23 | 罗梅 | Preparation and synthesizing method of 3-aminoaniline hydrochloride |
| CN107473198A (en) * | 2017-07-21 | 2017-12-15 | 淄博飞源化工有限公司 | It is a kind of to utilize the method that carbonyl fluoride is manufactured to trichloromethyl phenylisocyanate |
| CN107473198B (en) * | 2017-07-21 | 2018-07-13 | 淄博飞源化工有限公司 | A method of manufacturing carbonyl fluoride using to trichloromethyl phenylisocyanate |
| CN109305930A (en) * | 2018-05-28 | 2019-02-05 | 江阴市万丰化工物资有限公司 | The synthetic method of 3,3 '--4,4 '-biphenyl diisocyanates of dimethyl |
| CN109810024A (en) * | 2019-03-28 | 2019-05-28 | 南京工业大学 | A kind of spray circuits reactor being used to prepare penta diisocyanate and its application method |
| CN112062679A (en) * | 2019-06-11 | 2020-12-11 | 科思创知识产权两合公司 | Process for preparing amine hydrochloride suspensions |
| CN114749116A (en) * | 2021-01-11 | 2022-07-15 | 万华化学集团股份有限公司 | Method and reaction device for preparing polyisocyanate |
| CN114749116B (en) * | 2021-01-11 | 2024-04-09 | 万华化学集团股份有限公司 | Method and reaction device for preparing polyisocyanate |
| CN116239502A (en) * | 2022-12-14 | 2023-06-09 | 上海奕朗化工有限公司 | Method for synthesizing 1, 5-pentanediol by 1, 5-pentanediamine |
| CN116239501A (en) * | 2022-12-14 | 2023-06-09 | 上海奕朗化工有限公司 | Method for preparing low-chlorine 1, 5-pentanediisocyanate by high-temperature gas phase |
| CN116239502B (en) * | 2022-12-14 | 2024-06-07 | 上海奕朗化工有限公司 | Method for synthesizing 1, 5-pentanediol by 1, 5-pentanediamine |
| CN117820171A (en) * | 2024-01-09 | 2024-04-05 | 中国融通资源开发集团有限公司 | Process method for synthesizing toluene triisocyanate by using triamino toluene phosgene |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101671275A (en) | Method for continuously manufacturing toluene di-isocyanate | |
| KR101183756B1 (en) | A process for preparing polyisocyanates by the adiabatic phosgenation of primary amines | |
| CN1312123C (en) | Method for the continuous production of isocyanates | |
| CN101671273B (en) | Method for recycling phosgene in continuous production process of toluene di-isocyanate | |
| CN106554293B (en) | A kind of method for preparing colourless or light polyisocyanates | |
| CA1309721C (en) | Process for the continuous production of mono- and polyisocyanates | |
| CN101429138B (en) | Method for producing isocyanic ester in gas-phase | |
| CN104945283B (en) | A kind of method preparing isocyanate-monomer | |
| CN101735109B (en) | Method for continuously producing organic isocyanate | |
| JP2008007506A (en) | Method for continuously producing isocyanate | |
| PL180229B1 (en) | Method of obtaining isocyanates | |
| CN111170891B (en) | Process for preparing isocyanates by partially adiabatically operated phosgenation of the corresponding amines | |
| EP3808732A1 (en) | Method for preparing aliphatic isocyanates | |
| CN107011214A (en) | The method for preparing low-chlorine isocyanates | |
| US20090023963A1 (en) | Noncatalytic Conversion of Carbon Tetrachloride to Perchloroethylene | |
| GB2097789A (en) | Preparation of organic isocyanates | |
| JP4308776B2 (en) | Isocyanate production | |
| CN102471243A (en) | Method for producing diisocyanates by gas-phase phosgenation | |
| CN111170890B (en) | Process for preparing isocyanates by partially adiabatically operated phosgenation of the corresponding amines | |
| CN113880730B (en) | Industrial method for continuously preparing hexamethylene diisocyanate | |
| CN101811018B (en) | Reactor with inclined stirring paddles and system and method using same | |
| US4096165A (en) | Method of manufacturing aromatic isocyanates | |
| CN101671276A (en) | Method for recovering phosgene in continuous production process of toluene di-isocyanate | |
| KR20070084595A (en) | Method for producing polyisocyanates | |
| US11814339B2 (en) | Method for preparing isocyanate in gaseous phase |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20100317 |