CN2444949Y - Jet reactor for preparation of toluene vulcabond - Google Patents
Jet reactor for preparation of toluene vulcabond Download PDFInfo
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- CN2444949Y CN2444949Y CN 00258898 CN00258898U CN2444949Y CN 2444949 Y CN2444949 Y CN 2444949Y CN 00258898 CN00258898 CN 00258898 CN 00258898 U CN00258898 U CN 00258898U CN 2444949 Y CN2444949 Y CN 2444949Y
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Abstract
The utility model relates to an injection reactor for the preparation of toluene diisocyanate, composed of an injector body connected with a feed inlet, a firing pin connected with the feed inlet and a control structure on the lower part of the firing pin. The firing pin is respectively provided with a hollow cylindrical outlet end, a reverse conical part and a cylindrical firing pin body from top to bottom; the firing pin is inserted into a hollow inner cylinder on the lower part of the injector body; the outer side wall of the conical part of the firing pin, the inner side wall of the injector body and a convexity on the conical part form a raw material chamber and a circumambient channel; a rotary atomizer is arranged between the conical part of the firing pin and the upper part of the cylindrical firing pin body; the lower end of the firing pin body is provided with a convex shoulder which is provided with outer screws and is connected with the control structure, and the lower part of the control structure is connected with a cylinder through which the firing pin is driven to act.
Description
The utility model relates to the injection reactor of preparation tolylene diisocyanate, specifically, the utility model relates to the injection reactor that organic solution and phosgene reaction by tolylene diamine prepare tolylene diisocyanate continuously.
The preparation method of isocyanic ester and chemical reaction mechanism can be represented with following reaction formula I-(III): (I)
(II)
(III)
Above-mentioned (I) is commonly referred to photochmeical reaction, and in this reaction, the reaction between amido and the phosgene is very fast, under suitable condition, even also can react generation amido formyl chloride-amido hydrochloride at low temperatures.
The speed of response of above-mentioned (II) is slow usually, and reaction is difficult to carry out under cold condition, generally need be under about 100-180 ℃ temperature condition, and amido formyl chloride-amido hydrochloride could further react with phosgene and change into two amido formyl chlorides.
Meanwhile, two amido formyl chlorides further resolve into vulcabond, impel above-mentioned reaction (III) to finish.
The production of tolylene diisocyanate (TDI) in the world at present, generally adopt following two kinds of technologies:
First kind is to make solvent with dimethyl isophthalate (DEIP), carries out photochmeical reaction under condition of high voltage, promptly common alleged " heavy solvent production technique "; But in the photochmeical reaction of this technology, solvent dimethyl isophthalate (DEIP) easily with the phosgene generation m-ethyl ester Benzoyl chloride (CBC) that reacts, see following reaction formula IV, this material easily causes the obstruction of reactor; In addition, owing to costing an arm and a leg of dimethyl isophthalate (DEIP), its a large amount of consumption can increase the cost of the finished product tolylene diisocyanate (TDI); Moreover also there is another defective in this technology, for the remaining phosgene in the recovery system, need set up a cover phosgene retrieving arrangement, as the solvent that reclaims phosgene, has increased difficulty for the production control of TDI with toluene.
Second kind of technology is to make solvent with orthodichlorobenzene (ODCB), carries out photochmeical reaction under the low pressure condition, i.e. " the light naphtha production technique " that claims usually; The photochmeical reaction of this technology is to carry out in the reactor of belt stirrer, be difficult to avoid the reaction of tolylene diamine (TDA) and toluene diisocyanate (TDI) in the reaction process,, produce a large amount of residues simultaneously and bring burden because the generation of this reaction has reduced the yield of TDI product as reaction (V) to removing slag system; Another defective of this technology is, uses a large amount of solvent orthodichlorobenzenes (ODCB) at system's internal recycle, increased the consumption of the starting material and the power source of equipment, improved the production cost of TDI.
To sum up, the defective that exists in the technology of prior art roughly can be generalized into following a few class:
1, many residues, major part is the urea composition in the described residue, they have not only reduced product yield, and corrode line equipment, have increased production cost; Residue easily causes blocking and need stop production cleaning obturator in addition;
2, Fu Za phosgene sepn process will make phosgene increase the chance of leaking.
At the above-mentioned defective that exists, scientific and technical personnel have delivered a large amount of documents and have attempted to solve by the structure that changes reactor, are several typical explorations below.
CN1052473C discloses a kind of method, it is characterized in that tolylene diamine being introduced and in gas phase, being contacted with excess phosgene, reactant preferably adopts the nozzle injection method, described nozzle forms a central part and a ring part by two concentric tubes, and the amine compound photoreactive gas is introduced by this central part or ring part.
DE-OS2,950,216 disclose a kind of method, this method is that two kinds of reactants that present the sector shape injection stream collide mutually in a garden cylindricality mixing section, and this method not only requires inlet pressure very high, and not producing the mobile dead band at mixing section, this may stop up.
United States Patent (USP) 3,226,410 disclose a kind of method, and this method is by means of aperture horizontal in pipe, and amine compound solution is injected in the phosgene solution stream in the pipe, in order to obtain satisfied productive rate, this method requires reactant concn low, therefore, needs bigger energy consumption to reclaim solvent, in addition, scale problems neither be avoided on wall.
CN88105193 discloses a kind of preparation method of polyisocyanates, and this method also is to adopt the cross-drilled hole of introducing a great deal of on the wall of necking down, thereby a component is incorporated in another component; Also there is United States Patent (USP) 3,226 in same this method, 410 existing defectives; The document thinks that further necking down length is preferably the twice of its diameter, can provide intensive to mix in this case; Disclosed other parameters of the document comprise, reaction mixture is introduced in common reactor with the temperature of reaction that makes final product about 20～180 ℃, and stage number is preferably 20～50, and obstruct face becomes an angle of 90 degrees with flow direction.
Because known method must be implemented with the reactant of high dilution, also need high temperature and/or high pressure, have defectives such as the reaction yield is low, cost height, the used nozzle of reactor of prior art is because structure design is unreasonable simultaneously, stop up easily, and the obstruction that takes place forces stopping production to come cleaning equipment, thereby known method is uneconomic.
The utility model purpose is to be provided for preparing the injection reactor of tolylene diisocyanate, this injection reactor adopts particular design, not only can make reactant moment high speed thorough mixing and quick and complete reaction, and can not stop up, not have by product alluvial and obstruction.
The purpose of this utility model can be achieved in the following manner: a kind of injection-type reactor, by the injector body that is connected with opening for feed, be connected with the striker of opening for feed and the adjusted and controlled composition of its underpart, striker is the hollow cylinder exit end from top to bottom, rounding tapering and cylindrical striker main body, striker is inserted in the hollow interior cylinder of injector body bottom, the outer side wall of the conus portion of striker and the inner side-wall of injector body and on convex to form feed chamber and around the slit, be provided with rotary atomizer between the top of the conus portion of striker and cylindrical striker main body, the lower end of striker main body is provided with a convex shoulder, is provided with externally threaded convex shoulder and connects adjusted and controlled; The adjusted and controlled cylinder that makes the striker action that is connected with down.Between the outer wall of injector body lower inner wall and its striker main body of joining, be provided with tightness system.
Further, injector body is made of the hollow interior cylinder of bottom and the hollow female cone two portions on top, the internal diameter of female cone bottom, top is less than the internal diameter of cylinder in the bottom, make the female cone on top and the interior cylinder of bottom form an end bosses throat in the connection, a sidepiece of injector body bottom is connected with and is used to introduce tolylene diamine solution or phosgene opening for feed; The bottom of striker is a hollow cylinder portion, top is the nozzle exit end of rounding tapering and hollow cylinder, striker is inserted in bottom hollow of injector body in the cylinder, make the top of interior cylinder of injector body bottom and the outer wall in end bosses throat and rounding tapering form a feed chamber, top in feed chamber, between the sidewall in the end bosses throat of injector body and nozzle exit end and rounding tapering, form the material that enters by the injector body opening for feed through feed chamber spouting around passage; Be connected with the opening for feed that is used to introduce one of phosgene or tolylene diamine solution on the lower wall of the hollow cylinder portion of striker bottom, in striker hollow between cylinder top and the rounding tapering, be provided with and have a plurality of fan-shaped impellers and be the skewed tactic rotary atomizer that makes stock liquid stream high speed rotating atomize, go out to enter the reaction zone of injection reactor by the nozzle exit end rotary-jet; The lower end of described striker is provided with a convex shoulder, is provided with externally threaded convex shoulder and connects adjusted and controlled.Regulation device comprises: convex shoulder is enclosed within the endoporus of blind flange, the outside screw that is provided with internal thread and governor lever in the endoporus of blind flange closely cooperates, governor lever outside the endoporus of blind flange is provided with the locking handwheel, the control hand wheel of fixing on it is set in the end of governor lever, when unclamping the locking handwheel, the rotation control hand wheel can make the outside surface in striker rounding tapering and the end bosses throat of injector body inboard break away from, so just opened one of raw material enter injection reactor and the outlet with another raw material blended passage, to lock handwheel then and tighten, can fix the size of described passage; Can adjust the size of described passage according to the desired proportioning raw materials of reaction zone.
Be description of drawings below, be used for describing in detail and be applicable to and by to the description of accompanying drawing and in conjunction with the following detailed description, can be expressly understood the utility model by visual plant of the present utility model, specific as follows:
Accompanying drawing 3 is A-A sectional views of accompanying drawing 2 described injection reactors;
Accompanying drawing 4 is sectional views of accompanying drawing 2 described injection reactors, and different is that this sectional view has shown the sectional view when conical nozzle unclamps;
Accompanying drawing 5 is structural principle synoptic diagram of tower reactor described in the utility model;
Accompanying drawing 6 is sectional views of nozzle in the prior art.
To detailed description of the present utility model below, by describing in detail also in conjunction with the embodiments, can be clearer The utility model is understood on ground.
In the utility model, the organic amine that uses as raw material is toluenediamine (TDA), and is described pending It is of the present utility model photochemical anti-that the toluenediamine of phosgenation (TDA) adopts the form of the solution of atent solvent to introduce In answering.
It has been generally acknowledged that the concentration height of amine is easy to reclaim solvent, can be energy-conservation but by product is increased, productive rate descends, Find researcher of the present utility model, in following concentration, cooperate other technology ginsengs of the present utility model Number and equipment affect the yield of end product hardly, and the utility model adopts in atent solvent amine aqueous solution Concentration is 15～40% (weight), is preferably 21～35% (weight), is preferably 27% (weight).
Solvent comprises chlorinated aromatic hydrocarbons preferably, such as chlorobenzene, o-dichlorohenzene, paracide, a chlordiphenyl, to benzene Dioctyl phthalate dialkyl, diethyl phthalate, toluene and dimethylbenzene; These solvents can use separately also can Mix and use; The utility model preferably adopts o-dichlorohenzene (ODCB) as solvent.
The utility model does not adopt the solution form in the inert solvent to use phosgene, but directly use the phosgene that is lower than the phosgene boiling point, preferably the mixture through overcooled phosgene and orthodichlorobenzene (ODCB) and tolylene diamine (TDA) reacts, the mol ratio of phosgene and tolylene diamine is 1.5: 1-5: 1, preferred 2: 1-3: 1.
Selection process of the present utility model is to be the solvent of TDA with the orthodichlorobenzene, under condition of high voltage, carry out photochmeical reaction, adopt the main reactor of jet mixer, be called for short injection reactor, in injection reactor, mainly form the reaction of two amido formyl chlorides as the first step photochmeical reaction; Adopt the main reactor of distillation tower in the utility model as the second step photochmeical reaction, be called for short tower reactor, in this step reaction, two amido formyl chlorides are converted into tolylene diisocyanate, these two portions are keys of the utility model TDI production technique, the design basis of this technology is based on the mechanism of photochmeical reaction, and photochmeical reaction is mainly carried out in two steps in theory, and is as follows:
Wherein above-mentioned the first step reaction is carried out in injection reactor for thermopositive reaction, and raw material and reaction need not heating, and heat release raises temperature of reaction; The reaction of second step is thermo-negative reaction, finishes after heating in tower reactor.
Describe injection reactor of the present utility model (seeing accompanying drawing 1-4) below in detail, except that injection reactor, synthetic TDI also needs tower reactor (seeing accompanying drawing 5), and is specific as follows:
In the utility model, injection reactor is made up of adjusted and controlled 16 of injector body 3, striker 4 and its underpart connection; Injector body 3 is made of the hollow interior cylinder of bottom and hollow female cone 32 two portions on top, the internal diameter of female cone bottom, top is less than the internal diameter of cylinder in the bottom, make the female cone on top and the interior cylinder of bottom form an end bosses throat 12 in the connection, one sidepiece of the hollow interior cylinder of injector body 3 bottoms is connected with opening for feed 1, is used to introduce tolylene diamine solution or phosgene; The bottom of striker 4 is a hollow cylinder portion 41, striker main body just, top is the nozzle exit end 14 of rounding tapering 11 and hollow cylinder, striker 4 is inserted in bottom hollow of injector body 3 in the cylinder, make the cylindrical spout exit end 14 on striker 4 tops corresponding with the turning point and the end bosses throat 12 in the injector body 3 in rounding tapering 11, the top of the interior cylinder of injector body 3 bottoms and end bosses throat 12 form a feed chamber 16 with the outer wall in rounding tapering 11 like this, top in feed chamber, form between the sidewall in the end bosses throat 12 of injector body 3 and nozzle exit end 14 and rounding tapering 11 and contact 18, be connected with opening for feed 2 on the lower wall of the hollow cylinder portion 41 of striker 4 bottoms, be used to introduce one of phosgene or tolylene diamine solution, between striker 4 tops and the rounding tapering 11, be provided with rotary atomizer 13, rotary atomizer 13 is made up of a plurality of fan-shaped impellers, this device is similar to the impeller of fan, be skewed series arrangement, can make the atomizing of stock liquid stream high speed rotating, the raw material that enters by opening for feed 2, hollow cylinder portion 41 by striker 4 bottoms arrives rotary atomizer 13, rotary atomizer 13 rotates into the reaction zone 15 of injection reactor with the liquid raw material rotary-atomizing by nozzle exit end 14; The lower end of described striker 4 connects adjusted and controlled 16, one convex shoulder 9 is set in the lower end of striker 4, being provided with externally threaded convex shoulder 9 is enclosed within the endoporus of blind flange 5, the outside screw that is provided with internal thread and governor lever 10 in the endoporus of blind flange 5 closely cooperates, governor lever 10 outside the endoporus of blind flange 5 is provided with locking handwheel 6, the control hand wheel of fixing on it 7 is set in the end of governor lever 10, when unclamping locking handwheel 6, rotation control hand wheel 7 can make the outside surface in striker 4 rounding taperings 11 and the end bosses throat 12 of injector body 3 inboards break away from, form between the end bosses throat 12 that has so just opened injector body 3 and the sidewall in nozzle exit end 14 and rounding tapering 11 and contact 18, one of formation raw material enters injection reactor and is exporting and another raw material blended passage 17, to lock handwheel 6 then and tighten, can fix the size of described passage 17; Can adjust the size of described passage 17 according to reaction zone 15 desired proportioning raw materials.The nozzle body 18 of striker 4 and adjusted and controlled formation injection reactor.The material that is entered by opening for feed 1 can pass through feed chamber 16 and spouting around passage 17;
In injector body 3 bottoms hollow cylinder and and the outer wall of the hollow cylinder portion 41 of its striker that joins 4 bottoms between, be provided with tightness system 411, sealing materials such as tightness system 411 preferred organosilicons or tetrafluoroethylene, adjusted and controlled bottom is connected with the air cylinder device (not shown) that prior art adopts, the cylinder action, drive striker 4 vibration or displacements, its frequency is 1 second/time to 30 minutes/time, can not produce any obstruction with nozzle exit end 14 and the passage 17 of guaranteeing striker 4.
From the raw material and another raw material that adds from opening for feed 1 of the rotary-atomizing of nozzle exit end 14 ejection of striker 4, with forms by the end bosses throat 12 of injector body 3 and nozzle exit end 14 and rounding tapering 11 around passage 17 places around another raw material of injection in the reaction zone 15 of injection reactor evenly, rapidly, hybrid reaction tempestuously.When tolylene diamine solution is added fashionablely by opening for feed 1, liquid phosgene is added by charging opening 2; Otherwise when liquid phosgene is added fashionablely by opening for feed 1, tolylene diamine solution is added by charging opening 2.
In the utility model, the charging opening place, the charge temperature of raw material phosgene is-10 ℃-0 ℃, the charge temperature of tolylene diamine is 60 ℃ of-80 ℃ of feed pressure 15-25kg/cm
2, preferred phosgene keeps-5 ℃ of temperature and 18kg/cm
2Pressure; The concentration of tolylene diamine and solvent mixture is 27%, temperature is 71 ℃, pressure 18kg/cm
2
D: the internal diameter 5-40 mm of striker jet hole 14;
N1: the internal diameter of striker main body 4,50-300mm;
The diameter of N2 injector body opening for feed 1,40-250mm;
The maximum inner diameter of the discharge port of the injector body of N3 injection reactor, 60-400mm;
The mixture that comes out from injection reactor had been finished the first step photochmeical reaction before entering tower reactor, form two amido formyl chlorides and a small amount of urea chloride-semicarbazide hydrochloride.Two amido formyl chlorides, carbamyl chloro-semicarbazide hydrochloride, solvent, COCL
2Deng mixture, in tower, the bottom enters the photochmeical reaction tower, in tower reactor bottom after the heating of hydrocone type interchanger, carbamyl chloro-semicarbazide hydrochloride and phosgene further reaction obtain two amido formyl chlorides, two amido formyl chlorides are converted into tolylene diisocyanate (TDI), tolylene diisocyanate (TDI), hydrogenchloride (HCL) that reaction generates and excessive phosgene are separated on tower reactor top, highly purified phosgene is not needed further processing and is directly recycled the HCL of top of tower and COCL by the medial side linear flow pass-out of tower reactor
2Mixture enter the HCL rectifying tower.The service temperature of this tower is from 70 ℃-160 ℃, pressure 10-20kg/cm
2
The mixed reaction solution of injection reactor outlet enters tower reactor with 90-100 ℃ temperature, at the bottom of tower, a spot of toluino formyl chloride-semicarbazide hydrochloride and phosgene continue reaction and generate tolylene diamine base formyl chloride, then, the two a large amount of amido formyl chlorides that obtain together with the back reaction again are dissociated into isocyanic ester.And highly purified phosgene can be separated by the middle part of tower, and the purity of the phosgene that obtains can reach 99.2%, and overhead materials is phosgene and hydrogen chloride gas, can separate via subzero fractionation or another rectifying tower again.Tower reactor can carry out the high purity phosgene simultaneously, phosgene separates with hydrochloric acid mixture, also carrying out the further reaction of minute quantity carbamyl chloro-semicarbazide hydrochloride simultaneously is the chemical reaction that two amido formyl chlorides and two amido formyl chlorides are dissociated into isocyanic ester, has simplified technology and production unit.
Below in conjunction with equipment, the structure and the operation of complete description injection reactor described in the utility model:
Shown in Fig. 1-4, unclamping locking handwheel 6 and rotating control hand wheel 7 breaks away from the outside surface of striker 4 inverted upper conical end 11 and the end bosses throat 12 of injector body 3 inboards, so just opened amine mixt enter injection reactor and the outlet with phosgene blended passage, adjust channel sized according to the proportion of raw materials in the reaction zone 15, will lock handwheel 6 then and tighten.
Phosgene liquid or the tolylene diamine solution that is dissolved in solvent are imported from charging opening 2, send into rotary atomizer 13 and spray from nozzle exit end 14 high speed rotating through the lower hollow garden of striker post 41; Simultaneously tolylene diamine mixture solution or phosgene are by charging opening 1 adding that also is in a liquid state, the feed chamber 16 that end bosses throat 12 bottoms on process injector body 3 tops and rounding tapering 11 outer walls of striker 4 form, the place, slit around passage 17 that forms between the turning point by the hollow garden post on the rounding tapering 11 on injector body 3 end bosses throats 12 and striker 4 tops and top thereof is spouting, converge with phosgene or the tolylene diamine solution that is dissolved in solvent, in the reaction zone 15 of injection reactor after the moment hybrid reaction, the reaction mixture tolylene diamine base formyl chloride that obtains and toluino formyl chloride-semicarbazide hydrochloride through injection reactor discharge port 8 and corresponding pipeline in actinic reactor, the bottom enters tower reactor, heating at the bottom of the tower of actinic reactor, to carry out the reaction of tolylene diamine base formyl chloride and small amount of toluene carbamyl chloro-semicarbazide hydrochloride is the reaction of tolylene diisocyanate, and the separated product mixture, at the bottom of tower, obtain the final product tolylene diisocyanate, dichlorobenzene, the mixture of phosgene; Highly purified phosgene need not handled and directly be recycled by the medial side linear flow pass-out of tower reactor, and hydrogenchloride (HCL) that reaction generates and excessive phosgene mixture are separated and enter the HCL rectifying tower on tower reactor top.
Adjustment is 2-6mm around the wavelength width of a slit of passage 17, can guarantee that the mol ratio of reaction zone 15 interior phosgene and tolylene diamine is 1.5: 1-5: 1, preferred 2: 1-3: 1.
Prepared in the reaction process of TDI by tolylene diamine mixture solution and phosgene, by product is mainly HCL, isolates by-product hydrochloric acid and helps the carrying out that react.In the utility model, because tower reactor is a distillation tower, along with reaction is carried out, the HCL that reaction generates constantly is separated from product mixtures, promote toluino formyl chloride-semicarbazide hydrochloride reaction to be converted into tolylene diisocyanate for tolylene diamine base formyl chloride, tolylene diamine base formyl chloride, promote the reaction of tolylene diamine and phosgene simultaneously, therefore reaction is fast, side reaction is few, productive rate is high.
Tower reactor described in the utility model is made up of 6-25 piece column plate, preferred 10-20 piece column plate, and most preferably 18, tower diameter 1000mm-4000mm, preferred 1200-3000mm, 1500-2000mm most preferably is referring to accompanying drawing 5.The shape of tower can be the uniform cylindrical tower of diameter, also can be that lower diameter is bigger, the bicylindrical shape tower that upper diameter is less.Up-small and down-big and not simultaneously when the diameter of tower, because that reaction mixture and product are detained at the bottom of tower is longer, HCL can be separated fully fully, in the product mixtures that obtains at the bottom of the tower, the concentration of HCL helps obtaining highly purified TDI product less than 10ppm.
The tower top temperature of photochmeical reaction tower is 80-90 ℃, pressure 10-20 Kg/cm
2, preferred 84-86 ℃, 15Kg/cm
290-95 ℃ of tower middle part phosgene temperature out, preferred 93-95 ℃; Tower bottom TDI temperature out is 150-160 ℃, pressure 10-20 Kg/cm
2, preferred 154-156 ℃, 15Kg/cm
2, most preferably tower top temperature is 85 ℃, 94 ℃ of tower middle part phosgene temperature outs, 155 ℃ of tower bottom TDI temperature outs.
Adopt prior art will leave at the bottom of the tower then and the product of cat head and solvent mixture separate and distill.
Be specific embodiment of the utility model below, described embodiment is used to describe the utility model rather than restriction the utility model.
Embodiment one
1, carries out phosgenation reaction with injection reactor, with reference to the figure of injection reactor equipment shown in the figure 1-4,-5 ℃ of liquid phosgene are added by the rotary atomizer of charging opening 2 in injection reactor striker 4 (N1) with charge pump according to phosgene and 4: 1 ratio of dichlorobenzene, enter the reaction zone 15 of injection reactor by nozzle exit end 14 rotary-atomizings; The dichlorobenzene solution of 60 ℃ 21% tolylene diamine and the charging opening that is connected by injector body 3 sidepieces 1 input, enter reaction zone 15 through feed chamber 16 and passage 17 injections, reaction zone 15 (N3) at injection reactor locates to carry out hybrid reaction, about 120 ℃ of temperature of reaction, charging opening pressure 20kg/cm
2Striker vibrates 1 time for 4 p.s.s, to remove issuable precipitation.
2, enter phosgene-isocyanic ester knockout tower that dissociates at the 5th column plate place via the two amido formyl chlorides that obtain after the injection reactor reaction and solvent dichlorobenzene and excess phosgene mixing solutions, it is tower reactor, see accompanying drawing 5, tower reactor is made up of 20 blocks of column plates, tower diameter 1500mm.
Heating at the bottom of the tower of tower reactor, tolylene diamine base formyl chloride is dissociated into tolylene diisocyanate, at the bottom of tower, obtain the mixture of tolylene diisocyanate, dichlorobenzene photoreactive gas, adopt separating device commonly used to separate again, 98% high purity phosgene can be separated by the 13rd block of column plate at the middle part of tower and obtains, overhead materials is the mixture of phosgene and hydrogen chloride gas, can separate via subzero fractionation or another rectifying tower again.Phosgene-isocyanic ester knockout tower that dissociates can carry out the high purity phosgene simultaneously and separates, and also carries out tolylene diamine base formyl chloride and is dissociated into the chemical reaction of tolylene diisocyanate and separating of tolylene diisocyanate.The productive rate 95% of tolylene diisocyanate.
The service temperature cat head is 80 ℃, at the bottom of the tower 160 ℃, and 85 ℃ of tower middle part temperature, pressure 10kg/cm
2, with reference to figure 5.
Embodiment two
80 ℃ 15% tolylene diamine and the mixing solutions of diethyl terephthalate are introduced the injector reactor by opening for feed 2,1 respectively with-10 ℃ of phosgene, the mol ratio of reactant tolylene diamine and phosgene is 1: 1.5, temperature of reaction is controlled at 90 ℃, working pressure 15kg/cm
2Striker vibration in per 10 minutes once, reaction soln is sent to the bottom of tower reactor by injection reactor 15 (N3) exit end, this tower is made up of 10 blocks of column plates, tower diameter 2000mm, and behaviour's temperature is 160 ℃ at the bottom of the tower, cat head is 80 ℃, overhead materials is the mixture of phosgene and hydrogen chloride gas, 95 ℃ of tower middle part temperature, tower internal pressure 20 kg/cm
2, can Separation and Recovery in the tower obtaining the high purity phosgene more than 90%, the product mixtures that obtains adopts the method for prior art to separate, and can obtain yield and reach TDI product more than 92%.
Embodiment three
65 ℃ 40% tolylene diamine and the mixing solutions of dimethylbenzene enter phosgenation reactor from 2,0 ℃ of liquid phosgene of charging opening (COCL2) respectively from charging opening 1, the mol ratio of reactant tolylene diamine and phosgene is 1: 2, carries out the first step photochmeical reaction through spraying violent mixing of back.Temperature of reaction is 60 ℃, reaction pressure 25Kgcm
2" injection reactor " sees accompanying drawing 1-4.
The mixture that is come out by injection reactor enters tower reactor, is going on foot photochmeical reaction and is carrying out initial gross separation through finishing second after heating at the bottom of the tower.This tower is made up of 20 blocks of column plates, tower diameter 3000mm, and service temperature is 150 ℃ at the bottom of the tower, and cat head is 80 ℃, 95 ℃ of tower middle part temperature, tower internal pressure 15kg/cm
2, see accompanying drawing 5.Can obtain yield and reach TDI product more than 94%.
Embodiment four
According to phosgene and 5: 1 ratio of tolylene diamine, with high-pressure pump with the orthodichlorobenzene mixture solution of 70 ℃ 35% tolylene diamine from charging opening 2, through the striker 4 (N1) of injection reactor and add the rotation spraying gun and add, with-5 ℃ of liquid phosgene of the charging opening that is connected from injector body 3 sidepieces 1 input in reaction zone 15 violent hybrid reactions, temperature of reaction is controlled at 100 ℃, and the charging opening pressure-controlling is at 22kg/cm
2Reaction mixture is entering into " tower reactor " before, finishes the first step reaction and produces tolylene diamine base formyl chloride and part toluino formyl chloride-semicarbazide hydrochloride.
The photochmeical reaction tower is made up of 16 blocks of column plates, be divided into two portions, 10 blocks of column plates are arranged at top, diameter 1000mm, the 6 blocks of column plates in bottom, diameter 2500mm, after reaction mixture enters the photochmeical reaction tower with 90 ℃, tolylene diamine base formyl chloride and a spot of toluino formyl chloride-semicarbazide hydrochloride heat through thermosyphon reboiler at the bottom of tower, finish the reaction of second step, are decomposed into tolylene diisocyanate (TDI); The bottoms material is TDI, ODCB, and micro-phosgene and micro-residue, content of hydrochloric acid adopts the method for prior art further to separate productive rate 96% less than 10ppm.
Excessive phosgene reaches 98% at the tower first half through rectifying purity, is recovered to the phosgene storage tank and recycles.In HCL and a little of phosgene that the top of tower photochmeical reaction produces, deliver to the HCL rectifying tower.
Photochemical column bottom temperature is controlled at about 160 ℃, 80 ℃ of tower top temperatures, and tower top pressure is controlled at 10kg/cm
2
Embodiment (the best)
27% tolylene diamine (TDA) is dissolved in 73% orthodichlorobenzene (ODCB), at 71 ℃, 18kg/cm
2Add injection reactor by opening for feed 1 under the pressure;-5 ℃ phosgene is at 18kg/cm
2Pressure under add by opening for feed 2, spray by jet hole through rotary atomizer 13, in the reaction zone of injection reactor with tolylene diamine solution hybrid reaction, adjusting the size in passage 17 slits and the flow of raw material, is 1: 3 with the mol ratio that guarantees injection reactor reaction zone 15 interior phosgene and tolylene diamine and phosgene; Two amido formyl chlorides, orthodichlorobenzene (ODCB), phosgene (COCl
2), reaction mixtures such as HCl are delivered to tower reactor bottom by the outlet drainage conduit and are further reacted and separate 100 ℃ of the temperature of reaction; After reaction mixture entered the photochmeical reaction tower with 100 ℃ temperature, tolylene diamine base formyl chloride and toluino formyl chloride-semicarbazide hydrochloride heated through thermosyphon reboiler at the bottom of tower, finished the reaction of second step, were decomposed into tolylene diisocyanate (TDI); Excessive phosgene at tower middle part through rectifying directly obtain purity reach 99.2% can direct reusable phosgene, being recovered to the phosgene storage tank recycles, HCL and a little of phosgene in the generation of top of tower photochmeical reaction, deliver to the HCL rectifying tower, obtain the mixture of tolylene diisocyanate, dichlorobenzene photoreactive gas at tower bottom, adopt the method for prior art to separate productive rate 98%.
155 ℃ of photochemical column bottom temperatures, 95 ℃ at tower middle part, 85 ℃ of cats head, the pressure-controlling of tower is at 15.0-15.3kg/m
2Between, stage number is 18, tower diameter 1800mm.
The utlity model has following advantage:
Adopt Processes and apparatus of the present utility model, can under higher toluenediamine concentration, react, spray Penetrating reactor can fully mix the toluenediamine mixture that is dissolved in solvent rapidly with liquid phosgene, reduces negative The generation of reaction, the generation of minimizing residue, the reaction zone that is used for injection reactor described in the utility model is Taper, and react and outside nozzle exit end, carry out, striker constantly vibrates, with nozzle exit end 14 and passage The issuable precipitation in 17 places is in time removed, and therefore, there is not the problem of obstruction in injection reactor, and tapered Reaction zone 15 places do not have the dead angle, therefore, even produce a small amount of precipitation, also can be because of high velocity jet mixed Compound washes away sediment while dissolving, thereby can guarantee not form in injection reactor caking, and this point is existing There is technology all insurmountable. Special injector shortens course of reaction, and can improve the purity that reclaims phosgene, Isocyanate reaction more can be carried out effectively.
Claims (8)
1. the injection reactor for preparing tolylene diisocyanate, it is characterized in that injection reactor is by the injector body that is connected with opening for feed, be connected with the striker of opening for feed and the adjusted and controlled composition of its underpart, striker is respectively the hollow cylinder exit end from top to bottom, rounding tapering and cylindrical striker main body, striker is inserted in the hollow interior cylinder of injector body bottom, the outer side wall of the conus portion of striker and the inner side-wall of injector body and on convex to form feed chamber and around passage, be provided with rotary atomizer between the top of the conus portion of striker and cylindrical striker main body, the lower end of striker main body is provided with a convex shoulder, is provided with externally threaded convex shoulder and connects adjusted and controlled; The adjusted and controlled cylinder that makes the striker action that is connected with down; Between the outer wall of injector body lower inner wall and its striker main body of joining, be provided with tightness system.
2. the injection reactor of preparation tolylene diisocyanate according to claim 1, it is characterized in that injector body is made of the hollow interior cylinder of bottom and the hollow female cone two portions on top, the hollow female cone on top is the reaction zone of injection reactor gas, the internal diameter of hollow female cone bottom, top is less than the internal diameter of cylinder in the lower hollow, connection at the interior cylinder of the female cone on top and bottom forms an end bosses throat, and a sidepiece of injector body bottom is connected with and is used to introduce tolylene diamine solution or phosgene opening for feed.
3. according to the injection reactor of claim 1,3 described preparation tolylene diisocyanates, it is characterized in that being in the striker main body of striker hollow cylinder, in striker hollow between cylinder top and the rounding tapering, be provided with and have a plurality of fan-shaped impellers, be the skewed tactic rotary atomizer that makes stock liquid stream high speed rotating atomize, go out to enter the reaction zone of injection reactor by the nozzle exit end rotary-jet.
4. the injection reactor of preparation tolylene diisocyanate according to claim 1, it is characterized in that being inserted into the striker in the cylinder in bottom hollow of injector body, on the top of the interior cylinder of injector body bottom and the outer wall in the rounding tapering of end bosses throat and striker form a feed chamber, top in feed chamber, between the sidewall in the end bosses throat of injector body and nozzle exit end and rounding tapering, form the material that enters by the injector body opening for feed through feed chamber spouting around passage.
5. the injection reactor of preparation tolylene diisocyanate according to claim 1, it is characterized in that the striker bottom the striker main body lower wall on be connected with the opening for feed that is used to introduce one of phosgene or tolylene diamine solution.
6. the injection reactor of preparation tolylene diisocyanate according to claim 1, it is characterized in that adjusted and controlled comprising: convex shoulder is enclosed within the endoporus of blind flange, the outside screw that is provided with internal thread and governor lever in the endoporus of blind flange closely cooperates, governor lever outside the endoporus of blind flange is provided with the locking handwheel of fixing described channel sized, be provided with in the end of governor lever and fix on it, the outside surface in control striker rounding tapering and the end bosses throat of injector body inboard break away from, and one of control raw material enters injection reactor and at the control hand wheel of outlet with another raw material blended passage.
7. the injection reactor of preparation tolylene diisocyanate according to claim 1 is characterized in that sealing materials such as preferred organosilicon of tightness system or tetrafluoroethylene.
8. according to the injection reactor of claim 1, described preparation tolylene diisocyanate, it is characterized in that the internal diameter 5-40mm of striker jet hole; The internal diameter of striker main body, 50-300mm; The diameter of injector body opening for feed, 40-250mm; The maximum inner diameter 60-400mm of injection reactor jet body discharge port.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00258898 CN2444949Y (en) | 2000-12-29 | 2000-12-29 | Jet reactor for preparation of toluene vulcabond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00258898 CN2444949Y (en) | 2000-12-29 | 2000-12-29 | Jet reactor for preparation of toluene vulcabond |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN2444949Y true CN2444949Y (en) | 2001-08-29 |
Family
ID=33615053
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00258898 Expired - Fee Related CN2444949Y (en) | 2000-12-29 | 2000-12-29 | Jet reactor for preparation of toluene vulcabond |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN2444949Y (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670263B (en) * | 2009-09-03 | 2012-11-21 | 天津大学 | Reactor for preparing toluene diisocynate by gaseous phase method and operation method |
-
2000
- 2000-12-29 CN CN 00258898 patent/CN2444949Y/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101670263B (en) * | 2009-09-03 | 2012-11-21 | 天津大学 | Reactor for preparing toluene diisocynate by gaseous phase method and operation method |
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| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |