CN204125406U - A kind of river shape super-gravity device of continuous production tolylene diisocyanate - Google Patents
A kind of river shape super-gravity device of continuous production tolylene diisocyanate Download PDFInfo
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- CN204125406U CN204125406U CN201420540771.5U CN201420540771U CN204125406U CN 204125406 U CN204125406 U CN 204125406U CN 201420540771 U CN201420540771 U CN 201420540771U CN 204125406 U CN204125406 U CN 204125406U
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Abstract
The utility model belongs to the technical field that tolylene diisocyanate (TDI) is produced, specifically a kind of river shape super-gravity device of continuous production tolylene diisocyanate, when solving that in the production technique of existing tolylene diisocyanate, volume of material throughput ratio differs greatly, reaction preference is deteriorated, cause transformation efficiency to decline, the problem of the fault of reaction unit may be brought.Super-gravity device, comprise cold reactor and thermal reactor, described cold reactor comprises indefiniteness percussion flow structure and hypergravity structure, indefiniteness percussion flow structure comprises secondary feed-pipe I, secondary feed-pipe II and main feed-pipe, and the extended line of main feed-pipe nozzle and two secondary feed-pipe nozzles crosses to a bit.The utility model is complete by tolylene diamine primitive reaction, prevents sulfonylurea to generate, effectively prevent pipeline and reactor plugs, improves production of toluene diisocyanate efficiency.
Description
Technical field
The utility model belongs to the technical field that tolylene diisocyanate (TDI) is produced, and is specifically related to a kind of river shape super-gravity device of continuous production tolylene diisocyanate.
Background technology
Tolylene diisocyanate (TDI) is a kind of isocyanic ester of mixed type, and what industry was conventional is 2,4-TDI and 2,6-TDI, two kinds of isomer mass ratioes is the mixture of 80:20.Its production method mainly contains phosgenation and non-phosgene.But up to now, the method for domestic and international industrial production TDI mainly adopts light phosgenation technique, phosgenation is produced TDI and is mainly comprised five steps: (1) carbon monoxide and chlorine reaction generate phosgene; (2) toluene and nitric acid reaction generate dinitrotoluene (DNT) (DNT); (3) DNT and H-H reaction generate tolylene diamine (TDA); (4) the dry TDA processed and phosgene reaction generate (TDI); (5) purification of TDI.TDI produce phosgenation reaction refer to tolylene diamine (TDA) under inert solvent effect with the process of phosgene reaction, be divided into cold reaction and thermal response two steps to carry out.Convenient for describing problem, provide reaction process for tolylene diamine (TDA).
(1)
(2)
(3)
(4)
(5)
(6)
Reaction (1), (2) are the main reaction of preparation TDI, and other reactions are side reaction.Reaction (1) is called cold light gasification reaction, self releases large calorimetric, temperature of charge is raised.Reaction process is divided into two step: TDA a amino to be combined with phosgene, discharges a HCl, generates urea chloride (-NHCOCl); Another of TDA be amino to be combined with free HCl (generally catch be with in same molecule harsh become HCl) become semicarbazide hydrochloride (-NH
2﹒ HCl).The generation of urea chloride and semicarbazide hydrochloride is all very rapid, so reaction 1 is also called fast response.
Reaction (2) is called that thermal response is that the intermediate product of cold reaction reacts the process generating target product TDI and byproduct hydrogen chloride further.Also two steps are divided: semicarbazide hydrochloride (-NH
2﹒ HCl) be first dissociated into amino and free HCl, amino and phosgene reaction generates urea chloride (-NHCOCl) and a free HCl.Two steps that thermal process reactor relates to are all reversible, so isolate HCl in time to become the key improving speed of response, and reaction is thermo-negative reaction, so should suck heat, keeps temperature of reaction, ensures normally carrying out of reaction, therefore be referred to as the thermal response stage.
Reaction (3)-(6) are side reaction, mainly occur between several group, but its speed of reaction is all lower than reaction (1).Be specially the amino (-NH in raw material TDA
2), isocyanic ester (-N=C=O) reaction in the urea chloride (-NHCOCl) of intermediate product, product TDI generates insolubles urea, frequent blocking pipeline, yield reduce, and have a strong impact on the normal production of TDI.
According to the difference of the inert solvent used in phosgenation process, phosgenation process can be divided into heavy solvent method and light naphtha method.By heavy solvent method as dimethyl isophthalate (DEIP) makes solvent, carry out photochmeical reaction under elevated pressure conditions, namely usually alleged " heavy solvent production technique ".With light naphtha as solvent made by orthodichlorobenzene (ODCB), under lower pressure, carry out photochmeical reaction, " the light naphtha production technique " that namely usually claim.When adopting heavy solvent method to produce, solvent serves the effect of dispersion agent in the reaction, in separation, serve provide protection again, and it can make TDI reduce the chance occurred at the bottom of tower.So, adopt heavy solvent method to produce TDI and can reduce generation side reaction (3)-(6) to a certain extent, but the light naphtha method industrially mainly adopting solvent can not react with material is produced, this is the heavy solvent shortcoming that has it larger mainly: first, DEIP easily and phosgene reaction generate the boiling point of m-carbethoxyphenyl formyl chloride between TDI and DEI P, therefore accumulate in a solvent, and react further with TDA and generate amides (solid residue), thus reaction yield is reduced, blocking reactor, pipeline, separating device, affect working rate.Side reaction equation is (7)-(8).
(7)
(8)
To sum up analyze, adopt light naphtha method to produce in TDI process, because solvent does not react with product, then the side reaction occurred is mainly (3)-(6); Adopt heavy solvent method to produce in TDI process, although heavy solvent to a certain extent can containment objective product, suppress the generation of side reaction, have side reaction (7)-(8) and occur.By theoretical analysis and pilot-scale experiment known, be greater than that the characteristic reactive time of reaction (1) causes the generation of these side reactions time that mainly two strands of reaction masses complete microcosmic and micromixing.If the time of microcosmic and micromixing is less than the characteristic reactive time of reaction (1), the preferential and tolylene diamine of phosgene reacts, do not have amino then (3)-(6) after tolylene diamine reacts completely, the side reaction of (8) would not occur.So just can avoid blocking reactor, pipeline, separating device, the problem of power is opened in impact, and reacts (8) and can not occur, then the transformation efficiency reacting (7) reduces, and greatly reduces the loss of DEIP.
For convenience of description, macroscopic view, Determining Micromixing Characteristic Time is set forth on the impact of reaction product in order to lower equation:
A + C → D (9)
B + C → P (10)
Wherein (9) formula is fast response, and (10) formula is long response time.
Macroscopic mixing time is that sign two strands of liquid reach the spatially concentration homogeneous time, and now the mean concns of two bursts of reactant feed is the same anywhere, can be expressed as:
t
s= K
1(ε)
-1/3
ε represents the rapids energy dissipative shock wave of fluid, K
1represent scale-up factor constant, with type of reactor, feed location, feed way etc. are relevant.
Determining Micromixing Characteristic Time characterizes the time that two strands of liquid reach molecular level mixing, can be expressed as:
t
m=K
2(v/ε)
1/2
ε represents the rapids energy dissipative shock wave of fluid, K
2expression scale-up factor is constant.
If at macroscopic mixing time t
sbe greater than response feature time t
r, i.e. reactional equation (9), when (10) start to react, not yet reaches micromixing state in reactor, and the state reached in reactor as shown below 6 regions, wherein A, B, C represent three kinds of reactant molecules respectively.
If now the rapids energy dissipative shock wave ε of fluid meets respectively at t
m=k
2(v/ ε)
1/2<t
rand t
m=k
2(v/ ε)
1/2>=t
runder condition, reaction (7), the product situation of (8) sees the following form:
If at macroscopic mixing time t
sbe less than response feature time t
r, i.e. reactional equation (9), when (10) start to react, has reached micromixing state in reactor, the state reached in reactor as shown below 6 regions.Wherein A, B, C represent three kinds of reactant molecules respectively.
If now the rapids energy dissipative shock wave ε of fluid meets respectively at t
m=k
2(v/ ε)
1/2<t
rand t
m=k
2(v/ ε)
1/2>=t
runder condition, reaction (9), the product situation of (10) sees the following form:
To sum up analyze, in the technique of synthesizing isocyanate, avoid side reaction to occur, tolylene diamine must be completed within the response feature time of reaction (1) to mix with microcosmic with the micromixing of phosgene inertia solution, so just can make reaction (1) preferentially other side reactions react, thus reaction (1) ability complete reaction, there is no the amino generation just avoiding side reaction.
But in published patent in report, in order to reach mixed effect fast, adopting injection reactor more, mainly containing gas phase phosgenation and liquid phase phosgenation.Gas phase phosgenation is a kind of method adopting injection reactor gas phase to prepare aromatics polyisocyanate acid esters as patent CN1127248 discloses, and its transformation efficiency reaches more than 95%, but this method still temperature of reaction up to 320-350 DEG C.This method temperature of reaction is too high, and phosgene is easily revealed, and has production safety hidden danger.
Liquid phase phosgenation is produced TDI patent and is mainly contained: patent CN1304927A devises a kind of injection reactor of firing pin type, the liquid phosgene of direct use-5 ~-10 DEG C and the light naphtha inertia solution (orthodichlorobenzene) of tolylene diamine generate isocyanic ester, it can remove the solid by-product produced in hybrid chamber inside by vibration striker, but the reaction mass throughput ratio of phosgene and tolylene diamine inertia solution is approximately between 1:2 in disclosed example, when phosgene and about about the 1:1.6 of tolylene diamine inertia solution quality throughput ratio, feed pressure need up to about 2.5Mpa, yield can reach more than 94%.Patent CN 101612547 B discloses a kind of method that shell and tube impact flow reactor prepares tolylene diisocyanate, in example, the reaction appropriate volume throughput ratio of phosgene and tolylene diamine inertia solution (light naphtha) is approximately between 1:1.6, but when volume flow ratio is approximate reach 1:2.3 time, yield drops to 86.7%.Patent CN101774948A discloses one and utilizes injection reactor to adopt the liquid phosgene of 5 ~-10 DEG C and the heavy solvent inertia solution (DEIP) of tolylene diamine to generate the method for isocyanic ester, in disclosed example when phosgene and tolylene diamine inertia solution reaction mass rate 2:1, reinforced high pressure reaches 2.05Mpa, and yield reaches 98%.To sum up, adopt in current technique liquid low temperature phosgene to insulation of equipment and requirement of withstand voltage high, and in order to obtain excellent mixed effect, require that reaction volume flow (converting by mass rate) compares approximately equal, feed pressure is also comparatively large, and cost is uneconomical.
Patent CN10114595B discloses one and utilizes high-gravity technology to prepare the method for phenylbenzene diisocyanate resin (MDI), in optimum example, the mass rate of reaction mass and phosgene inertia solution is that under 1:0.9 (volumetric flow rate is similar to 1:1) condition, transformation efficiency is up to 98.3%.But, this method need polyamines photoreactive gas to be diluted to volume flow ratio is close just can reach high transformation efficiency, increase the consumption of inert solvent, and the following energy consumption be separated also can increase.This is mainly because the microcosmic mixed performance liquid body micromixing state impact of a large amount of bibliographical information hypergravity equipment is very large, especially when two bursts of volume of material throughput ratios differ greatly, hypergravity equipment is limited on the impact of strengthening Macro-mixing Process, the deterioration of micromixing performance causes microcosmic mixed performance degradation, selectivity is caused to decline, transformation efficiency reduces, thus still keeps away in the reactor and unavoidable side reaction occurs generate a certain amount of solid matter.Although patent points out that the solid matter produced can throw away under powerful centrifugal action from wire packing, be difficult to the solid by-product blocking reactor outlet avoiding producing.
In sum, disclosed at present, liquid phase phosgenation is produced in order to reach excellent mixed effect in TDI technique, and require reaction volume throughput ratio approximately equal, bring inert solvent usage quantity to increase, cost raises, and strengthens the difficulty of later separation.But when volume flow ratio is slightly large, reaction preference is deteriorated, and TDI transformation efficiency declines, and side reaction occurs, and easily causes equipment to block.In addition, technique is harsh to solvent requirement, singlely can only be applicable to light naphtha or heavy solvent.
Summary of the invention
The utility model in order to solve existing tolylene diisocyanate production technique in volume of material throughput ratio differ greatly when, reaction preference is deteriorated, and causes transformation efficiency to decline, may bring the problem of the fault of reaction unit.
The utility model adopts following technical scheme to realize:
The river shape super-gravity device of continuous production tolylene diisocyanate, comprise cold reactor and thermal reactor, it is characterized in that described cold reactor comprises indefiniteness percussion flow structure and hypergravity structure, indefiniteness percussion flow structure comprises secondary feed-pipe I, secondary feed-pipe II and main feed-pipe; Two secondary feed-pipes with main feed-pipe axis for symmetry axis is symmetrical arranged, symmetrical shape; Main feed-pipe is straight tube, front end is provided with main feed-pipe nozzle, and secondary feed-pipe leading portion is provided with elbow, and the end of elbow is secondary feed-pipe nozzle, and the extended line of main feed-pipe nozzle and two secondary feed-pipe nozzles crosses to a bit; Described hypergravity structure comprises housing, rotor, filler, motor and rotating shaft, housing bottom arranges liquid exit, indefiniteness percussion flow vibrational power flow is in the cavity of rotor, and three feed-pipes and nozzle in the same plane, main feed-pipe is fixed on the central axis of two secondary feed-pipes, with the central axes of hypergravity construction rotor, arrange a liquid shield in each nozzle front to be connected with rotor Inner edge, filler is in rotor hollow ring, and rotating shaft is rotated by the rotor driven that is connected with motor;
Two secondary feed-pipe entrances connect phosgene inertia solution original device, and main feed-pipe connects tolylene diamine inertia solution original device, and the liquid exit of hypergravity structure is connected with thermal reactor.
Main feed tube diameter d
5with main feed nozzle diameter D
1proportional range be 1-50; Secondary feed-pipe I diameter d
6with secondary feed-pipe II diameter d
7equal, and the proportional range 0.5-5 of secondary feed tube diameter and main feed tube diameter; Two secondary feed-pipe nozzle diameter D
2, D
3equal, and the proportional range of secondary feed tube diameter and secondary feed-pipe nozzle diameter is 1-50; The distance d of two secondary feed-pipe nozzle lines
1with two secondary feed-pipe nozzle diameter D
2, D
3proportional range be 1-50; Main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle diameter D
1proportional range be 1-50; Main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle to baffle plate distance d
8proportional range be 1-5; Rotor internal diameter d
4with two secondary feed-pipe spacing d
3proportional range is 1.5-10; The angle theta of secondary feed-pipe nozzle centre axis and main feed-pipe central axis
1, θ
2scope is 15 °-90 °.
Main feed-pipe length L
1with main feed tube diameter d
5ratio be 10 ~ 50, secondary feed-pipe length L
2with secondary feed tube diameter d
6, d
7ratio be 10 ~ 50.
Secondary feed-pipe I, secondary feed-pipe II and main feed-pipe connect and are fixed together, and form an one-piece construction.
Liquid shield is connected with rotor inner edge, protruding to nozzle side.
Based on the technique of the continuous production tolylene diisocyanate that the river shape super-gravity device of above-mentioned continuous production tolylene diisocyanate completes, step is as follows: volume flow ratio is that the phosgene inertia solution of 1-15 and tolylene diamine inertia solution are collided by indefiniteness impact flow reactor, and collide on further baffle plate, backwash, liquid completes rapidly micromixing and mixes with preliminary microcosmic, liquid enters the filler of rotation after leaving and clashing into planar central, powerful shearing force keeps material to have high rapids energy dissipative shock wave always, the liquid not reaching microcosmic mixing completes micro mixing rapidly, tolylene diamine (TDA) changes into intermediate product completely in cold reactor, and hypergravity structure is left after the shorter residence time, enter thermal reactor, then at 90-200 DEG C, continue reaction under absolute pressure 0.3-1.8MPa and generate tolylene diisocyanate TDI crude product.
The initial temperature 110-150 DEG C of tolylene diamine inertia solution, tolylene diamine massfraction 10%-40%; The initial temperature 70-110 DEG C of phosgene inertia solution, phosgene massfraction concentration is 20%-50%.
Described inert solvent is light naphtha or heavy solvent, and wherein light naphtha can be wherein one or more the mixture of benzene, toluene, chlorobenzene, orthodichlorobenzene, santochlor, a chlordiphenyl, preferred orthodichlorobenzene; Heavy solvent can be wherein one or more the mixture of diethyl terephthalate, diethyl phthalate or dimethyl isophthalate, preferred dimethyl isophthalate.
In hypergravity structure, filler speed range is 300-1000r/min; Temperature of reaction controls at 100-150 DEG C, and reaction absolute pressure is 1-2MPa.Liquid flows out hypergravity structure within the very short residence time, and the residence time is 0.1-2s, ensure that the heat of generation removes reactor rapidly.
With additive method ratio, the utility model has following remarkable difference:
(1) the cold reactor structure that the utility model adopts is different from traditional reactor, and it is made up of percussion flow and hypergravity structure two portions, to realize the requirement requiring in invented technology to complete Macrocosm and microcosm mixing within the response feature time.Percussion flow structure is also different from the structure of reactor of published production TDI: (a) does not have hybrid chamber, and the opposed collision rift of liquid directly forms the covering of the fan unrestrictedly dispersed, and can not form flowing " dead band "; B () is first divided into two bursts of opposed injections liquid larger for two bursts of volumetric flow rates, two strands of liquid kinetic transformations become static energy, the plane of a strong turbulence is formed at shock plane place, the liquid that volumetric flow rate is less enters to inject this strong turbulence plane at a certain angle, under strong turbulence effect, mass transfer process obtains strengthening, completes rapidly macroscopic view and preliminary microcosmic mixing; C () spray nozzle front end is provided with baffle plate, mixed liquid collides on baffle plate, backwash mixing, and the kinetic energy of liquid residual continues to change into static energy at this, forms again a Ge Gao turbulence district, further enhances mixing process.The conductometric titration of generally acknowledging is adopted to characterize the macroscopic mixing time of cold reactor and Determining Micromixing Characteristic Time with chemical method (parallel competition system), result is better than traditional reactor order of magnitude, and in volume flow ratio 1-15, mixed performance is without remarkable decline.
(2) technique of the present utility model is divided into two steps the strengthening of mixing process, first allow in the material short period of time and reach micromixing, then in hypergravity structure, its micro mixing is strengthened, make reaction mass in characteristic reactive time, complete both macro and micro mixing, in cold reaction exit, checked by chromatography, within the scope of volume flow ratio 1-15, tolylene diamine transformation efficiency reaches 99.5-99.7%, by complete for tolylene diamine primitive reaction, prevent sulfonylurea to generate, effectively prevent pipeline and reactor plugs, improve production of toluene diisocyanate efficiency.
(3) present method reaction volume throughput ratio scope of application is wide, and experimental verification has high transformation efficiency within the scope of volume flow ratio 1-15, can reduce the usage quantity of solvent, and is convenient to the quality control of product.
(4) present method highly versatile, goes for light naphtha method and heavy solvent method, is convenient to the transformation of factory to original technology.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of continuous production tolylene diisocyanate
Fig. 2 is cold reactor structure iron
In figure: 1-cold reactor; 2-thermal reactor; 3-tolylene diamine solution; 4-phosgene solution; The secondary feed-pipe I of 1.11-; The secondary feed-pipe II of 1.12-; The main feed-pipe of 1.2-; The main feed-pipe nozzle of 1.3-; 1.41-secondary feed-pipe I nozzle; 1.42-secondary feed-pipe II nozzle; 1.5-housing; 1.6-filler; 1.7-rotor; 1.8-motor; 1.9-rotating shaft; 1.10-liquid exit; 1.11-liquid shield.
Embodiment
By reference to the accompanying drawings embodiment of the present utility model is described further.
The river shape super-gravity device of continuous production tolylene diisocyanate, comprise cold reactor and thermal reactor, it is characterized in that described cold reactor comprises indefiniteness percussion flow structure and hypergravity structure, indefiniteness percussion flow structure comprises secondary feed-pipe I1.11, secondary feed-pipe II1.12 and main feed-pipe 1.2, two secondary feed-pipes with main feed-pipe axis for symmetry axis is symmetrical arranged, symmetrical shape, main feed-pipe 1.2 is straight tube, front end is provided with main feed-pipe nozzle 1.3, and secondary feed-pipe leading portion is provided with elbow, and the end of elbow is secondary feed-pipe nozzle, and the extended line of main feed-pipe nozzle and two secondary feed-pipe nozzles crosses to a bit, described hypergravity structure comprises housing 1.5, rotor 1.7, filler 1.6, motor 1.8 and rotating shaft 1.9, bottom housing 1.5, liquid exit is set, indefiniteness percussion flow vibrational power flow is in the cavity of rotor 1.7, and three feed-pipes and nozzle in the same plane, main feed-pipe is fixed on the central axis of two secondary feed-pipes, with the central axes of hypergravity construction rotor, arrange a liquid shield 1.11 to be connected with rotor 1.7 Inner edge in each nozzle front, filler 1.6 is in rotor hollow ring, rotating shaft 1.9 is rotated by the rotor driven that is connected with motor 1.8,
Two secondary feed-pipe entrances connect phosgene inertia solution original device, and main feed-pipe 1.2 connects tolylene diamine inertia solution original device, and the liquid exit of hypergravity structure is connected with thermal reactor.
Main feed tube diameter d
5with main feed nozzle diameter D
1proportional range be 1-50; Secondary feed-pipe I diameter d
6with secondary feed-pipe II diameter d
7equal, and the proportional range 0.5-5 of secondary feed tube diameter and main feed tube diameter; Two secondary feed-pipe nozzle diameter D
2, D
3equal, and the proportional range of secondary feed tube diameter and secondary feed-pipe nozzle diameter is 1-50; The distance d of two secondary feed-pipe nozzle lines
1with two secondary feed-pipe nozzle diameter D
2, D
3proportional range be 1-50; The distance d of main feed-pipe nozzle 1.3 to two secondary feed-pipe nozzle line
2with main feed-pipe nozzle diameter D
1proportional range be 1-50; The distance d of main feed-pipe nozzle 1.3 to two secondary feed-pipe nozzle line
2with main feed-pipe nozzle to baffle plate distance d
8proportional range be 1-5; Rotor internal diameter d
4with two secondary feed-pipe spacing d
3proportional range is 1.5-10; The angle theta of secondary feed-pipe nozzle centre axis and main feed-pipe central axis
1, θ
2scope is 15 °-90 °.
Main feed-pipe length L
1with main feed tube diameter d
5ratio be 10 ~ 50, secondary feed-pipe length L
2with secondary feed tube diameter d
6, d
7ratio be 10 ~ 50.
Secondary feed-pipe I1.11, secondary feed-pipe II1.12 and main feed-pipe 1.2 connect and are fixed together, and form an one-piece construction.
Described hypergravity structure can be deflector type, screw path type, rotor-stator formula, any of disc-type hypergravity structure.Described filler is porous medium, can be wire packing, the one of metal foam filler or corrugated plate packing or composition, and filling mode can be rule also can be random filling.
Liquid shield is circular or square, the relatively main feed-pipe of liquid shield and sleeve rotating arrange or with main feed-pipe and telescopic joint, baffle plate can for dull and stereotyped, cave inward or outwardly convex, baffle surface is level and smooth or coarse.The good outwardly convex of the utility model prioritizing selection microcosmic mixed effect, shaggy circular baffle plate.
The technique of continuous production tolylene diisocyanate, river shape super-gravity device completing steps based on above-mentioned continuous production tolylene diisocyanate is as follows: volume flow ratio be phosgene and the tolylene diamine of 1-15 with inertia solution by the opposed collision of indefiniteness impact flow reactor, and collide on baffle plate, backwash, liquid completes rapidly micromixing and mixes with preliminary microcosmic, liquid enters the filler of rotation after leaving and clashing into planar central, powerful shearing force keeps material to have high rapids energy dissipative shock wave always, the liquid not reaching microcosmic mixing completes micro mixing rapidly, after this, tolylene diamine (TDA) changes into intermediate product completely in cold reactor, and cold reactor is left after the shorter residence time, enter thermal reactor, at 90-200 DEG C, continue reaction under absolute pressure 0.3-1.8MPa and generate TDI crude product.
The temperature 110-150 DEG C of tolylene diamine solvent solution, massfraction 10%-40%; The temperature 70-110 DEG C of phosgene inert solvent solution, phosgene massfraction concentration is 20%-50%.Inert solvent is light naphtha or heavy solvent, and wherein light naphtha can be wherein one or more the mixture of benzene, toluene, chlorobenzene, orthodichlorobenzene, santochlor, a chlordiphenyl, the preferred orthodichlorobenzene of method described in the utility model; Heavy solvent can be wherein one or more the mixture of diethyl terephthalate, diethyl phthalate or dimethyl isophthalate, the preferred dimethyl isophthalate of method described in the utility model.
Filler speed range is 300-1000r/min; Temperature of reaction controls at 100-150 DEG C, and reaction absolute pressure is 1-2MPa.Liquid flows out cold reactor within the very short residence time, is characterised in that the residence time is 0.1-2s, ensure that the heat of generation removes reactor rapidly.
As Fig. 1, tolylene diamine and phosgene inertia solution enter in indefiniteness percussion flow structure from cold reaction 1, flow larger phosgene inertia solution is from secondary feed-pipe I1.11, secondary feed-pipe II1.12 divides two strands to enter, the tolylene diamine inertia solution that flow is less enters from main feed-pipe 1.2, three strands of liquid are from feed-pipe nozzle 1.3, secondary feed-pipe I nozzle 1.41 and secondary feed-pipe II1.42, impingement mix, and collide on liquid shield 1.11, backwash, form Gao Tuanneng dissipative shock wave district, three strands of liquid complete rapidly micromixing and mix with preliminary microcosmic, mixing liquid enters the filler 1.6 of high speed rotating, flow out from liquid exit 1.10 after flowing out packing layer and enter thermal reactor 2, then thermal reactor 2 completes thermal response and generates TDI crude product.
Embodiment 1:
Carry out pilot experiment at certain TDI manufacturer the utility model technique and device, orthodichlorobenzene light naphtha specific as follows as inert solvent, the temperature of the tolylene diamine inert solvent solution of configuration 110 DEG C, massfraction is 40%, and mass velocity is 1000Kg/h; The temperature 70 C of phosgene inert solvent solution, phosgene massfraction concentration is 20%, and mass velocity is 15240kg/h, phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 15:1, enter cold reactor to react, adopt rotary packed bed formula hypergravity structure, filler is wire packing; The main feed tube diameter d of cold reactor
5for 100mm, main feed tube diameter d
5with main feed nozzle diameter D
1proportional range be 50, main feed-pipe nozzle diameter D
1for 2mm; The proportional range 5 of secondary feed tube diameter and main feed tube diameter, secondary feed-pipe I diameter d
6with secondary feed-pipe II diameter d
7equal, secondary feed tube diameter d
6, d
7for 500mm; Secondary feed-pipe I nozzle diameter D
2with secondary feed-pipe II nozzle D
3equal, and the proportional range of secondary feed tube diameter and secondary feed-pipe nozzle diameter is 50, diameter D
2, D
3for 10mm; The distance d of two secondary feed-pipe nozzle lines
1with two secondary feed-pipe nozzle diameter D
2, D
3proportional range be the distance d of 18, two secondary feed-pipe nozzle lines
1for 180mm; Main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle diameter D
1proportional range be 50, d
2for 100mm; Main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle to liquid shield distance d
8proportional range be 5, d
8for 500mm; Rotor internal diameter d
4with two secondary feed-pipe spacing d
3proportional range is 1.5, two secondary feed-pipe spacing d
3for 1000mm, rotor internal diameter d
4for 1500mm.The angle of two secondary feed-pipe nozzle centre axis and main feed-pipe central axis is θ
1, scope is 15 °.Main feed-pipe length L
1with main feed tube diameter d
5ratio be 10, secondary feed-pipe length L
2with secondary feed tube diameter d
6, d
7ratio be 10.
Temperature of reaction controls at 100 DEG C, and reaction absolute pressure is 1MPa, and rotating speed is 1000r/min, reaction time 2s, introduces thermal reactor in exit after reaction, at 90 DEG C, continue reaction under absolute pressure 0.3MPa and generate TDI crude product, after follow-up workshop section purifies, TDI yield 99.4%.Within 8 months, there is not latch up phenomenon in plant running.
Be similar to the traditional technology of 1:1 according to volume flow ratio, then need separately to add approximate 14000kg/h orthodichlorobenzene light naphtha and dilute tolylene diamine as inert solvent, solvent cost improves, and later separation difficulty strengthens.
Embodiment 2:
Carry out pilot experiment at certain TDI manufacturer the utility model technique and device, orthodichlorobenzene light naphtha specific as follows as inert solvent, the temperature of the tolylene diamine inert solvent solution of configuration 150 DEG C, massfraction is 40%, and mass velocity is 9000Kg/h; The temperature of phosgene inert solvent solution 110 DEG C, phosgene massfraction concentration is 50%, mass velocity is 37800kg/h, and phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 4:1, enter cold reactor and react, adopt rotor-stator formula hypergravity structure, filler is metal foam filler; The main feed tube diameter d of cold reactor
5for 100mm, main feed tube diameter d
5with main feed nozzle diameter D
1proportional range be 1, main feed-pipe nozzle diameter D
1for 100mm; The proportional range 2 of secondary feed tube diameter and main feed tube diameter, secondary feed tube diameter d
6, d
7for 200mm; Two secondary feed-pipe nozzle diameter D
2, D
3equal, and be 1 with the proportional range of its caliber, diameter D
2, D
3for 200mm; The distance d of two secondary feed-pipe nozzle lines
1with two secondary feed-pipe nozzle diameter D
2, D
3proportional range be the distance d of 1, two secondary feed-pipe nozzle lines
1for 200mm, main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle diameter D
1proportional range be 1, d
2for 100mm; Main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle to baffle plate distance d
8proportional range be 1, d
8for 100mm; Rotor internal diameter d
4with two secondary feed-pipe spacing d
3proportional range is 6, two secondary feed-pipe spacing d
3for 350mm, rotor internal diameter d
4for 2100mm.The angle of secondary feed-pipe I nozzle centre axis and main feed-pipe central axis is θ
1, scope is 90 °, and the angle of secondary feed-pipe II nozzle 1.4 (2) central axis and main feed-pipe central axis is θ
2, scope is 90 °.Main feed-pipe length L
1with main feed tube diameter d
5ratio be 20, secondary feed-pipe length L
2with secondary feed tube diameter d
6, d
7) ratio be 10.
Temperature of reaction controls at 150 DEG C, reaction absolute pressure is 2MPa, rotating speed is 300r/min, reaction time 0.1s, introduces thermal reactor in exit after reaction, at 200 DEG C, continue reaction under absolute pressure 1.8MPa and generate TDI crude product, after follow-up workshop section purifies, TDI yield 99.2%, there is not latch up phenomenon in 8 months in plant running.
Be similar to the traditional technology of 1:1 according to volume flow ratio, then need separately to add approximate 28000kg/h orthodichlorobenzene light naphtha and dilute tolylene diamine as inert solvent, solvent cost improves, and later separation difficulty strengthens.
Embodiment 3:
Pilot experiment is carried out at certain TDI manufacturer the utility model technique and device, orthodichlorobenzene light naphtha specific as follows is as inert solvent, the temperature 120 DEG C of the tolylene diamine inert solvent solution of configuration, massfraction is 30%, and mass velocity is 10500Kg/h; The temperature of phosgene inert solvent solution 90 DEG C, phosgene massfraction concentration is 20%, mass velocity is 11300kg/h, phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 1:1 and enter cold reactor and react, adopt screw path type hypergravity structure, the main feed tube diameter diameter d of cold reactor
5for 100mm, main feed tube diameter d
5with main feed nozzle diameter D
1proportional range be 10, main feed-pipe nozzle diameter D
1for 10mm; The proportional range 0.5 of secondary feed tube diameter and main feed-pipe, secondary feed tube diameter d
6, d
7for 50mm; Two secondary feed-pipe nozzle diameter D
2, D
3equal, and be 10 with the proportional range of its caliber, diameter D
2, D
3for 5mm; The distance d of two secondary feed-pipe nozzle lines
1with two secondary feed-pipe nozzle diameter D
2, D
3proportional range be the distance d of 50, two secondary feed-pipe nozzle lines
1for 250mm, main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle diameter D
1proportional range be 8, d
2for 80mm; Main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle to baffle plate distance d
8proportional range be 2, d
8for 160mm; Rotor internal diameter d
4with two secondary feed-pipe spacing d
3proportional range is 10, two secondary feed-pipe spacing d
3for 200mm, rotor internal diameter d
4for 2000mm.The angle of secondary feed-pipe I nozzle centre axis and main feed-pipe 13.1 central axis is θ
1, scope is 45 °, and the angle of secondary feed-pipe II nozzle centre axis and main feed-pipe 13.1 central axis is θ
2, scope is 45 °.Main feed-pipe length L
1with main feed tube diameter d
5ratio be 15, secondary feed-pipe length L
2with secondary feed tube diameter d
6, d
7ratio be 50.
Temperature of reaction controls at 120 DEG C, reaction absolute pressure is 1.8MPa, rotating speed is 600r/min, reaction time 1.5s, introduces thermal reactor in exit after reaction, at 150 DEG C, continue reaction under absolute pressure 1.5MPa and generate TDI crude product, after follow-up workshop section purifies, TDI yield 99.4%, there is not latch up phenomenon in 8 months in plant running.
Embodiment four
Pilot experiment is carried out at certain TDI manufacturer the utility model technique and device, dimethyl isophthalate heavy solvent specific as follows is as inert solvent, the temperature 110 DEG C of the tolylene diamine inert solvent solution of configuration, massfraction is 30%, and mass velocity is 9980Kg/h; The temperature 70 C of phosgene inert solvent solution, phosgene massfraction concentration is 20%, mass velocity is 15110kg/h, and phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 15:1, enter cold reactor and react, adopt rotary packed bed formula hypergravity structure, filler is wire packing; The main feed tube diameter d of cold reactor
5for 100mm, main feed tube diameter d
5with main feed nozzle diameter D
1proportional range be 50, main feed-pipe nozzle diameter D
1for 2mm; The proportional range 5 of secondary feed tube diameter and main feed-pipe, secondary feed tube diameter d
6, d
7for 500mm; Secondary feed-pipe nozzle diameter D
2, D
3equal, and be 50 with the proportional range of its caliber, diameter D
2, D
3for 10mm; The distance d of two secondary feed-pipe nozzle lines
1with two secondary feed-pipe nozzle diameter D
2, D
3proportional range be the distance d of 10, two secondary feed-pipe nozzle lines
1for 100mm, main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle diameter D
1proportional range be 50, d
2for 100mm; Main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle to baffle plate distance d
8proportional range be 5, d
8for 500mm; Rotor internal diameter d
4with two secondary feed-pipe spacing d
3proportional range is 3, two secondary feed-pipe spacing d
3for 800mm, rotor internal diameter d
4for 2400mm.。The angle of secondary feed-pipe I nozzle centre axis and main feed-pipe 13.1 central axis is θ
1, scope is 15 °, and the angle of secondary feed-pipe II nozzle centre axis and main feed-pipe 13.1 central axis is θ
2, scope is 15 °.Main feed-pipe length L
1with main feed tube diameter d
5ratio be 50, secondary feed-pipe length L
2with secondary feed tube diameter d
6, d
7ratio be 10.
Temperature of reaction controls at 100 DEG C, and reaction absolute pressure is 1MPa, and rotating speed is 1000r/min, reaction time 2s, introduces thermal reactor in exit after reaction, at 90 DEG C, continue reaction under absolute pressure 0.3MPa and generate TDI crude product, after follow-up workshop section purifies, TDI yield 98.9%.Within 8 months, there is not latch up phenomenon in plant running.
Be similar to the traditional technology of 1:1 according to volume flow ratio, then need separately to add approximate 14000kg/h dimethyl isophthalate and dilute tolylene diamine as inert solvent, solvent cost improves, and later separation difficulty strengthens.:
Embodiment 5:
Pilot experiment is carried out at certain TDI manufacturer the utility model technique and device, dimethyl isophthalate heavy solvent specific as follows is as inert solvent, the temperature 150 DEG C of the tolylene diamine inert solvent solution of configuration, massfraction is 30%, and mass velocity is 9000Kg/h; The temperature of phosgene inert solvent solution 110 DEG C, phosgene massfraction concentration is 40%, mass velocity is 37800kg/h, and phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 4:1, enter cold reactor and react, adopt rotor-stator formula hypergravity structure, filler is metal foam filler; The main feed tube diameter d of cold reactor
5for 100mm, main feed tube diameter d
5with main feed nozzle diameter D
1proportional range be 1, main feed-pipe nozzle diameter D
1for 100mm; The secondary feed tube diameter d of proportional range 2, two of secondary feed tube diameter and main feed-pipe
6, d
7for 200mm; Two secondary feed-pipe nozzle diameter D
2, D
3equal, and be 1 with the proportional range of its caliber, diameter D
2, D
3for 200mm; The distance d of two secondary feed-pipe nozzle lines
1with two secondary feed-pipe nozzle diameter D
2, D
3) proportional range be the distance d of 1, two secondary feed-pipe nozzle lines
1for 200mm, main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle diameter D
1proportional range be 1, d
2for 100mm; Main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle to baffle plate distance d
8proportional range be 1.1, d
8for 110mm; Rotor internal diameter d
4with two secondary feed-pipe spacing d
3proportional range is 3, two secondary feed-pipe spacing d
3for 500mm, rotor internal diameter d
4for 1500mm.The angle of secondary feed-pipe I nozzle 1.4 central axis and main feed-pipe 13.1 central axis is θ
1, scope is 90 °, and the angle of secondary feed-pipe II nozzle centre axis and main feed-pipe 13.1 central axis is θ
2, scope is 90 °.Main feed-pipe length L
1with main feed tube diameter d
5ratio be 20, secondary feed-pipe length L
2with secondary feed tube diameter d
6, d
7ratio be 30.
Temperature of reaction controls at 150 DEG C, reaction absolute pressure is 2MPa, rotating speed is 300r/min, reaction time 0.1s, introduces thermal reactor in exit after reaction, at 200 DEG C, continue reaction under absolute pressure 1.8MPa and generate TDI crude product, after follow-up workshop section purifies, TDI yield 99.4%, there is not latch up phenomenon in 8 months in plant running.
Be similar to the traditional technology of 1:1 according to volume flow ratio, then need separately to add approximate 28000kg/h dimethyl isophthalate heavy solvent and dilute tolylene diamine as inert solvent, solvent cost improves, and later separation difficulty strengthens.
Embodiment 6:
Pilot experiment is carried out at certain TDI manufacturer the utility model technique and device, dimethyl isophthalate heavy solvent specific as follows is as inert solvent, the temperature 120 DEG C of the tolylene diamine inert solvent solution of configuration, massfraction is 10%, and mass velocity is 10500Kg/h; The temperature of phosgene inert solvent solution 90 DEG C, phosgene massfraction concentration is 30%, mass velocity is 11300kg/h, phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 1:1 and enter cold reactor and react, and adopt screw path type hypergravity structure, the main feed tube diameter d of cold reactor
5for 100mm, main feed tube diameter d
5with main feed nozzle diameter D
1proportional range be 10, main feed-pipe nozzle diameter D
1for 10mm; The secondary feed tube diameter d of proportional range 0.5, two of secondary feed tube diameter and main feed-pipe
6, d
7for 50mm; Two secondary feed-pipe nozzle diameter D
2, D
3equal, and be 10 with the proportional range of its caliber, diameter D
2, D
3for 5mm; The distance d of two secondary feed-pipe nozzle lines
1with two secondary feed-pipe nozzle diameter D
2, D
3proportional range be the distance d of 30, two secondary feed-pipe nozzle lines
1for 150mm, main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle diameter D
1proportional range be 8, d
2for 80mm; Main feed-pipe nozzle is to the distance d of two secondary feed-pipe nozzle lines
2with main feed-pipe nozzle to baffle plate distance d
8proportional range be 2, d
8for 160mm; Rotor internal diameter d
4with two secondary feed-pipe spacing d
3proportional range is 5, two secondary feed-pipe spacing d
3for 200mm, rotor internal diameter d
4for 1000mm.The angle of secondary feed-pipe I nozzle centre axis and main feed-pipe 13.1 central axis is θ
1, scope is 45 °, and the angle of secondary feed-pipe II nozzle centre axis and main feed-pipe 13.1 central axis is θ
2, scope is 45 °.Main feed-pipe length L
1with main feed tube diameter d
5ratio be 20, secondary feed-pipe length L
2with secondary feed tube diameter d
6, d
7ratio be 40.
Temperature of reaction controls at 120 DEG C, reaction absolute pressure is 1.8MPa, rotating speed is 600r/min, reaction time 1.5s, introduces thermal reactor in exit after reaction, at 150 DEG C, continue reaction under absolute pressure 1.5MPa and generate TDI crude product, after follow-up workshop section purifies, TDI yield 99.1%, there is not latch up phenomenon in 8 months in plant running.
Claims (5)
1. the river shape super-gravity device of a continuous production tolylene diisocyanate, comprise cold reactor and thermal reactor, it is characterized in that described cold reactor comprises indefiniteness percussion flow structure and hypergravity structure, indefiniteness percussion flow structure comprises secondary feed-pipe I(1.11), secondary feed-pipe II(1.12) and main feed-pipe (1.2), two secondary feed-pipes with main feed-pipe axis for symmetry axis is symmetrical arranged, symmetrical shape, main feed-pipe (1.2) is straight tube, front end is provided with main feed-pipe nozzle (1.3), secondary feed-pipe leading portion is provided with elbow, the end of elbow is secondary feed-pipe nozzle, and the extended line of main feed-pipe nozzle and two secondary feed-pipe nozzles crosses to a bit, described hypergravity structure comprises housing (1.5), rotor (1.7), filler (1.6), motor (1.8) and rotating shaft (1.9), housing (1.5) bottom arranges liquid exit, indefiniteness percussion flow vibrational power flow is in the cavity of rotor (1.7), and three feed-pipes and nozzle in the same plane, main feed-pipe is fixed on the central axis of two secondary feed-pipes, with the central axes of hypergravity construction rotor, arrange a liquid shield (1.11) in each nozzle front to be connected with rotor (1.7) Inner edge, filler (1.6) is in rotor hollow ring, rotating shaft (1.9) is rotated by the rotor driven that is connected with motor (1.8),
Two secondary feed-pipe entrances connect phosgene inertia solution original device, and main feed-pipe (1.2) connects tolylene diamine inertia solution original device, and the liquid exit of hypergravity structure is connected with thermal reactor.
2. the river shape super-gravity device of continuous production tolylene diisocyanate according to claim 1, is characterized in that main feed tube diameter (d
5) and main feed nozzle diameter (D
1) proportional range be 1-50; Secondary feed-pipe I diameter (d
6) and secondary feed-pipe II diameter (d
7) equal, and the proportional range 0.5-5 of secondary feed tube diameter and main feed tube diameter; Two secondary feed-pipe nozzle diameter (D
2), (D
3) equal, and the proportional range of secondary feed tube diameter and secondary feed-pipe nozzle diameter is 1-50; Distance (the d of two secondary feed-pipe nozzle lines
1) and two secondary feed-pipe nozzle diameter (D
2), (D
3) proportional range be 1-50; Main feed-pipe nozzle (1.3) is to the distance (d of two secondary feed-pipe nozzle lines
2) and main feed-pipe nozzle diameter (D
1) proportional range be 1-50; Main feed-pipe nozzle (1.3) is to the distance (d of two secondary feed-pipe nozzle lines
2) with main feed-pipe nozzle to baffle plate apart from (d
8) proportional range be 1-5; Rotor internal diameter (d
4) and two secondary feed-pipe spacing (d
3) proportional range is 1.5-10; Angle (the θ of secondary feed-pipe nozzle centre axis and main feed-pipe central axis
1), (θ
2) scope is 15 °-90 °.
3. the river shape super-gravity device of continuous production tolylene diisocyanate according to claim 1 and 2, is characterized in that main feed-pipe length (L
1) and main feed tube diameter (d
5) ratio be 10 ~ 50, secondary feed-pipe length (L
2) and secondary feed tube diameter (d
6), (d
7) ratio be 10 ~ 50.
4. the river shape super-gravity device of continuous production tolylene diisocyanate according to claim 3, it is characterized in that secondary feed-pipe I(1.11), secondary feed-pipe II(1.12) and main feed-pipe (1.2) connect and be fixed together, form an one-piece construction.
5. the river shape super-gravity device of continuous production tolylene diisocyanate according to claim 4, is characterized in that liquid shield is connected with rotor inner edge, protruding to nozzle side.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420540771.5U CN204125406U (en) | 2014-09-20 | 2014-09-20 | A kind of river shape super-gravity device of continuous production tolylene diisocyanate |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420540771.5U CN204125406U (en) | 2014-09-20 | 2014-09-20 | A kind of river shape super-gravity device of continuous production tolylene diisocyanate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496852A (en) * | 2014-09-20 | 2015-04-08 | 中北大学 | III-shaped hypergravity device and technology for continuous preparation of toluene diisocyanate |
-
2014
- 2014-09-20 CN CN201420540771.5U patent/CN204125406U/en not_active Withdrawn - After Issue
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104496852A (en) * | 2014-09-20 | 2015-04-08 | 中北大学 | III-shaped hypergravity device and technology for continuous preparation of toluene diisocyanate |
| CN104496852B (en) * | 2014-09-20 | 2016-09-14 | 中北大学 | A kind of river shape super-gravity device preparing toluene di-isocyanate(TDI) continuously and technique |
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