CN204125405U - A kind of list reflection super-gravity device of continuous production tolylene diisocyanate - Google Patents

Abstract

The utility model belongs to the technical field of production of toluene diisocyanate, be specifically related to a kind of list reflection 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, cold reactor comprises indefiniteness percussion flow structure and hypergravity structure, and indefiniteness percussion flow structure comprises the different main feed-pipe of caliber and sleeve pipe and baffle plate, and ferrule openings end and main feed-pipe nozzle-end form circumferential weld.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

A kind of list reflection super-gravity device of continuous production tolylene diisocyanate

Technical field

The utility model belongs to the technical field that tolylene diisocyanate (TDI) is produced, and is specifically related to a kind of list reflection super-gravity device of continuous production tolylene diisocyanate.

Background technology

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), phosgene is preferential to react with tolylene diamine, and do not have then (3)-(6) of amino 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 _d, 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 _dand t _m=k ₂(v/ ε) ^1/2>=t _dunder 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 _d, 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 _dand t _m=k ₂(v/ ε) ^1/2>=t _dunder 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 answers 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) is than 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:

A kind of list reflection super-gravity device of continuous production tolylene diisocyanate, comprise cold reactor and thermal reactor, it is characterized in that cold reactor comprises indefiniteness percussion flow structure and hypergravity structure, described indefiniteness percussion flow structure comprises the different main feed-pipe of caliber and sleeve pipe and baffle plate, the caliber of sleeve pipe is greater than the caliber of main feed-pipe, sleeve pipe is placed on outside main feed-pipe, main feed-pipe arranges main feed tube mouth away from one end of baffle plate, the other end near liquid shield arranges the main feed-pipe nozzle of flared, main feed-pipe nozzle-end center has discharge hole, one end of the corresponding main feed tube mouth of sleeve pipe is also provided with sleeve pipe opening for feed, the other end opening of the corresponding main feed-pipe nozzle of sleeve pipe, ferrule openings end and main feed-pipe nozzle-end form circumferential weld, discharge hole and circumferential weld are arranged at same plane, baffle plate is vertically arranged relative to the axis direction of main feed-pipe and sleeve pipe, baffle center is positioned on the axis of main feed-pipe and sleeve pipe, hypergravity structure comprises filler, rotating shaft, rotor, housing and liquid exit, described indefiniteness percussion flow vibrational power flow is in the cavity of rotor and arrange along rotor axis direction, and indefiniteness percussion flow structure axis overlaps with shaft axis, rotor is positioned at the middle part of housing, and filler is in rotor hollow ring, liquid exit is connected with thermal reactor in the bottom of housing, and rotating shaft is rotated by the rotor driven that is connected with motor.

Casing diameter d ₂with main feed tube diameter d ₃be 2-10 with ratio; Casing length L ₁with casing diameter d ₂ratio is 1-10; The internal diameter d of main feed-pipe ₃with nozzle discharge hole diameter D ₂ratio be 1-100; Circumferential weld width D ₁with nozzle discharge hole diameter D ₂ratio be 1-10, casing diameter d ₂with hypergravity structured packing inner edge to sleeve pipe distance d ₁ratio scope be 1-200, baffle plate is to indefiniteness percussion flow structure distance d ₄with main feed-pipe nozzle diameter D ₂ratio range is 1-50.

List reflection super-gravity device based on above-mentioned continuous production tolylene diisocyanate completes the technique preparing tolylene diisocyanate, step is as follows: volume flow ratio scope is the indefiniteness percussion flow structure that first the phosgene inert solvent solution of 1-15 and tolylene diamine inert solvent solution flow in cold reactor, tolylene diamine inert solvent solution is ejected in circumferential direction from annular space and mixes with the phosgene inert solvent solution that main feed-pipe nozzle discharge hole sprays, and collide on baffle plate, backwash, form Gao Tuanneng dissipative shock wave district, two strands of liquid complete rapidly micromixing and mix 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 hypergravity structure in cold reactor, and leave cold reactor in the residence time of 0.1-2s, 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 described tolylene diamine inert solvent solution, massfraction is 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 phthalate, diethyl phthalate or dimethyl isophthalate, the preferred dimethyl isophthalate of method described in the utility model.

In hypergravity structure, rotor speed scope is 300-1000r/min, and temperature of reaction controls at 100-150 DEG C, and reaction absolute pressure is 1-2MPa.

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; B () sleeve pipe adopts annular space nozzle, mix, ensure that all directions mix from the liquid of annular space nozzle ejection with the liquid that main feed-pipe nozzle sprays at circumferential direction; C () spray nozzle front end is provided with baffle plate, two strands of liquid collides on baffle plate, backwash mixing, and two strands of liquid become static energy at this kinetic transformation, form high turbulence district.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 its micro mixing is strengthened, make two strands of reaction masses 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 utility model schematic diagram,

Fig. 2 is cold reactor structure iron,

Fig. 3 ring type nozzle cross-section figure,

Fig. 4 is the baffle arrangement schematic diagram of outwardly convex,

Fig. 5 is dull and stereotyped baffle arrangement schematic diagram,

Fig. 6 is the baffle arrangement schematic diagram caved inward.

In figure: 1-cold reactor, 2-thermal reactor, 3-tolylene diamine solution, 4-phosgene solution, the main feed tube mouth of 1.1-, 1.2-sleeve pipe opening for feed, the main feed-pipe of 1.3-, 1.4-sleeve pipe, the main feed-pipe nozzle of 1.5-, 1.6-circumferential weld, 1.7-housing, 1.8-filler, 1.9-rotor, 1.10-motor, 1.11-rotating shaft, 1.12-liquid shield, 1.13-liquid exit.

Embodiment

As Fig. 1, shown in 2, the list reflection super-gravity device of continuous production tolylene diisocyanate, comprise cold reactor 1 and thermal reactor 2, cold reactor comprises indefiniteness percussion flow structure and hypergravity structure, described indefiniteness percussion flow structure comprises the different main feed-pipe 1.3 of caliber and sleeve pipe 1.4 and liquid shield 1.12, the caliber of sleeve pipe 1.4 is greater than the caliber of main feed-pipe 1.3, sleeve pipe 1.4 is placed on outside main feed-pipe 1.3, main feed-pipe 1.3 arranges main feed tube mouth 1.1 away from one end of liquid shield 1.12, the other end near liquid shield 1.12 arranges the main feed-pipe nozzle 1.5 of flared, center, main feed-pipe nozzle 1.5 end has discharge hole, one end of the corresponding main feed tube mouth of sleeve pipe 1.4 is also provided with sleeve pipe opening for feed 1.2, the other end opening of the corresponding main feed-pipe nozzle of sleeve pipe, ferrule openings end and main feed-pipe nozzle-end form circumferential weld 1.6, discharge hole and circumferential weld are arranged at same plane, baffle plate is vertically arranged relative to the axis direction of main feed-pipe and sleeve pipe, baffle center is positioned on the axis of main feed-pipe and sleeve pipe, hypergravity structure comprises filler 1.8, rotating shaft 1.11, rotor 1.9, housing 1.7 and liquid exit 1.13, described indefiniteness percussion flow vibrational power flow is in the cavity of rotor 1.9 and arrange along rotor axis direction, and its axis and rotor 1.9 dead in line, liquid shield 1.12 is connected with rotor Inner edge, rotor is positioned at the middle part of housing, and filler is in rotor hollow ring, liquid exit is connected with thermal reactor in the bottom of housing, and rotating shaft is rotated by the rotor driven that is connected with motor.

In order to be adapted to the mixing of non-equal-volume throughput ratio, ensure that liquid collision rift completes micromixing instantaneously, and enter hypergravity structure at short notice and complete micro mixing rapidly, casing diameter d ₂with main feed tube diameter d ₃be 2-10 with ratio; Casing length L ₁with casing diameter d ₂ratio is 1-10; The internal diameter d of main feed-pipe ₃with nozzle discharge hole diameter D ₂ratio be 1-100; Circumferential weld width D ₁with nozzle discharge hole diameter D ₂ratio be 1-10, casing diameter d ₂with hypergravity structured packing inner edge to sleeve pipe distance d ₁ratio scope be 1-200, baffle plate is to indefiniteness percussion flow structure distance d ₄with main feed-pipe nozzle diameter D ₂ratio range is 1-50.

Described hypergravity structure, comprises housing, open circles ring-shaped rotor, filler, baffle plate and rotating shaft.Hypergravity structure can be rotary packed bed formula, deflector type, screw path type, rotor-stator formula, any of disc-type hypergravity structure.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.

As shown in Figure 4,5, 6, baffle plate is circular, also can be square, and baffle plate is flat board, caves inward or outwardly convex, and baffle surface is level and smooth or coarse.The good outwardly convex of prioritizing selection microcosmic mixed effect, shaggy circular baffle plate.Baffle plate be fixed on rotary packed bed on, be connected with rotor inner edge, therewith rotate; Also can with percussion flow anatomical connectivity.The good outwardly convex of prioritizing selection microcosmic mixed effect, shaggy circular baffle plate.

Prepare the technique of tolylene diisocyanate, based on the list reflection super-gravity device of above-mentioned continuous production tolylene diisocyanate, step is as follows: volume flow ratio scope is the indefiniteness percussion flow structure that first phosgene of 1-15 and tolylene diamine inertia solution flow in cold reactor, tolylene diamine goes out from annular space nozzle jet the phosgene inertia solution sprayed at circumferential direction and main feed-pipe nozzle discharge hole and mixes, and on baffle plate collide, backwash, form Gao Tuanneng dissipative shock wave district, two strands of liquid complete rapidly micromixing and mix with preliminary microcosmic.After this, liquid is got rid of in the filler of high speed rotating by baffle plate, and filler constantly shears dispersion to liquid, thus maintains material and have high rapids energy dissipative shock wave always, has completed rapidly microcosmic mixing, thus ensure that reaction has high selectivity.Known by theoretical analysis, the size of the rapids energy dissipative shock wave of cold reaction is directly proportional to shock initial velocity and rotating speed, by the rotating speed of adjustment hypergravity structure and the flow of two strands of liquid, and can completing the time controling of both macro and micro in characteristic reactive time.In rotary packed bed, rotor speed scope is 300-1000r/min; Temperature of reaction controls at 100-150 DEG C, and reaction absolute pressure is 1-2MPa.This ensures that there tolylene diamine (TDA) to complete and change into intermediate product.After this, tolylene diamine (TDA) changes into intermediate product completely in cold reactor, and leaves cold reactor in the residence time of 0.1-2s, enters thermal reactor, at 90-200 DEG C, continues reaction and generate TDI crude product under absolute pressure 0.3-1.8MPa.

The temperature 110-150 DEG C of described tolylene diamine inert solvent solution, massfraction is 10%-40%; The temperature 70-110 DEG C of phosgene inert solvent solution, phosgene massfraction concentration is 20%-50%; Inert solvent can be wherein one or more the mixture of benzene, toluene, chlorobenzene, orthodichlorobenzene, santochlor, a chlordiphenyl, and inert solvent also can be wherein one or more the mixture of diethyl terephthalate, diethyl phthalate or dimethyl isophthalate.

As Fig. 1, tolylene diamine and phosgene inertia solution enter in 1 from cold reaction, and flow larger phosgene inertia solution enters from main opening for feed 1.3, and the tolylene diamine inertia solution that flow is less enters from sleeve pipe opening for feed 1.2.Phosgene inertia solution sprays from main feed-pipe nozzle 1.5, tolylene diamine inertia solution sprays from sleeve pipe and main feed-pipe circumferential weld 1.6, two strands of liquid collides through baffle plate 1.12, after backwash mixing, liquid enters the filler 1.8 of high speed rotating, flows out after flowing out packing layer from liquid exit 1.13; Then complete thermal response at thermal reactor 2 and generate TDI crude product.

Embodiment one:

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; Casing diameter d ₂for 200mm, casing diameter d ₂with main feed tube diameter d ₃be 2 with ratio, main feed tube diameter d ₃for 100mm; Casing length L ₁with casing diameter d ₂ratio is 10, casing length L ₁for 2000mm; The internal diameter d of main feed-pipe ₃with nozzle discharge hole diameter D ₂ratio be 100, nozzle discharge hole diameter D ₂for 1mm; Circumferential weld width D ₁with nozzle discharge hole diameter D ₂ratio be 10, circumferential weld width D ₁for 10mm; Casing diameter d ₂with hypergravity structured packing inner edge to sleeve pipe distance d ₁ratio be 1, hypergravity structured packing inner edge is to sleeve pipe distance d ₁for 200mm; Baffle plate is to indefiniteness percussion flow structure distance d ₄with main feed-pipe nozzle diameter D ₂ratio is 50, and baffle plate is to indefiniteness percussion flow structure distance d ₄for 50mm;

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 99.2%.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 two:

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 10%, and mass flow rate is 9000kg/h; The temperature of phosgene inert solvent solution 110 DEG C, phosgene massfraction concentration is 50%, and mass flow rate is 9500kg/h.Phosgene and tolylene diamine inertia liquor capacity flow approximation ratio are 1:1, enter cold reactor and react, and adopt rotor-stator formula hypergravity structure, filler is metal foam filler; Casing diameter d ₂for 200mm, casing diameter d ₂with main feed tube diameter d ₃be 10 with ratio, main feed tube diameter d ₃for 20mm; Casing length L ₁with casing diameter d ₂ratio is 1, casing length L ₁for 200mm; The internal diameter d of main feed-pipe ₃with nozzle discharge hole diameter D ₂ratio be 1, nozzle discharge hole diameter D ₂for 20mm; Circumferential weld width D ₁with nozzle discharge hole diameter D ₂ratio be 1, circumferential weld width D ₁for 20mm; Casing diameter d ₂with hypergravity structured packing inner edge to sleeve pipe distance d ₁ratio scope be 200, hypergravity structured packing inner edge is to sleeve pipe distance d ₁for 1mm; Baffle plate is to indefiniteness percussion flow structure distance d ₄with main feed-pipe nozzle diameter D ₂ratio range is 1, and baffle plate is to indefiniteness percussion flow structure distance d ₄for 20mm.

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 98.9%, there is not latch up phenomenon in 8 months in plant running.

Embodiment three:

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 140 DEG C, massfraction is 40%, and mass rate is 3020kg/h; The temperature of phosgene inert solvent solution 100 DEG C, phosgene massfraction concentration is 30%, and mass rate is 10820kg/h.Phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 3:1, enter cold reactor and react, and adopt screw path type hypergravity structure, filler is metal foam filler; It is characterized in that casing diameter d ₂for 150mm, casing diameter d ₂with main feed tube diameter d ₃be 3 with ratio, main feed tube diameter d ₃for 50mm; Casing length L ₁with casing diameter d ₂ratio is 2, casing length L ₁for 300mm; The internal diameter d of main feed-pipe ₃with nozzle discharge hole diameter D ₂ratio be 20, nozzle discharge hole diameter D ₂for 2.5mm; Circumferential weld width D ₁with nozzle discharge hole diameter D ₂ratio be 2, circumferential weld width D ₁for 5mm, casing diameter d ₂with hypergravity structured packing inner edge to sleeve pipe distance d ₁ratio be 10, hypergravity structured packing inner edge is to sleeve pipe distance d ₁for 15mm; Baffle plate is to indefiniteness percussion flow structure distance d ₄with main feed-pipe nozzle diameter D ₂ratio range is 10, and baffle plate is to indefiniteness percussion flow structure distance d ₄for 25mm.

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.

Be similar to the traditional technology of 1:1 according to volume flow ratio, then need separately to add approximate 7000kg/h orthodichlorobenzene light naphtha and dilute tolylene diamine as inert solvent, solvent cost improves, and later separation difficulty strengthens

Embodiment four:

Carry out pilot experiment at certain TDI manufacturer the utility model technique and device, dimethyl isophthalate heavy solvent specific as follows as inert solvent, the temperature of the tolylene diamine inert solvent solution of configuration 140 DEG C, massfraction is 30%; The temperature of phosgene inert solvent solution 80 DEG C, phosgene massfraction concentration is 36%.Phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 10:1, enter cold reactor and react, and adopt rotary packed bed formula hypergravity structure, filler is wire packing; Casing diameter d ₂for 200mm, casing diameter d ₂with main feed tube diameter d ₃be 2 with ratio, main feed tube diameter d ₃for 100mm; Casing length L ₁with casing diameter d ₂ratio is 10, casing length L ₁for 2000mm; The internal diameter d of main feed-pipe ₃with nozzle discharge hole diameter D ₂ratio be 100, nozzle discharge hole diameter D ₂for 1mm; Circumferential weld width D ₁with nozzle discharge hole diameter D ₂ratio be 10, circumferential weld width D ₁for 10mm; Casing diameter d ₂with hypergravity structured packing inner edge to sleeve pipe distance d ₁ratio be 1, hypergravity structured packing inner edge is to sleeve pipe distance d ₁for 200mm; Baffle plate is to indefiniteness percussion flow structure distance d ₄with main feed-pipe nozzle diameter D ₂ratio is 50, and baffle plate is to indefiniteness percussion flow structure distance d ₄for 50mm;

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 98.5%.Within 8 months, there is not latch up phenomenon in plant running.

Embodiment five:

Carry out pilot experiment at certain TDI manufacturer the utility model technique and device, dimethyl isophthalate heavy solvent specific as follows as inert solvent, the temperature of the tolylene diamine inert solvent solution of configuration 150 DEG C, massfraction is 45%; The temperature of phosgene inert solvent solution 110 DEG C, phosgene massfraction concentration is 30%.Phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 1:1, enter cold reactor and react, and adopt rotor-stator formula hypergravity structure, filler is metal foam filler; Casing diameter d ₂for 200mm, casing diameter d ₂with main feed tube diameter d ₃be 10 with ratio, main feed tube diameter d ₃for 20mm; Casing length L ₁with casing diameter d ₂ratio is 1, casing length L ₁for 200mm; The internal diameter d of main feed-pipe ₃with nozzle discharge hole diameter D ₂ratio be 1, nozzle discharge hole diameter D ₂for 20mm; Circumferential weld width D ₁with nozzle discharge hole diameter D ₂ratio be 1, circumferential weld width D ₁for 20mm; Casing diameter d ₂with hypergravity structured packing inner edge to sleeve pipe distance d ₁ratio scope be 200, hypergravity structured packing inner edge is to sleeve pipe distance d ₁for 1mm; Baffle plate is to indefiniteness percussion flow structure distance d ₄with main feed-pipe nozzle diameter D ₂ratio range is 1, and baffle plate is to indefiniteness percussion flow structure distance d ₄for 20mm.

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 99.5%, there is not latch up phenomenon in 8 months in plant running.

Embodiment six:

Carry out pilot experiment at certain TDI manufacturer the utility model technique and device, dimethyl isophthalate heavy solvent specific as follows as inert solvent, the temperature of the tolylene diamine inert solvent solution of configuration 145 DEG C, massfraction is 28%; The temperature of phosgene inert solvent solution 85 DEG C, phosgene massfraction concentration is 30%.Phosgene and tolylene diamine inertia liquor capacity throughput ratio are approximately 3:1, enter cold reactor and react, and adopt screw path type hypergravity structure, filler is metal foam filler; Casing diameter d ₂for 150mm, casing diameter d ₂with main feed tube diameter d ₃be 3 with ratio, main feed tube diameter d ₃for 50mm; Casing length L ₁with casing diameter d ₂ratio is 2, casing length L ₁for 300mm; The internal diameter d of main feed-pipe ₃with nozzle discharge hole diameter D ₂ratio be 20, nozzle discharge hole diameter D ₂for 2.5mm; Circumferential weld width D ₁with nozzle discharge hole diameter D ₂ratio be 2, circumferential weld width D ₁for 5mm, casing diameter d ₂with hypergravity structured packing inner edge to sleeve pipe distance d ₁ratio be 10, hypergravity structured packing inner edge is to sleeve pipe distance d ₁for 15mm; Baffle plate is to indefiniteness percussion flow structure distance d ₄with main feed-pipe nozzle diameter D ₂ratio range is 10, and baffle plate is to indefiniteness percussion flow structure distance d ₄for 25mm.

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.

Claims (3)

1. the list reflection super-gravity device of a continuous production tolylene diisocyanate, comprise cold reactor (1) and thermal reactor (2), it is characterized in that cold reactor comprises indefiniteness percussion flow structure and hypergravity structure, described indefiniteness percussion flow structure comprises the different main feed-pipe (1.3) of caliber and sleeve pipe (1.4) and baffle plate (1.12), the caliber of sleeve pipe (1.4) is greater than the caliber of main feed-pipe (1.3), sleeve pipe (1.4) is placed on outside main feed-pipe (1.3), main feed-pipe (1.3) arranges main feed tube mouth (1.1) away from one end of baffle plate (1.12), the other end near liquid shield (1.12) arranges the main feed-pipe nozzle (1.5) of flared, main feed-pipe nozzle (1.5) center, end has discharge hole, one end of the corresponding main feed tube mouth of sleeve pipe (1.4) is also provided with sleeve pipe opening for feed (1.2), the other end opening of the corresponding main feed-pipe nozzle of sleeve pipe, ferrule openings end and main feed-pipe nozzle-end form circumferential weld (1.6), discharge hole and circumferential weld are arranged at same plane, baffle plate is vertically arranged relative to the axis direction of main feed-pipe and sleeve pipe, baffle center is positioned on the axis of main feed-pipe and sleeve pipe, hypergravity structure comprises filler (1.8), rotating shaft (1.11), rotor (1.9), housing (1.7) and liquid exit (1.13), described indefiniteness percussion flow vibrational power flow is in the cavity of rotor (1.9) and arrange along rotor axis direction, and (1.9) dead in line of the axis of indefiniteness percussion flow structure and rotor, rotor is positioned at the middle part of housing, and filler is in rotor hollow ring, liquid exit is connected with thermal reactor in the bottom of housing, and rotating shaft is rotated by the rotor driven that is connected with motor.

2. the list reflection super-gravity device of continuous production tolylene diisocyanate according to claim 1, is characterized in that casing diameter (d ₂) and main feed tube diameter (d ₃) with ratio be 2-10; Casing length (L ₁) and casing diameter (d ₂) ratio is 1-10; Internal diameter (the d of main feed-pipe ₃) and nozzle discharge hole diameter (D ₂) ratio be 1-100; Circumferential weld width (D ₁) and nozzle discharge hole diameter (D ₂) ratio be 1-10, casing diameter (d ₂) with hypergravity structured packing inner edge to sleeve pipe apart from (d ₁) ratio scope be 1-200, baffle plate to indefiniteness percussion flow structure distance (d ₄) and main feed-pipe nozzle diameter (D ₂) ratio range is 1-50.

3. the list reflection super-gravity device of continuous production tolylene diisocyanate according to claim 1 and 2, it is characterized in that baffle plate is circular or square, the relatively main feed-pipe of baffle plate and the rotatable setting of sleeve pipe or with main feed-pipe and telescopic joint, baffle plate is outwardly convex, and baffle surface is coarse.