CN104402766B - Single reflection hypergravity device and process for continuous preparation of toluene diisocyanate - Google Patents
Single reflection hypergravity device and process for continuous preparation of toluene diisocyanate Download PDFInfo
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Abstract
The invention belongs to the technical field of toluene diisocyanate production, in particular relates to a single reflection hypergravity device and process for continuous preparation of toluene diisocyanate, and solves the problems of poor reaction selectivity, decreased conversion rate and possible reaction device fault under large flow volume ratio differences of materials in the existing production process of toluene diisocyanate. The hypergravity device includes a cold reactor and a heat reactor; the cold reactor comprises a non-limitative impinging stream structure and a hypergravity structure, and the non-restrictive impinging stream structure comprises a main feeding pipe and a casing pipe in different diameters and baffle plates. The process is as below: flowing a phosgene inert solvent solution and a toluenediamine inert solvent solution into the non-restrictive impinging stream structure, then following into a rotation packing, then flowing into the heat reactor, and reacting to generate a TDI crude product. According to the invention, toluenediamine almost reacts completely, so s to prevent generation of urea materials, effectively avoid plugging of the pipeline and reactor, and improve the production efficiency of toluene diisocyanate.
Description
Technical field
The invention belongs to toluene di-isocyanate(TDI)（TDI）The technical field of production, and in particular to one kind continuously prepares toluene
The single reflection super-gravity device of diisocyanate and technique.
Background technology
TDI is a kind of isocyanates of mixed type, and what industry was commonly used is two kinds of isomery weights of 2,4-TDI and 2,6-TDI
Than for 80:20 mixture.Its production method mainly has phosgenation and non-phosgene.But, so far, both at home and abroad industry is raw
The method for producing TDI mainly adopts light phosgenation technique, phosgenation production TDI mainly to include five steps：（1）Carbon monoxide and
Chlorine reaction generates phosgene；（2）Toluene generates dinitrotoluene (DNT) with nitric acid reaction（DNT）；（3）DNT generates toluene with hydrogen reaction
Diamines（TDA）；（4）The TDA that is dried for processing is generated with phosgene reaction（TDI）；（5）The purification of TDI.TDI produces phosgenation
Reaction refers to toluenediamine（TDA）Process under atent solvent effect with phosgene reaction, is divided into cold reaction and thermal response two
Step is carried out.It is convenient to describe problem, with toluenediamine（TDA）As a example by provide course of reaction.
（1）
（2）
（3）
（4）
（5）
（6）
Reaction（1）,（2）To prepare the main reaction of TDI, other reactions are side reaction.Reaction (1) is referred to as cold light gasified reverse
Should, itself releases big calorimetric so that temperature of charge is raised.Course of reaction is divided into two steps：One amino of TDA and phosgene
With reference to, a HCl is discharged, generate carbamyl chloride（-NHCOCl）；Another amino of TDA is combined with free HCl（Typically
Capture is the HCl just generated with same intramolecular）Into semicarbazide hydrochloride（-NH2﹒ HCl）.Carbamyl chloride and semicarbazide hydrochloride
Generation is all extremely rapid, so reaction 1 is also called fast response.
Reaction (2) is referred to as the intermediate product that thermal response is cold reaction and further reacts generation target product TDI and accessory substance
The process of hydrogen chloride.Also in two steps：Semicarbazide hydrochloride（-NH2﹒ HCl）First it is dissociated into amino and free HCl, amino and light
Solid/liquid/gas reactions generate carbamyl chloride（-NHCOCl）HCl free with one.Two steps that thermal process reactor is related to are reversible
, so isolating HCl in time becomes the key for improving reaction speed, and it is the endothermic reaction to react, so heat should be sucked, is protected
Hold reaction temperature, it is ensured that reaction is normally carried out, therefore referred to as thermal response stage.
Reaction（3）-（6）For side reaction, occur mainly between several groups, but its reaction rate is below reacted
（1）.Amino in specially raw material TDA（-NH2）, intermediate product carbamyl chloride（-NHCOCl）, isocyanide in product TDI
Acid esters（-N=C=O）Reaction generates insoluble matter urea, and being frequently occluded pipeline, yield reduces, and has a strong impact on the normal production of TDI.
According to the difference of the atent solvent used in phosgenation process, phosgenation process can be divided into heavy solvent method and light
Solvent method.With heavy solvent method such as dimethyl isophthalate（DEIP）Make solvent, photochemical reaction is carried out under elevated pressure conditions, that is, lead to
Often alleged " heavy solvent production technology ".With light naphtha such as o-dichlorohenzene（ODCB）Make solvent, carry out under lower pressure photochemical
Reaction, that is, " the light naphtha production technology " being commonly referred to as.When being produced using heavy solvent method, solvent serves in the reaction dispersant
Effect, protective effect is served in separation again, and it can make TDI reduce the chance occurred in bottom of towe.So, it is molten using weight
Agent method production TDI can to a certain extent reduce generation side reaction（3）-（6）But, industrially mainly will not using solvent
The light naphtha method production reacted with material, this is mainly heavy solvent that its is larger：First, DEIP is easily and phosgene
Reaction generates the boiling point of m-carbethoxyphenyl formyl chloride between TDI and DEI P, therefore accumulates in a solvent, and with
TDA further reacts generation amides compound (solid residue), so that reaction yield is reduced, blocks reactor, pipeline, divides
From equipment, the utilization of capacity is affected.Side reaction equation is（7）-（8）.
（7）
（8）
To sum up analyze, produced during TDI using light naphtha method, because solvent does not react with product, then occur
Side reaction is mainly（3）-（6）；During using heavy solvent method production TDI, although heavy solvent can be protected to a certain extent
Target product, suppresses the generation of side reaction, but has side reaction（7）-（8）Occur.Can by theory analysis and pilot-scale experiment
Know, mainly two strands reaction masses of generation of these side reactions complete the time of microcosmic and micromixing more than reaction（1）Spy
Levy caused by the reaction time.If the time of microcosmic and micromixing is less than reaction（1）Characteristic reactive time then phosgene is excellent
First react with toluenediamine, the completely rear presence without amino of toluenediamine reaction is then（3）-（6）,（8）Side reaction just
Will not occur.Thus can avoid blocking reactor, pipeline, separation equipment, the problem of power is opened in impact, and is reacted（8）
Will not occur, then react（7）Conversion ratio reduce, greatly reduce the loss of DEIP.
Describe for convenience, the impact of macroscopic view, Determining Micromixing Characteristic Time to product is illustrated with below equation：
A+C → D (9)
B+C → P (10)
Wherein (9) formula is fast response,（10）Formula is long response time.
Macroscopic mixing time is to characterize two strands of liquid to reach the spatially concentration homogeneous time, now two bursts of reactant feeds
Mean concentration be anywhere the same, can be expressed as：
ts= K1(ε)-1/3
ε represents the rapids energy dissipative shock wave of fluid, K1Proportionality coefficient constant is represented, with type of reactor, feed location, charging side
Formula etc. is relevant.
Determining Micromixing Characteristic Time characterizes the time that two strands of liquid reach molecular level mixing, can be expressed as：
tm= K2(v/ε)1/2
ε represents the rapids energy dissipative shock wave of fluid, K2Expression proportionality coefficient is constant.
If in macroscopic mixing time tsMore than response feature time tD, i.e. reactional equation（9）,（10）When starting reaction, instead
Answering micromixing state of not yet reach in device, the state reached in 6 regions of reactor as shown in Figure 7, wherein A, B, C difference
Represent three kinds of reactant molecules.
If now rapids energy dissipative shock wave ε of fluid is met respectively in tm= K2(v/ε)1/2<tDAnd tm= K2(v/ε)1/2≥tDCondition
Under, reaction（7）,（8）Product situation see the table below：
If in macroscopic mixing time tsLess than response feature time tD, i.e. reactional equation（9）,（10）When starting reaction, instead
Answer and reached in device micromixing state, the state reached in 6 regions of reactor as shown in Figure 8.Wherein A, B, C distinguish
Represent three kinds of reactant molecules.
If now rapids energy dissipative shock wave ε of fluid is met respectively in tm= K2(v/ε)1/2<tDAnd tm= K2(v/ε)1/2≥tDCondition
Under, reaction（9）,（10）Product situation see the table below：
To sum up analyze, avoid side reaction from occurring in the technique of synthesizing isocyanate, it is necessary in reaction（1）Response feature
Toluenediamine is completed in time to mix with microcosmic with the micromixing of phosgene inertia solution, so can just make reaction（1）It is preferential its
He reacts in side reaction, so as to react（1）Could react completely, the presence without amino avoids the generation of side reaction.
But it is main more using injection reactor in order to reach quick mixed effect in reporting in published patent
There are gas phase phosgenation and liquid phase phosgenation.Gas phase phosgenation such as patent CN1127248 discloses one kind and adopts injection reactor
The method that gas phase prepares aromatics polyisocyanate acid esters, its conversion ratio answers more than 95%, but still reaction temperature is up to the method
320-350℃.This method reaction temperature is too high, and phosgene is easily revealed, and has production safety hidden danger.
Liquid phase phosgenation production TDI patents mainly have：Patent CN1304927A devises a kind of injection reaction of firing pin type
Device, directly generates isocyanic acid using -5 ~ -10 DEG C of liquid phosgene with light naphtha inertia solution (o-dichlorohenzene) of toluenediamine
Ester, its pass through vibrate striker can remove inside hybrid chamber produce solid by-product, but in disclosed example phosgene and
The reaction mass flow-rate ratio of toluenediamine inertia solution is about 1:Between 2, when phosgene and toluenediamine inertia solution quality stream
Amount ratio about 1:When 1.6 or so, feed pressure need to be up to 2.5Mpa or so, and yield is up to more than 94%.Patent CN 101612547
B discloses a kind of method that shell and tube impact flow reactor prepares toluene di-isocyanate(TDI), phosgene and toluenediamine in example
The reaction appropriate volume flow-rate ratio of inertia solution (light naphtha) is about 1:Between 1.6, but when volume flow ratio is approximately up to 1:
When 2.3, yield drops to 86.7%.Patent CN101774948A discloses one kind using injection reactor using 5 ~ -10 DEG C
The method that liquid phosgene generates isocyanates with heavy solvent inertia solution (DEIP) of toluenediamine, in disclosed example phosgene is worked as
With toluenediamine inertia solution reaction mass flow 2:When 1, charging high pressure reaches 2.05Mpa, and yield is up to 98%.To sum up, current technique
Middle employing liquid low temperature phosgene to insulation of equipment and it is pressure have high demands, and in order to obtain excellent mixed effect, it is desirable to react
Volume flow（Convert by mass flow）Than approximately equal, feed pressure is also larger, and cost is uneconomical.
Patent CN10114595B discloses the side that one kind prepares diphenyl diisocyanate resin (MDI) using high-gravity technology
Method, reaction mass and the mass flow of phosgene inertia solution are 1 in optimum example:0.9 (volume flow approximate 1:1) under the conditions of, turn
Rate is up to 98.3%.But, the method need polyamines and phosgene must be diluted to volume flow ratio it is close can be only achieved it is high
Conversion ratio, increases the consumption of atent solvent, and following detached energy consumption also can increase.This is primarily due to substantial amounts of document
The microcosmic mixed performance liquid body micromixing state of report hypergravity equipment affects very big, especially in two strands of volume of material streams
In the case that amount is than differing greatly, hypergravity equipment affects limited, the deterioration of micromixing performance to strengthening Macro-mixing Process
Microcosmic mixed performance degradation is caused, causes selective decline, conversion ratio to reduce, sent out so as to still be not fee from the reactor
Raw side reaction generates a certain amount of solid matter.Although patent points out that the solid matter for producing can be in powerful centrifugal action
Under throw away from wire packing, but be difficult avoid produce solid by-product blocking reactor outlet.
In sum, in order to reach excellent mixed effect in presently disclosed liquid phase phosgenation production TDI techniques,
Negate and answer volume flow ratio approximately equal, bring atent solvent usage amount to increase, cost is raised, and increases the difficulty of later separation
Degree.But, when volume flow ratio is slightly larger, reaction selectivity is deteriorated, and TDI conversion ratios decline, and side reaction occurs, and easily makes
Forming apparatus are blocked.In addition, technique is harsh to solvent requirement, can only be single suitable for light naphtha or heavy solvent.
The content of the invention
The present invention differs greatly for volume of material flow-rate ratio in the production technology for solving existing toluene di-isocyanate(TDI)
In the case of, reaction selectivity is deteriorated, and causes conversion ratio to decline, and may bring the problem of the failure of reaction unit.
The present invention adopts the following technical scheme that realization：
A kind of single reflection super-gravity device for continuously preparing toluene di-isocyanate(TDI), including cold reactor and thermal reactor,
It is characterized in that cold reactor includes non-limiting shock flow structure and hypergravity structure, the non-limiting shock flow structure bag
The different main feed pipe of caliber and sleeve pipe and baffle plate are included, the caliber of sleeve pipe is more than the caliber of main feed pipe, and sleeve pipe is placed on master and enters
Outside expects pipe, main feed pipe arranges main feed pipe charging aperture, the other end near liquid shield and arranges and expand away from one end of baffle plate
Shape of the mouth as one speaks main feed pipe nozzle, main feed pipe nozzle-end center is provided with discharge opening, one end of sleeve pipe correspondence main feed pipe charging aperture
Sleeve pipe charging aperture is also equipped with, sleeve pipe corresponds to another end opening, ferrule openings end and the spray of main feed pipe of main feed pipe nozzle
Mouth end forms circumferential weld, and discharge opening is arranged at same plane with circumferential weld, and baffle plate is relative to main feed pipe and the axis side of sleeve pipe
To being vertically arranged, baffle center is located on the axis of main feed pipe and sleeve pipe；Hypergravity structure include filler, rotating shaft, rotor,
Housing and liquid outlet, described non-limiting percussion flow structure setting sets in the cavity of rotor and along rotor axis direction
Put, and non-limiting percussion flow structure axis overlaps with shaft axis, rotor is located at the middle part of housing, and filler is in rotor hollow ring
In；Liquid outlet is connected in the bottom of housing with thermal reactor, and rotating shaft is rotated by the rotor driven that is connected with motor.
Casing diameter d2With main feed pipe diameter d3It is 2-10 with ratio；Casing length L1With casing diameter d2Ratio is 1-
10；The internal diameter d of main feed pipe3With nozzle discharging bore dia D2Ratio be 1-100；Circumferential weld width D1With nozzle discharging bore dia D2
Ratio be 1-10, casing diameter d2With hypergravity structured packing inner edge to set pipe distance d1Ratio scope be 1-200, baffle plate is to non-
Limited shock flow structure is apart from d4With main feed pipe nozzle diameter D2Ratio range is 1-50.
A kind of technique for preparing toluene di-isocyanate(TDI), based on the above-mentioned single reflection for continuously preparing toluene di-isocyanate(TDI)
Super-gravity device is completed, and step is as follows：Volume flow ratio scope is the phosgene inert solvent solution and toluenediamine inertia of 1-15
Solvent solution flows into first the non-limiting shock flow structure in cold reactor, and toluenediamine inert solvent solution sprays from annular space
The phosgene inert solvent solution sprayed with main feed pipe nozzle discharge opening in circumferencial direction mixes, and collision, backwash on baffle plate,
Gao Tuanneng dissipative shock waves area is formed, two strands of liquid quickly complete micromixing and mix with preliminary microcosmic, liquid is left in shock plane
The filler of rotation is entered after the heart, powerful shearing force keeps material to have high rapids energy dissipative shock wave, not up to microcosmic mixing always
Liquid quickly complete micro mixing, hereafter, toluenediamine（TDA）Convert completely in hypergravity structure in cold reactor
Into intermediate product, and cold reactor is left in the time of staying of 0.1-2s, into thermal reactor, at 90-200 DEG C, absolute pressure
Continue to react under 0.3-1.8MPa to generate TDI crude products.
Temperature 110-150 DEG C of described toluenediamine inert solvent solution, mass fraction is 10%-40%；Phosgene inertia
Temperature 70-110 DEG C of solvent solution, phosgene mass fraction concentration is 20%-50%.
Atent solvent, is light naphtha or heavy solvent, wherein light naphtha can be benzene, toluene, chlorobenzene, o-dichlorohenzene, to two
Chlorobenzene, the one of which of a chlordiphenyl or several mixtures, the preferred o-dichlorohenzene of method of the present invention；Heavy solvent can be with
It is the one of which or several mixtures of diethyl phthalate, diethyl phthalate or dimethyl isophthalate,
The preferred dimethyl isophthalate of method of the present invention.
In hypergravity structure, rotor speed scope is 300-1000r/min, and reaction temperature is controlled at 100-150 DEG C, reaction
Absolute pressure is 1-2MPa.
With additive method ratio, the present invention has following dramatically different：
（1）The cold reactor structure that the present invention is adopted is different from traditional reactor, and it is by percussion flow and hypergravity structure two
Part constitutes, to realize invented technology in require to be completed within the response feature time requirement that macroscopic view mixes with microcosmic.Percussion flow
Structure of reactor of the structure also different from published production TDI：A () is directly formed without hybrid chamber, the opposed collision rift of liquid
The covering of the fan of unrestricted diverging；B () sleeve pipe adopts annular space nozzle, spray from liquid and the main feed pipe nozzle of the ejection of annular space nozzle
Liquid mixes in circumferencial direction, it is ensured that all directions are well mixed；C () spray nozzle front end is provided with baffle plate, two strands of liquid are in gear
Collision, backwash mixing on plate, two strands of liquid change into static energy, form high turbulence area in this kinetic energy.Using generally acknowledged conductance method
Macroscopic mixing time and the Determining Micromixing Characteristic Time of cold reactor are characterized with chemical method (parallel competition system), is as a result better than
Traditional reactor an order of magnitude, and in volume flow ratio 1-15, mixed performance is without being remarkably decreased.
（2）The technique of the present invention is divided into two steps the reinforcing of mixed process, allows in the material short time to reach macroscopic view mixed first
Close, then strengthen its micro mixing, make two strands of reaction masses that both macro and micro mixing is completed in characteristic reactive time,
In cold reaction exit, checked by chromatography, in the range of volume flow ratio 1-15, toluenediamine conversion ratio reaches 99.5-
99.7%, it is toluenediamine fundamental reaction is complete, it is therefore prevented that sulfonylurea is generated, and effectively prevent pipeline and reactor plugs, is carried
High production of toluene diisocyanate efficiency.
（3）This method reaction volume flow-rate ratio scope of application width, experimental verification has in the range of volume flow ratio 1-15
High conversion ratio, it is possible to reduce the usage amount of solvent, and it is easy to the quality control of product.
（4）This method highly versatile, goes for light naphtha method and heavy solvent method, is easy to factory to change original technology
Make.
Description of the drawings
Fig. 1 is the process chart for continuously preparing toluene di-isocyanate(TDI),
Fig. 2 is cold reactor structure chart,
Fig. 3 ring type nozzle cross-section figures,
Fig. 4 is the baffle arrangement schematic diagram of outwardly convex,
Fig. 5 is the baffle arrangement schematic diagram of flat board,
Fig. 6 is the baffle arrangement schematic diagram for caving inward,
Fig. 7 is that micromixing view is not yet reached in reactor,
Fig. 8 is that micromixing view is reached in reactor.
In figure：1- cold reactors, 2- thermal reactors, 3- toluenediamine solution, 4- phosgene solutions, the charging of 1.1- main feeds pipe
Mouthful, 1.2- sleeve pipe charging apertures, 1.3- main feed pipes, 1.4- sleeve pipes, 1.5- main feed pipe nozzles, 1.6- circumferential welds, 1.7- housings,
1.8- fillers, 1.9- rotors, 1.10- motors, 1.11- rotating shafts, 1.12- liquid shields, 1.13- liquid outlets.
Specific embodiment
As shown in Fig. 2 the single reflection super-gravity device of toluene di-isocyanate(TDI) is continuously prepared, including cold reactor 1 and heat
Reactor 2, cold reactor includes non-limiting shock flow structure and hypergravity structure, and the non-limiting shock flow structure includes
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 more than main feed pipe 1.3
Caliber, sleeve pipe 1.4 is placed on outside main feed pipe 1.3, and main feed pipe 1.3 arranges main feed pipe away from one end of liquid shield 1.12
Charging aperture 1.1, the other end near liquid shield 1.12 arrange flared main feed pipe nozzle 1.5, the end of main feed pipe nozzle 1.5
Portion center is provided with discharge opening, and one end of the corresponding main feed pipe charging aperture of sleeve pipe 1.4 is also equipped with sleeve pipe charging aperture 1.2, sleeve pipe pair
Answer another end opening of main feed pipe nozzle, ferrule openings end and main feed pipe nozzle-end to form circumferential weld 1.6, discharge opening with
Circumferential weld is arranged at same plane, and baffle plate is vertically arranged relative to the axis direction of main feed pipe and sleeve pipe, and baffle center is located at
On the axis of main feed pipe and sleeve pipe；Hypergravity structure includes filler 1.8, rotating shaft 1.11, rotor 1.9, housing 1.7 and liquid
Body outlet 1.13, described non-limiting percussion flow structure setting is arranged in the cavity of rotor 1.9 and along rotor axis direction,
And its axis and the dead in line of rotor 1.9, liquid shield 1.12 is connected with rotor Inner edge, and rotor is positioned at the middle part of housing, filler
In rotor hollow ring；Liquid outlet is connected in the bottom of housing with thermal reactor, and rotating shaft is driven by being connected with motor and turned
Son is rotated.
In order to be adapted to non-equal-volume flow-rate ratio mixing, it is ensured that liquid collision rift moment completes micromixing, and in short-term
Interior entrance hypergravity structure quickly completes micro mixing, casing diameter d2With main feed pipe diameter d3It is 2-10 with ratio；
Casing length L1With casing diameter d2Ratio is 1-10；The internal diameter d of main feed pipe3With nozzle discharging bore dia D2Ratio be 1-
100；Circumferential weld width D1With nozzle discharging bore dia D2Ratio be 1-10, casing diameter d2With hypergravity structured packing inner edge to set
Pipe distance d1Ratio scope be 1-200, baffle plate to it is non-limiting clash into flow structure apart from d4With main feed pipe nozzle diameter D2Ratio
Scope is 1-50.
Described hypergravity structure, including housing, open circles ring-shaped rotor, filler, baffle plate and rotating shaft.Hypergravity is tied
Structure, can be rotary packed bed formula, deflector type, screw path type, rotor formula, disc-type hypergravity structure any.
Filler is porous media, can be one kind or composition of wire packing, metal foam filler or corrugated plate packing, and filling mode can
Be rule can also be random filling.
As shown in Figure 4,5, 6, baffle plate is circle, or square, baffle plate is flat board, caves inward or outwardly convex,
Baffle surface is smooth or coarse.The preferable outwardly convex of prioritizing selection microcosmic mixed effect, shaggy circular baffle plate.Gear
Plate is fixed on rotary packed bed, is connected with rotor inner edge, is rotated with it；Can also be connected with flow structure is clashed into.Preferentially
Select the preferable outwardly convex of microcosmic mixed effect, shaggy circular baffle plate.
The technique for preparing toluene di-isocyanate(TDI) is overweight based on the above-mentioned single reflection for continuously preparing toluene di-isocyanate(TDI)
Power apparatus, step is as follows：Volume flow ratio scope flows into first cold reactor for the phosgene of 1-15 with toluenediamine inertia solution
In non-limiting shock flow structure, toluenediamine goes out in circumferencial direction and main feed pipe nozzle discharge opening from annular space nozzle jet
The phosgene inertia solution mixing of ejection, and collision, backwash on baffle plate, form Gao Tuanneng dissipative shock waves area, and two strands of liquid are complete rapidly
Mix with preliminary microcosmic into micromixing.Hereafter, liquid is got rid of in the filler of rotation at a high speed by baffle plate, and filler is constantly cut to liquid
Cutting dissipates, and has high rapids energy dissipative shock wave always so as to maintain material, quickly completes and completes microcosmic mixing, anti-so as to ensure that
There should be high selectivity.By theory analysis, the size of the rapids energy dissipative shock wave of cold reaction with clash into initial velocity and rotating speed into
Direct ratio, by adjusting the rotating speed of hypergravity structure and the flow of two strands of liquid, can be the time control for completing both macro and micro
In characteristic reactive time.In rotary packed bed, rotor speed scope is 300-1000r/min；Reaction temperature is controlled in 100-
150 DEG C, reaction absolute pressure is 1-2MPa.This ensures that there toluenediamine（TDA）Complete to change into intermediate product.Hereafter,
Toluenediamine（TDA）Intermediate product is fully converted in cold reactor, and cold reactor is left in the time of staying of 0.1-2s,
Into thermal reactor, at 90-200 DEG C, continue to react under absolute pressure 0.3-1.8MPa to generate TDI crude products.
Temperature 110-150 DEG C of described toluenediamine inert solvent solution, mass fraction is 10%-40%；Phosgene inertia
Temperature 70-110 DEG C of solvent solution, phosgene mass fraction concentration is 20%-50%；Atent solvent can for benzene, toluene, chlorobenzene,
O-dichlorohenzene, paracide, the one of which of a chlordiphenyl or several mixtures, atent solvent can also be terephthalic acid (TPA)
The one of which of diethylester, diethyl phthalate or dimethyl isophthalate or several mixtures.
Such as Fig. 1, toluenediamine is entered with phosgene inertia solution from 1 in cold reaction, the larger phosgene inertia solution of flow from
Main feed mouth 1.3 is entered, and the less toluenediamine inertia solution of flow is entered from sleeve pipe charging aperture 1.2.Phosgene inertia solution from
Main feed pipe nozzle 1.5 sprays, and toluenediamine inertia solution sprays from sleeve pipe and main feed pipe ring seam 1.6, two strands of liquid Jing gears
Plate 1.12 is collided, after backwash mixing, liquid enters the filler 1.8 of at a high speed rotation, flows out and is flowed from liquid outlet 1.13 after packing layer
Go out；Then complete thermal response in thermal reactor 2 and generate TDI crude products.
Embodiment one：
Pilot experiment is carried out with present invention process and device in certain TDI manufacturer, it is specific as follows gently molten with o-dichlorohenzene
Used as atent solvent, 110 DEG C of the temperature of the toluenediamine inert solvent solution of configuration, mass fraction is 40%, and mass velocity is for agent
1000Kg/h；The temperature 70 C of phosgene inert solvent solution, phosgene mass fraction concentration is 20%, and mass velocity is 15240kg/
H, phosgene is approximately 15 with toluenediamine inertia liquor capacity flow-rate ratio:1, reacted into cold reactor, using rotary filling
Material bed hypergravity structure, filler is wire packing；Casing diameter d2For 200mm, casing diameter d2With main feed pipe diameter d3With
Ratio is 2, main feed pipe diameter d3For 100mm；Casing length L1With casing diameter d2Ratio is 10, casing length L1For
2000mm；The internal diameter d of main feed pipe3With nozzle discharging bore dia D2Ratio be 100, nozzle discharging bore dia D2For 1mm；Circumferential weld
Width D1With nozzle discharging bore dia D2Ratio be 10, circumferential weld width D1For 10mm；Casing diameter d2In hypergravity structured packing
Edge is to set pipe distance d1Ratio be 1, hypergravity structured packing inner edge to cover pipe distance d1For 200mm；Baffle plate is to non-limiting shock
Flow structure is apart from d4With main feed pipe nozzle diameter D2Ratio is 50, and baffle plate is to non-limiting shock flow structure apart from d4For 50mm；
At 100 DEG C, reaction absolute pressure is 1MPa for reaction temperature control, and rotating speed is 1000r/min, reaction time
2s, thermal reactor is introduced after reaction in exit, at 90 DEG C, continues to react under absolute pressure 0.3MPa to generate TDI crude products, is passed through
After follow-up workshop section's purification, TDI yield 99.2%.There is not clogging in 8 months in plant running.
According to volume flow ratio approximate 1:1 traditional handicraft, then need separately to add approximate 14000kg/h o-dichlorohenzenes gently molten
Agent is diluted as atent solvent to toluenediamine, and solvent cost is improved, and later separation difficulty is increased.
Embodiment two：
Pilot experiment is carried out with present invention process and device in certain TDI manufacturer, it is specific as follows gently molten with o-dichlorohenzene
Used as atent solvent, 150 DEG C of the temperature of the toluenediamine inert solvent solution of configuration, mass fraction is 10%, and mass flowrate is for agent
9000kg/h；110 DEG C of the temperature of phosgene inert solvent solution, phosgene mass fraction concentration is 50%, and mass flowrate is 9500kg/
h.Phosgene is 1 with toluenediamine inertia liquor capacity flow approximation ratio:1, reacted into cold reactor, using rotor formula
Hypergravity structure, filler is metal foam filler；Casing diameter d2For 200mm, casing diameter d2With main feed pipe diameter d3With than
It is worth for 10, main feed pipe diameter d3For 20mm；Casing length L1With casing diameter d2Ratio is 1, casing length L1For 200mm；It is main
The internal diameter d of feed pipe3With nozzle discharging bore dia D2Ratio be 1, nozzle discharging bore dia D2For 20mm；Circumferential weld width D1With spray
Mouth discharging bore dia D2Ratio be 1, circumferential weld width D1For 20mm；Casing diameter d2With hypergravity structured packing inner edge to sleeve pipe away from
From d1Ratio scope be 200, hypergravity structured packing inner edge to cover pipe distance d1For 1mm；Baffle plate is to non-limiting shock flow structure
Apart from d4With main feed pipe nozzle diameter D2Ratio range is 1, and baffle plate is to non-limiting shock flow structure apart from d4For 20mm.
At 150 DEG C, reaction absolute pressure is 2MPa for reaction temperature control, and rotating speed is 300r/min, reaction time
0.1s, thermal reactor is introduced after reaction in exit, at 200 DEG C, continues to react under absolute pressure 1.8MPa to generate TDI crude products,
After the purification of follow-up workshop section, there is not clogging in 8 months in TDI yield 98.9%, plant running.
Embodiment three：
Pilot experiment is carried out with present invention process and device in certain TDI manufacturer, it is specific as follows gently molten with o-dichlorohenzene
Used as atent solvent, 140 DEG C of the temperature of the toluenediamine inert solvent solution of configuration, mass fraction is 40%, and mass flow is for agent
3020kg/h；100 DEG C of the temperature of phosgene inert solvent solution, phosgene mass fraction concentration is 30%, and mass flow is 10820kg/
h.Phosgene is approximately 3 with toluenediamine inertia liquor capacity flow-rate ratio:1, reacted into cold reactor, using helical duct
Formula hypergravity structure, filler is metal foam filler；It is characterized in that casing diameter d2For 150mm, casing diameter d2With main feed
Pipe diameter d3It is 3 with ratio, main feed pipe diameter d3For 50mm；Casing length L1With casing diameter d2Ratio is 2, casing length L1
For 300mm；The internal diameter d of main feed pipe3With nozzle discharging bore dia D2Ratio be 20, nozzle discharging bore dia D2For 2.5mm；Ring
Seam width D1With nozzle discharging bore dia D2Ratio be 2, circumferential weld width D1For 5mm, casing diameter d2In hypergravity structured packing
Edge is to set pipe distance d1Ratio be 10, hypergravity structured packing inner edge to cover pipe distance d1For 15mm；Baffle plate is to non-limiting shock
Flow structure is apart from d4With main feed pipe nozzle diameter D2Ratio range is 10, and baffle plate is to non-limiting shock flow structure apart from d4For
25mm。
At 120 DEG C, reaction absolute pressure is 1.8MPa for reaction temperature control, and rotating speed is 600r/min, reaction time
1.5s, thermal reactor is introduced after reaction in exit, at 150 DEG C, continues to react under absolute pressure 1.5MPa to generate TDI crude products,
After the purification of follow-up workshop section, there is not clogging in 8 months in TDI yield 99.4%, plant running.
According to volume flow ratio approximate 1:1 traditional handicraft, then need separately to add approximate 7000kg/h o-dichlorohenzenes gently molten
Agent is diluted as atent solvent to toluenediamine, and solvent cost is improved, and later separation difficulty is increased
Example IV：
Pilot experiment, use M-phthalic acid two specific as follows are carried out with present invention process and device in certain TDI manufacturer
Used as atent solvent, 140 DEG C of the temperature of the toluenediamine inert solvent solution of configuration, mass fraction is 30% to ethyl ester heavy solvent；Light
80 DEG C of the temperature of gas inert solvent solution, phosgene mass fraction concentration is 36%.Phosgene and toluenediamine inertia liquor capacity flow
Than being approximately 10:1, reacted into cold reactor, using rotary packed bed formula hypergravity structure, filler is wire packing；
Casing diameter d2For 200mm, casing diameter d2With main feed pipe diameter d3It is 2 with ratio, main feed pipe diameter d3For 100mm；Set
Length of tube L1With casing diameter d2Ratio is 10, casing length L1For 2000mm；The internal diameter d of main feed pipe3It is straight with nozzle discharge opening
Footpath D2Ratio be 100, nozzle discharging bore dia D2For 1mm；Circumferential weld width D1With nozzle discharging bore dia D2Ratio be 10, circumferential weld
Width D1For 10mm；Casing diameter d2With hypergravity structured packing inner edge to set pipe distance d1Ratio be 1, hypergravity structured packing
Inner edge is to set pipe distance d1For 200mm；Baffle plate is to non-limiting shock flow structure apart from d4With main feed pipe nozzle diameter D2Ratio
For 50, baffle plate is to non-limiting shock flow structure apart from d4For 50mm；
At 100 DEG C, reaction absolute pressure is 1MPa for reaction temperature control, and rotating speed is 1000r/min, reaction time
2s, thermal reactor is introduced after reaction in exit, at 90 DEG C, continues to react under absolute pressure 0.3MPa to generate TDI crude products, is passed through
After follow-up workshop section's purification, TDI yield 98.5%.There is not clogging in 8 months in plant running.
Embodiment five：
Pilot experiment, use M-phthalic acid two specific as follows are carried out with present invention process and device in certain TDI manufacturer
Used as atent solvent, 150 DEG C of the temperature of the toluenediamine inert solvent solution of configuration, mass fraction is 45% to ethyl ester heavy solvent；Light
110 DEG C of the temperature of gas inert solvent solution, phosgene mass fraction concentration is 30%.Phosgene and toluenediamine inertia liquor capacity stream
Amount ratio is approximately 1:1, reacted into cold reactor, using rotor formula hypergravity structure, filler is metal foam filler；
Casing diameter d2For 200mm, casing diameter d2With main feed pipe diameter d3It is 10 with ratio, main feed pipe diameter d3For 20mm；Set
Length of tube L1With casing diameter d2Ratio is 1, casing length L1For 200mm；The internal diameter d of main feed pipe3With nozzle discharging bore dia
D2Ratio be 1, nozzle discharging bore dia D2For 20mm；Circumferential weld width D1With nozzle discharging bore dia D2Ratio be 1, circumferential weld width D1
For 20mm；Casing diameter d2With hypergravity structured packing inner edge to set pipe distance d1Ratio scope be 200, hypergravity structured packing
Inner edge is to set pipe distance d1For 1mm；Baffle plate is to non-limiting shock flow structure apart from d4With main feed pipe nozzle diameter D2Ratio model
Enclose for 1, baffle plate is to non-limiting shock flow structure apart from d4For 20mm.
At 120 DEG C, reaction absolute pressure is 1.8MPa for reaction temperature control, and rotating speed is 600r/min, reaction time
1.5s, thermal reactor is introduced after reaction in exit, at 150 DEG C, continues to react under absolute pressure 1.5MPa to generate TDI crude products,
After the purification of follow-up workshop section, there is not clogging in 8 months in TDI yield 99.5%, plant running.
Embodiment six：
Pilot experiment, use M-phthalic acid two specific as follows are carried out with present invention process and device in certain TDI manufacturer
Used as atent solvent, 145 DEG C of the temperature of the toluenediamine inert solvent solution of configuration, mass fraction is 28% to ethyl ester heavy solvent；Light
85 DEG C of the temperature of gas inert solvent solution, phosgene mass fraction concentration is 30%.Phosgene and toluenediamine inertia liquor capacity flow
Than being approximately 3:1, reacted into cold reactor, using screw path type hypergravity structure, filler is metal foam filler；
Casing diameter d2For 150mm, casing diameter d2With main feed pipe diameter d3It is 3 with ratio, main feed pipe diameter d3For 50mm；Set
Length of tube L1With casing diameter d2Ratio is 2, casing length L1For 300mm；The internal diameter d of main feed pipe3With nozzle discharging bore dia
D2Ratio be 20, nozzle discharging bore dia D2For 2.5mm；Circumferential weld width D1With nozzle discharging bore dia D2Ratio be 2, circumferential weld width
Degree D1For 5mm, casing diameter d2With hypergravity structured packing inner edge to set pipe distance d1Ratio be 10, in hypergravity structured packing
Edge is to set pipe distance d1For 15mm；Baffle plate is to non-limiting shock flow structure apart from d4With main feed pipe nozzle diameter D2Ratio model
Enclose for 10, baffle plate is to non-limiting shock flow structure apart from d4For 25mm.
At 120 DEG C, reaction absolute pressure is 1.8MPa for reaction temperature control, and rotating speed is 600r/min, reaction time
1.5s, thermal reactor is introduced after reaction in exit, at 150 DEG C, continues to react under absolute pressure 1.5MPa to generate TDI crude products,
After the purification of follow-up workshop section, there is not clogging in 8 months in TDI yield 99.4%, plant running.
Claims (6)
1. a kind of single reflection super-gravity device for continuously preparing toluene di-isocyanate(TDI), including cold reactor（1）And thermal reactor
（2）, it is characterised in that cold reactor includes non-limiting shock flow structure and hypergravity structure, the non-limiting percussion flow knot
Structure includes the different main feed pipe of caliber（1.3）And sleeve pipe（1.4）And baffle plate（1.12）, sleeve pipe（1.4）Caliber more than master
Feed pipe（1.3）Caliber, sleeve pipe（1.4）It is placed on main feed pipe（1.3）Outside, main feed pipe（1.3）Away from baffle plate（1.12）
One end arrange main feed pipe charging aperture（1.1）, near baffle plate（1.12）The other end arrange flared main feed pipe nozzle
（1.5）, main feed pipe nozzle（1.5）End center is provided with discharge opening, sleeve pipe（1.4）One end of correspondence main feed pipe charging aperture
It is provided with sleeve pipe charging aperture（1.2）, another end opening of sleeve pipe correspondence main feed pipe nozzle, ferrule openings end and main feed pipe
Nozzle-end forms circumferential weld（1.6）, discharge opening and circumferential weld be arranged at same plane, and baffle plate is relative to main feed pipe and sleeve pipe
Axis direction is vertically arranged, and baffle center is located on the axis of main feed pipe and sleeve pipe；Hypergravity structure includes filler
（1.8）, rotating shaft（1.11）, rotor（1.9）, housing（1.7）And liquid outlet（1.13）, described non-limiting percussion flow knot
Structure is arranged at rotor（1.9）Cavity in and along rotor axis direction arrange, and it is non-limiting clash into flow structure axis with turn
Son（1.9）Dead in line, rotor be located at housing middle part, filler is in rotor hollow ring；Liquid outlet is at the bottom of housing
Portion is connected with thermal reactor, rotating shaft by with motor（1.10）Connected rotor driven is rotated.
2. the single reflection super-gravity device for continuously preparing toluene di-isocyanate(TDI) according to claim 1, it is characterised in that
Casing diameter（d2）With the internal diameter of main feed pipe（d3）Ratio is 2-10；Casing length（L1）With casing diameter（d2）Ratio is 1-
10；The internal diameter of main feed pipe（d3）With nozzle discharging bore dia（D2）Ratio be 1-100；Circumferential weld width（D1）With nozzle discharge opening
Diameter（D2）Ratio be 1-10, casing diameter（d2）With hypergravity structured packing inner edge to set pipe distance（d1）Ratio scope be 1-
200, baffle plate is to non-limiting shock flow structure distance（d4）With nozzle discharging bore dia（D2）Ratio range is 1-50.
3. the single reflection super-gravity device for continuously preparing toluene di-isocyanate(TDI) according to claim 1 and 2, its feature exists
In baffle plate for circular or square, baffle plate with respect to main feed pipe and the rotatable setting of sleeve pipe or with main feed pipe and sleeve pipe connection,
Baffle plate is outwardly convex, and baffle surface is coarse.
4. a kind of technique for preparing toluene di-isocyanate(TDI), based on continuously preparing toluene diisocynate as claimed in claim 3
The single reflection super-gravity device of ester is completed, it is characterised in that step is as follows：Volume flow ratio scope is molten for the phosgene inertia of 1-15
Agent solution flows into first the non-limiting shock flow structure in cold reactor with toluenediamine inert solvent solution, and toluenediamine is lazy
Property solvent solution spray from annular space, the phosgene inert solvent solution sprayed in circumferencial direction and main feed pipe nozzle discharge opening is mixed
Close, and collision, backwash on baffle plate, Gao Tuanneng dissipative shock waves area is formed, two strands of liquid quickly complete micromixing with preliminary microcosmic
Mixing, liquid leaves and clashes into the filler that rotation is entered after planar central, and powerful shearing force keeps material to have high rapids always
Energy dissipative shock wave, the liquid of not up to microcosmic mixing quickly completes micro mixing, hereafter, toluenediamine（TDA）In cold reaction
Intermediate product is fully converted in device in hypergravity structure, and cold reactor is left in the time of staying of 0.1-2s, it is anti-into heat
Device is answered, at 90-200 DEG C, continues to react under absolute pressure 0.3-1.8MPa to generate toluene di-isocyanate(TDI)（TDI）Crude product.
5. the technique for preparing toluene di-isocyanate(TDI) according to claim 4, it is characterised in that described toluenediamine is lazy
Temperature 110-150 DEG C of property solvent solution, mass fraction 10%-40%；Temperature 70-110 DEG C of phosgene inert solvent solution, phosgene
Mass fraction concentration is 20%-50%.
6. the technique for preparing toluene di-isocyanate(TDI) according to claim 4, it is characterised in that in hypergravity structure, rotor
The range of speeds is 300-1000r/min, and at 100-150 DEG C, operation absolute pressure is 1-2MPa for reaction temperature control.
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