CN110327848A - A kind of production technology of device for phosgenation reaction, phosgenation reaction - Google Patents
A kind of production technology of device for phosgenation reaction, phosgenation reaction Download PDFInfo
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- CN110327848A CN110327848A CN201910457802.8A CN201910457802A CN110327848A CN 110327848 A CN110327848 A CN 110327848A CN 201910457802 A CN201910457802 A CN 201910457802A CN 110327848 A CN110327848 A CN 110327848A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0033—Other features
- B01D5/0036—Multiple-effect condensation; Fractional condensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
- B01J8/067—Heating or cooling the reactor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
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Abstract
The present invention provides a kind of device for phosgenation reaction, including reaction kettle, tubular reactor, phosgene intake line, Matter Transfer pump, first cooler, reaction kettle is connected with material intake line, bottom valve and outlet valve are on same pipeline, pipeline where bottom valve and outlet valve intersects and communicates with phosgene intake line, phosgene intake line is connected with Matter Transfer pump, Matter Transfer pump is connected with tubular reactor, tubular reactor reaction mass output pipe is passed through in reaction kettle, it is connected at the top of reaction kettle evaporant output pipe and the first cooler, first cooler is also connected with the second output pipe.The present invention also provides a kind of production technologies of phosgenation reaction.Device is in closed state when the device of the invention and production technology can be such that reaction carries out taking human as control, and reactant can recycle always in whole device, cooperates the use of tubular reactor and cooler, the utilization rate and reaction rate of phosgene can be improved.
Description
Technical field
The present invention relates to technical field of chemistry more particularly to a kind of devices for phosgenation reaction, phosgenation reaction
Production technology.
Background technique
Phosgene, also known as phosgene, high poison is non-ignitable, and chemical reactivity is higher, is used as organic synthesis, pesticide, drug, dye
The intermediate of material and other heavy chemicals.
Phosgene and amine carry out N- acylation reaction, can synthesizing isocyanate, urea derivative and carbamyl chloride etc..Phosgene and certain
A little alcohol or phenolic hydroxyl group carry out O- acylation reaction (also known as esterification), can synthesize carbonochloridic acid ester and carbonic ester series of products.Light
Gas and molten state carboxylic acid reaction can synthesize acyl chlorides series of products, be mainly used for the centre as pesticide, medicine, Dyestuff synthesis
Body.
Isocyanates is important organic synthesis intermediate, and nucleophilic addition can occurs in it, participates in unsaturated system
Cycloaddition, carry out Diels-Alder reaction, or with bifunctional compound addition production Hete rocyclic derivatives etc..This kindization
Object is closed to have a wide range of applications in pesticide synthesis.Isocyanates is reacted with alcohol, amine prepares derivative, it may also be used for compound
Identification.Currently, prepare the main method of isocyanates first is that using phosgenation, i.e., amine and phosgene reaction release hydrogen chloride and
Obtain corresponding isocyanates.
Organic carbonate is a kind of widely used chemicals, chemical industry, in terms of have a wide range of applications.It is organic
The synthetic method of carbonic ester mainly has traditional phosgenation, ester-interchange method, oxidation carbonylation method, urea method etc..
Acyl chlorides is a kind of important carboxylic acid derivates, organic synthesis, in terms of suffer from important application,
Acyl chlorides is most active acylting agent.Prepare acyl chlorides method it is most common have thionyl chloride, phosphorus trichloride, phosphorus pentachloride,
Phosphorus oxychloride, carbon tetrachloride, oxalyl chloride method, phosgenation, Diphosgene and triphosgene etc..Wherein, phosphorus trichloride method has by-product
Object phosphorous acid, phosphorus pentachloride method have by-product phosphorus oxychloride, and phosphorus oxychloride method has byproduct phosphoric acid, and carbon tetrachloride method needs and three
Phenylphosphine shares, and has by-product triphen oxygen phosphorus, and it is residual to have trace when the post-processing of acyl chlorides purifies distillation for these above-mentioned by-products
It stays, it is difficult to prepare high-purity acyl chlorides.Phosgenation prepares the advantage that there are acyl chlorides above-mentioned various methods not have, i.e. by-product only has two
Carbonoxide and hydrogen chloride, both gases are easy to comprehensively utilize by water and Alkali absorption.
Currently, isocyanates, urea derivative, carbamyl chloride, carbonochloridic acid ester and carbonic ester series of products, acyl chlorides series
Traditional phosgenation used in product preparation is that react phosgene directly with raw material, and generally use is tank reactor,
By-product is more, and product yield is low, and reaction time is long, and phosgene utilization rate is low, so need to be passed through excessive phosgene, and it is excessive
Phosgene to will cause by-product processing difficult.Therefore, urgent need one kind can be improved reaction efficiency, make full use of light at present
Gas solves the problem in the above phosgene reaction convenient for the device of phosgene by-product processing.
Summary of the invention
For overcome the deficiencies in the prior art, it is an object of the present invention to provide a kind of dresses for phosgenation reaction
Set, including reaction kettle, tubular reactor, phosgene intake line, Matter Transfer pump, the first cooler, make reaction raw materials, phosgene and
Reaction gained mixture recycles always inside the device entirely for phosgenation reaction, until reaction raw materials are remaining in reaction kettle
Amount stops reaction when reaching acceptance value, reacts reaction raw materials and phosgene sufficiently, and the utilization rate of phosgene is high, and the present invention is used for light
The tubular reactor of solid/liquid/gas reactions be it is a kind of in a tubular form, the very big continuous manipulation reactor of draw ratio, back-mixing is small, unit volume production
Ability is high, greatly reduces the reaction time.
In order to achieve the goal above, the invention is realized by the following technical scheme.
A kind of device for phosgenation reaction provided by the invention, including reaction kettle, tubular reactor, phosgene input pipe
Road, Matter Transfer pump, the first cooler；
The reaction kettle is connected with material intake line, and the bottom valve of the reactor bottom is arranged in and is arranged in kettle
On same pipeline, pipeline where the bottom valve and outlet valve intersects the outlet valve of bottom valve lower end with the phosgene intake line
And communicate, the phosgene intake line is connected with Matter Transfer pump, the Matter Transfer pump and the tubular reactor
It is connected, the tubular reactor reaction mass output pipe is passed through in the reaction kettle, the reaction kettle evaporant efferent duct
It is connected at the top of road and first cooler, the bottom of first cooler is connected with the first output pipe, and described
The one output pipe other end is connected with the reaction kettle, and first cooler is also connected with the second output pipe；
Wherein, the material intake line is material to be passed through in reaction kettle, and the Matter Transfer pump is to will be from light
The reaction raw materials come out after the bottom valve of phosgene and opening reaction kettle that gas intake line is passed through are pumped into the tubular reactor,
The reaction raw materials and phosgene are reacted in the tubular reactor, the mixture after reaction under the action of Matter Transfer pump
Into in reaction kettle, it is anti-that the phosgene that material and the phosgene intake line are passed through in reaction kettle is recycled into the tubular type together
Device is answered, during reaction, the outlet valve is in close state, to realize that material is reacted in tubular reactor-is recycled into
The circulation process that the cooled and tubular reactor that flows back-enter back into is reacted after reaction kettle, evaporation；Light in the reaction kettle
Gas and byproduct of reaction hydrogen chloride evaporate into first cooler, and the cooling temperature of first cooler is lower than phosgene
Boiling point, phosgene is cooled to flow back into the reaction kettle, and by-product is discharged to outside device by second output pipe.
It preferably, further include solvent measuring tank, the bottom of the solvent measuring tank is connected with the 5th output pipe, described
5th output pipe is connected with the reaction kettle.
Preferably, further include the second cooler, third output pipe one end of the bottom of second cooler with it is described
Reaction kettle is connected, and the top of second cooler is connected with second output pipe, and second cooler also connects
It is connected to the 4th output pipe；
The temperature of first cooler is higher than the cooling temperature in second cooler, to respectively by the reaction
Substance needed for the different reactions being evaporated in kettle, which carries out cooling, flows back into it in reaction kettle；In second cooler
By-product is discharged to outside device by the 4th output pipe.
Preferably, the reaction kettle further includes blender, temperature monitor；The reaction kettle outer wall further includes heating layer,
One upper side of heating layer is equipped with intake line, is equipped with output pipe below the heating layer other side.
Preferably, the tubular reactor is equipped with segmentally heating or sub-sectional cooling unit.
Preferably, the quantity of the tubular reactor is 2-6；The outlet valve of the tubular reactor is nearby equipped with temperature
Detector and pressure-regulating valve；One upper side of tubular reactor is equipped with intake line, is equipped with output pipe below the other side.
It preferably, further include third cooler, the bottom of the third cooler and the reaction kettle pass through piping connection,
The top of the third cooler is connect with the 4th output pipe to be connected, and the third cooler further includes by described
By-product in three coolers is discharged to the output pipe outside device.
Preferably, one upper side of cooler is equipped with output pipe, is equipped with intake line below the cooler other side.
A second object of the present invention is to provide a kind of production technologies of phosgenation reaction, using provided by the present invention
For the device of phosgenation reaction, include the following steps:
S1, bottom valve is closed, reaction raw materials is added in the reaction kettle by material intake line；Turn on agitator into
Row stirring；Steam is passed through from the intake line of reaction kettle heating layer to be heated, and makes to enter material temperature in Matter Transfer pump
Degree is in target zone；
S2, the first cooler is opened；It is passed through steam from the intake line of a upper side of tubular reactor, gives pipe reaction
Device heating；The outlet mass temperatures for detecting to control the tubular reactor by the temperature monitor of tubular reactor exist
In target zone；
Wherein, the first cooler is to cooling by the phosgene entered in the first cooler from reaction kettle and flow back into reaction
In kettle；By-product is discharged to outside device by second output pipe；
S3, Matter Transfer pump, bottom valve are opened, closes outlet valve, is passed through phosgene；
Wherein, Matter Transfer pump is to promote circulating for material in the device for phosgenation reaction；
S4, sampling simultaneously measure, and when detecting that the residual of the reaction raw materials in reaction kettle reaches acceptance value, stop reaction, beat
It opens outlet valve and collects the mixture after phosgene reaction.
Preferably, include the following steps:
S1, bottom valve is closed, solvent needed for reacting is added in the reaction kettle by solvent measuring tank, and reaction is former
Material is added in the reaction kettle by material intake line, and turn on agitator is stirred；From the input pipe of reaction kettle heating layer
Road is passed through steam and is heated, and reaction raw materials is made to be completely dissolved in solvent, and makes to enter temperature of charge in Matter Transfer pump
In target zone；
S2, the first cooler, the second cooler are opened；Steaming is passed through from the intake line of a upper side of tubular reactor
Vapour is heated to tubular reactor；It detects to control the tubular reactor by the temperature monitor of tubular reactor
Outlet mass temperatures are in target zone；
Wherein, the first cooler is cooling to the solvent for evaporating reaction kettle and flows back into reaction kettle；Second is cooling
Device is cooling to the phosgene for evaporating reaction kettle and flows back into reaction kettle；By-product is discharged by the 4th output pipe
To outside device；
S3, Matter Transfer pump, bottom valve are opened, closes outlet valve, is passed through phosgene；
Wherein, Matter Transfer pump is to promote circulating for material in the device for phosgenation reaction；
S4, sampling simultaneously measure, and when detecting that the residual of the reaction raw materials in reaction kettle reaches acceptance value, stop reaction, beat
It opens outlet valve and collects the mixture after phosgene reaction.
Compared with prior art, the beneficial effects of the present invention are:
(1) device for phosgenation reaction of the invention, during reaction, entire reaction unit are closed state, are made
Reaction raw materials, phosgene, reaction gained mixture recycle always in the device entirely for phosgenation reaction, until in reaction kettle
The residual quantity of reaction raw materials stops reaction when reaching acceptance value.In addition, phosgene reaction of the invention is complete in tubular reactor
At the unit volume production capacity of tubular reactor is high, and therefore, the required reaction time is shorter.Since device is closed during reaction,
The part evaporant of phosgene enters back into tubular reactor and participates in phosgene reaction by cold-zone device cooling for reflux to reaction kettle, because
This phosgene can be fully utilized.
(2) in some preferred embodiments of the invention, tubular reactor quantity can be 2-6, and multiple tubular reactors make
The reaction raw materials and phosgene recycled in a device increase reaction contact time and touch opportunity, accelerate reaction, improve reaction efficiency.
(3) in some preferred embodiments of the invention, can be for cooler is multiple, when being used for phosgenation using of the invention
The reaction of the device of reaction is related to reaction raw materials, solvent, catalyst, phosgene, according to reaction raw materials, solvent, catalyst, phosgene
Respective boiling point judges that it evaporates situation, so as to increase and decrease the number of cooler, and the cooling of the corresponding cooler of setting
Temperature.Easy to operate, the increase and decrease operation of cooler is easy.
(4) production technology of a kind of phosgenation reaction provided by the invention, using of the invention for phosgenation reaction
Device, during reaction, reaction raw materials, phosgene, phosgenation reaction gained mixture recycle inside whole device always, recycle
Process is " to react-be cooled and flow back after being recycled into reaction kettle, evaporation-in tubular reactor and enter back into pipe reaction
Device " stops reaction when reaction raw materials residual quantity reaches acceptance value in reaction kettle, discharges and collects reaction gained mixture.
It is utilized phosgene sufficiently, phosgene utilization rate is high.In addition, phosgenation reaction is carried out in tubular reactor, reaction is improved
Rate shortens the reaction time.
The above description is only an overview of the technical scheme of the present invention, in order to better understand the technical means of the present invention,
And can be implemented in accordance with the contents of the specification, it is described in detail below with some embodiments.A specific embodiment of the invention
It is shown in detail by following embodiment.
Detailed description of the invention
The drawings described herein are used to provide a further understanding of the present invention, constitutes part of this application, this hair
Bright illustrative embodiments and their description are used to explain the present invention, and are not constituted improper limitations of the present invention.In the accompanying drawings:
Fig. 1 is the structural diagram of the present invention one；
Fig. 2 is structural schematic diagram two of the invention；
Fig. 3 is the enlarged diagram at the A of Fig. 2；
Fig. 4 is technological process of production schematic diagram of the invention.
In figure: 1, reaction kettle；2, tubular reactor；3, phosgene intake line；4, light passing valve；5, outlet valve；6, inlet valve；
7, Matter Transfer pumps；8, the first cooler；9, the second cooler；10, solvent measuring tank；11, blender；12, reaction kettle steam
Inlet valve；13, material intake line, 14, reaction kettle evaporant output pipe；15, reaction kettle steam condensate outlet valve；16,
Bottom valve；2, tubular reactor；21, steam inlet valve；22, steam condensate outlet valve；23, tubular reactor reaction mass goes out
Mouth valve；24, tubular reactor reaction mass output pipe；81, first circulation water inlet valve；82, first circulation water outlet valve；
83, the first output pipe；84, the second output pipe；91, second circulation water inlet valve；92, second circulation water outlet valve；93,
Three output pipes；94, the 4th output pipe；101, solvent measuring tank intake line；102, the 5th output pipe；103, the 6th is defeated
Pipeline out.
Specific embodiment
In order to which invention described herein can be more fully understood by, following embodiment is illustrated.It should understand that these embodiments
It being merely to illustrate property purpose and is understood not to limit the invention in any way.
It should explain, " reaction raw materials " herein refer to the raw material chemically reacted with phosgene.
Embodiment 1
As shown in Figure 1, a kind of device for phosgenation reaction provided by the invention, including reaction kettle 1, tubular reactor
2, phosgene intake line 3, Matter Transfer pump the 7, first cooler 8, and the reaction kettle 1 is connected with material intake line 13, if
Set 1 bottom of reaction kettle bottom valve 16 and the outlet valve 5 of 16 lower end of bottom valve is set on same pipeline, the kettle
Bottom valve 16 and 5 place pipeline of outlet valve intersect and communicate with the phosgene intake line 3, the phosgene intake line 3 with it is described
Matter Transfer pump 7 is connected, and the Matter Transfer pump 7 is connected with the tubular reactor 2, the tubular reactor reactant
Material output pipe 24 is passed through in the reaction kettle 1, the top of the reaction kettle evaporant output pipe 14 and first cooler 8
Portion is connected, and the bottom of first cooler 8 is connected with the first output pipe 83,83 other end of the first output pipe with
The reaction kettle 1 is connected, and first cooler 8 is also connected with the second output pipe 84.
As shown in Figure 1, 2, 3, the reaction kettle 1 further includes blender 11 and temperature monitor T1, and blender 11 is to right
The stirring of material in reaction kettle 1, temperature of the temperature monitor T1 to detect reaction kettle 1.The phosgene intake line 3 is equipped with
Light passing valve 4 is passed through situation to control phosgene.Inlet valve 6,6 He of inlet valve are installed on the phosgene intake line 3
The light passing valve is located at the two sides of 5 place pipeline of the bottom valve 16 and the outlet valve, and inlet valve 6 is to control reaction raw materials
The case where entering tubular reactor with phosgene.
As shown in Figure 1, 2,1 outer wall of reaction kettle is equipped with heating layer, and one upper side of heating layer is equipped with intake line, input
Reaction kettle steam inlet valve 12 is installed on access, output pipe is equipped with below the heating layer other side, is equipped on output pipe
Reaction kettle steam condensate outlet valve 15.
As shown in Figure 1, 2, 3, the number of the tubular reactor 2 is 4；2 one upper side of tubular reactor is equipped with
Intake line is equipped with steam inlet valve 21 on intake line, output pipe is equipped with below the other side, is equipped on output pipe
Steam condensate outlet valve 22.
As shown in figure 3,23 close beneath of outlet valve of 4 tubular reactors 2 is equipped with temperature monitor T and pressure is adjusted
Valve P.It can control by temperature monitor T1, T2, T3, T4 and pressure-regulating valve P1, P2, P3, P4 anti-inside tubular reactor
Answer temperature and reaction pressure.
As shown in Figure 1,8 one upper side of the first cooler is equipped with output pipe, first is equipped on output pipe and is followed
Ring water outlet valve 82, other side lower section are equipped with intake line, are equipped with first circulation water inlet valve 81 on intake line.Described
One cooler 8 is also connected with the second output pipe 84, and second output pipe 84 is by the byproduct hydrogen chloride in reaction unit
It arranges to outside and carries out subsequent by-product treatment process.
Embodiment 2
As shown in Fig. 2, on the basis of the technical solution of embodiment 1, to increase solvent measuring tank 10, second cold for the present embodiment
But device 9.
The top of the solvent measuring tank 10 is connected with solvent measuring tank intake line 101, the bottom of described dose of measuring tank 10
Portion is connected with one end of the 5th output pipe 102, and the other end of the 5th output pipe 102 is connected with the reaction kettle 1
It connects.
The solvent measuring tank 10 is also connected with the 6th output pipe 103, and the 6th output pipe 103 will be for will entirely react
Byproduct hydrogen chloride in device in recycled material, which is arranged to outside, enters subsequent by-product treatment process.
The top of second cooler 9 is connected with second output pipe 84, the bottom end of second cooler 9
It is connected with the third output pipe 93, second cooler 9 is also connected with the 4th output pipe 94, the 4th output
Pipeline 94, which is used to arrange the byproduct hydrogen chloride in entire reaction unit in recycled material to outside, enters the processing of subsequent by-product
Process.
Second cooler, 9 one upper side is equipped with output pipe, is equipped with second circulation water outlet valve on output pipe
92, heating layer other side lower section is equipped with intake line, is equipped with second circulation water inlet valve 91 on intake line.
It should be appreciated that the number of the tubular reactor 2 in the device for phosgenation reaction of the invention is 2-6,
It is that specific embodiment is illustrated that embodiment 1,2, which is only 4 with the quantity of tubular reactor 2, and above embodiments should not be to this
The content of invention imposes any restrictions.
It should be appreciated that not needed when the phosgenation reaction carried out using the device for phosgenation reaction of the invention
When adjusting pressure, pressure-regulating valve P1, P2, P3, P4 described in above embodiments are in the state of not using.
A kind of device for phosgenation reaction provided by the invention, during reaction, reaction raw materials, phosgene, phosgenation
Reaction gained mixture recycles inside whole device always, should also include solvent, catalysis when reaction is related to solvent, catalyst
Agent, circulation process are " to react-be cooled and flow back after being recycled into reaction kettle, evaporation-in tubular reactor and enter back into tubular type
Reactor " stops reaction when reaction raw materials residual quantity reaches acceptance value in reaction kettle, discharges and collects reaction gained mixing
Object.And it can need to increase and decrease the quantity of tubular reactor 2 and the quantity of cooler according to reaction.In entire reaction process,
The phosgene being passed through can sufficiently participate in reacting, and phosgene reaction carries out in tubular reactor, and reaction is very fast, and byproduct of reaction
For hydrogen chloride, byproduct of reaction is few and simple, handles convenient for subsequent by-product.
The present invention also provides a kind of production technologies of phosgenation reaction, are illustrated below by way of specific embodiment.
Embodiment 3
Using the device for phosgenation reaction as shown in Figure 1, the production craft step of specific phosgenation reaction is as follows:
800Kg isononanoic acid is added in the reaction kettle 1 by S1, bottom valve 16 by material intake line 13, and unlatching is stirred
It mixes, stirring rate 85r/min, opens reaction kettle steam inlet valve 12 and reaction kettle steam condensate outlet valve 15 to reaction kettle
1 heating, is heated to 100 DEG C, stirs and heat 1 hour,；
S2, open the first cooler 8, tubular reactor 2, Matter Transfer pump 7, close outlet valve 5, open light passing valve 4, into
Expect valve 6, bottom valve 16, steam inlet valve 21, steam condensate outlet valve 22, tubular reactor reacting material outlet valve 23, the
One recirculated water inlet valve 81, first circulation water outlet valve 82 are passed through steaming from the intake line of a upper side of tubular reactor (2)
Vapour is heated to tubular reactor (2)；
Wherein, cooling temperature controls between 0-8 DEG C in the first cooler 8；First cooler 8 is to will be from reaction kettle 1
In the phosgene that is recycled in the first cooler 8 by the first output pipe 83 it is cooling and flow back into phosgene in reaction kettle 1, make light
Gas, which is again introduced into tubular reactor 2, participates in reaction, and phosgene is made sufficiently to participate in reacting, and enters the by-product in the first cooler 8
Object hydrogen chloride is by 84 row of the second output pipe to outside hence into subsequent by-product treatment process；The Matter Transfer pump 7
To promote circulating for material in the device for phosgenation reaction；It is detected by the temperature monitor of tubular reactor
It is 110 DEG C -120 DEG C to artificially control the outlet mass temperatures of the tubular reactor 2；
S3, Matter Transfer pump 7, bottom valve 16 are opened, closes outlet valve 5, is passed through phosgene；
Wherein, Matter Transfer pump 7 is to promote circulating for material in the device for phosgenation reaction；
S4, sampling simultaneously measure, and when detecting that the residual of the isononanoic acid in reaction kettle 1 reaches acceptance value, i.e., isononanoic acid remains
Amount is less than the 0.5% of S1 step input amount, stops reaction, opens outlet valve 5 and collects the mixture after phosgene reaction；
Reaction time is 8 hours by 16 hours original shortening half, and phosgene intake is consumed by traditional still reaction
800 kilograms of phosgene amount are reduced to 650 kilograms.
Embodiment 4
Using the device for phosgenation reaction as shown in Figure 1, specific phosgene reaction processing step is as follows:
S1, bottom valve 16 is closed, 800Kg benzylalcohol is added in the reaction kettle 1 by material intake line 13, is opened
Stirring, stirring rate 85r/min open reaction kettle steam inlet valve 12 and reaction kettle steam condensate outlet valve 15 to reaction
Kettle 1 heats, and is heated to 100 DEG C, stirs and heat 1 hour；
S2, open the first cooler 8, tubular reactor 2, Matter Transfer pump 7, close outlet valve 5, open light passing valve 4, into
Expect valve 6, bottom valve 16, steam inlet valve 21, steam condensate outlet valve 22, tubular reactor reacting material outlet valve 23, the
One recirculated water inlet valve 81, first circulation water outlet valve 82 are passed through steaming from the intake line of a upper side of tubular reactor (2)
Vapour is heated to tubular reactor (2)；
Wherein, cooling temperature controls between 0-8 DEG C in the first cooler 8；First cooler 8 is to will be from reaction kettle 1
In the phosgene that is recycled in the first cooler 8 by the first output pipe 83 it is cooling and flow back into phosgene in reaction kettle 1, make light
Gas, which is again introduced into tubular reactor 2, participates in reaction, and phosgene is made sufficiently to participate in reacting, and enters the by-product in the first cooler 8
Object hydrogen chloride is by 84 row of the second output pipe to outside hence into subsequent by-product treatment process；The Matter Transfer pump 7
To promote circulating for material in the device for phosgenation reaction；It is detected by the temperature monitor of tubular reactor
It is 100 DEG C -110 DEG C to artificially control the outlet mass temperatures of the tubular reactor 2；
S3, Matter Transfer pump 7, bottom valve 16 are opened, closes outlet valve 5, is passed through phosgene；
Wherein, Matter Transfer pump 7 is to promote circulating for material in the device for phosgenation reaction；
S4, sampling simultaneously measure, and when detecting that the residual of the benzylalcohol in reaction kettle 1 reaches acceptance value, i.e. benzylalcohol residual quantity is small
In the 0.5% of S1 step input amount, stop reaction, opens outlet valve 5 and collect the mixture after phosgene reaction；
Reaction time is 8 hours by 16 hours original shortening half, and phosgene intake is consumed by traditional still reaction
1100 kilograms of phosgene amount are reduced to 950 kilograms.
Embodiment 5
As shown in figure 4, the production technology of the phosgenation reaction of the present embodiment, includes the following steps:
S3, Matter Transfer pump (7), bottom valve (16) are opened, closes outlet valve (5), is passed through phosgene；
Wherein, Matter Transfer pump (7) is to promote circulating for material in the device for phosgenation reaction；
S4, sampling simultaneously measure, and when detecting that the residual of the reaction raw materials in reaction kettle (1) reaches acceptance value, stop reaction,
It opens outlet valve (5) and collects the mixture after phosgene reaction.
Using the device for phosgenation reaction as shown in Figure 2, specific phosgene reaction processing step is as follows:
S1, bottom valve 16 is closed, solvent toluene needed for 4000L is reacted is added to the reaction by solvent measuring tank 10
In kettle 1,1600Kg para-phenylene diamine dihydrochloride is added in the reaction kettle 1 by material intake line 13, turn on agitator 11
It is stirred, stirring rate 85r/min, opens reaction kettle steam inlet valve 12 and reaction kettle steam condensate outlet valve 15 is given
Reaction kettle 1 heats, and is heated to 100 DEG C, stirs and heat 1 hour；
S2, the first cooler 8, the second cooler 9, tubular reactor 2, Matter Transfer pump 7 are opened, closes outlet valve 5, beats
Open light valve 4, inlet valve 6, bottom valve 16, steam inlet valve 21, steam condensate outlet valve 22, tubular reactor reaction mass
Outlet valve 23, first circulation water inlet valve 81, first circulation water outlet valve 82, second circulation water inlet valve 91, second circulation water
Outlet valve 92 is passed through steam from the intake line of a upper side of tubular reactor (2), heats to tubular reactor (2)；
Wherein, cooling temperature control is between 50-60 DEG C in the first cooler 8, and cooling temperature controls in the second cooler 9
Between 0-8 DEG C；First cooler 8 from the first output pipe 83 is passed through in reaction kettle 1 will be recycled in the first cooler 8
Mixture in phosgene it is cooling and flow back into phosgene in reaction kettle 1, the second cooler 9 to will be recycled from reaction kettle 1 into
Enter cooling to the solvent toluene in 9 mixture of the second cooler and flow back into reaction kettle 1, to make phosgene, solvent toluene again
It is secondary to enter participation reaction in tubular reactor 2, make phosgene sufficiently participate in reacting, reduces the loss of solvent, and it is cooling to enter second
Byproduct hydrogen chloride in device 9 passes through 94 row of the 4th output pipe to outside hence into subsequent by-product treatment process；；It is described
Matter Transfer pump 7 is to promote circulating for material in the device for phosgenation reaction；Pass through the temperature of tubular reactor
Detector is 110 DEG C -120 DEG C come the outlet mass temperatures for detecting artificially to control the tubular reactor 2.
S3, Matter Transfer pump 7, bottom valve 16 are opened, closes outlet valve 5, is passed through phosgene；
Wherein, Matter Transfer pump 7 is to promote circulating for material in the device for phosgenation reaction；
S4, sampling simultaneously measure, when detecting that the residual of the para-phenylene diamine dihydrochloride in reaction kettle 1 reaches acceptance value, i.e., pair
Phenylenediamine hydrochloride salt residual quantity is less than the 0.5% of S1 step input amount, stops reaction, after opening the collection phosgene reaction of outlet valve 5
Mixture；
Reaction time was shorten to 48 hours by original 150 hours, and phosgene intake consumes light by traditional still reaction
5000 kilograms of tolerance are reduced to 2000 kilograms.
It should be appreciated that when phosgene reaction also relates to catalyst, and catalyst temperature range set by reaction kettle 2
Interior easy evaporation, then needing to add third cooler flows back into it in reaction kettle 1 to carry out cooling to catalyst, further into
Enter in tubular reactor 2 and has continued catalytic action.
It should be appreciated that a kind of production technology of phosgenation provided by the present invention, is not only limited in the above implementation
The production technology for the specific phosgenation reaction that example is illustrated, can be used for the reaction of phosgene and amine, wherein amine includes monoamine, two
The amine of amine, triamine or higher functionality；Preferably use monoamine or diamines.It can be also used for phosgenation and prepare carbonochloridic acid ester and carbon
Acid esters series of products, subtituted acid ester and carbonic ester series of products include but is not limited to ethyl chloroformate, chloro-carbonic acid 2- bromine ethyl ester, chlorine
Propyl formate, isopropyl chlorocarbonate, propene carbonate, diethylene glycol bis-allyl carbonate.It can be also used for phosgenation and prepare acyl
Chlorine series of products, wherein acyl chlorides series of products include but is not limited to o-methyl-benzene formyl chloride, m-methyl benzoyl formyl chloride, adjacent chlorobenzene first
Acyl chlorides.
The production technology of a kind of phosgenation reaction provided by the invention, using the dress for phosgenation reaction of the invention
It sets, during reaction, the phosgene being passed through recycles in whole device always, continues to participate in when entering back into tubular reactor 2 anti-
It answers, i.e., phosgene can be fully utilized, and improve the utilization rate of phosgene.And according to the difference of reaction, the quantity of cooler is determined, it is more
Grade cooler can cool down solvent, catalyst, phosgene respectively and be flowed back into reaction kettle 1, and byproduct hydrogen chloride
Boiling point is extremely low, is -85 DEG C, through subcooler without being cooled to liquid, gaseous state is still kept, to lead to the external world from cooler
Output pipe and be discharged, and then enter subsequent by-product treatment process.
Although the embodiments of the present invention have been disclosed as above, but its is not only in the description and the implementation listed
With it can be fully applied to various fields suitable for the present invention, for those skilled in the art, can be easily
Realize other modification, therefore without departing from the general concept defined in the claims and the equivalent scope, the present invention is simultaneously unlimited
In specific details and embodiment shown here.
Claims (10)
1. a kind of device for phosgenation reaction, which is characterized in that defeated including reaction kettle (1), tubular reactor (2), phosgene
Enter pipeline (3), Matter Transfer pump (7), the first cooler (8)；
The reaction kettle (1) is connected with material intake line (13), and the bottom valve (16) in the reaction kettle (1) bottom is arranged
With setting bottom valve (16) lower end outlet valve (5) on same pipeline, managed where the bottom valve (16) and outlet valve (5)
Road intersects and communicates with the phosgene intake line (3), and the phosgene intake line (3) is connected with Matter Transfer pump (7)
It connects, the Matter Transfer pump (7) is connected with the tubular reactor (2), the tubular reactor reaction mass output pipe
(24) it is passed through in the reaction kettle (1), the top of the reaction kettle evaporant output pipe (14) and first cooler (8)
It is connected, the bottom of first cooler (8) is connected with the first output pipe (83), and first output pipe (83) is another
End is connected with the reaction kettle (1), and first cooler (8) is also connected with the second output pipe (84)；
Wherein, the material intake line (13) is material to be passed through in reaction kettle (1), the Matter Transfer pump (7) to
The reaction raw materials that the phosgene being passed through from phosgene intake line (13) and the bottom valve (16) for opening reaction kettle come out afterwards are pumped into institute
It states in tubular reactor (2), the reaction raw materials and phosgene are reacted in the tubular reactor (2), in Matter Transfer
Mixture enters in reaction kettle (1) after reacting under the action of pump (7), and material and the phosgene intake line (3) are logical in reaction kettle
The phosgene entered is recycled into the tubular reactor (2) together, and during reaction, the outlet valve (5) is in close state, from
And realizing that material reacts in tubular reactor ,-be cooled and flow back after being recycled into reaction kettle, evaporation-enters back into pipe reaction
The circulation process that device is reacted；Phosgene and byproduct of reaction hydrogen chloride in the reaction kettle (1) evaporate into described first
In cooler (8), the cooling temperature of first cooler (8) is lower than the boiling point of phosgene, phosgene is cooled flow back into it is described anti-
It answers kettle (1), by-product is discharged to outside device by second output pipe (84).
2. the device according to claim 1 for phosgenation reaction, which is characterized in that further include solvent measuring tank
(10), the bottom of the solvent measuring tank (10) is connected with the 5th output pipe (102), the 5th output pipe (102)
It is connected with the reaction kettle (1).
3. the device according to claim 2 for phosgenation reaction, which is characterized in that it further include the second cooler (9),
Third output pipe (93) one end of the bottom of second cooler (9) is connected with the reaction kettle (1), and described second is cold
But the top of device (9) is connected with second output pipe (84), and second cooler (9) is also connected with the 4th efferent duct
Road (94)；
The temperature of first cooler (8) be higher than second cooler (9) in cooling temperature, to respectively will it is described instead
Substance needed for answering the different reactions being evaporated in kettle (1), which carries out cooling, flows back into it in reaction kettle (1)；Described second is cold
But the by-product in device (9) is discharged to outside device by the 4th output pipe (94).
4. the device for phosgenation reaction according to claim 1 to 3, which is characterized in that the reaction kettle
It (1) further include blender (11), temperature monitor；Reaction kettle (1) outer wall further includes heating layer, and one upper side of heating layer is set
There is intake line, is equipped with output pipe below the heating layer other side.
5. the device according to claim 1 for phosgenation reaction, which is characterized in that the tubular reactor (2) sets
There are segmentally heating or sub-sectional cooling unit.
6. the device for phosgenation reaction according to claim 1 to 3, which is characterized in that the tubular type is anti-
The quantity for answering device (2) is 2-6；The outlet valve (23) of the tubular reactor (2) is nearby equipped with temperature monitor and pressure tune
Save valve；(2) one upper side of tubular reactor is equipped with intake line, is equipped with output pipe below the other side.
7. the device according to claim 3 for phosgenation reaction, which is characterized in that further include third cooler, institute
The bottom and the reaction kettle (1) for stating third cooler pass through piping connection, the top of the third cooler and the described 4th
Output pipe connection (94) is connected, and the third cooler further includes that the by-product in the third cooler is discharged to device
Outer output pipe.
8. according to claim 1, being used for the device of phosgenation reaction described in 2,3,5,7 any one, which is characterized in that described
One upper side of cooler is equipped with output pipe, is equipped with intake line below the cooler other side.
9. a kind of production technology of phosgenation reaction, which comprises the steps of:
S1, bottom valve (16) are closed, reaction raw materials is added in the reaction kettle (1) by material intake line (13)；It opens
Blender (11) is stirred；Steam is passed through from the intake line of reaction kettle heating layer to be heated, and makes to follow into the material
Temperature of charge is in target zone in ring pump (7)；
S2, the first cooler (8) are opened；It is passed through steam from the intake line of a upper side of tubular reactor (2), it is anti-to tubular type
Device (2) are answered to heat；It detects to control going out for the tubular reactor (2) by the temperature monitor of tubular reactor (2)
Mouth temperature of charge is in target zone；
Wherein, the first cooler (8) is to cooling by the phosgene entered in the first cooler (8) from reaction kettle (1) and flow back
To in reaction kettle (1)；By-product is discharged to outside device by second output pipe (84)；
S3, Matter Transfer pump (7), bottom valve (16) are opened, closes outlet valve (5), is passed through phosgene；
Wherein, Matter Transfer pump (7) is to promote circulating for material in the device for phosgenation reaction；
S4, sampling simultaneously measure, and when detecting that the residual of the reaction raw materials in reaction kettle (1) reaches acceptance value, stop reaction, open
Outlet valve (5) collects the mixture after phosgene reaction.
10. the production technology of phosgenation reaction according to claim 9, which comprises the steps of:
S1, bottom valve (16) are closed, solvent needed for reacting is added in the reaction kettle (1) by solvent measuring tank (10),
Reaction raw materials are added in the reaction kettle (1) by material intake line (13), turn on agitator (11) is stirred；From anti-
It answers the intake line of kettle heating layer to be passed through steam to be heated, reaction raw materials is made to be completely dissolved in solvent, and make to enter the object
Expect that temperature of charge is in target zone in circulating pump (7)；
S2, the first cooler (8), the second cooler (9) are opened；It is logical from the intake line of a upper side of tubular reactor (2)
Enter steam, is heated to tubular reactor (2)；It detects to control the pipe by the temperature monitor of tubular reactor (2)
The outlet mass temperatures of formula reactor (2) are in target zone；
Wherein, the first cooler (8) is cooling to the solvent for evaporating reaction kettle (1) and flows back into reaction kettle (1)；Second
Cooler (9) is cooling to the phosgene for evaporating reaction kettle (1) and flows back into reaction kettle (1)；By-product passes through described the
Four output pipes (94) are discharged to outside device；
S3, Matter Transfer pump (7), bottom valve (16) are opened, closes outlet valve (5), is passed through phosgene；
Wherein, Matter Transfer pump (7) is to promote circulating for material in the device for phosgenation reaction；
S4, sampling simultaneously measure, and when detecting that the residual of the reaction raw materials in reaction kettle (1) reaches acceptance value, stop reaction, open
Outlet valve (5) collects the mixture after phosgene reaction.
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