CN110327848B - Device for phosgenation reaction and production process of phosgenation reaction - Google Patents
Device for phosgenation reaction and production process of phosgenation reaction Download PDFInfo
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- CN110327848B CN110327848B CN201910457802.8A CN201910457802A CN110327848B CN 110327848 B CN110327848 B CN 110327848B CN 201910457802 A CN201910457802 A CN 201910457802A CN 110327848 B CN110327848 B CN 110327848B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- 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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- 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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- C07—ORGANIC CHEMISTRY
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- C07C263/00—Preparation of derivatives of isocyanic acid
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Abstract
The invention provides a device for phosgenation reaction, which comprises a reaction kettle, a tubular reactor, a phosgene input pipeline, a material circulating pump and a first cooler, wherein the reaction kettle is connected with the material input pipeline, a kettle bottom valve and a discharge valve are arranged on the same pipeline, the pipeline where the kettle bottom valve and the discharge valve are arranged is crossed and communicated with the phosgene input pipeline, the phosgene input pipeline is connected with the material circulating pump, the material circulating pump is connected with the tubular reactor, a reaction material output pipeline of the tubular reactor is introduced into the reaction kettle, an evaporant output pipeline of the reaction kettle is connected with the top of the first cooler, and the first cooler is also connected with a second output pipeline. The invention also provides a production process of the phosgenation reaction. The device and the production process can be manually controlled to ensure that the device is in a closed state when the reaction is carried out, reactants can be always circulated in the whole device, and the utilization rate and the reaction rate of phosgene can be improved by matching with the use of the tubular reactor and the cooler.
Description
Technical Field
The invention relates to the technical field of chemistry, in particular to a device for a phosgenation reaction and a production process of the phosgenation reaction.
Background
Phosgene, also known as phosgene, is highly toxic, non-flammable, and highly reactive, and is used as an intermediate for organic synthesis, pesticides, pharmaceuticals, dyes, and other chemical products.
Phosgene and amine are subjected to N-acylation reaction, so that isocyanate, urea derivative, carbamoyl chloride and the like can be synthesized. Phosgene and certain alcohol or phenolic hydroxyl group are subjected to O-acylation reaction (also called esterification reaction) to synthesize chloroformate and carbonate series products. Phosgene and molten carboxylic acid react to synthesize acyl chloride series products, which are mainly used as intermediates for synthesizing pesticides, medicines and dyes.
Isocyanate is an important organic synthesis intermediate, and can perform nucleophilic addition reaction, participate in cycloaddition of an unsaturated system, perform Diels-Alder reaction, or produce heterocyclic derivatives by addition with bifunctional compounds, and the like. The compounds have wide application in pesticide synthesis. The isocyanate reacts with alcohol and amine to prepare derivatives, and can also be used for identifying compounds. At present, one of the main processes for preparing isocyanates is the phosgene process, i.e. the reaction of amines with phosgene to liberate hydrogen chloride and give the corresponding isocyanates.
The organic carbonate is a chemical with wide application, and has wide application in the aspects of chemical industry, pharmacy and the like. The synthesis method of the organic carbonate mainly comprises the traditional phosgene method, ester exchange method, oxidative carbonylation method, urea method and the like.
Acyl chloride is an important carboxylic acid derivative and has important application in organic synthesis, drug synthesis and the like, and the acyl chloride is the most active acylation reagent. The most commonly used methods for preparing acid chlorides are thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride, carbon tetrachloride, the oxalyl chloride method, the phosgene method, the diphosgene method, the triphosgene method, and the like. The phosphorus trichloride method has a byproduct of phosphorous acid, the phosphorus pentachloride method has a byproduct of phosphorus oxychloride, the phosphorus oxychloride method has a byproduct of phosphoric acid, the carbon tetrachloride method needs to be combined with triphenylphosphine, and has a byproduct of triphenoxy phosphorus, and the byproducts have trace residues during post-treatment, purification and distillation of acyl chloride, so that high-purity acyl chloride is difficult to prepare. The phosgene method for preparing acyl chloride has the advantages that the methods do not have, namely, the byproducts only comprise carbon dioxide and hydrogen chloride, and the two gases are easily absorbed and comprehensively utilized by water and alkali.
At present, the traditional phosgene method used for preparing isocyanate, urea derivatives, carbamyl chloride, chloroformate, carbonate series products and acyl chloride series products is to directly react phosgene with raw materials, a kettle type reactor is generally adopted, the number of byproducts is large, the product yield is low, the reaction period is long, the phosgene utilization rate is low, excessive phosgene needs to be introduced, and the excessive phosgene can cause difficulty in processing the byproducts. Therefore, there is an urgent need for a device capable of improving reaction efficiency, fully utilizing phosgene, and facilitating phosgene byproduct treatment to solve the above problems in the phosgene reaction.
Disclosure of Invention
In order to overcome the defects of the prior art, one object of the invention is to provide a device for phosgenation reaction, which comprises a reaction kettle, a tubular reactor, a phosgene input pipeline, a material circulating pump and a first cooler, wherein the reaction raw materials, phosgene and a mixture obtained by reaction are circulated in the whole device for phosgenation reaction all the time, and the reaction is stopped until the residual amount of the reaction raw materials in the reaction kettle reaches a qualified value, so that the reaction raw materials and phosgene are fully reacted, and the phosgene utilization rate is high.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
The invention provides a device for phosgenation reaction, which comprises a reaction kettle, a tubular reactor, a phosgene input pipeline, a material circulating pump and a first cooler, wherein the reaction kettle is connected with the tubular reactor through a pipeline;
the reaction kettle is connected with a material input pipeline, a kettle bottom valve arranged at the bottom of the reaction kettle and a discharge valve arranged at the lower end of the kettle bottom valve are arranged on the same pipeline, pipelines where the kettle bottom valve and the discharge valve are arranged are crossed and communicated with the phosgene input pipeline, the phosgene input pipeline is connected with the material circulating pump, the material circulating pump is connected with the tubular reactor, a reaction material output pipeline of the tubular reactor is led into the reaction kettle, an evaporant output pipeline of the reaction kettle is connected with the top of the first cooler, the bottom of the first cooler is connected with a first output pipeline, the other end of the first output pipeline is connected with the reaction kettle, and the first cooler is also connected with a second output pipeline;
the material input pipeline is used for introducing materials into the reaction kettle, the material circulating pump is used for pumping phosgene introduced from the phosgene input pipeline and reaction raw materials discharged after a kettle bottom valve of the reaction kettle is opened into the tubular reactor, the reaction raw materials and the phosgene react in the tubular reactor, a mixture obtained after the reaction enters the reaction kettle under the action of the material circulating pump, the materials in the reaction kettle and the phosgene introduced from the phosgene input pipeline circulate together into the tubular reactor, and the discharge valve is in a closed state during the reaction, so that a circulation flow that the materials react in the tubular reactor, circularly enter the reaction kettle, are cooled after being evaporated and flow back and then enter the tubular reactor for reaction is realized; phosgene and reaction by-product hydrogen chloride in the reaction kettle are evaporated and enter the first cooler, the cooling temperature of the first cooler is lower than the boiling point of the phosgene, the phosgene is cooled and flows back to the reaction kettle, and the by-product is discharged out of the device through the second output pipeline.
Preferably, the reactor further comprises a solvent metering tank, the bottom of the solvent metering tank is connected with a fifth output pipeline, and the fifth output pipeline is connected with the reaction kettle.
Preferably, the reactor further comprises a second cooler, one end of a third output pipeline at the bottom of the second cooler is connected with the reaction kettle, the top of the second cooler is connected with the second output pipeline, and the second cooler is further connected with a fourth output pipeline;
the temperature of the first cooler is higher than that of the second cooler, and the first cooler is used for respectively cooling different substances required by the reaction evaporated from the reaction kettle to enable the substances to flow back to the reaction kettle; the by-product in the second cooler is discharged to the outside of the apparatus through the fourth outlet line.
Preferably, the reaction kettle further comprises a stirrer and a temperature detector; the outer wall of the reaction kettle further comprises a heating layer, an input pipeline is arranged above one side of the heating layer, and an output pipeline is arranged below the other side of the heating layer.
Preferably, the tubular reactor is provided with a staged heating or staged cooling unit.
Preferably, the number of said tubular reactors is from 2 to 6; a temperature detector and a pressure regulating valve are arranged near an outlet valve of the tubular reactor; an input pipeline is arranged above one side of the tubular reactor, and an output pipeline is arranged below the other side of the tubular reactor.
Preferably, the reactor further comprises a third cooler, the bottom of the third cooler is connected with the reaction kettle through a pipeline, the top of the third cooler is connected with the fourth output pipeline, and the third cooler further comprises an output pipeline which discharges byproducts in the third cooler to the outside of the reactor.
Preferably, an output pipeline is arranged above one side of the cooler, and an input pipeline is arranged below the other side of the cooler.
The second purpose of the invention is to provide a production process of phosgenation reaction, and the device for phosgenation reaction provided by the invention comprises the following steps:
s1, closing a bottom valve of the kettle, and adding reaction raw materials into the reaction kettle through a material input pipeline; starting a stirrer for stirring; introducing steam from an input pipeline of a heating layer of the reaction kettle for heating, so that the temperature of the material entering the material circulating pump is in a target range;
s2, starting the first cooler; introducing steam from an input pipeline above one side of the tubular reactor to heat the tubular reactor; detecting through a temperature detector of the tubular reactor so as to control the temperature of the material at the outlet of the tubular reactor within a target range;
the first cooler is used for cooling phosgene entering the first cooler from the reaction kettle and refluxing the phosgene to the reaction kettle; the by-product is discharged out of the device through the second output pipeline;
s3, opening a material circulating pump and a kettle bottom valve, closing a discharge valve, and introducing phosgene;
wherein the material circulating pump is used for promoting the circulating flow of materials in the device for the phosgenation reaction;
and S4, sampling and measuring, stopping the reaction when the residue of the reaction raw materials in the reaction kettle is detected to reach a qualified value, and opening a discharge valve to collect the mixture after the phosgene reaction.
Preferably, the method comprises the following steps:
s1, closing a bottom valve of the kettle, adding a solvent required by the reaction into the reaction kettle through a solvent metering tank, adding a reaction raw material into the reaction kettle through a material input pipeline, and starting a stirrer for stirring; introducing steam from an input pipeline of a heating layer of the reaction kettle for heating, so that the reaction raw materials are fully dissolved in the solvent, and the temperature of the materials entering the material circulating pump is in a target range;
s2, starting the first cooler and the second cooler; introducing steam from an input pipeline above one side of the tubular reactor to heat the tubular reactor; detecting through a temperature detector of the tubular reactor so as to control the temperature of the material at the outlet of the tubular reactor within a target range;
wherein the first cooler is used for cooling the solvent evaporated from the reaction kettle and refluxing the solvent to the reaction kettle; the second cooler is used for cooling phosgene evaporated from the reaction kettle and refluxing the phosgene to the reaction kettle; the by-product is discharged out of the device through the fourth output pipeline;
s3, opening a material circulating pump and a kettle bottom valve, closing a discharge valve, and introducing phosgene;
wherein the material circulating pump is used for promoting the circulating flow of materials in the device for the phosgenation reaction;
and S4, sampling and measuring, stopping the reaction when the residue of the reaction raw materials in the reaction kettle is detected to reach a qualified value, and opening a discharge valve to collect the mixture after the phosgene reaction.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the device for the phosgenation reaction, the whole reaction device is in a closed state during the reaction, so that the reaction raw materials, the phosgene and the mixture obtained by the reaction are circulated in the whole device for the phosgenation reaction, and the reaction is stopped until the residual quantity of the reaction raw materials in the reaction kettle reaches a qualified value. In addition, the phosgene reaction according to the invention is carried out in a tubular reactor, which has a high capacity per unit volume and therefore requires a short reaction time. Because the device is closed during the reaction, part of evaporant of the phosgene is cooled by the cold zone device and flows back to the reaction kettle, and then enters the tubular reactor to participate in the phosgene reaction, so that the phosgene can be fully utilized.
(2) In some preferred embodiments of the present invention, the number of the tubular reactors may be 2 to 6, and a plurality of tubular reactors increase the reaction contact time and the contact chance of the reaction raw materials and phosgene circulating in the apparatus, accelerate the reaction, and improve the reaction efficiency.
(3) In some preferred embodiments of the present invention, there may be a plurality of coolers, and when the reaction using the apparatus for a phosgenation reaction of the present invention involves a reaction raw material, a solvent, a catalyst, and phosgene, the evaporation thereof is judged according to the respective boiling points of the reaction raw material, the solvent, the catalyst, and the phosgene, the number of coolers may be increased or decreased, and the cooling temperature of the corresponding cooler may be set. The operation is simple and convenient, and the increase and decrease operations of the cooler are easy.
(4) The invention provides a production process of phosgenation reaction, which adopts the device for the phosgenation reaction, during the reaction period, the reaction raw materials, phosgene and the mixture obtained by the phosgenation reaction are always circulated in the whole device, the circulation process comprises the steps of reacting in a tubular reactor, circularly entering a reaction kettle, cooling and refluxing after evaporation, and then entering the tubular reactor, and the reaction is stopped, the material is discharged and the mixture obtained by the reaction is collected until the residual quantity of the reaction raw materials in the reaction kettle reaches a qualified value. The phosgene is fully utilized, and the phosgene utilization rate is high. In addition, the phosgenation reaction is carried out in a tubular reactor, thus improving the reaction rate and shortening the reaction time.
The foregoing description is only an overview of the technical solutions of the present invention, and some embodiments are described in detail below in order to make the technical solutions of the present invention more clearly understood and to implement the technical solutions according to the content of the description. Specific embodiments of the present invention are given in detail by the following examples.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, illustrate embodiment(s) of the invention and together with the description serve to explain the invention without limiting the invention. In the drawings:
FIG. 1 is a first schematic structural diagram of the present invention;
FIG. 2 is a second schematic structural view of the present invention;
FIG. 3 is an enlarged schematic view at A of FIG. 2;
FIG. 4 is a schematic view of the production process of the present invention.
In the figure: 1. a reaction kettle; 2. a tubular reactor; 3. a phosgene input pipeline; 4. a light-passing valve; 5. a discharge valve; 6. a feed valve; 7. a material circulating pump; 8. a first cooler; 9. a second cooler; 10. a solvent metering tank; 11. a stirrer; 12. a steam inlet valve of the reaction kettle; 13. a material input pipeline, 14 and a reaction kettle evaporant output pipeline; 15. a reaction kettle vapor condensate outlet valve; 16. a kettle bottom valve; 2. a tubular reactor; 21. a steam inlet valve; 22. a vapor condensate outlet valve; 23. a tubular reactor reaction material outlet valve; 24. a tubular reactor reaction material output pipeline; 81. a first circulating water inlet valve; 82. a first circulating water outlet valve; 83. a first output line; 84. a second output line; 91. a second circulating water inlet valve; 92. a second circulating water outlet valve; 93. a third output line; 94. a fourth output line; 101. a solvent metering tank input line; 102. a fifth output line; 103. and a sixth output pipeline.
Detailed Description
In order that the invention described herein may be more fully understood, the following examples are set forth. It should be understood that these examples are for illustrative purposes only and are not to be construed as limiting the invention in any way.
It should be construed that "reaction raw material" herein refers to a raw material that chemically reacts with phosgene.
Example 1
As shown in fig. 1, the apparatus for phosgenation provided by the present invention comprises a reaction kettle 1, a tubular reactor 2, a phosgene input pipeline 3, a material circulating pump 7, and a first cooler 8, wherein the reaction kettle 1 is connected with a material input pipeline 13, a kettle bottom valve 16 arranged at the bottom of the reaction kettle 1 and a discharge valve 5 arranged at the lower end of the kettle bottom valve 16 are arranged on the same pipeline, the pipeline where the kettle bottom valve 16 and the discharge valve 5 are arranged is crossed and communicated with the phosgene input pipeline 3, the phosgene input pipeline 3 is connected with the material circulating pump 7, the material circulating pump 7 is connected with the tubular reactor 2, the tubular reactor reaction material output pipeline 24 is introduced into the reaction kettle 1, the reaction kettle evaporant output pipeline 14 is connected with the top of the first cooler 8, the bottom of the first cooler 8 is connected with a first output pipeline 83, the other end of the first output pipeline 83 is connected with the reaction kettle 1, and the first cooler 8 is further connected with a second output pipeline 84.
As shown in fig. 1, 2 and 3, the reaction kettle 1 further includes a stirrer 11 and a temperature detector T1, the stirrer 11 is used for stirring the materials in the reaction kettle 1, and the temperature detector T1 is used for detecting the temperature of the reaction kettle 1. And the phosgene input pipeline 3 is provided with a light valve 4 for controlling the introduction of phosgene. The phosgene input pipeline 3 is provided with a feed valve 6, the feed valve 6 and the light valve are positioned at two sides of the pipeline where the kettle bottom valve 16 and the discharge valve 5 are positioned, and the feed valve 6 is used for controlling the condition that reaction raw materials and phosgene enter the tubular reactor.
As shown in fig. 1 and 2, a heating layer is arranged on the outer wall of the reaction kettle 1, an input pipeline is arranged above one side of the heating layer, a reaction kettle steam inlet valve 12 is arranged on the input passage, an output pipeline is arranged below the other side of the heating layer, and a reaction kettle steam condensate outlet valve 15 is arranged on the output pipeline.
As shown in fig. 1, 2 and 3, the number of the tubular reactors 2 is 4; an input pipeline is arranged above one side of the tubular reactor 2, a steam inlet valve 21 is arranged on the input pipeline, an output pipeline is arranged below the other side of the tubular reactor, and a steam condensate outlet valve 22 is arranged on the output pipeline.
As shown in fig. 3, a temperature detector T and a pressure regulating valve P are provided in the vicinity below the outlet valves 23 of the 4 tubular reactors 2. The reaction temperature and the reaction pressure inside the tubular reactor can be controlled by temperature detectors T1, T2, T3 and T4 and pressure regulating valves P1, P2, P3 and P4.
As shown in fig. 1, an output pipeline is arranged above one side of the first cooler 8, a first circulating water outlet valve 82 is installed on the output pipeline, an input pipeline is arranged below the other side of the first cooler, and a first circulating water inlet valve 81 is installed on the input pipeline. The first cooler 8 is further connected to a second output line 84, and the second output line 84 discharges the by-product hydrogen chloride in the reaction apparatus to the outside for a subsequent by-product treatment process.
Example 2
As shown in fig. 2, in this embodiment, a solvent metering tank 10 and a second cooler 9 are added to the solution of embodiment 1.
A solvent metering tank input pipeline 101 is connected above the solvent metering tank 10, the bottom of the solvent metering tank 10 is connected with one end of a fifth output pipeline 102, and the other end of the fifth output pipeline 102 is connected with the reaction kettle 1.
The solvent metering tank 10 is further connected to a sixth output pipeline 103, and the sixth output pipeline 103 is used for discharging the byproduct hydrogen chloride in the circulating material in the whole reaction device to the outside and entering a subsequent byproduct treatment process.
The upper part of the second cooler 9 is connected with the second output pipeline 84, the bottom end of the second cooler 9 is connected with the third output pipeline 93, the second cooler 9 is further connected with a fourth output pipeline 94, and the fourth output pipeline 94 is used for discharging byproduct hydrogen chloride in the circulating substances in the whole reaction device to the outside to enter a subsequent byproduct treatment process.
An output pipeline is arranged above one side of the second cooler 9, a second circulating water outlet valve 92 is installed on the output pipeline, an input pipeline is arranged below the other side of the heating layer, and a second circulating water inlet valve 91 is installed on the input pipeline.
It should be understood that the number of the tubular reactors 2 in the apparatus for phosgenation reaction of the present invention is 2 to 6, and examples 1 and 2 are only illustrated by the specific example of the number of the tubular reactors 2 being 4, and the above examples should not limit the content of the present invention in any way.
It should be understood that the pressure regulating valves P1, P2, P3, P4 described in the above embodiments are in a non-use state when the phosgenation reaction carried out using the apparatus for a phosgenation reaction of the present invention does not require pressure regulation.
According to the device for the phosgenation reaction, during the reaction period, the reaction raw materials, phosgene and a mixture obtained by the phosgenation reaction always circulate in the whole device, when the reaction involves a solvent and a catalyst, the solvent and the catalyst are included, the circulation process comprises the steps of reacting in a tubular reactor, circularly entering a reaction kettle, cooling and refluxing after evaporation, and then entering the tubular reactor again, and the reaction is stopped, the discharging is carried out, and the mixture obtained by the reaction is collected until the residual quantity of the reaction raw materials in the reaction kettle reaches a qualified value. And the number of the tubular reactors 2 and the number of the coolers can be increased or decreased according to the reaction needs. In the whole reaction process, the introduced phosgene can fully participate in the reaction, the phosgene reaction is carried out in the tubular reactor, the reaction is fast, the reaction by-product is hydrogen chloride, the reaction by-product is less and simple, and the subsequent by-product treatment is convenient.
The invention also provides a production process of the phosgenation reaction, which is illustrated by the specific examples below.
Example 3
With the apparatus for the phosgenation reaction shown in fig. 1, the specific production process steps of the phosgenation reaction are as follows:
s1, a kettle bottom valve 16, adding 800Kg of isononanoic acid into the reaction kettle 1 through a material input pipeline 13, starting stirring at the stirring speed of 85r/min, opening a reaction kettle steam inlet valve 12 and a reaction kettle steam condensate outlet valve 15 to heat the reaction kettle 1 to 100 ℃, stirring and heating for 1 hour;
s2, opening the first cooler 8, the tubular reactor 2 and the material circulating pump 7, closing the discharge valve 5, opening the light valve 4, the feed valve 6, the kettle bottom valve 16, the steam inlet valve 21, the steam condensate outlet valve 22, the tubular reactor reaction material outlet valve 23, the first circulating water inlet valve 81 and the first circulating water outlet valve 82, introducing steam from an input pipeline above one side of the tubular reactor (2), and heating the tubular reactor (2);
wherein the cooling temperature in the first cooler 8 is controlled between 0 ℃ and 8 ℃; the first cooler 8 is used for cooling phosgene which circulates from the reaction kettle 1 to the first cooler 8 through the first output pipeline 83 and enabling the phosgene to flow back to the reaction kettle 1, so that the phosgene enters the tubular reactor 2 again to participate in reaction, the phosgene is enabled to participate in the reaction fully, and the byproduct hydrogen chloride entering the first cooler 8 is discharged outside through the second output pipeline 84 so as to enter a subsequent byproduct treatment process; the material circulating pump 7 is used for promoting the circulating flow of materials in the device for the phosgenation reaction; the temperature of the material at the outlet of the tubular reactor 2 is manually controlled to be 110-120 ℃ by detecting through a temperature detector of the tubular reactor;
s3, opening the material circulating pump 7 and the kettle bottom valve 16, closing the discharge valve 5, and introducing phosgene;
wherein the material circulating pump 7 is used for promoting the circulation flow of the materials in the device for the phosgenation reaction;
s4, sampling and measuring, stopping the reaction when the residue of isononanoic acid in the reaction kettle 1 is detected to reach a qualified value, namely the residue of isononanoic acid is less than 0.5% of the input amount in the step S1, and opening a discharge valve 5 to collect a mixture after phosgene reaction;
the reaction time is shortened by half from the original 16 hours to 8 hours, and the phosgene input is reduced to 650 kilograms from 800 kilograms of phosgene consumed by the traditional kettle type reaction.
Example 4
With the apparatus for phosgenation as shown in FIG. 1, the specific phosgene reaction process steps were as follows:
s1, closing a kettle bottom valve 16, adding 800Kg of benzyl alcohol into the reaction kettle 1 through a material input pipeline 13, starting stirring at the stirring speed of 85r/min, opening a reaction kettle steam inlet valve 12 and a reaction kettle steam condensate outlet valve 15 to heat the reaction kettle 1, heating to 100 ℃, stirring and heating for 1 hour;
s2, opening the first cooler 8, the tubular reactor 2 and the material circulating pump 7, closing the discharge valve 5, opening the light valve 4, the feed valve 6, the kettle bottom valve 16, the steam inlet valve 21, the steam condensate outlet valve 22, the tubular reactor reaction material outlet valve 23, the first circulating water inlet valve 81 and the first circulating water outlet valve 82, introducing steam from an input pipeline above one side of the tubular reactor (2), and heating the tubular reactor (2);
wherein the cooling temperature in the first cooler 8 is controlled between 0 ℃ and 8 ℃; the first cooler 8 is used for cooling phosgene which circulates from the reaction kettle 1 to the first cooler 8 through the first output pipeline 83 and enabling the phosgene to flow back to the reaction kettle 1, so that the phosgene enters the tubular reactor 2 again to participate in reaction, the phosgene is enabled to participate in the reaction fully, and the byproduct hydrogen chloride entering the first cooler 8 is discharged outside through the second output pipeline 84 so as to enter a subsequent byproduct treatment process; the material circulating pump 7 is used for promoting the circulating flow of materials in the device for the phosgenation reaction; the temperature of the material at the outlet of the tubular reactor 2 is manually controlled to be 100-110 ℃ by detecting through a temperature detector of the tubular reactor;
s3, opening the material circulating pump 7 and the kettle bottom valve 16, closing the discharge valve 5, and introducing phosgene;
wherein the material circulating pump 7 is used for promoting the circulation flow of the materials in the device for the phosgenation reaction;
s4, sampling and measuring, stopping the reaction when the residual amount of the benzyl alcohol in the reaction kettle 1 is detected to reach a qualified value, namely the residual amount of the benzyl alcohol is less than 0.5 percent of the input amount in the step S1, and opening a discharge valve 5 to collect a mixture after the phosgene reaction;
the reaction time is shortened by half from the original 16 hours to 8 hours, and the phosgene input is reduced from 1100 kg of phosgene consumed by the traditional kettle type reaction to 950 kg.
Example 5
As shown in fig. 4, the production process of the phosgenation reaction of the present embodiment includes the following steps:
s3, opening a material circulating pump (7) and a kettle bottom valve (16), closing a discharge valve (5), and introducing phosgene;
wherein the material circulation pump (7) is used for promoting the circulation flow of the materials in the device for the phosgenation reaction;
s4, sampling and measuring, stopping the reaction when detecting that the residue of the reaction raw materials in the reaction kettle (1) reaches the qualified value, and opening a discharge valve (5) to collect the mixture after the phosgene reaction.
With the apparatus for phosgenation as shown in FIG. 2, the specific phosgene reaction process steps were as follows:
s1, closing a bottom valve 16 of the reactor, adding 4000L of toluene solvent required by the reaction into the reaction kettle 1 through a solvent metering tank 10, adding 1600Kg of p-phenylenediamine hydrochloride into the reaction kettle 1 through a material input pipeline 13, starting a stirrer 11 for stirring at a stirring speed of 85r/min, opening a steam inlet valve 12 of the reaction kettle and a condensate outlet valve 15 of the reaction kettle to heat the reaction kettle 1, heating to 100 ℃, stirring and heating for 1 hour;
s2, opening a first cooler 8, a second cooler 9, a tubular reactor 2 and a material circulating pump 7, closing a discharge valve 5, opening a light-passing valve 4, a feed valve 6, a kettle bottom valve 16, a steam inlet valve 21, a steam condensate outlet valve 22, a tubular reactor reaction material outlet valve 23, a first circulating water inlet valve 81, a first circulating water outlet valve 82, a second circulating water inlet valve 91 and a second circulating water outlet valve 92, introducing steam from an input pipeline above one side of the tubular reactor (2), and heating the tubular reactor (2);
wherein the cooling temperature in the first cooler 8 is controlled between 50 ℃ and 60 ℃, and the cooling temperature in the second cooler 9 is controlled between 0 ℃ and 8 ℃; the first cooler 8 is used for cooling phosgene in the mixture which is circulated from the reaction kettle 1 to the first cooler 8 through the first output pipeline 83 and making the phosgene flow back to the reaction kettle 1, the second cooler 9 is used for cooling solvent toluene which is circulated from the reaction kettle 1 to the second cooler 9 and making the solvent toluene flow back to the reaction kettle 1, so that the phosgene and the solvent toluene enter the tubular reactor 2 again to participate in the reaction, the phosgene is fully participated in the reaction, the loss of the solvent is reduced, and the byproduct hydrogen chloride which enters the second cooler 9 is discharged to the outside through the fourth output pipeline 94 so as to enter a subsequent byproduct treatment process; (ii) a The material circulating pump 7 is used for promoting the circulating flow of materials in the device for the phosgenation reaction; the temperature of the outlet material of the tubular reactor 2 is manually controlled to be 110-120 ℃ by detecting through a temperature detector of the tubular reactor.
S3, opening the material circulating pump 7 and the kettle bottom valve 16, closing the discharge valve 5, and introducing phosgene;
wherein the material circulating pump 7 is used for promoting the circulation flow of the materials in the device for the phosgenation reaction;
s4, sampling and measuring, stopping the reaction when detecting that the residue of the p-phenylenediamine hydrochloride in the reaction kettle 1 reaches a qualified value, namely the residue of the p-phenylenediamine hydrochloride is less than 0.5 percent of the input amount in the step S1, and opening a discharge valve 5 to collect a mixture after the phosgene reaction;
the reaction time is shortened from the original 150 hours to 48 hours, and the phosgene input is reduced from 5000 kg of phosgene consumed in the traditional kettle type reaction to 2000 kg.
It should be understood that when the phosgene reaction also involves a catalyst, and the catalyst is easy to evaporate in the temperature range set by the reaction kettle 2, a third cooler is needed to cool the catalyst to make the catalyst flow back to the reaction kettle 1, and then the catalyst further enters the tubular reactor 2 to continue to play a catalytic role.
It should be understood that a phosgenation process of manufacture as provided by the present invention, not limited to the specific phosgenation process set forth in the examples above, may be used for the reaction of phosgene with amines including monoamines, diamines, triamines or higher functionality amines; preferably, a monoamine or a diamine is used. The method can also be used for preparing chloroformate and carbonate series products by phosgenation, and the chloroformate and carbonate series products include but are not limited to ethyl chloroformate, 2-bromoethyl chloroformate, propyl chloroformate, isopropyl chloroformate, propylene carbonate and diethylene glycol bis (allyl carbonate). It can also be used for preparing acyl chloride series products by phosgenation, wherein the acyl chloride series products include but are not limited to o-methyl benzoyl chloride, m-methyl benzoyl chloride and o-chloro benzoyl chloride.
According to the production process of the phosgenation reaction, provided by the invention, by adopting the device for the phosgenation reaction, during the reaction period, the introduced phosgene is always circulated in the whole device and continuously participates in the reaction when entering the tubular reactor 2, namely the phosgene can be fully utilized, and the utilization rate of the phosgene is improved. And according to the difference of the reaction, the number of the coolers is determined, the multi-stage coolers can respectively cool the solvent, the catalyst and the phosgene and return the solvent, the catalyst and the phosgene to the reaction kettle 1, the boiling point of the byproduct hydrogen chloride is extremely low and is-85 ℃, the byproduct hydrogen chloride cannot be cooled to be liquid after passing through the coolers and still keeps in a gas state, and therefore the byproduct hydrogen chloride is discharged from the coolers to an external output pipeline and further enters a subsequent byproduct treatment process.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of adaptation of the invention, and further modifications can be easily implemented by those skilled in the art, so that the invention is not limited to the specific details and the examples shown herein, without departing from the general concept defined by the claims and the scope of equivalents.
Claims (6)
1. A device for phosgenation reaction is characterized by comprising a reaction kettle (1), a tubular reactor (2), a phosgene input pipeline (3), a material circulating pump (7) and a first cooler (8);
the reaction kettle (1) is connected with a material input pipeline (13), a kettle bottom valve (16) arranged at the bottom of the reaction kettle (1) and a discharge valve (5) arranged at the lower end of the kettle bottom valve (16) are arranged on the same pipeline, pipelines in which the kettle bottom valve (16) and the discharge valve (5) are arranged are crossed and communicated with the phosgene input pipeline (3), the phosgene input pipeline (3) is connected with the material circulating pump (7), the material circulating pump (7) is connected with the tubular reactor (2), a tubular reactor reaction material output pipeline (24) is introduced into the reaction kettle (1), a reaction kettle evaporant output pipeline (14) is connected with the top of the first cooler (8), the bottom of the first cooler (8) is connected with a first output pipeline (83), and the other end of the first output pipeline (83) is connected with the reaction kettle (1), the first cooler (8) is also connected with a second output pipeline (84);
the tubular reactor (2) is provided with a sectional heating or cooling unit; the number of the tubular reactors (2) is 2-6; a temperature detector and a pressure regulating valve are arranged near an outlet valve (23) of the tubular reactor (2); an input pipeline is arranged above one side of the tubular reactor (2), and an output pipeline is arranged below the other side of the tubular reactor;
wherein the material input pipeline (13) is used for introducing materials into the reaction kettle (1), the material circulating pump (7) is used for pumping phosgene introduced from the phosgene input pipeline (3) and reaction raw materials discharged after a kettle bottom valve (16) of the reaction kettle is opened into the tubular reactor (2), the reaction raw materials and the phosgene react in the tubular reactor (2), the mixture enters the reaction kettle (1) after reaction under the action of the material circulating pump (7), the materials in the reaction kettle and the phosgene introduced from the phosgene input pipeline (3) are circulated together and enter the tubular reactor (2), the discharge valve (5) is in a closed state during the reaction, thereby realizing the circulation flow of the materials in the tubular reactor, circularly entering the reaction kettle, being cooled and reflowing after evaporation, and then entering the tubular reactor for reaction; phosgene and reaction by-product hydrogen chloride in the reaction kettle (1) are evaporated into the first cooler (8), the cooling temperature of the first cooler (8) is lower than the boiling point of the phosgene, the phosgene is cooled and flows back to the reaction kettle (1), and the by-product is discharged out of the device through the second output pipeline (84);
the device is characterized by further comprising a solvent metering tank (10), wherein the bottom of the solvent metering tank (10) is connected with a fifth output pipeline (102), and the fifth output pipeline (102) is connected with the reaction kettle (1);
the reaction kettle further comprises a second cooler (9), one end of a third output pipeline (93) at the bottom of the second cooler (9) is connected with the reaction kettle (1), the top of the second cooler (9) is connected with the second output pipeline (84), and the second cooler (9) is further connected with a fourth output pipeline (94);
the temperature of the first cooler (8) is higher than that of the second cooler (9) so as to respectively cool different substances required by the reaction evaporated from the reaction kettle (1) and make the substances flow back to the reaction kettle (1); the by-product in the second cooler (9) is discharged to the outside of the apparatus through the fourth outlet line (94).
2. The apparatus for a phosgenation reaction according to claim 1, characterized in that the reaction vessel (1) further comprises a stirrer (11), a temperature detector; the outer wall of the reaction kettle (1) further comprises a heating layer, an input pipeline is arranged above one side of the heating layer, and an output pipeline is arranged below the other side of the heating layer.
3. The apparatus for a phosgenation reaction according to claim 1, further comprising a third cooler, the bottom of which is connected to the reaction vessel (1) by a pipe, the top of which is connected to the fourth outlet pipe (94), and an outlet pipe for discharging the by-products in the third cooler to the outside of the apparatus.
4. The apparatus for a phosgenation reaction according to any one of claims 1, 2 and 3, wherein an output line is provided above one side of the cooler and an input line is provided below the other side of the cooler.
5. A production process of phosgenation reaction is characterized by comprising the following steps:
s1, closing a kettle bottom valve (16), and adding reaction raw materials into the reaction kettle (1) through a material input pipeline (13); starting the stirrer (11) for stirring; introducing steam from an input pipeline of a heating layer of the reaction kettle for heating, so that the temperature of the material entering the material circulating pump (7) is in a target range;
s2, starting the first cooler (8); introducing steam from an input pipeline above one side of the tubular reactor (2) to heat the tubular reactor (2); detecting through a temperature detector of the tubular reactor (2) so as to control the temperature of the outlet material of the tubular reactor (2) within a target range;
wherein the first cooler (8) is used for cooling phosgene entering the first cooler (8) from the reaction kettle (1) and refluxing the phosgene to the reaction kettle (1); the by-product is discharged out of the apparatus through a second outlet line (84);
s3, opening a material circulating pump (7) and a kettle bottom valve (16), closing a discharge valve (5), and introducing phosgene;
wherein the material circulation pump (7) is used for promoting the circulation flow of the materials in the device for the phosgenation reaction;
s4, sampling and measuring, stopping the reaction when detecting that the residue of the reaction raw materials in the reaction kettle (1) reaches the qualified value, and opening a discharge valve (5) to collect the mixture after the phosgene reaction.
6. A process for the production of a phosgenation reaction according to claim 5, characterized by the steps of:
s1, closing a kettle bottom valve (16), adding a solvent required by the reaction into the reaction kettle (1) through a solvent metering tank (10), adding a reaction raw material into the reaction kettle (1) through a material input pipeline (13), and starting a stirrer (11) for stirring; introducing steam from an input pipeline of a heating layer of the reaction kettle for heating, so that the reaction raw materials are fully dissolved in the solvent, and the temperature of the materials entering the material circulating pump (7) is in a target range;
s2, starting the first cooler (8) and the second cooler (9); introducing steam from an input pipeline above one side of the tubular reactor (2) to heat the tubular reactor (2); detecting through a temperature detector of the tubular reactor (2) so as to control the temperature of the outlet material of the tubular reactor (2) within a target range;
wherein the first cooler (8) is used for cooling the solvent evaporated from the reaction kettle (1) and refluxing the solvent into the reaction kettle (1); the second cooler (9) is used for cooling phosgene evaporated from the reaction kettle (1) and refluxing the phosgene to the reaction kettle (1); the by-product is discharged out of the apparatus through a fourth outlet line (94);
s3, opening a material circulating pump (7) and a kettle bottom valve (16), closing a discharge valve (5), and introducing phosgene;
wherein the material circulation pump (7) is used for promoting the circulation flow of the materials in the device for the phosgenation reaction;
s4, sampling and measuring, stopping the reaction when detecting that the residue of the reaction raw materials in the reaction kettle (1) reaches the qualified value, and opening a discharge valve (5) to collect the mixture after the phosgene reaction.
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| CN113121444B (en) * | 2019-12-30 | 2024-03-15 | 大丰海嘉诺药业有限公司 | Method for synthesizing vitamin H intermediate through pipeline |
| CN114749116B (en) * | 2021-01-11 | 2024-04-09 | 万华化学集团股份有限公司 | Method and reaction device for preparing polyisocyanate |
| HUP2300387A1 (en) * | 2021-01-11 | 2024-01-28 | Wanhua Chemical Ningbo Co | Method for preparing polyisocyanate and reaction device therefor |
| CN115155490A (en) * | 2022-06-16 | 2022-10-11 | 安徽广信农化股份有限公司 | Continuous preparation device for reducing unit consumption of isocyanate solvent and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003074477A1 (en) * | 2002-03-01 | 2003-09-12 | Basf Aktiengesellschaft | Method for producing isocyanates |
| JP2006312619A (en) * | 2005-04-04 | 2006-11-16 | Mitsui Chemicals Polyurethanes Inc | Installation and method for producing polyisocyanate |
| CN101151242A (en) * | 2005-04-05 | 2008-03-26 | 三井化学聚氨酯株式会社 | Apparatus for continuously producing polyisocyanate |
| CN101302174A (en) * | 2006-05-13 | 2008-11-12 | 拜尔材料科学股份公司 | Method for producing isocyanates |
| WO2009023989A1 (en) * | 2007-08-21 | 2009-02-26 | Ningbo Wanhua Polyurethanes Co., Ltd. | Jet reactor with flow ducts and process for preparing isocyanates using it |
| CN203602530U (en) * | 2013-12-12 | 2014-05-21 | 沧州大化股份有限公司 | Device for producing toluene diisocynate by virtue of phosgenation reaction |
| CN104892458A (en) * | 2015-06-24 | 2015-09-09 | 青岛科技大学 | Method for preparing isocyanate via reaction distillation method |
-
2019
- 2019-05-29 CN CN201910457802.8A patent/CN110327848B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003074477A1 (en) * | 2002-03-01 | 2003-09-12 | Basf Aktiengesellschaft | Method for producing isocyanates |
| JP2006312619A (en) * | 2005-04-04 | 2006-11-16 | Mitsui Chemicals Polyurethanes Inc | Installation and method for producing polyisocyanate |
| CN101151242A (en) * | 2005-04-05 | 2008-03-26 | 三井化学聚氨酯株式会社 | Apparatus for continuously producing polyisocyanate |
| CN101302174A (en) * | 2006-05-13 | 2008-11-12 | 拜尔材料科学股份公司 | Method for producing isocyanates |
| WO2009023989A1 (en) * | 2007-08-21 | 2009-02-26 | Ningbo Wanhua Polyurethanes Co., Ltd. | Jet reactor with flow ducts and process for preparing isocyanates using it |
| CN203602530U (en) * | 2013-12-12 | 2014-05-21 | 沧州大化股份有限公司 | Device for producing toluene diisocynate by virtue of phosgenation reaction |
| CN104892458A (en) * | 2015-06-24 | 2015-09-09 | 青岛科技大学 | Method for preparing isocyanate via reaction distillation method |
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