TWI686377B - Apparatus and method for manufacturing dimethylhexane-1,6-dicarbamate - Google Patents

Abstract

An apparatus and a method for manufacturing dimethylhexane-1,6-dicarbamate (HDC) are provided. The apparatus includes a reactor, a supply device of 1,6-hexanediamine (HDA), a supply device of dimethyl carbonate (DMC) and a first distillation column. The supply device of HDA is connected to the reactor. The supply device of DMC is connected to the reactor. The first distillation column is connected to a product outlet of the reactor. The first distillation column includes an upper column, a lower column and a compressor. The compressor is connected between a gas outlet of the lower column and a gas inlet of the upper column. The apparatus and the method for manufacturing HDC can effectively reduce the energy consumption and the production cost in the production of HDC.

Description

Manufacturing device and manufacturing method of hexamethylene-1,6-dicarbamic acid methyl ester

The invention relates to a compound manufacturing device and manufacturing method, and in particular to a manufacturing device and manufacturing of hexamethylene-1,6-dicarbamate (HDC) method.

Hexamethylene-1,6-diisocyanate (hexadiethylene-1,6-diisocyanate, HDI) such as aliphatic isocyanate is an important raw material for the polyurethane (PU) industry, PU produced by HDI has color retention, gloss retention, resistance Powdering, light resistance, oil resistance, wear resistance, etc., this is unmatched by PU produced by aromatic isocyanate.

HDI is traditionally synthesized from 1,6-hexanediamine (HDA) via phosgenation, but this method has the disadvantages of extreme toxicity of phosgene and severe corrosion of by-product hydrochloric acid. Therefore, the effective and environmentally friendly synthesis method of HDI has received high attention. Recently, a non-phosgene method using two steps to synthesize HDI using HDA as a raw material has attracted much attention. The first step is the synthesis of HDC, and the second step is the thermal cracking of HDC to generate HDI. In this method, HDC is an intermediate, and its synthesis plays an important role in the entire HDI production process.

However, the energy consumption and production cost when producing HDC are high. Therefore, how to effectively reduce the energy consumption and production cost in the production of HDC is the goal of continuous efforts at present.

The invention provides an HDC manufacturing device and manufacturing method, which can greatly reduce the energy consumption and production cost when producing HDC.

The invention provides an HDC manufacturing device, including a reactor, an HDA supply device, a dimethyl carbonate (DMC) supply device, and a first distillation tower. The HDA supply device is connected to the reactor. The DMC supply device is connected to the reactor. The first distillation column is connected to the discharge port of the reactor. The first distillation column includes an upper column, a lower column and a compressor. The compressor is connected between the gas outlet of the lower tower and the gas inlet of the upper tower.

According to an embodiment of the present invention, in the above HDC manufacturing apparatus, a catalyst may be provided in the reactor.

According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the liquid outlet of the upper column can be connected to the liquid inlet of the lower column.

According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the temperature of the gas product at the top of the upper column is higher than the temperature of the liquid product at the bottom of the lower column.

According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the temperature of the gas product at the top of the upper column may be higher than the temperature of the liquid product at the bottom of the lower column by more than 5°C.

According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the pressure in the upper column is greater than the pressure in the lower column.

According to an embodiment of the invention, the HDC manufacturing device further includes a first reboiler. The first reboiler is connected to the bottom of the lower column. The top gas product of the upper column can be used as the heat source of the first reboiler.

According to an embodiment of the present invention, the HDC manufacturing apparatus further includes a second reboiler. The second reboiler is connected to the bottom of the lower column.

According to an embodiment of the present invention, the HDC manufacturing device further includes a second distillation column. The second distillation column is connected to the bottom of the lower column.

According to an embodiment of the present invention, the HDC manufacturing apparatus further includes an extractive distillation column. The extractive distillation column is connected to the top of the upper column.

According to an embodiment of the present invention, the HDC manufacturing device further includes an extractant recovery tower. The extractant recovery tower is connected to the bottom of the extractive distillation tower.

According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the liquid product at the bottom of the second distillation column can be used as a reboiler connected to the bottom of the extractive distillation column and connected to the extractant recovery column. The reboiler at the bottom of the column and the heat source of at least one of the heat exchangers connected between the upper column and the extractive distillation column.

According to an embodiment of the present invention, in the above HDC manufacturing apparatus, the bottom liquid product of the extractant recovery column can be used as the heat source of the heat exchanger connected between the upper column and the extractive distillation column.

The invention provides a method for manufacturing HDC, including the following steps. In the reactor, HDA and DMC are reacted in the presence of a catalyst to produce a product after the reaction. The product after the reaction enters the first distillation column to produce the first gas product at the top of the column and the liquid product at the bottom of the first column. The first distillation column includes an upper column, a lower column and a compressor. The first overhead gas product is produced from the upper column. The first bottom liquid product is produced from the lower column. The compressor is connected between the gas outlet of the lower tower and the gas inlet of the upper tower.

According to an embodiment of the present invention, in the above HDC manufacturing method, the liquid outlet of the upper column can be connected to the liquid inlet of the lower column.

According to an embodiment of the present invention, in the above HDC manufacturing method, the temperature of the gas product at the top of the upper column is higher than the temperature of the liquid product at the bottom of the lower column.

According to an embodiment of the present invention, in the above HDC manufacturing method, the temperature of the gas product at the top of the upper column may be higher than the temperature of the liquid product at the bottom of the lower column by more than 5°C.

According to an embodiment of the present invention, in the above HDC manufacturing method, the pressure in the upper column is greater than the pressure in the lower column.

According to an embodiment of the present invention, in the above HDC manufacturing method, in the reaction of HDA and DMC, excess DMC may be used as a reactant.

According to an embodiment of the present invention, in the above HDC manufacturing method, in the reaction of HDA and DMC, the feed molar ratio of DMC to HDA is, for example, 3 to 9.

According to an embodiment of the present invention, in the above HDC manufacturing method, the products after the reaction may include HDC, methanol (MeOH), and DMC. The first overhead gas product may include MeOH and DMC. The first bottom liquid product may include HDC and DMC.

According to an embodiment of the present invention, in the above HDC manufacturing method, the first overhead gas product of the upper column can be used as the heat source of the reboiler connected to the bottom of the lower column.

According to an embodiment of the present invention, in the above-mentioned HDC manufacturing method, it may further include allowing the first bottom liquid product to enter the second distillation column to produce a second top liquid product and a second bottom liquid product .

According to an embodiment of the invention, in the above HDC manufacturing method, the second overhead liquid product may include DMC. The second bottom liquid product may include HDC.

According to an embodiment of the present invention, in the above HDC manufacturing method, it may further include that the first overhead liquid product and the extractant obtained after the condensation of the first overhead gas product are condensed into an extractive distillation column to produce The liquid product at the top of the third column and the liquid product at the bottom of the third column.

According to an embodiment of the invention, in the above HDC manufacturing method, the third overhead liquid product may include MeOH. The third bottom liquid product may include DMC and extractant.

According to an embodiment of the present invention, in the above-mentioned HDC manufacturing method, it may further include allowing the third bottom liquid product to enter the extractant recovery column to produce a fourth top liquid product and a fourth bottom liquid product .

According to an embodiment of the present invention, in the above HDC manufacturing method, the fourth overhead liquid product may include DMC. The fourth bottom liquid product may include an extractant.

According to an embodiment of the present invention, in the above-mentioned HDC manufacturing method, the second bottom liquid product of the second distillation column can be used as a reboiler connected to the bottom of the extractive distillation column and connected to the extractant recovery The reboiler at the bottom of the column and the heat source of at least one of the heat exchangers connected between the upper column and the extractive distillation column.

According to an embodiment of the present invention, in the above HDC manufacturing method, the fourth bottom liquid product of the extractant recovery column can be used as the heat source of the heat exchanger connected between the upper column and the extractive distillation column.

Based on the above, in the above-mentioned HDC manufacturing apparatus and manufacturing method, since the lower column is operated at a low pressure, the bottom reboiler energy consumption (reboiler duty) of the lower column can be effectively reduced. In addition, since the DMC composition of the DMC-MeOH azeotrope will decrease with increasing pressure, the pressure of the upper column will increase due to the addition of the compressor, which will tend to collect more DMC to the bottom of the lower column. It can significantly reduce the temperature difference between the bottom of the lower tower and the top of the upper tower, greatly reducing the equipment cost and operating cost of the compressor, and the gas product at the top of the upper tower can become the bottom of the lower tower under high temperature and high pressure. The heat source of the boiler. On the other hand, since the DMC composition of the top gas product of the upper column is closer to the DMC composition of the DMC-MeOH azeotrope, this will reduce the equipment cost and operating cost required for the extractive distillation system to separate the DMC and MeOH mixture. The architecture proposed by the invention can greatly reduce the energy consumption and production cost of the entire process of producing HDC.

In order to make the above-mentioned features and advantages of the present invention more obvious and understandable, the embodiments are specifically described below in conjunction with the accompanying drawings for detailed description as follows.

FIG. 1 is a schematic diagram of an HDC manufacturing apparatus according to an embodiment of the invention.

Referring to FIG. 1, the HDC manufacturing device 100 includes a reactor 102, an HDA supply device 104, a DMC supply device 106 and a distillation column 108. The HDC manufacturing apparatus 100 is suitable for reacting HDA and DMC in the presence of a catalyst to manufacture HDC.

The reactor 102 includes a continuous reactor or a batch reactor. In this embodiment, the number of reactors 102 is described as an example, but the invention is not limited thereto. Those skilled in the art can adjust the number of reactors 102 according to the process design. For example, in other embodiments, the number of the reactor 102 may be more than two. In addition, there may be a catalyst in the reactor 102. The catalyst can improve the reaction conversion rate of the reactants and can accelerate the reaction. The catalyst is, for example, manganese acetate (Mn(OAc) ₂ ) or sodium phenolate (C ₆ H ₅ ONa).

The HDA supply device 104 is connected to the reactor 102 and can be used to provide HDA into the reactor 102. The DMC supply device 106 is connected to the reactor 102 and can be used to provide DMC into the reactor 102. In one embodiment, a storage tank (not shown) may be provided between the HDA supply device 104 and the reactor 102 and between the DMC supply device 106 and the reactor 102, whereby HDA and DMC may be performed in the storage tank Premix, and then supply the mixture of HDA and DMC in the storage tank to the reactor 102, but the invention is not limited to this. In another embodiment, the delivery pipeline of the HDA supply device 104 and the delivery pipeline of the DMC supply device 106 may be first merged and then connected to the reactor 102, whereby the HDA and DMC may be pre-treated in the delivery pipeline Mix, and then supply the mixture of HDA and DMC to the reactor 102. In another embodiment, the HDA supply device 104 and the DMC supply device 106 can also supply HDA and DMC to the reactor 102, respectively.

Based on the above, the reactions that can occur in the reactor 102 are as follows. HDA + DMC → HMC + MeOH HMC + DMC → HDC + MeOH The overall reaction formula of the above reaction is as follows. HDA + 2DMC → HDC + 2MeOH where HMC is hexamethylene-1,6-monocarbamate (dimethylhexane-1,6-monocarbamate). HDC is the main product of the reaction system.

The distillation column 108 is connected to the discharge port 102a of the reactor 102. The distillation column 108 includes an upper column 110, a lower column 112, and a compressor 114, and may further include a pressure relief valve 115. In this embodiment, the example in which the upper column 110 is connected to the discharge port 102a of the reactor 102 is taken as an example, but the present invention is not limited thereto. The compressor 114 is connected between the gas outlet 112a of the lower column 112 and the gas inlet 110a of the upper column 110. In addition, the liquid outlet 110b of the upper column 110 may be connected to the liquid inlet 112b of the lower column 112. The pressure relief valve 115 may be connected between the liquid outlet 110b of the upper column 110 and the liquid inlet 112b of the lower column 112. For example, the gas inlet 110a and the liquid outlet 110b of the upper tower 110 may be located at the bottom of the upper tower 110, and the gas outlet 112a and the liquid inlet 112b of the lower tower 112 may be located at the top of the lower tower 112, but the present invention Not limited to this.

By the operation of the compressor 114, the pressure in the upper column 110 is greater than the pressure in the lower column 112. Since the lower column 112 operates at a low pressure, the energy consumption of the reboiler at the bottom of the lower column 112 can be effectively reduced, thereby greatly reducing the energy consumption and production cost when producing HDC.

In addition, since the compressor 114 can increase the pressure in the upper column 110, DMC tends to be more favorable to collect from the bottom of the lower column 112, which will make the DMC composition at the top of the upper column 110 closer to the DMC-MeOH azeotrope The DMC composition reduces the energy consumption and cost of the extractive distillation system. In addition, when reducing the content of DMC in the upper column 110, the contents of MeOH and DMC in the gas product at the top of the upper column 110 must be considered simultaneously. For example, if the ratio of the content of MeOH and DMC in the top gas product of the upper column 110 is close to the azeotropic composition, the energy consumption of the reboiler at the bottom of the lower column 112 will be greatly increased, so the upper column 110 The content ratio of MeOH to DMC in the overhead gas product is optimized.

In addition, when the pressure in the upper column 110 is increased, the temperature of the top gas product of the upper column 110 can be increased, which is beneficial to the subsequent utilization of the product (for example, the top gas product of the upper column 110 can be used as a reboiler 116 heat source), which in turn reduces energy consumption and production costs when producing HDC. The temperature of the gas product at the top of the upper column 110 is higher than the temperature of the liquid product at the bottom of the lower column 112. For example, the temperature of the gas product at the top of the upper column 110 may be higher than the temperature of the liquid product at the bottom of the lower column 112 by more than 5°C. In one embodiment, the temperature of the gas product at the top of the upper column 110 may be higher than the temperature of the liquid product at the bottom of the lower column 112 by more than 10°C.

The HDC manufacturing apparatus 100 can optionally include a reboiler 116, a reboiler 118, a reflux drum 120, a condenser 122, a distillation column 124, a reboiler 126, a reflux tank 128, a condenser 130, Extractive distillation column 132, heat exchanger 134, reboiler 136, reboiler 138, reflux tank 140, condenser 142, extractant recovery tower 144, reboiler 146, reboiler 148, reflux tank 150, condenser 152. At least one of the heat exchanger 154 and the condenser 156.

The reboiler 116 is connected to the bottom of the lower column 112 to provide heat to the lower column 112. Since the temperature of the top gas product of the upper column 110 is higher than the temperature of the bottom liquid product of the lower column 112, the top gas product of the upper column 110 can be used as the heat source of the reboiler 116, and by performing the above heat integration Further reduce energy consumption and production costs. In detail, the overhead gas product of the upper column 110 can release latent heat to the reboiler 116 of the lower column 110, thereby reducing the temperature of the overhead gas product or making the overhead gas product an overhead liquid product.

The reboiler 118 is connected to the bottom of the lower column 112 and can serve as an auxiliary heat source for the lower column 112. In the case where the reboiler 116 can provide sufficient heat to the lower column 112, the reboiler 118 can also be omitted.

The reflux tank 120 is connected to the top of the upper tower 110, and can be used to store the top gas product of the upper tower 110 through the reboiler 116 for heat exchange or condensed by the condenser 122, and the top liquid product in the reflux tank 120 A part of the liquid product at the top of the column can be refluxed into the upper column 110.

The condenser 122 is connected between the reboiler 116 and the reflux tank 120. The top gas product or top liquid product after heat exchange in the reboiler 116 can be condensed by the condenser 122 and then enter the reflux tank 120. In another embodiment, the condenser 122 may be omitted when the top gas product of the upper column 110 after heat exchange in the reboiler 116 has become the top liquid product at a predetermined temperature.

The distillation column 124 is connected to the bottom of the lower column 112. The reboiler 126 is connected to the bottom of the distillation column 124 to provide heat to the distillation column 124. The reflux tank 128 is connected to the top of the distillation column 124, and can be used to store the overhead liquid product of the distillation column 124, and a part of the overhead liquid product in the reflux tank 128 can be refluxed into the distillation column 124. The condenser 130 is connected between the top of the distillation column 124 and the reflux tank 128. The gas product at the top of the distillation column 124 can be condensed by the condenser 130 and then enter the reflux tank 128.

The extractive distillation column 132 is connected to the top of the upper column 110. In this embodiment, the reflux tank 120 may be connected between the top of the upper column 110 and the extractive distillation column 132. The heat exchanger 134 is connected between the reflux tank 120 and the extractive distillation column 132 to heat the feed from the reflux tank 120, thereby reducing the energy consumption of the reboiler at the bottom of the extractive distillation column 132. The extractant added in the extractive distillation column 132 is, for example, aniline or phenol. The extractant can be used to extract DMC in the distillation column 132. The reboiler 136 is connected to the bottom of the extractive distillation column 132 to provide heat to the extractive distillation column 132. The reboiler 138 is connected to the bottom of the extractive distillation column 132 and can be used as an auxiliary heat source for the extractive distillation column 132. In addition, in the case where the reboiler 136 can provide sufficient heat to the extractive distillation column 132, the reboiler 138 can also be omitted. The reflux tank 140 is connected to the top of the extractive distillation column 132, and can be used to store the overhead liquid product of the extractive distillation column 132, and part of the overhead liquid product in the reflux tank 140 can be refluxed into the extractive distillation column 132. The condenser 142 is connected between the top of the extractive distillation column 132 and the reflux tank 140. The gas product at the top of the extractive distillation column 132 can be condensed by the condenser 142 before entering the reflux tank 140.

The extractant recovery column 144 is connected to the bottom of the extractive distillation column 132. The reboiler 146 is connected to the bottom of the extractant recovery column 144 to provide heat to the extractant recovery column 144. The reboiler 148 is connected to the bottom of the extractant recovery tower 144 and can be used as an auxiliary heat source for the extractant recovery tower 144. In the case where the reboiler 146 can provide sufficient heat to the extractant recovery column 144, the reboiler 148 can also be omitted. The reflux tank 150 is connected to the top of the extractant recovery column 144, and can be used to store the top liquid product of the extractant recovery column 144, and a part of the top liquid product in the reflux tank 150 can be refluxed into the extractant recovery column 144. The condenser 152 is connected between the top of the extractant recovery column 144 and the reflux tank 150. The gas product at the top of the extractant recovery column 144 can be condensed by the condenser 152 before entering the reflux tank 150. The extractant in the liquid product at the bottom of the extractant recovery column 144 can be refluxed into the extractive distillation column 132.

In addition, since the temperature of the bottom liquid product of the distillation column 124 can be higher than the temperature of the bottom liquid product of the extractive distillation column 132, the temperature of the bottom liquid product of the extractant recovery column 144 and the feed temperature of the extractive distillation column 132, it can be The bottom liquid product of the distillation column 124 serves as a reboiler 136 connected to the bottom of the extractive distillation column 132, a reboiler 146 connected to the bottom of the extractant recovery column 144, and is connected to the upper column 110 and the extractive distillation column 132 The heat source of at least one of the heat exchangers 134 in between, and by performing the above heat integration, energy consumption and production costs can be further reduced.

The heat exchanger 154 is connected between the reflux tank 120 and the extractive distillation column 132 to heat the feed from the reflux tank 120, thereby reducing the energy consumption of the reboiler at the bottom of the extractive distillation column 132. Since the temperature of the bottom liquid product of the extractant recovery column 144 can be higher than the feed temperature of the extractive distillation column 132, the bottom liquid product of the extractant recovery column 144 can be connected between the upper column 110 and the extractive distillation column 132 The heat source of the heat exchanger 154, and by performing the above heat integration can further reduce energy consumption and production costs.

The condenser 156 is connected between the bottom of the extractant recovery column 144 and the extractive distillation column 132. The liquid product at the bottom of the extractant recovery column 144 after heat exchange in the heat exchanger 154 can be condensed by the condenser 156 and then enter the extractive distillation column 132.

FIG. 2 is a manufacturing flowchart of an HDC according to an embodiment of the invention. Hereinafter, a method of manufacturing an HDC according to an embodiment of the present invention will be described with reference to FIG. 2. The device used in the manufacturing method of FIG. 2 is an example of the HDC manufacturing device 100 of FIG. 1, but the invention is not limited thereto. In addition, for details of each component in the HDC manufacturing apparatus 100 of FIG. 1, reference may be made to the above-mentioned embodiment, and the description will not be repeated.

Referring to FIG. 2, step S100 is performed. In the reactor 102, HDA and DMC are reacted in the presence of a catalyst to produce a product after the reaction. The products after the reaction may include HDC, MeOH, and DMC, and may further include trace amounts of HDA, trace amounts of high-boiling intermediate products (HMC), and trace amounts of high-boiling impurities. For example, the HDA supply device 104 and the DMC supply device 106 can provide HDA and DMC to the reactor 102 to perform the reaction. In the reaction of HDA and DMC, excess DMC can be used as a reactant. In the reaction of HDA and DMC, the feed molar ratio of DMC to HDA is, for example, 3 to 9. In one embodiment, in the reaction of HDA and DMC, the feed molar ratio of DMC to HDA is, for example, 4 to 8. The catalyst is, for example, manganese acetate (Mn(OAc) ₂ ) or sodium phenolate (C ₆ H ₅ ONa).

Step S102 is carried out, so that the products after the reaction enter the distillation column 108 to produce the first gas product at the top of the column and the liquid product at the bottom of the first column. The first overhead gas product may include MeOH and DMC. The first bottom liquid product may include HDC and DMC, and may further include trace amounts of HDA, trace amounts of MeOH, trace amounts of high-boiling intermediate products (HMC) and trace amounts of high-boiling impurities.

The distillation column 108 includes an upper column 110, a lower column 112, and a compressor 114, and may further include a pressure relief valve 115. The first overhead gas product is produced from the upper column 110. The first bottom liquid product is produced from the lower column 112. The compressor 114 is connected between the gas outlet 112a of the lower column 112 and the gas inlet 110a of the upper column 110. The liquid outlet 110b of the upper column 110 may be connected to the liquid inlet 112b of the lower column 112. The pressure relief valve 115 may be connected between the liquid outlet 110b of the upper column 110 and the liquid inlet 112b of the lower column 112. For example, the gas inlet 110a and the liquid outlet 110b of the upper tower 110 may be located at the bottom of the upper tower 110, and the gas outlet 112a and the liquid inlet 112b of the lower tower 112 may be located at the top of the lower tower 112, but the present invention Not limited to this.

By the operation of the compressor 114, the pressure in the upper column 110 is greater than the pressure in the lower column 112. The temperature of the top gas product of the upper column 110 is higher than the temperature of the bottom liquid product of the lower column 112, so the first top gas product of the upper column 110 can be used as the heat source of the reboiler 116 connected to the bottom of the lower column 112 And, by performing the above heat integration, energy consumption and production costs can be further reduced. For example, the temperature of the gas product at the top of the upper column 110 may be higher than the temperature of the liquid product at the bottom of the lower column 112 by more than 5°C. In one embodiment, the temperature of the gas product at the top of the upper column 110 may be higher than the temperature of the liquid product at the bottom of the lower column 112 by more than 10°C.

Based on the above, since the lower column 112 operates at a low pressure, the bottom reboiler duty of the lower column 112 can be effectively reduced. In addition, since the DMC composition of the DMC-MeOH azeotrope decreases with increasing pressure, the pressure of the upper column 110 increases due to the addition of the compressor 114, which will tend to allow more DMC to go to the bottom of the lower column 112 Collecting, this can significantly reduce the temperature difference between the bottom of the lower tower 112 and the top of the upper tower 110, greatly reducing the equipment cost and operating cost of the compressor, and the gas products at the top of the upper tower 110 at high temperature and pressure can become The heat source of the bottom reboiler of the lower column 112. On the other hand, since the DMC composition of the top gas product of the upper column 110 is closer to the DMC composition of the DMC-MeOH azeotrope, this will reduce the equipment cost and operating cost required for the extractive distillation system to separate the DMC and MeOH mixture. The architecture proposed by the present invention can greatly reduce the energy consumption and production cost of the entire manufacturing process of HDC.

In addition, step S104 may be performed to make the first bottom liquid product enter the distillation column 124 to generate a second top liquid product and a second bottom liquid product. The second overhead liquid product may include DMC, and may further include traces of MeOH. The second bottom liquid product may include HDC, and may further include trace amounts of HDA, trace amounts of high-boiling intermediate products (HMC), and trace amounts of high-boiling impurities.

In addition, step S106 may be performed, so that the first overhead liquid product and the extractant obtained after the condensation of the first overhead gas product enter the extractive distillation column 132 to produce the third overhead liquid product and the third overhead liquid product . For example, the first overhead gas product may release latent heat to the reboiler 116 of the lower column 110 to become the overhead liquid product or condensed into the overhead liquid product by the condenser 122 and enter the reflux tank 120, the reflux tank 120 A part of the liquid product at the top of the column can be refluxed to the upper column 110, a part of the liquid product at the top of the column is collected in the reflux tank 120, and then the liquid product at the top of the column and the extractant enter the extractive distillation column. The extractant can be used to extract DMC in the distillation column 132. The extractant added in the extractive distillation column 132 is, for example, aniline or phenol. The third overhead liquid product may include MeOH, and may even include trace amounts of DMC. The bottom liquid product of the third column may include DMC and extractant, and may further include a small amount of MeOH.

Next, step S108 may be performed to make the third bottom liquid product enter the extractant recovery column 144 to produce a fourth top liquid product and a fourth bottom liquid product. The fourth overhead liquid product may include DMC, and may further include traces of MeOH. The fourth bottom liquid product may include an extractant, and may further include a trace amount of DMC.

On the other hand, the second bottom liquid product of the distillation column 124 can be used as the reboiler 136 connected to the bottom of the extractive distillation column 132, and the reboiler 146 connected to the bottom of the extractant recovery column 144 is connected to The heat source of at least one of the heat exchangers 134 between the upper column 110 and the extractive distillation column 132 can further reduce energy consumption and production costs by performing the above heat integration. In addition, the fourth bottom liquid product of the extractant recovery column 144 can be used as the heat source of the heat exchanger 154 connected between the upper column 110 and the extractive distillation column 132, and the energy can be further reduced by performing the above heat integration Consumption and production costs. In addition, the path of heat integration shown in FIG. 1 (indicated by dotted lines) is only an example, and the present invention is not limited thereto. Those of ordinary skill in the art can refer to the teachings of the above embodiments and adjust the path of thermal integration according to requirements.

Based on the above embodiment, it can be seen that in the above HDC manufacturing apparatus and manufacturing method, since the lower column 112 is operated at a low pressure, the energy consumption of the reboiler at the bottom of the lower column 112 can be effectively reduced, thereby greatly reducing the production HDC energy consumption and production costs. In addition, the compressor 114 can increase the pressure in the upper column 110, thereby reducing the content of DMC in the upper column 110, and can simultaneously increase the content of DMC in the lower column 112, and can increase the top gas of the upper column 110 The product temperature serves as a heat source for the reboiler, which in turn reduces energy consumption and production costs when producing HDC.

In summary, in the HDC manufacturing apparatus and manufacturing method of the above embodiment, since the compressor is connected between the gas outlet of the lower tower and the gas inlet of the upper tower, it can be greatly reduced by the action of the compressor Energy consumption and production costs when producing HDC.

Although the present invention has been disclosed as above with examples, it is not intended to limit the present invention. Any person with ordinary knowledge in the technical field can make some changes and modifications without departing from the spirit and scope of the present invention. The scope of protection of the present invention shall be subject to the scope defined in the appended patent application.

100: HDC manufacturing device 102: Reactor 102a: Outlet 104: HDA supply device 106: DMC supply device 108, 124: distillation tower 110: Upper tower 110a: gas inlet 110b: Liquid outlet 112: Lower tower 112a: gas outlet 112b: Liquid inlet 114: Compressor 115: Pressure relief valve 116, 118, 126, 136, 138, 146, 148: reboiler 120, 128, 140, 150: reflux tank 122, 130, 142, 152, 156: condenser 132: Extractive distillation tower 134, 154: heat exchanger 144: Extractant recovery tower S100, S102, S104, S106, S108: steps

FIG. 1 is a schematic diagram of an HDC manufacturing apparatus according to an embodiment of the invention. FIG. 2 is a manufacturing flowchart of an HDC according to an embodiment of the invention.

100: HDC manufacturing device

102: Reactor

102a: Outlet

104: HDA supply device

106: DMC supply device

108, 124: distillation tower

110: Upper tower

110a: gas inlet

110b: Liquid outlet

112: Lower tower

112a: gas outlet

112b: Liquid inlet

114: Compressor

115: Pressure relief valve

116, 118, 126, 136, 138, 146, 148: reboiler

120, 128, 140, 150: reflux tank

122, 130, 142, 152, 156: condenser

132: Extractive distillation tower

134, 154: heat exchanger

144: Extractant recovery tower

Claims (30)

A manufacturing device of methyl hexamethylene-1,6-dicarbamate includes: a reactor; a 1,6-hexanediamine supply device connected to the reactor; a dimethyl carbonate supply device connected to The reactor; and a first distillation column connected to the outlet of the reactor, and including: an upper column; a lower column; and a compressor, connected to the gas outlet of the lower column and the upper column Between gas inlets. The manufacturing apparatus for methyl hexamethylene-1,6-dicarbamate as described in item 1 of the patent application scope, wherein a catalyst is provided in the reactor. The manufacturing apparatus of methyl hexamethylene-1,6-dicarbamate as described in item 1 of the patent application scope, wherein the liquid outlet of the upper column is connected to the liquid inlet of the lower column. The manufacturing device of methyl hexamethylene-1,6-dicarbamate as described in item 1 of the patent application scope, wherein the temperature of the gas product at the top of the upper column is higher than the liquid product at the bottom of the lower column temperature. According to the manufacturing device of methyl hexamethylene-1,6-dicarbamate described in item 1 of the patent application scope, the temperature of the gas product at the top of the upper column is higher than the temperature of the liquid product at the bottom of the lower column Above 5°C. The manufacturing device of methylhexamethylene-1,6-dicarbamate as described in item 1 of the scope of the patent application, wherein the pressure in the upper column is greater than the pressure in the lower column. The manufacturing device for methyl hexamethylene-1,6-dicarbamate as described in item 1 of the scope of the patent application further includes: a first reboiler connected to the bottom of the lower column, wherein the The top gas product of the upper column serves as the heat source of the first reboiler. The manufacturing device for methyl hexamethylene-1,6-dicarbamate as described in item 7 of the scope of the patent application further includes: a second reboiler connected to the bottom of the lower column. The manufacturing apparatus for methyl hexamethylene-1,6-dicarbamate as described in item 1 of the scope of the patent application further includes: a second distillation column connected to the bottom of the lower column. The manufacturing apparatus for methyl hexamethylene-1,6-dicarbamate as described in item 9 of the scope of the patent application further includes: an extractive distillation column connected to the top of the upper column. The manufacturing apparatus for methyl hexamethylene-1,6-dicarbamate as described in item 10 of the scope of the patent application further includes: an extractant recovery tower connected to the bottom of the extractive distillation tower. The manufacturing apparatus of methyl hexamethylene-1,6-dicarbamate as described in item 11 of the patent application scope, wherein the bottom liquid product of the second distillation column is connected to the extractive distillation column A heat source of at least one of a reboiler at the bottom of the column, a reboiler connected to the bottom of the extractant recovery column, and a heat exchanger connected between the upper column and the extractive distillation column. The manufacturing apparatus for methyl hexamethylene-1,6-dicarbamate as described in item 11 of the patent application scope, wherein the bottom liquid product of the extractant recovery column is connected as the upper column and the The heat source of the heat exchanger between the extractive distillation towers. A method for manufacturing methyl hexamethylene-1,6-dicarbamate includes: in a reactor, reacting 1,6-hexanediamine and dimethyl carbonate in the presence of a catalyst, and Producing a product after the reaction; and causing the product after the reaction to enter the first distillation column to produce the first gas product at the top of the column and the liquid product at the bottom of the first column, wherein the first distillation column includes: an upper column, wherein The first column top gas product is produced from the upper column; the lower column column, wherein the first column bottom liquid product is produced from the lower column; and the compressor, which is connected to the gas outlet of the lower column and the Between the gas inlets of the upper tower. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 14 of the patent application scope, wherein the liquid outlet of the upper column is connected to the liquid inlet of the lower column. The method for producing methyl hexamethylene-1,6-dicarbamate as described in item 14 of the patent application scope, wherein the temperature of the gas product at the top of the upper column is higher than the liquid product at the bottom of the lower column temperature. According to the method for manufacturing methyl hexamethylene-1,6-dicarbamate described in item 14 of the patent application scope, the temperature of the gas product at the top of the upper column is higher than the temperature of the liquid product at the bottom of the lower column Above 5°C. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 14 of the patent application scope, wherein the pressure in the upper column is greater than the pressure in the lower column. The method for producing methyl hexamethylene-1,6-dicarbamate as described in item 14 of the patent application scope, wherein in the reaction of the 1,6-hexanediamine with the dimethyl carbonate, An excess of the dimethyl carbonate was used as a reactant. The method for producing methyl hexamethylene-1,6-dicarbamate as described in item 19 of the patent application scope, wherein in the reaction of the 1,6-hexanediamine with the dimethyl carbonate, The feed molar ratio of the dimethyl carbonate to the 1,6-hexanediamine is 3 to 9. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 14 of the patent application scope, wherein the product after the reaction includes methyl hexamethylene-1,6-dicarbamate , Methanol and the dimethyl carbonate, the first overhead gas product includes the methanol and the dimethyl carbonate, and the first bottom liquid product includes the hexamethylene-1,6 -Methyl dicarbamate and the dimethyl carbonate. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 14 of the scope of patent application, wherein the first overhead gas product of the upper column is connected to the lower column The heat source of the reboiler at the bottom of the tower. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 14 of the scope of the patent application further includes: causing the liquid product at the bottom of the first column to enter the second distillation column to produce the first The liquid product at the top of the second column and the liquid product at the bottom of the second column. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 23 of the patent application scope, wherein the second overhead liquid product includes the dimethyl carbonate, and the second The bottom liquid product includes methyl hexamethylene-1,6-dicarbamate. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 23 of the scope of the patent application further includes: a first overhead liquid obtained by condensing the first overhead gas product The product and extractant enter the extractive distillation column to produce a third overhead liquid product and a third overhead liquid product. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 25 of the patent application scope, wherein the third overhead liquid product includes methanol, and the third bottom liquid product includes The dimethyl carbonate and the extractant. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 25 of the scope of the patent application further includes: causing the liquid product at the bottom of the third column to enter the extractant recovery column, and producing the first The liquid product at the top of the fourth column and the liquid product at the bottom of the fourth column. The method for manufacturing methyl hexamethylene-1,6-dicarbamate as described in item 27 of the patent application scope, wherein the fourth overhead liquid product includes the dimethyl carbonate, and the fourth The bottom liquid product includes the extractant. The method for producing methyl hexamethylene-1,6-dicarbamate as described in item 27 of the patent application scope, wherein the second bottom liquid product of the second distillation column is connected to the At least one of a reboiler at the bottom of the extractive distillation column, a reboiler connected to the bottom of the extractant recovery column, and a heat exchanger connected between the upper column and the extractive distillation column Heat source. The method for producing methyl hexamethylene-1,6-dicarbamate as described in Item 27 of the patent application scope, wherein the fourth bottom liquid product of the extractant recovery column is connected to the The heat source of the heat exchanger between the upper column and the extractive distillation column.

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