TWI585072B - Apparatus for manufacturing dichlorohydrin and manufacturing method thereof - Google Patents

Description

Dichloropropanol manufacturing device and manufacturing method thereof

The present invention relates to a process for producing dichloropropanol, and more particularly to a process for producing dichloropropanol having a phase separator.

At present, the main preparation method of dichloropropanol is propene high-temperature chlorination, which comprises two steps: chlorinating propylene to allyl chloride at high temperature, and using an excessive amount of industrial water. The chloropropene is reacted with a chlorinating agent to form dichloropropanol. However, the use of propylene high temperature chlorination produces large amounts of wastewater and other waste materials, thus causing technical and environmental problems.

Therefore, a method of directly reacting glycerol with a chlorinating agent in the case of a catalyst to produce dichloropropanol has been developed, which does not generate a large amount of waste water and waste, and is therefore a relatively economical and environmentally friendly manufacturing method.

However, when dichloropropanol is prepared by this method, an azeotrope of dichloropropanol and water is formed, and an extractant is added to separate azeotrope. Obtaining dichloropropanol will increase the manufacturing cost, and the extractant may also form an azeotrope with the catalyst, which may cause difficulty in recycling the catalyst.

The present invention provides a manufacturing apparatus and a manufacturing method of dichloropropanol, which can reduce the manufacturing cost.

The present invention provides a device for producing dichloropropanol which is suitable for reacting glycerin with an aqueous hydrogen chloride solution in the presence of a catalyst to produce dichloropropanol. The manufacturing apparatus of dichlorohydrin includes at least one reactor, a thermally coupled distillation apparatus, a first phase separator, and a first water supply apparatus. A thermally coupled distillation unit is coupled to at least one reactor. A first phase separator is coupled to the top of the thermally coupled distillation unit to form a first aqueous phase product and a first organic phase product comprising dichlorohydrin in the first phase separator. The first water supply device is directly connected to the first phase separator.

In an embodiment of the invention, in the above-described apparatus for producing dichlorohydrin, the thermally coupled distillation apparatus may include a side stream outlet to take out the side stream product. The side stream product comprises water having a purity of from 85 wt% to 100 wt%.

In an embodiment of the invention, in the above-described apparatus for producing dichlorohydrin, the purity of water may be from 90% by weight to 99.99% by weight.

In an embodiment of the invention, in the above-described apparatus for producing dichlorohydrin, the purity of water may be from 95% by weight to 99.95% by weight.

In an embodiment of the present invention, in the above apparatus for producing dichlorohydrin, the thermally coupled distillation apparatus may include a first distillation column, a second distillation column, and a first A pipeline. The first distillation column is connected to at least one reactor, and the top of the first distillation column is connected to the first phase separator. The second distillation column is connected to the first distillation column. The first line is connected between the feed port of the second distillation column and the bottom of the first distillation column. A portion of the gas in the second distillation column is refluxed along the first line to the bottom of the first distillation column. The liquid at the bottom of the first distillation column flows along the first line to the feed port of the second distillation column.

In an embodiment of the invention, in the above-described apparatus for producing dichlorohydrin, the first aqueous phase product may be refluxed to the first distillation column.

In an embodiment of the invention, the apparatus for manufacturing dichloropropanol may further comprise a second phase separator. A second phase separator is coupled to the top of the second distillation column to form a second aqueous phase product and a second organic phase product comprising dichlorohydrin in the second phase separator.

In an embodiment of the invention, the apparatus for manufacturing dichloropropanol may further comprise a second water supply device. The second water supply device is directly connected to the second phase separator.

In an embodiment of the invention, in the above-described apparatus for producing dichlorohydrin, the second aqueous phase product may be refluxed to the second distillation column.

In an embodiment of the present invention, the apparatus for producing dichloropropanol may further include a third distillation column and a second conduit. The third distillation column is connected between at least one reactor and the first distillation column. The second line is connected between the third distillation column and the first distillation column.

In an embodiment of the present invention, in the above apparatus for producing dichlorohydrin, the second line may be connected to the top of the third distillation column and the inlet of the first distillation column. between. Part of the liquid in the first distillation column may be refluxed along the second line to the top of the third distillation column, and the gas at the top of the third distillation column may flow along the second line to the feed port of the first distillation column. .

In an embodiment of the present invention, the apparatus for producing dichloropropanol may further include a fourth distillation column and a third conduit. The second distillation column is connected between the first distillation column and the fourth distillation column, and the fourth distillation column is connected to at least one reactor. The third line is connected between the second distillation column and the fourth distillation column.

In an embodiment of the invention, in the above apparatus for producing dichlorohydrin, the third line may be connected between the bottom of the second distillation column and the feed port of the fourth distillation column. A portion of the gas of the fourth distillation column may be refluxed along the third line to the bottom of the second distillation column. The liquid at the bottom of the second distillation column can flow along the third line to the feed port of the fourth distillation column.

In an embodiment of the present invention, in the above apparatus for producing dichlorohydrin, the thermally coupled distillation apparatus may be a partition wall distillation column. The partition wall distillation column includes a first chamber, a second chamber, a first partition wall, and a third chamber. The first chamber is connected to the first phase separator, and the first chamber and the second chamber are adjacent to each other and are located at an upper portion of the partition wall distillation column. The first partition wall may extend from the interior of the dividing wall distillation column to the top and between the first chamber and the second chamber. The third chamber is located below the first chamber and the second chamber and is in communication with the first chamber and the second chamber, respectively.

In an embodiment of the invention, in the above apparatus for producing dichlorohydrin, the first aqueous phase product may be refluxed to the first chamber of the dividing wall distillation column.

In an embodiment of the invention, the apparatus for producing dichloropropanol is more A second phase splitter can be included. A second phase separator is coupled to the second chamber to form a second aqueous phase product and a second organic phase product comprising dichlorohydrin in the second phase separator.

In an embodiment of the invention, the apparatus for manufacturing dichloropropanol may further comprise a second water supply device. The second water supply device is directly connected to the second phase separator.

In an embodiment of the invention, in the above-described apparatus for producing dichlorohydrin, the second aqueous phase product may be refluxed to the second chamber of the dividing wall distillation column.

In an embodiment of the present invention, the apparatus for producing dichloropropanol may further include a fifth distillation column and a fourth conduit. The fifth distillation column is connected between at least one reactor and the partition wall distillation column, and the fourth line is connected between the fifth distillation column and the partition wall distillation column.

In an embodiment of the invention, in the above-described apparatus for producing dichlorohydrin, the fourth line may be connected between the top of the fifth distillation column and the feed port of the partition wall distillation column. Part of the liquid in the dividing wall distillation column may be refluxed along the fourth line to the top of the fifth distillation column, and the gas at the top of the fifth distillation column may flow along the fourth line to the inlet of the dividing wall distillation column. .

In an embodiment of the present invention, in the above apparatus for producing dichlorohydrin, the partition wall distillation column may further include a fourth chamber, a second partition wall, and a fifth chamber. The second chamber is located between the first chamber and the fourth chamber. The second partition wall may extend from the interior of the dividing wall distillation column to the top and between the fourth chamber and the second chamber and between the fourth chamber and the third chamber. The fifth chamber is located at the bottom of the partition wall distillation column, the third chamber and the fourth chamber are located above the fifth chamber, and the fifth chamber is in communication with the third chamber and the fourth chamber.

The present invention provides a method for producing dichloropropanol comprising the following steps. In at least one reactor, glycerin is reacted with an aqueous hydrogen chloride solution in the presence of a catalyst to produce an initial product. The first feed from the initial product is passed to a thermally coupled distillation unit coupled to a first phase separator to produce an overhead product and a bottoms product. The overhead product is condensed into the first phase separator, and the first water supply device is directly connected to the first phase separator, and the first aqueous phase product and the first organic phase product are formed in the first phase separator. Wherein the first organic phase product comprises dichloropropanol. The first organic phase product is removed.

In an embodiment of the present invention, in the above method for producing dichlorohydrin, the step of allowing the first feed to enter the thermally coupled distillation apparatus may further comprise producing a side stream product, and the side stream product may include a purity of 85 wt%. Up to 100% by weight of water.

In an embodiment of the invention, in the above method for producing dichlorohydrin, the purity of water may be from 90% by weight to 99.99% by weight.

In an embodiment of the invention, in the above method for producing dichloropropanol, the purity of water may be from 95% by weight to 99.95% by weight.

In an embodiment of the invention, in the above method for producing dichlorohydrin, the thermally coupled distillation apparatus comprises a first distillation column and a second distillation column, and the step of producing the overhead product and the bottom product comprises the following steps . The first feed is passed to the first distillation column to produce a first overhead product and a first bottoms product. The first bottoms product is passed as a second feed to the second distillation column to produce a second overhead product and a second bottoms product. A part of the gas in the second distillation column is refluxed to the bottom of the first distillation column. The overhead product comprises a first overhead product and a second overhead product, and the bottom product comprises a first bottom product And the second bottom product. The overhead product that enters the first phase separator after condensation is the first overhead product.

In an embodiment of the invention, the method for producing dichloropropanol further comprises refluxing the first aqueous phase product to the first distillation column.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise: condensing the second overhead product into a second phase separator connected to the second distillation column to form a second water. The phase product is a product of a second organic phase comprising dichlorohydrin.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise directly connecting the second water supply device to the second phase separator.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise refluxing the second aqueous phase product to the second distillation column.

In an embodiment of the present invention, the method for producing dichloropropanol may further comprise: introducing a third feed comprising an initial product into a third distillation column to produce a third overhead product and a third bottom product, And passing the third overhead product to the first distillation column, wherein the first feed is the third overhead product.

In an embodiment of the invention, the method for producing dichloropropanol described above may further comprise refluxing the third bottoms product to at least one reactor.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise refluxing a portion of the liquid in the first distillation column to the top of the third distillation column.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise: passing the second bottom product as a fourth feed to the fourth distillation column to produce a fourth overhead product and a fourth bottom a product, wherein the fourth bottom product is an aqueous hydrogen chloride solution The concentration is greater than the concentration of the aqueous solution of hydrogen chloride in the first bottom product.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise refluxing the fourth bottoms product to at least one reactor.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise refluxing a portion of the gas in the fourth distillation column to the bottom of the second distillation column.

In an embodiment of the present invention, in the above method for producing dichlorohydrin, the thermally coupled distillation apparatus may be a partition wall distillation column. The partition wall distillation column includes a first chamber, a second chamber, and a third chamber. The first chamber and the second chamber are located at an upper portion of the partition wall distillation column and are separated from each other by a first partition wall, wherein the first chamber is connected to the first phase separator. The third chamber is located below the first chamber and the second chamber and is in communication with the first chamber and the second chamber. In the step of producing the overhead product and the bottom product, the first feed is heated and partially evaporated at the bottom of the partition wall distillation column, and the evaporated first feed is raised to the first chamber and the second through the third chamber. a first chamber product and a second chamber product are formed in the chamber, respectively, in the first chamber and the second chamber, and the un-evaporated first feed is located at the bottom of the partition wall distillation column to form a bottom product . The overhead product includes a first chamber product and a second chamber product, wherein the overhead product entering the first phase separator is a first chamber product.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise refluxing the first aqueous phase product to the first chamber of the dividing wall distillation column.

In an embodiment of the invention, the method for producing dichloropropanol described above may further comprise refluxing the bottoms product to at least one reactor.

In an embodiment of the invention, the method for producing dichloropropanol is more The second chamber product may be condensed into a second phase separator connected to the second chamber to form a second aqueous phase product and a second organic phase product comprising dichloropropanol.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise directly connecting the second water supply device to the second phase separator.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise refluxing the second aqueous phase product to the second chamber of the dividing wall distillation column.

In an embodiment of the present invention, the method for producing dichloropropanol may further comprise: introducing an initial product into a fifth distillation column to produce a fifth overhead product and a fifth bottom product, and making the fifth column top The product was used as the first feed.

In an embodiment of the invention, the method for producing dichloropropanol described above may further comprise refluxing the fifth bottoms product to at least one reactor.

In an embodiment of the invention, the method for producing dichloropropanol may further comprise refluxing a portion of the liquid of the dividing wall distillation column to the top of the fifth distillation column.

In an embodiment of the invention, in the above method for producing dichloropropanol, the partition wall distillation column may further include a fourth chamber and a fifth chamber. The second chamber is located between the first chamber and the fourth chamber, and the second chamber and the fourth chamber are separated by a second partition wall between the third chamber and the fourth chamber. The fifth chamber is located at the bottom of the partition wall distillation column, wherein the third chamber and the fourth chamber are located above the fifth chamber, and the fifth chamber is in communication with the third chamber and the fourth chamber. In the step of producing the overhead product and the bottom product, the first feed is heated in the fifth chamber to partially evaporate, and a portion of the first feed is evaporated and then rises through the third chamber to the first chamber and the first chamber. The two chambers are respectively formed to form the first chamber product and the second chamber product, and the other portion of the first feed steam After the rise, it rises into the fourth chamber to form a fourth chamber product. The overhead product includes the first chamber product, the second chamber product, and the fourth chamber product, and the unvaporized first feed is located in the fifth chamber to form the bottoms product.

Based on the above, in the apparatus for producing dichloropropanol proposed by the present invention and the method for producing the same, the dichloropropanol is taken out by separating the azeotrope by using a phase separator, thereby avoiding the addition of an extractant and reducing the manufacturing cost. . In addition, since the extractant is not required, the problem that the extractant and the catalyst may form an azeotrope and the catalyst is difficult to recycle may be avoided. In addition, the concentration of the aqueous solution of hydrogen chloride in the phase separator can be directly adjusted by the water supply device, and the overhead product of the condensed distillation column is effectively phase-separated to smoothly obtain dichloropropanol. Furthermore, by providing a thermally coupled distillation apparatus, the energy consumed to carry out the distillation can be reduced, and the number of reboiler settings can be reduced. In other words, the manufacturing cost of dichloropropanol can be reduced.

The above described features and advantages of the invention will be apparent from the following description.

100, 200, 300, 400‧ ‧ dichloropropanol manufacturing device

102, 202, 402, 420‧‧‧reactor

104, 204‧‧‧ Thermally coupled distillation unit

106, 120, 206, 220, 406, 416‧ ‧ phase splitter

108, 122, 208, 222, 408, 418‧‧‧ water supply devices

110, 112, 210, 212, 410, 414‧‧‧ sidestream outlets

114, 116, 124, 128, 224, 404, 412‧‧ ‧ distillation tower

118, 123, 130, 223‧‧‧ pipeline

118a, 130a‧‧‧ gas flow path

118b, 130b‧‧‧ liquid flow path

125, 132, 215, 225, 405, 413‧‧ ‧ reboilers

126, 131, 226, 231‧‧ ‧ reflux tank

214‧‧‧ partition wall distillation tower

214a~214e‧‧‧室

216, 218‧‧‧ partition wall

S100, S102, S104, S106, S108, S110, S112, S114, S200, S202, S204, S206, S208, S210, S400, S402, S404, S406, S408, S410, S412, S414, S416, S418, S420‧ ‧‧step

S104a~S104d‧‧‧ substeps

Fig. 1A is a schematic view showing a manufacturing apparatus of dichloropropanol according to a first embodiment of the present invention.

Fig. 1B is a flow chart showing the manufacture of dichloropropanol according to the first embodiment of the present invention.

Fig. 2A is a schematic view showing a manufacturing apparatus of dichloropropanol according to a second embodiment of the present invention.

Figure 2B is a flow chart showing the manufacture of dichloropropanol in accordance with a second embodiment of the present invention.

Fig. 3 is a schematic view showing a manufacturing apparatus of dichloropropanol according to a third embodiment of the present invention.

Fig. 4A is a schematic view showing a manufacturing apparatus of dichloropropanol according to a fourth embodiment of the present invention.

Figure 4B is a flow chart showing the manufacture of dichloropropanol in accordance with a fourth embodiment of the present invention.

Fig. 1A is a schematic view showing a manufacturing apparatus of dichloropropanol according to a first embodiment of the present invention. Fig. 1B is a flow chart showing the manufacture of dichloropropanol according to the first embodiment of the present invention.

Referring to FIG. 1A, a first embodiment provides a apparatus 100 for producing dichloropropanol, which is suitable for reacting glycerin with an aqueous solution of hydrogen chloride in the presence of a catalyst to produce dichloropropanol. The manufacturing apparatus 100 of dichlorohydrin includes at least one reactor 102, a thermally coupled distillation apparatus 104, a phase separator 106, and a water supply apparatus 108. The thermally coupled distillation unit 104 is coupled to the reactor 102. A phase separator 106 is coupled to the top of the thermally coupled distillation unit 104 to form an aqueous phase product in the phase separator 106 with an organic phase product comprising dichlorohydrin. The water supply device 108 is directly connected to the phase splitter 106.

The thermally coupled distillation unit 104 can include a side stream outlet 110 and a side stream outlet 112 to extract side stream products. The side stream product of the thermally coupled distillation unit 104 includes water having a purity of from 85 wt% to 100 wt%. In other embodiments, the water of the side stream product of the thermally coupled distillation unit 104 may have a purity of from 90 wt% to 99.99 wt%, optimally 95 wt%. To 99.95 wt%.

In the first embodiment, the thermally coupled distillation unit 104 includes a distillation column 114, a distillation column 116, and a line 118. Distillation column 114 is coupled to reactor 102, and the top of distillation column 114 is coupled to phase separator 106, wherein the aqueous phase product of phase separator 106 can be refluxed to distillation column 114. The distillation column 116 is connected to the distillation column 114, and the line 118 is connected between the feed port of the distillation column 116 and the bottom of the distillation column 114. A portion of the gas in the distillation column 116 is refluxed along the line 118 to the bottom of the distillation column 114, and the liquid at the bottom of the distillation column 114 flows along the line 118 to the feed port of the second distillation column 116. In an embodiment, the line 118 may include a gas flow path 118a and a liquid flow path 118b such that a portion of the gas in the distillation column 116 may be refluxed along the gas flow path 118a to the bottom of the distillation column 114, and the distillation column 114 is caused. The liquid at the bottom can flow along the liquid flow path 118b to the feed port of the distillation column 116.

The dichlorohydrin manufacturing apparatus 100 may further include a phase separator 120 coupled to the top of the distillation column 116 to form an aqueous phase product and an organic phase product including dichloropropanol in the phase separator 120. The manufacturing apparatus 100 of dichlorohydrin may further include a water supply device 122 that is directly connected to the phase separator 120. The aqueous phase product of phase separator 120 can be refluxed to distillation column 116.

The dichlorohydrin manufacturing apparatus 100 may further include a distillation column 124 and a line 123 connected between the distillation column 124 and the distillation column 114, wherein the distillation column 124 is connected between the reactor 102 and the distillation column 114, and the piping 123 may be connected between the top of the distillation column 124 and the feed port of the distillation column 114. The gas at the top of the distillation column 124 can be stored in the reflux tank 126 after being condensed by a condenser (not shown), and the reflux tank 126 The liquid in the liquid can be partially returned to the distillation column 124 along the line 123 and partially to the distillation column 114.

In other embodiments, a portion of the liquid in distillation column 114 can be refluxed along line 123 to the top of distillation column 124, and the gas at the top of distillation column 124 flows along line 123 to the feed port of distillation column 114. Therefore, part of the liquid in the distillation column 114 can be thermally coupled with the gas at the top of the distillation column 124 while cooling the gas at the top of the distillation column 124. Accordingly, the cost of providing the condenser in the distillation column 124 can be eliminated.

The thermally coupled distillation unit 104 may further include a distillation column 128 and a line 130. The distillation column 116 is connected between the distillation column 114 and the distillation column 128, and the distillation column 128 is connected to the reactor 102, and the line 130 is connected between the distillation column 116 and the distillation column 128. The line 130 can be connected between the bottom of the distillation column 116 and the feed port of the distillation column 128. A portion of the gas from distillation column 128 may be refluxed along line 130 to the bottom of distillation column 116, and liquid at the bottom of distillation column 116 may flow along line 130 to the feed port of distillation column 128. In an embodiment, the line 130 may include a gas flow path 130a and a liquid flow path 130b such that a portion of the gas in the distillation column 128 may be refluxed along the gas flow path 130a to the bottom of the distillation column 116, and the distillation column 116 is allowed to pass. The liquid at the bottom flows to the feed port of the distillation column 128 along the liquid flow path 130b.

Referring to FIG. 1A and FIG. 1B simultaneously, the first embodiment further provides a method for producing dichloropropanol, which comprises the following steps in sequence.

In step S100, in at least one reactor 102, glycerin and an aqueous hydrogen chloride solution are reacted in the presence of a catalyst to produce an initial product. Reactor 102 includes a continuous reactor or a batch reactor. In the following examples, The description is made by taking one reactor 102 as an example, but the invention is not limited thereto, and those skilled in the art can adjust the number of reactors 102 according to the process design. Glycerin is, for example, a by-product of the production of biodiesel or a chemically synthesized glycerol. The catalyst is, for example, acetic acid or adipic acid. The initial products include dichloropropanol and monochloropropanol, of which dichloropropanol is the main product and monochloropropanol is the intermediate product. The initial product may further comprise an unreacted aqueous solution of hydrogen chloride, glycerin and a catalyst.

Next, step S102 can be selectively performed to cause the initial product to enter the distillation column 124 as a feed to produce an overhead product and a bottoms product. The initial product can be reacted and separated in distillation column 124. The bottom product of the distillation column 124 mainly includes unreacted glycerin, and may further include a small amount of dichloropropanol, a small amount of monochloropropanol, a small amount of an aqueous hydrogen chloride solution, and a catalyst. The bottoms of distillation column 124 can be refluxed to reactor 102 for continued recycle to increase reaction conversion. The overhead product of distillation column 124 includes a large amount of dichloropropanol, a large amount of monochloropropanol, a large amount of aqueous hydrogen chloride solution, a catalyst and a small amount of glycerin. Distillation column 124 can have a reboiler 125 for heating distillation column 124.

Proceeding to step S104, the feed from the initial product is passed to a thermally coupled distillation unit 104 coupled to a phase separator 106 to produce an overhead product and a bottoms product.

In the present embodiment, the thermally coupled distillation unit 104 includes a distillation column 114 and a distillation column 116. The overhead product of the thermally coupled distillation unit 104 includes the overhead product of the distillation column 114 and the overhead product of the distillation column 116. The bottom product of the thermally coupled distillation unit 104 includes the bottoms of the distillation column 114 and the bottoms of the distillation column 116. Based on the above, step S104 may further include sub-steps S104a-S104d.

Sub-step S104a is performed to cause the feed to the thermally coupled distillation unit 104 to enter the distillation column 114 to produce an overhead product and a bottoms product.

The large amount of dichlorohydrin in the distillation column 114 forms a lower boiling azeotrope with water to form the overhead product of the distillation column 114. Therefore, the content of dichlorohydrin in the overhead product of the distillation column 114 may be greater than the content of dichloropropanol in the bottom product of the distillation column 114. The overhead product of distillation column 114 may further comprise a solution of monochloropropanol and hydrogen chloride. The bottom product of distillation column 114 includes a large amount of aqueous hydrogen chloride solution and a large amount of catalyst, and may further include a small amount of dichloropropanol and a small amount of glycerin.

Additionally, distillation column 114 can include a side stream outlet 110 to remove side stream products. The side stream product of distillation column 114 comprises water having a purity of from 85 wt% to 100 wt%, and in other embodiments the purity of water may be from 90 wt% to 99.99 wt%, optimally from 95 wt% to 99.95% wt%. The feed to the distillation column 114 contains unreacted glycerol and aqueous hydrogen chloride solution derived from the initial product and a catalyst, so that the feed to the distillation column 114 continues to react in the distillation column 114 to produce dichloropropanol and monochloropropanol. And water. According to this, the high-purity water (reaction product) of the distillation column 114 is taken out from the side outlet 110, and the chemical equilibrium of the above reaction can be progressed in the direction of increasing the reaction product, so that the reaction conversion ratio of the reactant can be increased, and the reaction rate can be improved. The yield of chloropropanol and/or monochloropropanol.

This embodiment is described by taking the case of performing step S102 as an example. At this time, the feed of the distillation column 114 is the overhead product of the distillation column 124. The overhead product of distillation column 124 can be stored in reflux tank 126 after being condensed by a condenser (not shown), and the liquid in reflux tank 126 can be partially returned to distillation column 124 along line 123, while the partial stream To the distillation column 114. In other embodiments, step S102 may be selected not to be performed. The initial product is used as a feed to the distillation column 114.

Sub-step S104b may be optionally performed to return a portion of the liquid in distillation column 114 to the top of distillation column 124. In detail, a portion of the liquid in the distillation column 114 can be refluxed along the line 123 to the top of the distillation column 124, and the gaseous overhead product of the distillation column 124 flows along the line 123 to the distillation column 114. Thus, a portion of the liquid in distillation column 114 can be thermally coupled to the gaseous overhead product of distillation column 124 while cooling the gaseous overhead product of distillation column 124. Accordingly, the cost of providing the condenser in the distillation column 124 can be eliminated.

Sub-step S104c is performed to cause the bottoms product of distillation column 114 to enter the distillation column 116 as a feed to produce overhead product and bottoms product.

The bottoms of distillation column 114 can be passed along line 118 to the feed port of distillation column 116. In other embodiments, the bottoms of distillation column 114 can flow further along the liquid flow path 118b of line 118 to the distillation. The feed port of the tower 116. The overhead product of distillation column 116 comprises dichlorohydrin after condensation and may further comprise an aqueous solution of hydrogen chloride. The bottom product of distillation column 116 includes a large amount of aqueous hydrogen chloride solution with a large amount of catalyst, and may further include a small amount of dichloropropanol and a small amount of glycerin. Distillation column 116 can include a side stream outlet 112 to remove side stream products. The side stream product of distillation column 116 includes water having a purity of from 85 wt% to 100 wt%, and in other embodiments water may be from 90 wt% to 99.99 wt%, most preferably from 95 wt% to 99.95% by weight. Similar to the side stream product of the distillation column 114 taken out in the sub-step S104a, the side stream product of the distillation column 116 is taken out from the side stream outlet 112 in the sub-step S104c to increase the reaction conversion ratio of the reactant and the dichloropropanol and / or the yield of monochloropropanol.

Sub-step S104d is performed to return a portion of the gas in the distillation column 116 to the bottom of the distillation column 114.

A portion of the gas in distillation column 116 may be refluxed along line 118 to the bottom of distillation column 114. In other embodiments, a portion of the gas in distillation column 116 may be returned to distillation column 114 along gas flow path 118a of line 118. bottom of. Therefore, a part of the gas in the distillation column 116 can heat the distillation column 114, and the feed of the distillation column 114 can be smoothly heated and distilled and separated. Based on the above, the cost of providing the reboiler in the distillation column 114 and the consumption of energy can be eliminated.

Step S106 is performed to condense the overhead product of the thermal coupling distillation unit 104 into the phase separator, and directly connect the water supply unit to the phase separator, and form an aqueous phase product and an organic phase product in the phase separator. In the present embodiment, the thermally coupled distillation unit 104 includes a distillation column 114 and a distillation column 116, so the overhead product of the thermally coupled distillation unit 104 includes the overhead product of the distillation column 114 and the overhead product of the distillation column 116.

Based on the above, step S106 can include two parts. First, the overhead product of distillation column 114 is condensed and passed to phase separator 106, and feedwater unit 108 is directly coupled to phase separator 106 to form an aqueous phase product and an organic phase product in phase separator 106. The organic phase product of phase separator 106 comprises dichlorohydrin wherein the aqueous phase product is in the upper layer and the organic phase product is in the lower layer. The organic phase product of phase separator 106 comprises dichlorohydrin and more preferably monochloropropanol. Since the phase separator 106 can separate the azeotrope in the distillation column 114 and take out the dichloropropanol, no additional extractant is required. In addition, since the extractant is not required, the problem that the extractant and the catalyst may form an azeotrope and the catalyst is difficult to recycle may be avoided. Directly by the water supply device 108 The concentration of the aqueous solution of hydrogen chloride in the phase separator 106 is adjusted, and the overhead product of the distillation column 114 is effectively phase-separated after condensation. The aqueous phase product of phase separator 106 includes an aqueous hydrogen chloride solution, and the aqueous phase product of phase separator 106 can be refluxed to distillation column 114.

Second, the overhead product of distillation column 116 can be condensed and passed to phase separator 120 coupled to distillation column 116 to form an aqueous phase product and an organic phase product. The organic phase product of phase separator 120 includes dichloropropanol. Since the phase separator 120 can separate the azeotrope in the distillation column 116 and take out the dichloropropanol, the dichloropropanol in the distillation column 116 can be further recovered. Therefore, the recovery rate of the main product dichloropropanol can be further improved. In addition, since the extractant is not required, the problem that the extractant and the catalyst may form an azeotrope and the catalyst is difficult to recycle may be avoided. The aqueous phase product of phase separator 120 can include water, and the aqueous phase product of phase separator 120 can be refluxed to distillation column 116. In addition, when the aqueous phase product of the phase separator 120 includes an aqueous solution of hydrogen chloride, the water supply device 122 can be directly connected to the phase separator 120 to directly adjust the concentration of the aqueous hydrogen chloride solution in the phase separator 120, and the condensed distillation column The overhead product of 116 is effectively phased.

In step S108, the organic phase product of the phase separator is taken out. In the present embodiment, the phase splitter of the thermally coupled distillation apparatus 104 includes a phase splitter 106 and, moreover, a phase splitter 120. Accordingly, the organic phase product of the phase separator of the thermally coupled distillation unit 104 includes the organic phase product of the phase separator 106, and may further include the organic phase product of the phase separator 120.

Based on the above, step S108 can include two parts. First, the organic phase product of phase separator 106 is taken. Second, the organic phase product of phase separator 120 can be taken.

Step S110 is selectively performed to make the bottom product of the distillation column 116 as The feed enters distillation column 128 to produce overhead product and bottoms product. The bottoms of distillation column 116 may enter distillation column 128 along line 130, and in other embodiments the bottoms of distillation column 116 may enter distillation column 128 along liquid flow path 130b of line 130. The overhead product of distillation column 128 includes a substantial amount of water and may even include a small amount of dichloropropanol. The bottom product includes a large amount of aqueous hydrogen chloride solution with a large amount of catalyst, and may further include a small amount of glycerin. The concentration of the aqueous hydrogen chloride solution of the bottom product of the distillation column 128 is greater than the concentration of the aqueous hydrogen chloride solution of the bottom product of the distillation column 114, which can be attributed to the separation of the overhead product including a large amount of water in the distillation column 128, thereby making the distillation column The concentration of the aqueous hydrogen chloride solution in the bottom product of 128 is increased. The bottoms of distillation column 128 can be refluxed to reactor 102 for recycling. Further, since the concentration of the aqueous hydrogen chloride solution in the bottom product of the distillation column 128 has been increased, when the aqueous hydrogen chloride solution is recycled, there is no problem that the concentration of the aqueous hydrogen chloride solution is too low, and the reaction rate is largely lowered. Additionally, the condensed overhead product in distillation column 128 can be stored in reflux tank 131 and the condensed overhead product can be partially refluxed to distillation column 128. Distillation column 128 can have a reboiler 132 for heating distillation column 128.

Step S112 may be selectively performed to return a portion of the gas in the distillation column 128 to the bottom of the distillation column 116. A portion of the gas in distillation column 128 may be refluxed along line 130 to the bottom of distillation column 116. In other embodiments, a portion of the gas in distillation column 128 may flow along gas flow path 130a of line 130 to distillation column 116. bottom of. Accordingly, a part of the gas in the distillation column 128 can heat the distillation column 116, and the feed of the distillation column 116 can be smoothly heated and distilled and separated. Therefore, the cost of providing the reboiler in the distillation column 116 and the consumption of energy can be eliminated. So if you choose not to In step S112, a reboiler is required in the distillation column 116 to heat the feed of the distillation column 116 for distillation and separation.

Based on the above examples, it can be seen that by separating the azeotrope using the phase separator 106 and taking out the dichloropropanol, it is possible to avoid additional addition of the extractant and reduce the manufacturing cost. In addition, since the extractant is not required, the problem that the extractant and the catalyst may form an azeotrope and the catalyst is difficult to recycle may be avoided. In addition, the concentration of the aqueous solution of hydrogen chloride in the phase separator 106 can be directly adjusted by the water supply device 108, and the overhead product of the condensed distillation column 114 can be effectively phase-separated to smoothly obtain the main product dichloropropanol. Further, by returning a part of the gas in the distillation column 116 to the bottom of the distillation column 114, the distillation column 114 can be heated by the heat energy of a part of the gas in the distillation column 116. Therefore, the cost of providing the reboiler in the distillation column 114 can be eliminated, and energy consumption can be saved.

Fig. 2A is a schematic view showing a manufacturing apparatus of dichloropropanol according to a second embodiment of the present invention. Figure 2B is a flow chart showing the manufacture of dichloropropanol in accordance with a second embodiment of the present invention.

Referring to FIG. 2A, the first embodiment is similar to the second embodiment except that the thermally coupled distillation apparatus 204 of the second embodiment is a partition wall distillation column 214. The second embodiment provides a manufacturing apparatus 200 for dichloropropanol which is suitable for reacting glycerin with an aqueous hydrogen chloride solution in the presence of a catalyst to produce dichloropropanol. The dichlorohydrin manufacturing apparatus 200 includes at least one reactor 202, a thermally coupled distillation apparatus 204, a phase separator 206, and a water supply apparatus 208. Thermally coupled distillation unit 204 is coupled to reactor 202. A phase separator 206 is coupled to the top of the thermally coupled distillation unit 204 to form water in the phase separator 206 The phase product is an organic phase product comprising dichlorohydrin. The water supply device 208 is directly connected to the phase splitter 206.

The thermally coupled distillation unit 204 can include a side stream outlet 210 and a side stream outlet port 212 to extract side stream products. The side stream product is water having a purity of from 85 wt% to 100 wt%. In other embodiments, the water of the side stream product of the thermally coupled distillation unit 204 may have a purity of from 90 wt% to 99.99 wt%, and most preferably from 95 wt% to 99.95% wt%.

Referring to FIG. 1A and FIG. 2A simultaneously, in the second embodiment, the thermally coupled distillation apparatus 204 is a partition wall distillation column 214. The partition wall distillation column 214 includes a chamber 214a, a chamber 214b, a partition wall 216, and a chamber 214c. Wherein, the chamber 214a is connected to the phase separator 206, and the aqueous phase product of the phase separator 206 can be returned to the chamber 214a of the partition wall distillation column 214. The chamber 214a and the second chamber 214b are adjacent to each other and are located at an upper portion of the partition wall distillation column 214. The partition wall 216 extends from the inside of the partition wall distillation column 214 to the top, and the partition wall 216 is located between the chamber 214a and the chamber 214b. The chamber 214c is located below the chamber 214a and the chamber 214b and is in communication with the chamber 214a and the chamber 214b, respectively. The partition wall distillation column 214 may further include a reboiler 215 for heating the partition wall distillation column 214.

The dichlorohydrin manufacturing apparatus 200 may further include a phase separator 220 coupled to the two chambers 214b to form an aqueous phase product and an organic phase product including dichloropropanol in the phase separator 220. The manufacturing apparatus 200 of dichlorohydrin may further include a water supply device 222 directly connected to the phase separator 220. The aqueous phase product of phase separator 220 can be refluxed to chamber 214b of dividing wall distillation column 214.

The dichlorohydrin manufacturing apparatus 200 may further include a distillation column 224 and a line 223 connected between the distillation column 224 and the partition wall distillation column 214, wherein the distillation column 224 It is connected between the reactor 202 and the partition wall distillation column 214, and the line 223 can be connected between the top of the distillation column 224 and the chamber 214a of the partition wall distillation column 214. The gas at the top of the distillation column 224 can be stored in the reflux tank 226 after being condensed by a condenser (not shown), and the liquid in the reflux tank 226 can be partially returned to the distillation column 224 along the line 223, and the partial flow To the chamber 214a of the partition wall distillation column 214.

In other embodiments, a portion of the liquid in the dividing wall distillation column 214 may be refluxed along the line 223 to the top of the distillation column 224, and the gas at the top of the distillation column 224 flows along the line 223 to the dividing wall distillation column 214. Chamber 214a. Therefore, part of the liquid in the partition wall distillation column 214 can be thermally coupled with the gas at the top of the distillation column 224, while the gas at the top of the distillation column 224 is cooled. Accordingly, the cost of providing the condenser in the distillation column 224 can be eliminated.

Referring to FIG. 2A and FIG. 2B simultaneously, the second embodiment further provides a method for producing dichloropropanol, which comprises the following steps in sequence. In the following description, the contents similar to those of the first embodiment are omitted, and only the differences between the second embodiment and the first embodiment will be explained.

First, in step S200, in at least one reactor 202, glycerin and an aqueous hydrogen chloride solution are reacted in the presence of a catalyst to produce an initial product. The initial products include dichloropropanol and monochloropropanol, of which dichloropropanol is the main product and monochloropropanol is the intermediate product. The initial product may further comprise an unreacted aqueous solution of hydrogen chloride, glycerin and a catalyst.

Next, step S202 can be selectively performed to cause the initial product to enter the distillation column 224 as a feed to produce an overhead product and a bottoms product. The initial product can be distilled Reaction and separation are carried out in column 224. The bottom product of the distillation column 224 mainly includes unreacted glycerin, and may further include a small amount of dichloropropanol, a small amount of monochloropropanol, a small amount of an aqueous hydrogen chloride solution, and a catalyst. The bottoms product of distillation column 224 can be refluxed to reactor 202 for continued recycle to increase reaction conversion. The overhead product of distillation column 224 is condensed to include a large amount of dichloropropanol, a large amount of monochloropropanol, a large amount of aqueous hydrogen chloride solution, a catalyst and a small amount of glycerin. Distillation column 224 can have a reboiler 225 for heating distillation column 224.

Proceeding to step S204, the feed from the initial product is passed to a thermally coupled distillation unit 204 coupled to a phase separator 206 to produce an overhead product and a bottoms product.

In the present embodiment, the thermally coupled distillation unit 204 is a partition wall distillation column 214. The partition wall distillation column includes a chamber 214a, a chamber 214b, and a chamber 214c, wherein the chamber 214a and the chamber 214b are located at an upper portion of the partition wall distillation column 214 and are spaced apart from each other by a partition wall 216. The chamber 214c is located below the chamber 214a and the chamber 214b and is in communication with the chamber 214a and the chamber 214b.

Based on the above, in step S204, the feed derived from the initial product can be reacted and separated in the partition wall distillation column 214. After the feed of the partition wall distillation column 214 enters the chamber 214a of the partition wall distillation column 214, it flows down to the bottom of the chamber 214c. The feed at the bottom of the chamber 214c is partially evaporated by heating through the reboiler 215, and the vaporized gas rises from the chamber 214c into the chamber 214a and the chamber 214b, respectively, in the chamber 214a and the chamber 214b. The product of chamber 214a and the product of chamber 214b are formed. The gas rising from the bottom of chamber 214c can be thermally coupled to the feed entering chamber 214a so that heat entering the chamber 214a can be obtained. According to this, it can be reduced The energy consumption of the reboiler 215.

In the present embodiment, the overhead product of the thermally coupled distillation unit 204 includes the product of the chamber 214a and the product of the chamber 214b. Additionally, the unvaporized feed in the bottom of chamber 214c forms the bottoms product of thermally coupled distillation unit 204, and the bottoms of thermally coupled distillation unit 204 can be refluxed into reactor 202.

In addition, the partition wall distillation column 214 may further include a side flow outlet 210 and a side flow outlet 212 to take out the side stream product. The side stream product of the partition wall distillation column 214 includes water having a purity of from 85 wt% to 100 wt%, and in other embodiments, the purity of water may be from 90 wt% to 99.99 wt%, most preferably from 95 wt% to 99.95% by weight. The feed to the dividing wall distillation column 214 contains unreacted glycerol and aqueous hydrogen chloride solution derived from the initial product and a catalyst, so that the feed to the dividing wall distillation column 214 continues to react in the dividing wall distillation column 214 to produce dichloropropane. Alcohol, monochloropropanol and water. According to this, the high-purity water (reaction product) in the partition wall distillation column 214 is taken out from the side outlet 210 and the side outlet 212, so that the chemical equilibrium of the above reaction can be progressed in the direction of increasing the reaction product, so that the reaction of the reactant can be enhanced. Conversion rate and yield of dichloropropanol and/or monochloropropanol.

This embodiment is described by taking the case of performing step S202 as an example. At this time, the feed of the partition wall distillation column 214 is the overhead product of the distillation column 224. The overhead product of the distillation column 224 can be stored in the reflux tank 226 after being condensed by a condenser (not shown), and the liquid in the reflux tank 226 can be partially returned to the distillation column 224 along the line 223, and the partial flow To the chamber 214a of the partition wall distillation column 214. In other embodiments, step S202 may be selected without the initial product being used as a feed to the dividing wall distillation column 214.

Going to step S206, the top product of the thermally coupled distillation unit 204 is cooled. After condensing, the phase separator is introduced, and the water supply device is directly connected to the phase separator, and the aqueous phase product and the organic phase product are formed in the phase separator. In the present embodiment, the thermally coupled distillation unit 204 is a dividing wall distillation column 214, and the overhead product of the thermally coupled distillation unit 204 includes the product of the chamber 214a and the product of the chamber 214b.

Based on the above, step S206 can include two parts. First, the product of chamber 214a is condensed and passed to phase separator 206, and feedwater unit 208 is directly coupled to phase separator 206, and aqueous phase product and organic phase product are formed within phase separator 206. The organic phase product of phase separator 206 comprises dichlorohydrin. The aqueous phase product of phase separator 206 includes an aqueous solution of hydrogen chloride, and the aqueous phase product can be refluxed to dividing wall distillation column 214.

Second, the product of chamber 214b can be condensed into a phase separator 220 coupled to chamber 214b to form an aqueous phase product and an organic phase product. The organic phase product of phase separator 220 comprises the main product dichloropropanol. The aqueous phase product of phase separator 220 can include water and can be refluxed to chamber 214b of dividing wall distillation column 214. In addition, when the aqueous phase product of the phase separator 220 includes an aqueous hydrogen chloride solution, the water supply device 222 can be directly connected to the phase separator 220 to directly adjust the concentration of the aqueous hydrogen chloride solution in the phase separator 220, and the condensed chamber. The product of 214b is effectively phased.

Step S208 is performed to take out the organic phase product of the phase separator. In the present embodiment, the organic phase product of the phase separator of the thermally coupled distillation unit 204 includes the organic phase product of the phase separator 206 and the phase separator 220. Based on the above, step S208 can include two parts. First, the organic phase product of phase separator 206 is taken. Second, the organic phase product of phase separator 220 can be removed.

Step S210 may be selectively performed to make a part of the liquid of the partition wall distillation column 214 The body is refluxed to the top of distillation column 224. A portion of the liquid of the dividing wall distillation column 214 may be refluxed along the line 223 to the top of the distillation column 224, and the gaseous overhead product of the distillation column 224 flows along the line 223 to the dividing wall distillation column 214. Thus, a portion of the liquid in the dividing wall distillation column 214 can be thermally coupled to the gaseous overhead product of the distillation column 224. Accordingly, the cost of providing the condenser in the distillation column 224 can be eliminated.

Referring to FIG. 1A and FIG. 2A simultaneously, it can be seen from the above embodiment that the partition wall distillation column 214 of the second embodiment can be analogous to the combination of the distillation column 114 and the distillation column 116 in the first embodiment. Specifically, the distillation column 114 of FIG. 1A, the top of the distillation column 116, and the bottom of the distillation column 116 can be sequentially analogized to the chamber 214a, the chamber 214b, and the bottom of the chamber 214c of the partition wall distillation column 214 of FIG. 2A. In FIG. 1A, a portion of the liquid at the bottom of the distillation column 116 is evaporated by heating, a portion of the vaporized gas rises to the top of the distillation column 116, and a portion of the gas is refluxed along the line 118 to the distillation column 114 to heat the distillation column 114. Feeding. Similarly, in Fig. 2A, the liquid at the bottom of the chamber 214c is partially evaporated by heating, the vaporized portion of the gas rises to the chamber 214b, and the other portion of the gas rises to the chamber 214a of the partition wall distillation column 214 to be heated into the chamber. Feed of chamber 214a. Based on the above, the partition wall distillation column 214 of the second embodiment is similar to the distillation column 114, the line 118 of the first embodiment, and the distillation column 116, so that thermal coupling similar to the first embodiment can be performed, thereby reducing manufacturing cost.

Fig. 3 is a schematic view showing a manufacturing apparatus of dichloropropanol according to a third embodiment of the present invention.

3 and FIG. 2A, the third embodiment is similar to the second embodiment except that the partition wall distillation column 214 of the apparatus 1 for producing dichloropropanol of the third embodiment is similar. It further includes a chamber 214d, a partition wall 218, and a chamber 214e. In the present embodiment, the same or similar elements as those of the second embodiment will be described by the same reference numerals. Further, in the following description, the contents similar to those of the second embodiment are omitted, and only the differences between the third embodiment and the second embodiment will be explained.

In the third embodiment, the partition wall distillation column 214 includes a chamber 214a, a chamber 214b, a partition wall 216, a chamber 214c, a chamber 214d, a partition wall 218, and a chamber 214e. The chamber 214b is located between the chamber 214a and the chamber 214d. The partition wall 218 extends from the interior of the partition wall distillation column 214 to the top, and the partition wall 218 is located between the chamber 214d and the chamber 214b and between the chamber 214d and the chamber 214c. In addition, the length of the partition wall 218 needs to be greater than the length of the partition wall 216. The chamber 214e is located below the chamber 214c and the chamber 214d, and the chamber 214e is in communication with the chamber 214c and the chamber 214d, respectively.

The thermally coupled distillation unit 204 can include a side stream outlet (not shown) to remove the side stream product. The side stream product is water having a purity of from 85 wt% to 100 wt%. In other embodiments, the water of the side stream product of the thermally coupled distillation unit 204 may have a purity of from 90 wt% to 99.99 wt%, and most preferably from 95 wt% to 99.95% wt%.

Further, the steps of the method for producing dichloropropanol of the third embodiment are the same as those of the second embodiment (as shown in Fig. 2B). The following only describes the differences.

Referring to FIG. 3 and FIG. 2B simultaneously, in step S204 of the third embodiment, the feed from the initial product is passed to the dividing wall distillation column 214 to produce an overhead product and a bottom product. In the present embodiment, the thermally coupled distillation unit 204 is a partition wall distillation column 214, and the partition wall distillation column 214 includes a chamber 214a, a chamber 214b, a chamber 214c, a chamber 214d, and a chamber 214e. The chamber 214b is located in the chamber 214a and the chamber 214d Between the chamber 214b and the chamber 214d and between the chamber 214c and the chamber 214d are separated by a partition wall 218. The chamber 214e is located at the bottom of the partition wall distillation column 214, and the chamber 214c and the chamber 214d are located above the chamber 214e. Further, the chamber 214e is in communication with the chamber 214c and the chamber 214d.

Based on the above, in step S204, the feed derived from the initial product can be reacted and separated in the partition wall distillation column 214. The feed to the dividing wall distillation column 214 enters the chamber 214a and flows down through the chamber 214c to the chamber 214e. The feed in chamber 214e is partially evaporated by heating via reboiler 215, and a portion of the gas rises into chamber 214a and chamber 214b via chamber 214c, forming a cavity in chamber 214a and chamber 214b, respectively. The product of chamber 214a and the product of chamber 214b. This portion of the gas can be thermally coupled to the feed to chamber 214a so that heat can be obtained by the feed to chamber 214a. Accordingly, the energy consumption of the reboiler 215 can be reduced. In addition, another portion of the gas rises directly from chamber 214e into chamber 214d to form the product of chamber 214d. The product of chamber 214d can be stored in a reflux drum 231 after condensation, and the product of the condensed chamber 214d can be partially returned to chamber 214d.

The overhead product of the thermally coupled distillation unit 204 includes the product of chamber 214a, the product of chamber 214b, and the product of chamber 214d. Further, the unvaporized feed in the chamber 214e of the dividing wall distillation column 214 forms the bottoms product of the thermally coupled distillation unit 204, and the bottoms product of the thermally coupled distillation unit 204 can be refluxed into the reactor 202.

Referring to FIG. 3 and FIG. 1A simultaneously, based on the above embodiment, the partition wall distillation column 214 of the third embodiment can be analogized to the distillation column 114 and the distillation column in the first embodiment. 116 is combined with distillation column 128. Specifically, the distillation column 114 of FIG. 1, the top of the distillation column 116, the bottom of the distillation column 116, the top of the distillation column 128, and the bottom of the distillation column 128 can be sequentially compared to the chamber of the partition wall distillation column 214 of FIG. 214a, chamber 214b, chamber 214c, chamber 214d, and chamber 214e. In FIG. 1A, the liquid at the bottom of the distillation column 128 is partially evaporated by heating, a portion of the vaporized gas rises to the top of the distillation column 128, and another portion of the gas is refluxed along the line 130 to the bottom of the distillation column 116 to heat the distillation column. 116 feed. The liquid at the bottom of the distillation column 116 is partially evaporated by heating, the vaporized portion of the gas rises to the top of the distillation column 116, and another portion of the gas is refluxed along the line 118 to the distillation column 114 to heat the feed of the distillation column 114. Similarly, in the third embodiment, part of the liquid in the chamber 214e of the partition wall distillation column 214 is partially evaporated by heating, part of the vaporized gas rises to the chamber 214d, and part of the gas enters the chamber 214c to heat the chamber. The liquid in chamber 214c. The liquid in chamber 214c is partially vaporized by heating, the vaporized portion of the gas rises to chamber 214b, and another portion of the gas rises to chamber 214a to heat the feed into chamber 214a.

Based on the above, the partition wall distillation column 214 of the third embodiment is similar to the distillation column 114, the line 118, the distillation column 116, the line 130, and the distillation column 128 of the first embodiment, thereby reducing the number of distillation columns And can further reduce manufacturing costs.

Fig. 4A is a schematic view showing a manufacturing apparatus of dichloropropanol according to a fourth embodiment of the present invention. Figure 4B is a flow chart showing the manufacture of dichloropropanol in accordance with a fourth embodiment of the present invention.

Referring to FIG. 4A, a fourth embodiment provides a manufacturing apparatus 400 for dichlorohydrin comprising at least one reactor 402, a distillation column 404, a phase separator 406, and a water supply device 408. Distillation column 404 is coupled to reactor 402. Distillation column 404 includes a side stream outlet 410 to extract the side stream product of distillation column 404. The side stream product of distillation column 404 includes water having a purity of from 85 wt% to 100 wt%, and in other embodiments, the purity of water may be from 90 wt% to 99.99 wt%, and most preferably from 95 wt% to 99.95% wt%. The position of the side stream outlet 410 is, for example, the position where the purity of water in the distillation column 404 is the highest. The dichlorohydrin manufacturing apparatus 400 may further include a reboiler 405 connected to the bottom of the distillation column 404.

A phase separator 406 is coupled to distillation column 404 to form an aqueous phase product in the phase separator 406 with an organic phase product comprising dichloropropanol, wherein the aqueous phase product can be refluxed to distillation column 404. The water supply unit 408 is directly connected to the phase splitter 406.

The dichlorohydrin production apparatus 400 may further include a distillation column 412. Distillation column 404 is coupled between distillation column 412 and reactor 402. Distillation column 412 includes a side stream outlet 414 to remove side stream products. The side stream product of distillation column 412 includes water having a purity of from 85 wt% to 100 wt%, and in other embodiments, the purity of water may be from 90 wt% to 99.99 wt%, and most preferably from 95 wt% to 99.95% wt%. The position of the side stream outlet 414 is, for example, the position where the purity of water in the distillation column 412 is the highest. The dichlorohydrin manufacturing apparatus 400 may further include a reboiler 413 connected to the bottom of the distillation column 412 to heat the distillation column 412.

A phase separator 416 is coupled to the distillation column 412 to form an aqueous phase product in the phase separator 416 with an organic phase product comprising dichloropropanol, wherein the aqueous phase product can be refluxed to steam Column 412. The water supply unit 418 is directly connected to the phase splitter 416.

The dichlorohydrin production apparatus 400 may further include a reactor 420 connected between the distillation column 404 and the distillation column 412.

Referring to FIG. 4A and FIG. 4B simultaneously, the fourth embodiment also provides a method for producing dichloropropanol, which comprises the following steps. Portions of the fourth embodiment that are similar to the first to third embodiments are omitted below, and only the differences will be described.

In step S400, glycerin and aqueous hydrogen chloride are reacted in a reactor 402 in the presence of a catalyst to produce an initial product.

Step S402 is selectively performed to find the position where the purity of the water in the distillation column 404 is the highest as the side stream outlet 410.

Step S404 is performed to cause the initial product to enter the distillation column 404 to which the phase separator 406 is connected as a feed to produce an overhead product, a side stream product, and a bottom product.

Step S406 is performed to extract the side stream product of the distillation column 404 at the side stream outlet 410 between the top and bottom of the distillation column 404. The side stream product of distillation column 404 includes water having a purity of from 85 wt% to 100 wt%, and in other embodiments, the purity of water may be from 90 wt% to 99.99 wt%, and most preferably from 95 wt% to 99.95% wt%. The feed to distillation column 404 comprises unreacted glycerol and aqueous hydrogen chloride solution derived from the initial product and a catalyst, so that the feed to distillation column 404 will continue to react in distillation column 404 to produce dichloropropanol, monochloropropanol. And water. According to this, the high-purity water (reaction product) of the distillation column 404 is taken out from the side outlet 410, and the chemical equilibrium of the above reaction can be progressed in the direction of increasing the reaction product, so that the reaction conversion ratio of the reactant and the dichloropropane can be increased. The yield of alcohol and/or monochloropropanol.

Step S408 is performed to condense the overhead product of distillation column 404 to phase separator 406, and directly connect water feed unit 408 to phase separator 406 to form an aqueous phase product and an organic phase product in phase separator 406. Wherein the organic phase product of phase separator 406 comprises dichlorohydrin and the aqueous phase product of phase separator 406 can be refluxed to distillation column 404.

In step S410, the organic phase product of the phase separator 406 is taken out.

Step S412 is selectively performed to cause the bottom product of the distillation column 404 to enter the reactor 420 to produce a reaction product of the reactor 420.

Step S414 is selectively performed to find the position where the purity of the water in the distillation column 412 is the highest as the side stream outlet 414.

Step S416 can be performed to cause the bottoms product from distillation column 404 to enter the distillation column 412 as a feed to produce overhead products, side stream products, and bottoms products. The bottoms of distillation column 412 can be refluxed to reactor 402. In the present embodiment, the step S412 is taken as an example, in which case the reaction product of the reactor 420 is fed as the distillation column 412. In other embodiments, if step S414 is not directly performed without performing step S412, the feed to distillation column 412 is the bottom product of distillation column 404.

Step S418 may be performed to extract the side stream product of the distillation column 412 at the side stream outlet 414 between the top and bottom of the distillation column 412. The side stream product of distillation column 412 includes water having a purity of from 85 wt% to 100 wt%, and in other embodiments, the purity of water may be from 90 wt% to 99.99 wt%, and most preferably from 95 wt% to 99.95% wt%. Similar to step S406, the removal of high purity water in distillation column 412 can increase the reaction conversion of the reactants, as well as the yield of dichloropropanol and/or monochloropropanol.

Step S420 may be performed to condense the overhead product of distillation column 412 into phase separator 416 coupled to distillation column 412 to form an aqueous phase product and an organic phase product comprising dichlorohydrin. The aqueous phase product of the phase separator 416 can be refluxed to the distillation column 412, and the water supply device 418 can be directly connected to the phase separator 416. Thereafter, the organic phase product of phase separator 416 can be removed.

Based on the above examples, it is understood that the high-purity water as the reaction product in the distillation column 404 can be taken out, and the chemical equilibrium of the reaction can be progressed in the direction of increasing the reaction product, so that the reaction conversion ratio of the reactant and the yield of the main product can be improved. . Since the high purity water is discharged to increase the concentration of the reactants, the reaction rate can also be increased.

In summary, in the apparatus for producing dichloropropanol proposed in the above embodiments and the method for producing the same, the dichlorohydrin can be taken out by separating the azeotrope by using a phase separator, thereby avoiding the addition of an extractant. Reduce manufacturing costs. In addition, since the extractant is not required, the problem that the extractant and the catalyst may form an azeotrope and the catalyst is difficult to recycle may be avoided. In addition, the concentration of the aqueous solution of hydrogen chloride in the phase separator can be directly adjusted by the water supply device, and the overhead product of the condensed distillation column is effectively phase-separated to smoothly obtain dichloropropanol. Furthermore, by providing a thermally coupled distillation apparatus, the energy consumed to carry out the distillation can be reduced, and the number of reboiler settings can be reduced. In other words, the manufacturing cost of dichloropropanol can be reduced.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the present invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the present invention. The scope of the invention is defined by the scope of the appended claims.

100‧‧‧ Dichloropropanol manufacturing equipment

102‧‧‧Reactor

104‧‧‧ Thermally coupled distillation unit

106, 120‧‧ ‧ phase splitter

108, 122‧‧‧ water supply device

110, 112‧‧‧ sidestream outlet

114, 116, 124, 128‧‧‧ distillation tower

118, 123, 130‧‧‧ pipeline

118a, 130a‧‧‧ gas flow path

118b, 130b‧‧‧ liquid flow path

125, 132‧‧‧ reboiler

126, 131‧‧ ‧ reflux tank

Claims (46)

A device for producing dichloropropanol, which is suitable for reacting glycerin with an aqueous solution of hydrogen chloride in the presence of a catalyst to produce dichloropropanol, the apparatus for producing the dichlorohydrin comprising: at least one reactor; thermally coupled distillation a device coupled to the at least one reactor; a first phase separator coupled to the top of the thermally coupled distillation apparatus to form a first aqueous phase product and comprising dichloropropanol in the first phase separator a first organic phase product; and a first water supply device directly connected to the first phase separator. The apparatus for producing dichloropropanol according to claim 1, wherein the thermally coupled distillation apparatus comprises a side stream outlet for taking out a side stream product, the side stream product comprising a purity of 85 wt% to 100 wt% water. The apparatus for producing dichloropropanol according to claim 2, wherein the water has a purity of from 90% by weight to 99.99% by weight. The apparatus for producing dichloropropanol according to claim 2, wherein the water has a purity of 95% by weight to 99.95% by weight. The apparatus for producing dichloropropanol according to claim 1, wherein the thermally coupled distillation apparatus comprises: a first distillation column connected to the at least one reactor, and a top of the first distillation column Connected to the first phase separator; a second distillation column connected to the first distillation column; a first line connected between the feed port of the second distillation column and the bottom of the first distillation column, wherein a portion of the gas in the second distillation column is refluxed along the first line to The bottom of the first distillation column, and the liquid at the bottom of the first distillation column flows along the first line to the feed port of the second distillation column. The apparatus for producing dichloropropanol according to claim 5, wherein the first aqueous phase product is refluxed to the first distillation column. The apparatus for producing dichloropropanol according to claim 5, further comprising a second phase separator connected to the top of the second distillation column to form a second in the second phase separator The aqueous phase product is combined with a second organic phase product comprising dichlorohydrin. The apparatus for producing dichloropropanol according to claim 7, further comprising a second water supply device directly connected to the second phase separator. The apparatus for producing dichloropropanol according to claim 7, wherein the second aqueous phase product is refluxed to the second distillation column. The apparatus for producing dichloropropanol according to claim 5, further comprising: a third distillation column connected between the at least one reactor and the first distillation column; and a second pipe, It is connected between the third distillation column and the first distillation column. The apparatus for producing dichloropropanol according to claim 10, wherein the second conduit is connected to the top of the third distillation column and the first distillation Between the feed ports of the column, wherein a portion of the liquid in the first distillation column is refluxed along the second line to the top of the third distillation column, and the gas edge at the top of the third distillation column The second line flows to the feed port of the first distillation column. The apparatus for producing dichloropropanol according to claim 5, further comprising: a fourth distillation column, wherein the second distillation column is connected between the first distillation column and the fourth distillation column And the fourth distillation column is connected to the at least one reactor; and the third line is connected between the second distillation column and the fourth distillation column. The apparatus for producing dichloropropanol according to claim 12, wherein the third conduit is connected between a bottom of the second distillation column and a feed port of the fourth distillation column, wherein a part of the gas of the fourth distillation column is refluxed along the third line to the bottom of the second distillation column, and the liquid at the bottom of the second distillation column flows along the third line to the bottom The feed port of the fourth distillation column. The apparatus for producing dichloropropanol according to claim 1, wherein the thermally coupled distillation apparatus is a partition wall distillation column, comprising: a first chamber and a second chamber, wherein the first chamber Connecting to the first phase separator, the first chamber and the second chamber are adjacent to each other and are located at an upper portion of the partition wall distillation column; a first partition wall extending from an interior of the partition wall distillation column to a top portion and located between the first chamber and the second chamber; and a third chamber located in the first chamber Below the second chamber, and in communication with the first chamber and the second chamber, respectively. The apparatus for producing dichloropropanol according to claim 14, wherein the first aqueous phase product is refluxed to the first chamber of the partition wall distillation column. The apparatus for producing dichloropropanol according to claim 14, further comprising a second phase separator connected to the second chamber to form a second aqueous phase in the second phase separator The product is a product of a second organic phase comprising dichlorohydrin. The apparatus for producing dichloropropanol according to claim 16, further comprising a second water supply device directly connected to the second phase separator. The apparatus for producing dichloropropanol according to claim 16, wherein the second aqueous phase product is refluxed to the second chamber of the partition wall distillation column. The apparatus for producing dichloropropanol according to claim 14, further comprising: a fifth distillation column connected between the at least one reactor and the partition wall distillation column; and a fourth pipe, It is connected between the fifth distillation column and the partition wall distillation column. The apparatus for producing dichloropropanol according to claim 19, wherein the fourth conduit is connected between a top of the fifth distillation column and a feed port of the partition wall distillation column, wherein a portion of the liquid in the dividing wall distillation column is refluxed along the fourth line to the top of the fifth distillation column, and the gas at the top of the fifth distillation column flows along the fourth line to The feed port of the partition wall distillation column. The apparatus for producing dichloropropanol according to claim 14, wherein the partition wall distillation column further comprises: a fourth chamber, wherein the second chamber is located in the first chamber and the Between the fourth chambers; a second partition wall extending from the interior of the partition wall distillation column to the top portion, and between the fourth chamber and the second chamber and the Between the four chambers and the third chamber; and a fifth chamber at the bottom of the partition wall distillation column, the third chamber and the fourth chamber being located in the fifth chamber Above, and the fifth chamber is in communication with the third chamber and the fourth chamber. A method for producing dichloropropanol, comprising: reacting glycerin with an aqueous solution of hydrogen chloride in an atmosphere in which a catalyst is present in at least one reactor to produce an initial product; and causing a first feed derived from the initial product Entering the thermal coupling distillation unit connected with the first phase separator to generate the overhead product and the bottom product; the top product is condensed to enter the first phase separator, and the first water supply device is directly connected And forming a first aqueous phase product and a first organic phase product in the first phase separator, wherein the first organic phase product comprises Dichloropropanol; and the first organic phase product is withdrawn. The method for producing dichloropropanol according to claim 22, wherein the step of introducing the first feed into the thermally coupled distillation apparatus further comprises producing a side stream product comprising a purity of 85 wt% to 100 wt% water. The method for producing dichloropropanol according to claim 23, wherein the water has a purity of from 90% by weight to 99.99% by weight. The method for producing dichloropropanol according to claim 23, wherein the water has a purity of 95% by weight to 99.95% by weight. The method for producing dichloropropanol according to claim 22, wherein the thermally coupled distillation apparatus comprises a first distillation column and a second distillation column, and the top product and the bottom product are produced. The step includes: passing the first feed to the first distillation column to produce a first overhead product and a first bottoms product; and causing the first bottoms product to enter the second distillation as a second feed a column to produce a second overhead product and a second bottoms product; and refluxing a portion of the gas in the second distillation column to the bottom of the first distillation column, wherein the overhead product comprises the first a top product and the second overhead product, and the bottom product includes the first bottom product and the second bottom product, wherein the condensation enters the first phase separator The overhead product is the first overhead product. The method for producing dichloropropanol according to claim 26, further comprising refluxing the first aqueous phase product to the first distillation column. The method for producing dichloropropanol according to claim 26, further comprising: condensing the second overhead product into a second phase separator connected to the second distillation column to form The second aqueous phase product is a second organic phase product comprising dichlorohydrin. The method for producing dichloropropanol according to claim 28, further comprising directly connecting the second water supply device to the second phase separator. The method for producing dichloropropanol according to claim 28, further comprising refluxing the second aqueous phase product to the second distillation column. The method for producing dichloropropanol according to claim 26, further comprising: introducing the initial product as a third feed into the third distillation column to produce a third overhead product and a third bottom product, And passing the third overhead product to the first distillation column, wherein the first feed is the third overhead product. The method for producing dichloropropanol according to claim 31, further comprising refluxing the third bottom product into the at least one reactor. The method for producing dichloropropanol according to claim 31, further comprising refluxing a portion of the liquid in the first distillation column to the top of the third distillation column. The method for producing dichloropropanol according to claim 26, further comprising the step of causing the second bottom product to enter the fourth distillation column as a fourth feed. A fourth overhead product and a fourth bottoms product are produced, wherein the concentration of the aqueous hydrogen chloride solution of the fourth bottom product is greater than the concentration of the aqueous hydrogen chloride solution of the first bottom product. The method for producing dichloropropanol according to claim 34, further comprising refluxing the fourth bottom product into the at least one reactor. The method for producing dichloropropanol according to claim 34, further comprising refluxing a part of the gas in the fourth distillation column to the bottom of the second distillation column. The method for producing dichloropropanol according to claim 22, wherein the thermal coupling distillation device is a partition wall distillation column, and the partition wall distillation column comprises: a first chamber and a second chamber, located at An upper portion of the partition wall distillation column and separated from each other by a first partition wall, wherein the first chamber is connected to the first phase separator; and a third chamber is located in the first chamber a lower portion of the second chamber and in communication with the first chamber and the second chamber, wherein in the step of generating the overhead product and the bottom product, the first feed Heating at the bottom of the dividing wall distillation column to partially evaporate, and evaporating the first feed rises through the third chamber into the first chamber and the second chamber, respectively Forming a first chamber product and a second chamber product in the first chamber and the second chamber, and the first feed that is not evaporated is located at a bottom of the partition wall distillation column to form the a bottom product, wherein the overhead product comprises the first chamber product and the second chamber product, entering the first phase separation The overhead product is the first product chamber. A method for producing dichloropropanol as described in claim 37, Further comprising refluxing the first aqueous phase product to the first chamber of the dividing wall distillation column. The method for producing dichloropropanol according to claim 37, further comprising refluxing the bottom product into the at least one reactor. The method for producing dichloropropanol according to claim 37, further comprising: condensing the second chamber product into a second phase separator connected to the second chamber to form The second aqueous phase product is a second organic phase product comprising dichlorohydrin. The method for producing dichloropropanol according to claim 40, further comprising directly connecting the second water supply device to the second phase separator. The method for producing dichloropropanol according to claim 41, further comprising refluxing the second aqueous phase product to the second chamber of the partition wall distillation column. The method for producing dichloropropanol according to claim 37, further comprising: introducing the initial product into a fifth distillation column to produce a fifth overhead product and a fifth bottom product, and Five tops were used as the first feed. The method for producing dichloropropanol according to claim 43, further comprising refluxing the fifth bottom product into the at least one reactor. The method for producing dichloropropanol according to claim 43, further comprising refluxing a portion of the liquid of the partition wall distillation column to the top of the fifth distillation column. The method for producing dichloropropanol according to claim 37, wherein the partition wall distillation column further comprises: a fourth chamber, wherein the second chamber is located in the first chamber and the Between the fourth chambers, and between the second chamber and the fourth chamber and between the third chamber and the fourth chamber are separated by a second partition; and a five chamber located at a bottom of the partition wall distillation column, wherein the third chamber and the fourth chamber are located above the fifth chamber, and the fifth chamber and the third chamber The chamber and the fourth chamber are in communication, wherein in the step of producing the overhead product and the bottom product, the first feed is heated in the fifth chamber to partially evaporate, a portion The first feed evaporates and rises through the third chamber into the first chamber and the second chamber to form the first chamber product and the second chamber product, respectively And another portion of the first feed evaporates and rises into the fourth chamber to form a fourth chamber product, wherein the overhead product comprises Product of said first chamber, said second chamber to said fourth chamber product of the product, and not the evaporation of the first feed is located in the fifth chamber to form the bottom product.