TWI627156B - Apparatus and method for manufacturing dichlorohydrin via vapor recompression - Google Patents

Abstract

A manufacturing apparatus and a manufacturing method of dichloropropanol are 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 first distillation column, a first phase separator, a first gas compression device, and a first heat exchange device. The first distillation column is connected to at least one reactor. The first phase separator and the first gas compression device are connected to the top of the first distillation column. The first heat exchange device is connected between the first gas compression device and the first phase separator via the first flow path, and is connected to the side wall of the first distillation column via the second flow path.

Description

Dichloropropanol vapor recompression type manufacturing device and manufacturing method

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 if an extractant is added to separate the azeotrope to obtain dichloropropanol, the production will be improved. The cost, and the extractant may also form an azeotrope with the catalyst, causing difficulties in recycling the catalyst.

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

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 first distillation column, a first phase separator, a first gas compression device, and a first heat exchange device. The first distillation is connected to at least one reactor. The first phase separator is connected to the top of the first distillation column. The first gas compression device is connected to the top of the first distillation column. The first heat exchange device is connected between the first gas compression device and the first phase separator via the first flow path, and is connected to the side wall of the first distillation column via the second flow path.

In an embodiment of the invention, the apparatus for manufacturing dichloropropanol further comprises a first water supply device directly connected to the first phase separator.

In an embodiment of the invention, the gas originating from the first gas compression device in the first flow path and the liquid originating in the first distillation column in the second flow path are in the first heat exchange device After the heat exchange, the flow proceeds to the first phase separator and the first distillation column, respectively.

In an embodiment of the invention, the apparatus for manufacturing dichloropropanol further includes a second gas compression device and a second heat exchange device. The first gas compression device is coupled between the top of the first distillation column and the second gas compression device. The second heat exchange device is connected between the second gas compression device and the first phase separator via the third flow path, and is connected to the side wall or the bottom of the first distillation column via the fourth flow path.

In an embodiment of the invention, the gas originating from the second gas compression device in the third flow path and the liquid in the first distillation column in the fourth flow path are heated in the second heat exchange device After the exchange, it flows to the first phase separator and the first distillation column, respectively.

In an embodiment of the invention, the apparatus for producing dichloropropanol further comprises a second distillation column. The first distillation column is connected between at least one reactor and the second distillation column.

In an embodiment of the invention, the apparatus for manufacturing dichloropropanol further comprises a heat exchange line connected between the bottom of the first distillation column and the feed port of the second distillation column to make the first The liquid at the bottom of the distillation column flows along the heat exchange line to the feed port of the second distillation column, and a part of the gas in the second distillation column is refluxed along the heat exchange line to the bottom of the first distillation column.

In an embodiment of the invention, the first distillation column comprises a partition wall extending from the inside of the first distillation column to the top to make the upper portion of the first distillation column the first chamber and the second chamber.

In an embodiment of the invention, the first gas compression device is coupled to the top of the first chamber, and the first heat exchange device is coupled to the sidewall of the first chamber via the second flow path.

In an embodiment of the invention, the apparatus for manufacturing dichloropropanol further comprises a second phase separator, a third gas compression unit, and a third heat exchange unit. The second phase separator and the third gas compression device are coupled to the top of the second chamber. The third heat exchange device is connected between the third gas compression device and the second phase separator via the fifth flow path, and is connected to the side wall of the second chamber via the sixth flow path.

In an embodiment of the invention, the gas originating from the third gas compression device in the fifth flow path and the liquid originating in the second chamber in the sixth flow path are performed in the third heat exchange device After the heat exchange, it flows to the second phase separator and the second chamber, respectively.

In an embodiment of the invention, the first distillation column comprises a first side stream outlet for withdrawing the first side stream product. The first side stream product comprises water having a purity of from 85% to 100%.

An embodiment of the present invention provides a method 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 method for producing dichlorohydrin includes 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 first distillation column to which the first phase separator is connected to produce a first overhead product and a first bottoms product. A portion of the first overhead product is passed to the first gas compression device to produce a first compressed product. Passing the first compressed product to the first phase separator via the first flow path through the first heat exchange device to form a first aqueous phase product and a first organic phase product including dichloropropanol in the first phase separator . The liquid flowing out from the side wall of the first distillation column is returned to the first distillation column through the first heat exchange device through the second flow path, wherein the first compressed product in the first flow path and the liquid in the second flow path are in the first Heat exchange takes place in the heat exchange device. The first organic phase product is removed.

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

In an embodiment of the invention, the method for producing dichloropropanol further comprises: introducing a portion of the first overhead product into the first phase separator, wherein the first column in the first phase separator The product forms a first aqueous phase product and a first organic phase product with the first compressed product.

In an embodiment of the invention, the method for producing dichloropropanol further comprises passing a portion of the first compressed product into the second gas compression device to produce a second compressed product. Passing the second compressed product to the first phase separator by the third flow path through the second heat exchange device, wherein the first compressed product in the first phase splitter forms a first aqueous phase product with the second compressed product The first organic phase product. The liquid flowing out of the side wall or the bottom of the first distillation column is refluxed to the first distillation column through the second heat exchange means through the fourth flow path. The second compressed product in the third flow path exchanges heat with the liquid in the fourth flow path in the second heat exchange device.

In an embodiment of the invention, the method for producing dichloropropanol further comprises: passing the liquid at the bottom of the first distillation column along the heat exchange line into the second distillation column to produce a second overhead product and Second bottom product. A part of the gas in the second distillation column is refluxed along the heat exchange line to the bottom of the first distillation column.

In an embodiment of the invention, the first distillation column comprises a partition wall extending from the inside of the first distillation column to the top to make the upper portion of the first distillation column the first chamber and the second chamber.

In an embodiment of the invention, the first overhead product enters the first phase separator from the first chamber, and the liquid flowing out from the sidewall of the first chamber passes through the first heat exchange through the second flow path. The device is returned to the first chamber.

In an embodiment of the invention, the method for producing dichloropropanol further comprises passing a portion of the first overhead product from the second chamber to the third gas compression device to produce a third compressed product. The third compressed product is passed through the third flow path to the second phase separator through the third heat exchange device, and the second aqueous phase product and the second organic phase including dichloropropanol are formed in the second phase separator. product. The liquid flowing out from the sidewall of the second chamber is returned to the second chamber through the third heat transfer device via the third heat exchange device, wherein the third compressed product in the fifth flow path and the liquid in the sixth flow path are The heat exchange is performed in the third heat exchange device. The second organic phase product is removed.

In an embodiment of the invention, the method for producing dichloropropanol further comprises: passing a portion of the first overhead product from the second chamber to the second phase splitter, wherein the second phase splitter is An overhead product and a third compressed product form a second aqueous phase product and a second organic phase product.

In an embodiment of the invention, the method for producing dichloropropanol further comprises removing the first side stream product at a first side stream outlet between the top of the first distillation column and the bottom of the column. The first side stream product comprises water having a purity of from 85 wt% to 100 wt%.

Based on the above, the use of a phase separator to separate the azeotrope and take out the dichloropropanol avoids the additional addition of the extractant, thereby reducing the manufacturing cost of the dichloropropanol. Furthermore, the problem that the extractant forms an azeotrope with the catalyst and the catalyst is difficult to recycle can be avoided. In addition, the high-temperature and high-pressure gas compressed by the gas compression device can exchange heat with the liquid of the distillation column in the heat exchange device to provide a part of the heat energy required for the separation of the distillation column, thereby reducing the energy consumption required for the distillation column. Therefore, the manufacturing cost of dichloropropanol can be further reduced.

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

1A and 1B are respectively a schematic view showing a manufacturing apparatus of dichlorohydrin and a flow chart for producing dichloropropanol according to an embodiment of the present invention.

Referring to FIG. 1A, the present embodiment provides a manufacturing apparatus 100 for dichlorohydrin which is suitable for reacting glycerin with an aqueous hydrogen chloride solution in the presence of a catalyst to produce dichloropropanol. The manufacturing apparatus 100 of dichlorohydrin includes at least one reactor 102, a distillation column 108, a phase separator 110, a gas compression device 116, and a heat exchange device 118. Distillation column 108 is coupled to reactor 102. The phase separator 110 is connected to the gas compression device 116 to the top of the distillation column 108. The heat exchange device 118 is connected between the gas compression device 116 and the phase separator 110 via the flow path P1, and is connected to the side wall of the distillation column 108 via the flow path P2.

In an embodiment, the manufacturing apparatus 100 of dichlorohydrin may further include a water supply device 120 that is directly connected to the phase separator 110. The gas originating from the gas compression device 116 in the flow path P1 and the liquid derived from the distillation column 108 in the flow path P2 can be heat-exchanged in the heat exchange device 118, and then flow to the phase splitter separately. 110 and distillation column 108. Additionally, distillation column 108 may further include a side stream outlet S1 to remove side stream products. The side stream product of distillation column 108 can include water having a purity of 85% to 100%. In other embodiments, the purity of the water in the side stream product of distillation column 108 can range from 90 wt% to 99.99 wt%, optimally from 95 wt% to 99.95% wt%.

Referring to FIG. 1A and FIG. 1B simultaneously, the embodiment further provides a method for manufacturing dichloropropanol, which comprises the following steps. First, in step S100, glycerin and an aqueous hydrogen chloride solution are reacted in at least one reactor 102 in the presence of a catalyst to produce an initial product. Reactor 102 can include a continuous reactor or a batch reactor. In the present embodiment, 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. In one embodiment, glycerol may be a by-product of the production of biodiesel or chemically synthesized glycerol. The catalyst can include 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 104 as a feed to produce an overhead product and a bottom product. The initial product can be reacted and separated in distillation column 104. In one embodiment, distillation column 104 can have a reboiler 106 to provide the thermal energy required for distillation column 104 to separate. The bottom product of the distillation column 104 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 104 can be refluxed to reactor 102 for continued recycle to increase reaction conversion. The overhead product of distillation column 104 comprises a large amount of dichlorohydrin, a large amount of monochloropropanol, a large amount of aqueous hydrogen chloride solution, a catalyst and a small amount of glycerin.

Step S104 is performed to cause the feed from the initial product to enter the distillation column 108 to which the phase separator 110 is connected, thereby producing an overhead product and a bottom product. In the present embodiment, the overhead product of the distillation column 104 can be used as a feed to the distillation column 108, and the reaction and separation are carried out in the distillation column 108. Specifically, the overhead product of the distillation column 104 can be stored in the reflux tank 107 after being condensed via the condenser 105, and then partially refluxed to the distillation column 104 and partially to the distillation column 108. Distillation column 108 can have reboiler 112 to provide the thermal energy required for distillation column 108 to separate. The large amount of dichlorohydrin in the distillation column 108 forms a lower boiling azeotrope with water, and forms the overhead product of the distillation column 108, so the content of dichloropropanol in the overhead product of the distillation column 108 can be It is larger than the content of dichloropropanol in the bottom product of the distillation column 108. The overhead product of distillation column 108 may further comprise a solution of monochloropropanol and hydrogen chloride. The bottom product of distillation column 108 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. Further, in the method for producing dichloropropanol of the present embodiment, the side stream product including the purity of 85 wt% to 100 is further included at the side stream outlet S1 between the top of the distillation column 108 and the bottom of the column. For wt% water, the purity of water in other embodiments may range from 90 wt% to 99.99 wt%, optimally from 95 wt% to 99.95 wt%. The high-purity water (reaction product) of the distillation column 108 is taken out from the side stream outlet S1, 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 can be increased and dichloropropanol and/or The yield of monochloropropanol.

In other embodiments, step S102 may not be performed. As such, the feed to distillation column 108 can be the initial product of reactor 102. In other words, the initial product of reactor 102 can be passed directly to distillation column 108.

Thereafter, step S108, step S110a, and step S110b may be performed. Specifically, step S108 may be first performed to cause the overhead product of a portion of the distillation column 108 to enter the gas compression device 116 to produce a compressed product. Gas compression unit 116 compresses the overhead product of gaseous distillation column 108 to increase its temperature and pressure. Therefore, the temperature and pressure of the compressed product of the gas compression device 116 can be higher than the temperature and pressure of the overhead product of the distillation column 108.

Next, step S110a may be performed to cause the compressed product of the gas compression device 116 to flow to the phase splitter 110 via the heat exchange device 118 via the flow path P1. As such, an aqueous phase product and an organic phase product comprising dichlorohydrin are formed in phase separator 110. At the same time as step S110a, step S110b may be performed to cause the liquid flowing out of the side wall of the distillation column 108 to be refluxed to the distillation column 108 via the heat exchange unit 118 through the flow path P2. The compressed product of the gas compression device 116 in the flow path P1 exchanges heat with the liquid in the flow path P2 in the heat exchange device 118. As a result, the temperature of the liquid flowing out of the distillation column 108 can be increased so that the distillation column 108 can be heated while flowing back to the distillation column 108 along the flow path P2. Therefore, the energy consumption of the reboiler 112 can be reduced. On the other hand, the temperature of the compressed product of the gas compression device 116 can be lowered and subsequently flowed to the phase splitter 110. In one embodiment, if the compressed product of the gas compression device 116 is not completely condensed into a low temperature liquid state after heat exchange, it may be condensed along the flow path P1 through the condenser 114 before entering the phase separator 110. In other embodiments, if the compressed product of the gas compression device 116 is completely condensed into a low temperature liquid state after heat exchange, it may flow directly to the phase separator 110 without passing through the condenser 114.

It is to be noted that when the latent heat of the overhead product of the distillation column 108 is large and the temperature difference between the top of the distillation column 108 and the bottom of the column is small, more energy consumption of the reboiler 112 can be saved. In one embodiment, the overhead product of distillation column 108 can include water having a weight percent greater than or equal to 80, at which point the compressed product of gas compression unit 116 (derived from the overhead product of distillation column 108) can release significant amounts of latent heat. . In addition, the temperature difference between the top of the distillation column 108 and the bottom of the column may be less than or equal to 25 °C. In this way, the overall energy consumption of the distillation column 108 can be further reduced, that is, the manufacturing cost of the dichlorohydrin can be further reduced.

While performing step S108, step S110a, and step S110b, step S106 may be performed to cause the overhead product of the portion of the distillation column 108 to enter the phase separator 110. As such, the overhead product of the distillation column 108 in the phase separator 110 and the compressed product of the gas compression device 116 form the aqueous phase product and organic phase product of the phase separator 110. In one embodiment, a condenser 114 may be disposed between the top of the distillation column 108 and the phase separator 110 such that a portion of the overhead product of the distillation column 108 is condensed by the condenser 114 before entering the phase separator 110. .

The organic phase product in phase separator 110 comprises dichlorohydrin and more preferably monochloropropanol. The aqueous phase product of phase separator 110 includes an aqueous hydrogen chloride solution and the aqueous phase product can be refluxed to distillation column 108. Since the density of the aqueous phase product is lower than the density of the organic phase product, the aqueous phase product is located in the upper layer of the organic phase product. The phase separator 110 can separate the azeotrope in the distillation column 108 to take out the dichloropropanol, so that no additional extractant is required. In this way, the problem that the extractant and the catalyst may form an azeotrope and the catalyst is difficult to recycle may be avoided. In an embodiment, the water supply device 120 can be directly connected to the phase splitter 110. The water supply unit 120 can directly adjust the concentration of the aqueous hydrogen chloride solution in the phase separator 110, and can effectively separate the overhead product of the distillation column 108 from the compressed product of the gas compression unit 116.

Next, in step S112, the organic phase product in the phase separator 110 is taken out to obtain the main product dichloropropanol. In one embodiment, the bottoms product of distillation column 108 can be returned to reactor 102 for recycling.

Based on the above examples, it can be seen that the separation of the azeotrope by using the phase separator 110 removes the dichloropropanol, thereby avoiding the additional addition of the extractant and reducing the manufacturing cost. Furthermore, the problem that the extractant and the catalyst may form an azeotrope and the catalyst is difficult to recycle may be avoided. In addition, heat exchange of the compressed product of the gas compression unit 116 with the liquid in the distillation column 108 in the heat exchange unit 118 provides a portion of the thermal energy required for the distillation column 108 to separate, thereby reducing the energy required for the distillation column 108. Consumption. Therefore, the manufacturing cost of dichloropropanol can be further reduced.

2A and 2B are respectively a schematic view showing a manufacturing apparatus of dichloropropanol and a manufacturing flow chart of dichloropropanol according to an embodiment of the present invention.

Referring to FIG. 2A, the apparatus for manufacturing dichloropropanol of the present embodiment is similar to the apparatus 100 for manufacturing dichloropropanol shown in FIG. 1A, but the apparatus for manufacturing dichloropropanol 200 may further include a gas compression device 202 and Heat exchange device 204. A gas compression device 116 is coupled between the top of the distillation column 108 and the gas compression device 202. The heat exchange device 204 is connected between the gas compression device 202 and the phase separator 110 via the flow path P3, and is connected to the distillation column 108 via the flow path P4. In the present embodiment, the heat exchange device 204 can be connected to the side wall of the distillation column 108 via the flow path P4. In other embodiments, the heat exchange device 204 may be further connected to the bottom of the distillation column 108 via a flow path P4. The gas originating from the gas compression device 202 in the flow path P3 and the liquid derived from the distillation column 108 in the flow path P4 can be heat-exchanged in the heat exchange device 204, and then can be separately flowed to the phase splitter 110 and distillation column 108.

Referring to FIG. 2A and FIG. 2B simultaneously, the method for producing dichloropropanol of the present embodiment is similar to the method for producing dichloropropanol shown in FIG. 1B, and the differences will be described below, and the same or similar points will not be described again. . In the method for producing dichloropropanol of the present embodiment, after performing step S108, step S200, steps S202a, and S202b may be further included. Specifically, while performing steps S110a and S110b, step S200 may be performed to cause a portion of the compressed product of the gas compression device 116 to enter the gas compression device 202 to produce a compressed product. As such, the temperature and pressure of the compressed product of the gas compression device 202 can be higher than the temperature and pressure of the compressed product of the gas compression device 116.

Thereafter, step S202a may be performed to cause the compressed product of the gas compression device 202 to flow to the phase splitter 110 via the heat exchange device 204 via the flow path P3. At the same time as step S202a, step S202b may be performed to cause the liquid flowing out of the distillation column 108 to be refluxed to the distillation column 108 via the heat exchange unit 204 through the flow path P4. In the present embodiment, part of the liquid in the distillation column 108 may flow out from the side wall of the distillation column 108 and be returned to the distillation column 108 via the heat exchange unit 204 through the flow path P4. In other embodiments, a portion of the liquid in distillation column 108 may also flow from the bottom of distillation column 108 and be refluxed to distillation column 108 via heat exchange unit 204 via flow path P4. The compressed product of the gas compression device 202 in the flow path P3 exchanges heat with the liquid in the flow path P4 in the heat exchange device 204. Therefore, the liquid flowing out of the distillation column 108 can be heated and returned to the distillation column 108 to heat the distillation column 108. On the other hand, the temperature of the compressed product of the gas compression device 202 can be lowered and then flowed to the phase separator 110. In one embodiment, in phase separator 110, the compressed product of heat exchanged gas compression device 116 and the compressed product of gas compression device 202 form an aqueous phase product with an organic phase product comprising dichlorohydrin. In the embodiment in which step S106 is selected, the overhead product of a portion of distillation column 108 enters phase separator 110 to form a portion of the aqueous phase product of phase separator 110 and the organic phase product. In one embodiment, if the compressed product of the gas compression device 202 is not completely condensed into a low temperature liquid state after heat exchange, it may be condensed along the flow path P3 through the condenser 114 before entering the phase separator 110. In other embodiments, if the compressed product of the gas compression device 202 is completely condensed into a low temperature liquid state after heat exchange, it may flow directly to the phase separator 110 without passing through the condenser 114.

In the present embodiment, the distillation column 108 can be further reduced by providing two gas compression devices (gas compression device 116 and gas compression device 202) and two heat exchange devices (heat exchange device 118 and heat exchange device 204). The energy consumption, which further reduces the manufacturing cost of dichloropropanol.

3A and 3B are respectively a schematic view showing a manufacturing apparatus of dichloropropanol and a flow chart for producing dichloropropanol according to an embodiment of the present invention.

Referring to FIG. 3A, the apparatus for producing dichloropropanol of the present embodiment is similar to the apparatus 100 for producing dichlorohydrin shown in FIG. 1A, but the apparatus for producing dichloropropanol 300 may further include a distillation column 302. Distillation column 108 is coupled between reactor 102 and distillation column 302. In one embodiment, the dichlorohydrin manufacturing apparatus 300 may further include a heat exchange line L connected between the bottom of the distillation column 108 and the feed port of the distillation column 302 to allow the bottom of the distillation column 108. The liquid flows along the heat exchange line L to the feed port of the distillation column 302, and a part of the gas in the distillation column 302 is returned to the bottom of the distillation column 108 along the heat exchange line L. In an embodiment, the entire liquid of the bottom of the distillation column 108 may flow along the heat exchange line L to the feed port of the distillation column 302.

In an embodiment, the manufacturing apparatus 300 of dichlorohydrin may further include a phase separator 306, a gas compression device 310, and a heat exchange device 312. The phase separator 306 and the gas compression device 310 can be connected to the top of the distillation column 302. The heat exchange device 312 can be connected between the gas compression device 310 and the phase separator 306 via the flow path P5, and connected to the side wall of the distillation column 302 via the flow path P6. In addition, the manufacturing apparatus 300 of dichlorohydrin may further include a water supply device 314 directly connected to the phase separator 306.

Referring to FIG. 3A and FIG. 3B, the method for producing dichloropropanol of the present embodiment is similar to the method for producing dichloropropanol shown in FIG. 1B, and the differences will be described below, and the same or similar portions will not be described again. In this embodiment, after step S112, step S300 may be further included to cause the liquid at the bottom of the distillation column 108 to enter the distillation column 302 along the heat exchange line L to produce an overhead product and a bottom product. In one embodiment, all of the liquid at the bottom of the distillation column 108 can be passed along the heat exchange line L to the feed port of the distillation column 302. In particular, all of the liquid at the bottom of the distillation column 108 can flow to the distillation column 302 along the liquid flow path L1 of the heat exchange line L. Distillation column 302 can have a reboiler 304 to provide the thermal energy required for separation by distillation column 302. The overhead product of distillation column 302, after condensation, comprises dichlorohydrin, and may further comprise an aqueous solution of hydrogen chloride. The bottom product of distillation column 302 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 302 can include a side stream outlet S2 to remove side stream products. The side stream product of distillation column 302 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%, most preferably from 95 wt% to 99.95% wt%. Similar to the side stream product from which the distillation column 108 is withdrawn, the side stream product of the distillation column 302 is withdrawn from the side stream outlet S2 to increase the reaction conversion ratio of the reactants with the yield of dichloropropanol and/or monochloropropanol.

Next, step S302 may be performed to return a part of the gas in the distillation column 302 to the bottom of the distillation column 108 along the heat exchange line L. In particular, the above gas has thermal energy and can be refluxed to the distillation column 108 along the gas flow path L2 of the heat exchange line L. As such, a portion of the gas in the distillation column 302 and the gas or liquid heated in the heat exchange unit 118 to reflux to the distillation column 108 can heat the distillation column 108 so that the feed to the distillation column 108 can be smoothly heated. Distillation and separation are carried out. Therefore, in the present embodiment, the cost of providing the reboiler in the distillation column 108 can be eliminated and the energy consumption can be reduced.

Thereafter, step S306, step S308a, and step S308b may be performed. Specifically, step S306 is first performed to cause the overhead product of a portion of the distillation column 302 to enter the gas compression device 310 to produce a compressed product.

Next, in step S308a, the compressed product of the gas compression device 310 is caused to flow to the phase splitter 306 via the heat exchange device 312 via the flow path P5. At the same time as step S308a, step S308b is performed, and the liquid flowing out of the side wall of the distillation column 302 is returned to the distillation column 302 via the heat exchange means 312 via the flow path P6. The compressed product of the gas compression device 310 in the flow path P5 exchanges heat with the liquid in the flow path P6 in the heat exchange device 312. In one embodiment, if the compressed product of the gas compression device 310 is not completely condensed into a low temperature liquid state after heat exchange, it may be condensed along the flow path P5 through the condenser 308 before entering the phase separator 306.

At the same time as step S306, step S308a and step S308b, step S304 may be performed to cause the overhead product of the portion of the distillation column 302 to enter the phase separator 306. As such, the overhead product of distillation column 302 in phase separator 306 and the compressed product of gas compression device 310 form the aqueous phase product and organic phase product of phase separator 306. In one embodiment, a condenser 308 may be disposed between the top of the distillation column 302 and the phase separator 306 such that the overhead product of a portion of the distillation column 302 is condensed before entering the phase separator 306.

The organic phase product in phase separator 306 comprises dichlorohydrin, and the aqueous phase product of phase separator 306 can comprise an aqueous hydrogen chloride solution. In an embodiment, the aqueous phase product of phase separator 306 can be refluxed to distillation column 302. In addition, when the aqueous phase product of the phase separator 306 includes an aqueous solution of hydrogen chloride, the water supply device 314 can be directly connected to the phase separator 306 to directly adjust the concentration of the aqueous hydrogen chloride solution in the phase separator 306 to make the aqueous phase product and the organic term. The product is effectively layered.

Next, in step S310, the organic phase product in the phase separator 306 is taken out to obtain the main product dichloropropanol. In one embodiment, the bottoms product of distillation column 302 can be further refluxed to reactor 102 for recycle.

In the present embodiment, the distillation column 108 may be heated by a gas having thermal energy in the distillation column 302 and a gas or liquid heated to the distillation column 108 by heating in the heat exchange unit 118. Therefore, the cost of providing the reboiler in the distillation column 108 can be eliminated, and energy consumption can be saved. Further, in the present embodiment, the gas compression device and the heat exchange device are both provided in the distillation column 108 and the distillation column 302 as an example, but the invention is not limited thereto. In other embodiments, the gas compression device and the heat exchange device may be provided only in one of the distillation column 108 and the distillation column 302.

4A and 4B are respectively a schematic view showing a manufacturing apparatus of dichlorohydrin and a flow chart for producing dichloropropanol according to an embodiment of the present invention.

Referring to FIG. 4A, the apparatus for manufacturing dichloropropanol of the present embodiment is similar to the apparatus 100 for producing dichloropropanol shown in FIG. 1A, but the distillation column 108 of the present embodiment may further include a partition wall W. The partition wall W extends from the inside of the distillation column 108 to the top to make the upper portion of the distillation column 108 the chamber C1 and the chamber C2.

In an embodiment, the gas compression device 116 can be coupled to the top of the chamber C1 and the heat exchange device 118 can be coupled to the sidewall of the chamber C1 via the flow path P2. In addition, the manufacturing apparatus 400 of the dichlorohydrin may further include a phase separator 402, a gas compression device 404, and a heat exchange device 406. A phase splitter 402 and a gas compression device 404 can be coupled to the top of the chamber C2. The heat exchange device 406 can be connected between the gas compression device 404 and the phase splitter 402 via the flow path P7 and connected to the side wall of the chamber C2 via the flow path P8. The gas originating from the gas compression device 404 in the flow path P7 and the liquid derived from the chamber C2 in the flow path P8 can be heat-exchanged in the heat exchange device 406, and then flow to the phase separator 402 and the cavity, respectively. Room C2. In one embodiment, the dichlorohydrin manufacturing apparatus 400 may further include a water supply unit 408 that is directly coupled to the phase splitter 402.

Referring to FIG. 4A and FIG. 4B simultaneously, the method for producing dichloropropanol of the present embodiment is similar to the method for producing dichloropropanol shown in FIG. 1B, and the differences will be described below, and the same or similar points will not be described again. . In step S104 of the present embodiment, the feed of the distillation column 108 enters the chamber C2 and then flows down to the bottom of the distillation column 108. The feed to the bottom of distillation column 108 is partially vaporized by heating via reboiler 112, and the vaporized gas rises into chamber C1 and chamber C2 to collectively form the overhead product of distillation column 108. The gas rising from the bottom of the distillation column 108 can exchange heat with the feed entering the chamber C2, so that the feed entering the chamber C2 can obtain thermal energy. Accordingly, the energy consumption of the reboiler 112 can be reduced. In addition, the distillation column 108 may further include a side stream outlet S1 and a side stream outlet port S3 to take out the side stream product. The side stream outlet S3 may be located at a side wall of the chamber C2, and the side stream outlet S1 may be located at a side wall of the chamber C1. The side stream product of the distillation column 108 flowing out from the side stream outlet S1 and the side stream outlet S3 may include water having a purity of 85% to 100%. In other embodiments, the purity of the water in the side stream product of distillation column 108 can range from 90 wt% to 99.99 wt%, optimally from 95 wt% to 99.95% wt%.

In step S106 of the present embodiment, the overhead product of a portion of the distillation column 108 enters the phase separator 110 via the chamber C1. Further, in step S110b of the present embodiment, the liquid flowing out of the side wall of the chamber C1 of the distillation column 108 is returned to the chamber C1 of the distillation column 108 via the heat exchange means 118 through the flow path P2.

In addition to this, after step S104 is performed, step S402, step S404a, step S404b, and step S406 are further performed. Specifically, while performing step S108, step S402 may be performed to cause the overhead product of a portion of the distillation column 108 to enter the gas compression device 404 through the chamber C2 to produce a compressed product.

Next, step S404a may be performed to cause the compressed product of the gas compression device 404 to flow through the heat exchange unit 406 to the phase separator 402 via the flow path P7 to form an aqueous phase product and an organic phase product including dichloropropanol. Simultaneously with step S404a, step S404b may be performed to cause the liquid flowing out of the side wall of the chamber C2 to flow back to the chamber C2 via the heat exchange means 406 through the flow path P8. The compressed product of the gas compression device 404 in the flow path P7 exchanges heat with the liquid in the flow path P8 in the heat exchange device 406.

The organic phase product in phase separator 402 comprises dichlorohydrin and the aqueous phase product of phase separator 402 can comprise an aqueous hydrogen chloride solution. In an embodiment, the aqueous phase product of phase separator 402 can be refluxed to chamber C2 of distillation column 108. In addition, when the aqueous phase product of the phase separator 402 includes an aqueous solution of hydrogen chloride, the water supply device 408 can be directly connected to the phase separator 402 to directly adjust the concentration of the aqueous hydrogen chloride solution in the phase separator 402 to make the aqueous phase product and the organic term. The product is effectively layered.

At the same time as step S108 and step S402, step S400 may be performed to cause the overhead product of a portion of the distillation column 108 to enter the phase separator 402 through the chamber C2. As such, the aqueous phase product of the phase separator 402 and the organic phase product may include the overhead product of the distillation column 108. In one embodiment, a condenser 410 may be disposed between the top of the chamber C2 and the phase splitter 402 such that the overhead product of a portion of the distillation column 108 described above is condensed before entering the phase separator 402.

Thereafter, in step S406, the organic phase product in the phase separator 402 is taken out to obtain the main product dichloropropanol.

In the present embodiment, the distillation column 108 having the partition wall W can be analogous to the combination of the distillation column 108 and the distillation column 302 in Fig. 3A. Specifically, the distillation column 108 of FIG. 3A, the top of the distillation column 302, and the bottom of the distillation column 302 can be sequentially compared to the chamber C2 of FIG. 4A, the chamber C1, and the bottom of the distillation column 108. In the embodiment shown in FIG. 3A, the liquid at the bottom of the distillation column 302 is heated to evaporate, part of the vaporized gas rises to the top of the distillation column 302, and part of the gas flows back to the distillation column 108 along the heat exchange line L. The feed to the distillation column 108 is heated. Similarly, in the embodiment shown in FIG. 4A, the liquid at the bottom of the distillation column 108 is partially evaporated by heating, the vaporized portion of the gas rises to the chamber C1, and the other portion of the gas rises to the chamber C2 to heat the chamber. Feed of chamber C2. In other words, the distillation column 108 shown in FIG. 4A is similar to the distillation column 108, the heat exchange line L and the distillation column 302 shown in FIG. 3A for heat exchange, so that the manufacturing cost can be reduced.

In the present embodiment, the gas compression device and the heat exchange device are connected to both the chamber C1 and the chamber C2 as an example, but the invention is not limited thereto. In other embodiments, only one of chamber C1 and chamber C2 is coupled to a gas compression device and a heat exchange device.

5A and 5B are respectively a schematic view showing a manufacturing apparatus of dichloropropanol and a manufacturing flow chart of dichloropropanol according to an embodiment of the present invention.

Referring to FIG. 5A, the apparatus for manufacturing dichloropropanol of the present embodiment is similar to the apparatus for manufacturing dichloropropanol shown in FIG. 4A, but the apparatus for producing dichloropropanol of the present embodiment may further include a gas. Compression device 502 and heat exchange device 504. Gas compression device 116 is coupled between the top of distillation column 108 and gas compression device 502. The heat exchange device 504 is connected between the gas compression device 502 and the phase separator 110 via the flow path P9, and is connected to the distillation column 108 via the flow path P10. In the present embodiment, the heat exchange device 504 can be connected to the side wall of the distillation column 108 via the flow path P10. In other embodiments, the heat exchange device 504 is further connectable to the bottom of the distillation column 108 via the flow path P10. The gas originating from the gas compression device 502 in the flow path P9 and the liquid derived from the distillation column 108 in the flow path P10 can be heat-exchanged in the heat exchange device 504, and then can be separately flowed to the phase splitter 110 and distillation column 108.

Referring to FIG. 5A and FIG. 5B simultaneously, the method for producing dichloropropanol of the present embodiment is similar to the method for producing dichloropropanol shown in FIG. 4B, and the differences will be described below, and the same or similar points will not be described again. . In the method for producing dichloropropanol of the present embodiment, after performing step S108, step S500, step S502a, and step S502b may be further included.

Specifically, while step S110a and step S110b are performed, step S500 is performed to cause a portion of the compressed product of the gas compression device 116 to enter the gas compression device 502 to generate a compressed product. As such, the temperature and pressure of the compressed product of the gas compression device 502 can be higher than the temperature and pressure of the compressed product of the gas compression device 116.

Thereafter, step S502a is performed to cause the compressed product of the gas compression product 502 to flow to the phase separator 110 via the heat exchange device 504 via the flow path P9. At the same time as step S502a, step S502b is performed to cause the liquid flowing out of the distillation column 108 to be refluxed to the distillation column 108 via the heat exchange means 504 via the flow path P10. In the present embodiment, part of the liquid in the distillation column 108 may flow out from the side wall below the chamber C1 of the distillation column 108, and is returned to the distillation column 108 via the heat exchange unit 504 through the flow path P10. In other embodiments, a portion of the liquid in distillation column 108 may also flow from the bottom of distillation column 108 and be refluxed to distillation column 108 via heat exchange unit 504 via flow path P10. The compressed product of the gas compression device 502 in the flow path P9 exchanges heat with the liquid in the flow path P10 in the heat exchange device 504. Therefore, the liquid flowing out of the distillation column 108 can be heated and returned to the distillation column 108 to heat the distillation column 108. On the other hand, the temperature of the compressed product of the gas compression device 502 can be lowered and then flowed to the phase separator 110. In one embodiment, in phase separator 110, the compressed product of heat exchanged gas compression device 116 and the compressed product of gas compression device 502 form an aqueous phase product with an organic phase product comprising dichlorohydrin. In the embodiment in which step S106 is selected, the overhead product of a portion of distillation column 108 enters phase separator 110 to form a portion of the aqueous phase product of phase separator 110 and the organic phase product. In one embodiment, if the compressed product of the gas compression device 502 is not completely condensed into a low temperature liquid state after heat exchange, it may be condensed along the flow path P9 through the condenser 114 before entering the phase separator 110. In other embodiments, if the compressed product of the gas compression device 502 is completely condensed into a low temperature liquid state after heat exchange, it may flow directly to the phase separator 110 without passing through the condenser 114.

Further, in the present embodiment, the chamber C2 may not be connected to the gas compression device and the heat exchange device (the gas compression device 404 and the heat exchange device 406 shown in Fig. 4A). In other words, in the method for producing dichloropropanol of the present embodiment, step S402, step S404a, and step S404b shown in Fig. 4B may not be selected. However, one of ordinary skill in the art can connect at least one gas compression device and at least one heat exchange device to at least one of the chamber C1 and the chamber C2 according to the process requirements, and the invention is not limited thereto.

In summary, the separation of the azeotrope by the phase separator removes the dichloropropanol, thereby avoiding the additional addition of the extractant, and reducing the manufacturing cost of the dichloropropanol. In addition, the problem that the extractant forms an azeotrope with the catalyst and the catalyst is difficult to recycle can be avoided. In addition, the compressed product compressed by the gas compression device can be heat exchanged with the liquid in the distillation column in the heat exchange unit to provide a portion of the heat energy required for the distillation column to separate, thereby reducing the energy consumption required for the distillation column. Therefore, the manufacturing cost of dichloropropanol can be further 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, 200, 300, 400, 500‧‧‧ dichloropropanol manufacturing equipment

102‧‧‧Reactor

104, 108, 302‧‧‧ distillation tower

105, 114, 308, 410‧‧ ‧ condenser

106, 112, 304‧‧‧ reboiler

107‧‧‧Reflow tank

110, 306, 402‧ ‧ phase splitter

116, 202, 310, 404, 502‧‧‧ gas compression devices

118, 204, 312, 406, 504‧‧‧ heat exchange devices

120, 314, 408‧‧‧ water supply device

C1, C2‧‧‧ chamber

L‧‧‧Heat exchange line

L1‧‧‧Liquid flow path

L2‧‧‧ gas flow path

P1, P2, P3, P4, P5, P6, P7, P8, P9, P10‧‧‧ flow paths

S1, S2, S3‧‧‧ sidestream outlet

S100, S102, S104, S106, S108, S110a, S110b, S112, S200, S202a, S202b, S300, S302, S304, S306, S308a, S308b, S310, S400, S402, S404a, S404b, S406, S500, S502a, S502b‧‧‧Steps

1A and 1B are respectively a schematic view showing a manufacturing apparatus of dichlorohydrin and a flow chart for producing dichloropropanol according to an embodiment of the present invention. 2A and 2B are respectively a schematic view showing a manufacturing apparatus of dichloropropanol and a manufacturing flow chart of dichloropropanol according to an embodiment of the present invention. 3A and 3B are respectively a schematic view showing a manufacturing apparatus of dichloropropanol and a flow chart for producing dichloropropanol according to an embodiment of the present invention. 4A and 4B are respectively a schematic view showing a manufacturing apparatus of dichlorohydrin and a flow chart for producing dichloropropanol according to an embodiment of the present invention. 5A and 5B are respectively a schematic view showing a manufacturing apparatus of dichloropropanol and a manufacturing flow chart of dichloropropanol according to an embodiment of the present invention.

Claims (24)

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 dichloropropanol comprising: at least one reactor; first distillation a column connected to the at least one reactor; a first phase separator connected to the top of the first distillation column; a first gas compression device connected to the top of the first distillation column; a first heat exchange device connected between the first gas compression device and the first phase separator via a first flow path and connected to a sidewall of the first distillation column via a second flow path, wherein The gas originating from the first gas compression device in the first flow path and the liquid derived from the first distillation column in the second flow path are heated in the first heat exchange device After the exchange, it flows to the first phase separator and the first distillation column, respectively. The apparatus for producing dichloropropanol according to claim 1, further comprising a first water supply device directly connected to the first phase separator. The apparatus for producing dichloropropanol according to claim 1, further comprising: a second gas compression device, wherein the first gas compression device is connected to the top and the bottom of the first distillation column Between the second gas compression devices; a second heat exchange device connected between the second gas compression device and the first phase separator via a third flow path and connected to a sidewall or a bottom of the first distillation column via a fourth flow path . The apparatus for producing dichloropropanol according to claim 3, wherein a gas derived from the second gas compression device in the third flow path is in the fourth flow path The liquid in the first distillation column is subjected to heat exchange in the second heat exchange device, and then flows to the first phase separator and the first distillation column, respectively. The apparatus for producing dichloropropanol according to claim 1, further comprising a second distillation column, wherein the first distillation column is connected between the at least one reactor and the second distillation column. The apparatus for producing dichloropropanol according to claim 5, further comprising a heat exchange line connected between the bottom of the first distillation column and the feed port of the second distillation column, So that the liquid of the bottom of the first distillation column flows along the heat exchange line to the feed port of the second distillation column, and a portion of the gas in the second distillation column is along The heat exchange line is refluxed to the bottom of the first distillation column. The apparatus for producing dichloropropanol according to claim 1, wherein the first distillation column comprises a partition wall extending from an inside of the first distillation column to a top to be the first distillation column The upper portion is the first chamber and the second chamber. The apparatus for producing dichloropropanol according to claim 7, wherein the first gas compression device is connected to a top of the first chamber, and the first heat exchange device is via the second A flow path is connected to a sidewall of the first chamber. The apparatus for manufacturing dichloropropanol according to claim 8, further comprising: a second phase separator connected to the top of the second chamber, and a third gas compression device connected to the second The top of the chamber; and a third heat exchange device connected between the third gas compression device and the second phase separator via a fifth flow path and connected to the first via a sixth flow path The side wall of the two chambers. The apparatus for producing dichloropropanol according to claim 9, wherein a gas derived from the third gas compression device in the fifth flow path is derived from the sixth flow path After the liquid in the second chamber is heat-exchanged in the third heat exchange device, it flows to the second phase separator and the second chamber, respectively. The apparatus for producing dichloropropanol according to claim 9, further comprising: a second gas compression device, wherein the first gas compression device is connected to the top and the bottom of the first distillation column Between the second gas compression devices; and a second heat exchange device connected between the second gas compression device and the first phase separator via a third flow path, and connected to the second flow path via the fourth flow path The side wall or the bottom of the first distillation column. The apparatus for producing dichloropropanol according to claim 11, wherein the gas originating from the second gas compression device in the third flow path is in the fourth flow path The liquid in the first distillation column is in the second heat exchange After performing heat exchange in the apparatus, it flows to the first phase separator and the first distillation column, respectively. The apparatus for producing dichloropropanol according to claim 1, wherein the first distillation column comprises a first side stream outlet for taking out the first side stream product, the first side stream product comprising a purity of 85 % to 100% water. A method for producing dichloropropanol, which is suitable for reacting glycerin with an aqueous hydrogen chloride solution in the presence of a catalyst to produce dichloropropanol, and the method for producing the dichlorohydrin comprises: at least one reactor Glycerol reacts with an aqueous solution of hydrogen chloride in the presence of a catalyst to produce an initial product; the first feed derived from the initial product is passed to a first distillation column to which a first phase separator is connected to produce a first column a top product and a first bottom product; causing a portion of the first overhead product to enter a first gas compression device to produce a first compressed product; causing the first compressed product to pass through the first heat transfer device through the first flow path Flowing to the first phase separator to form a first aqueous phase product and a first organic phase product comprising dichloropropanol in the first phase separator; flowing the sidewall of the first distillation column The liquid is refluxed to the first distillation column by the second flow path through the first heat exchange device, wherein the first compressed product in the first flow path and the liquid in the second flow path In the first heat exchange Centering heat exchanger; and removing the first organic phase product. The method for producing dichloropropanol according to claim 14, further comprising directly connecting the first water supply device to the first phase separator. The method for producing dichloropropanol according to claim 14, further comprising: introducing a portion of the first overhead product into the first phase separator, wherein in the first phase separator The first overhead product forms the first aqueous phase product and the first organic phase product with the first compressed product. The method for producing dichloropropanol according to claim 14, further comprising: introducing a portion of the first compressed product into the second gas compression device to produce a second compressed product; and causing the second compressed product Flowing through the third flow path to the first phase separator via a second heat exchange device, wherein the first compressed product in the first phase splitter forms the first An aqueous phase product and the first organic phase product; and the liquid flowing out of the side wall or the bottom of the first distillation column is refluxed to the first distillation through the second heat exchange device through the fourth flow path a tower, wherein the second compressed product in the third flow path exchanges heat with the liquid in the fourth flow path in the second heat exchange device. The method for producing dichloropropanol according to claim 14, further comprising: passing the liquid in the bottom of the first distillation column into the second distillation column along the heat exchange line to produce a second a top product and a second bottom product; A portion of the gas in the second distillation column is refluxed along the heat exchange line to the bottom of the first distillation column. The method for producing dichloropropanol according to claim 14, wherein the first distillation column comprises a partition wall extending from the inside of the first distillation column to the top to be the first distillation column The upper portion is the first chamber and the second chamber. The method for producing dichloropropanol according to claim 19, wherein the first overhead product enters the first phase separator from the first chamber, and from the first chamber The liquid flowing out of the side wall is returned to the first chamber through the first heat exchange device by the second flow path. The method for producing dichloropropanol according to claim 20, further comprising: causing a portion of the first overhead product to enter the third gas compression device from the second chamber to produce a third compressed product And causing the third compressed product to flow through the third flow path to the second phase separator through the third heat exchange device, and forming the second aqueous phase product and including the dichloropropyl group in the second phase separator a second organic phase product of alcohol; causing liquid flowing out of a sidewall of the second chamber to flow back to the second chamber through the third heat exchange device via a sixth flow path, wherein the fifth stream The third compressed product in the road exchanges heat with the liquid in the sixth flow path in the third heat exchange device; and the second organic phase product is taken out. The method for producing dichloropropanol according to claim 21, further comprising: causing a portion of the first overhead product to enter the second phase separator from the second chamber, wherein the second The first overhead product in the phase separator and the third compressed product form the second aqueous phase product and the second organic phase product. The method for producing dichloropropanol according to claim 21, further comprising: causing a portion of the first compressed product to enter a second gas compression device to produce a second compressed product; and the second compressed product Flowing through the third flow path to the first phase separator via a second heat exchange device, wherein the first compressed product in the first phase splitter forms the first An aqueous phase product and the first organic phase product; and the liquid flowing out of the side wall or the bottom of the first distillation column is refluxed to the first distillation through the second heat exchange device through the fourth flow path a tower, wherein the second compressed product in the third flow path exchanges heat with the liquid in the fourth flow path in the second heat exchange device. The method for producing dichloropropanol according to claim 14, further comprising: taking out the first side stream product at a first side stream outlet between the top of the first distillation column and the bottom of the column, wherein The first side stream product comprises water having a purity of from 85 wt% to 100 wt%.