CN115850028A - Method for purifying and refining trimethylolpropane by multi-tower series extraction rectification - Google Patents
Method for purifying and refining trimethylolpropane by multi-tower series extraction rectification Download PDFInfo
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- CN115850028A CN115850028A CN202211618245.1A CN202211618245A CN115850028A CN 115850028 A CN115850028 A CN 115850028A CN 202211618245 A CN202211618245 A CN 202211618245A CN 115850028 A CN115850028 A CN 115850028A
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Abstract
The invention discloses a method for extracting, rectifying, purifying and refining trimethylolpropane by multi-tower series connection, which is characterized in that in the production of trimethylolpropane by a calcium method, the impurities are purified and refined by multi-tower series connection and negative pressure reaction, light components are separated, and simultaneously, heat energy of a rectifying system is utilized, and an acid catalyst is used for reaction treatment of heavy components, so that trimethylolpropane cyclic formal CTF with economic value is obtained. The method specifically comprises 5 steps of extraction, a solvent recovery tower, a TMP rectifying tower, a main tower and a flash tower. In the production of trimethylolpropane by calcium method, more high boiling point impurities are generated, a reaction catalytic rectification technology is adopted, and a proper catalyst is selected to remove part of the high boiling point impurities. High boiling point impurity is easy to dissolve in organic solvent, and multiple-tower series technology is adopted, so that the rectification separation efficiency is improved, and the rectification quality of trimethylolpropane is improved. The method reduces the fluctuation of the rectifying tower by utilizing automatic control, and the quality of the trimethylolpropane obtained by the measures can reach 99.5 percent.
Description
Technical Field
The invention belongs to the technical field of chemical production methods, and particularly relates to a trimethylolpropane multi-tower series extraction rectification impurity removal refining method.
Background
Formaldehyde and n-butyl aldehyde are subjected to condensation reaction under the condition of calcium hydroxide to generate trimethylolpropane. Condensation side reactions produce high boiling impurities and low boiling impurities. During production, separation is carried out by adopting a rectification mode according to different boiling points of impurities. In the traditional rectification process in the prior art, light components are not completely separated, trimethylolpropane contains part of light components, the content of the extracted trimethylolpropane is low, and the production requirement cannot be met. Partial heavy components are generated by condensation side reaction, the viscosity of the heavy components is high, the separation is difficult, trihydroxy and ditrimethylol are easily carried, and the yield and the quality of the ditrimethylol are influenced. The product quality in the prior art can only reach 99.1 percent.
Disclosure of Invention
The invention provides a method for purifying and refining trimethylolpropane by multi-tower series extraction rectification in order to overcome the defects in the prior art.
The invention is realized by the following technical scheme: the invention discloses a method for extracting, rectifying, purifying and refining trimethylolpropane by a multi-tower series connection method, which comprises the steps of rectifying, purifying and refining by utilizing multi-tower series connection and negative pressure reaction in the production of trimethylolpropane by a calcium method, separating light components, and simultaneously utilizing the heat energy of a rectifying system and reacting and treating heavy components by utilizing an acid catalyst so as to obtain trimethylolpropane cyclic formal CTF with economic value;
the method for purifying and refining by extractive distillation specifically comprises the following steps:
(1) Extraction: concentrating the condensed liquid to separate calcium formate to obtain a refined raw material, adding a solvent into the refined raw material to extract an organic phase and a water phase in the refined raw material for separation;
(2) A solvent recovery tower: the temperature of the tower kettle is 180-190 ℃, the temperature of the tower top is 115-125 ℃, and the solvent is recovered;
(3) TMP rectifying tower: adding an acid catalyst into the organic phase without the solvent, feeding the organic phase into a TMP (trimethylolpropane) rectifying tower, treating high-boiling-point impurities at the tower kettle temperature of 180-190 ℃ and the tower top temperature of 110-130 ℃, separating the CTF obtained by treating the high-boiling-point impurities at high temperature from the tower top, feeding the CTF and light components in the materials into a light component recovery tower together, and feeding the materials in the tower kettle into a TMP main tower;
(4) A main tower: the temperature of the tower kettle is 180-190 ℃, the temperature of the tower top is 110-130 ℃, the material is basically trimethylolpropane, and the content of the trimethylolpropane reaches 99.5 percent by rectification and refining;
(5) Flash tower: the material in the tower bottom in the main tower mainly contains high boiling point impurities and ditrimethylol, contains a small amount of trimethylolpropane, and part of trimethylolpropane is recovered by flash evaporation.
In a preferred embodiment of the present invention, in the extraction in the step (1), the ratio of the purification raw material to the acidic catalyst is 15 to 20. The acidic catalyst is one or more of formic acid, acetic acid, phosphoric acid, hypophosphorous acid, methanesulfonic acid and cation exchange resin.
The tower kettle enters a main tower to recover the trihydroxy, and TMP is extracted from the lateral line of the main tower by reflux; by the rectification mode, the quality of the trimethylolpropane product reaches 99.5 percent, and a small amount of heavy components are obtained by flash evaporation of the tower bottom of the main tower, so that a crude product of the ditrimethylolpropane is obtained.
In the solvent recovery column of the step (2), the temperature of the bottom of the column is 185 ℃ and the temperature of the top of the column is 120 ℃. In the TMP rectifying tower in the step (3), the tower kettle temperature is 185 ℃ and the tower top temperature is 120 ℃. In the main tower in the step (4), the temperature of the tower kettle is 185 ℃ and the temperature of the tower top is 120 ℃.
The method mainly uses equipment comprising a solvent recovery tower for recovering the solvent, a TMP rectifying tower for separating light components, a TMP main tower for improving the quality of the trimethylolpropane and a flash tower for recovering the residual trimethylolpropane.
The invention has the beneficial effects that: the invention discloses a method for refining trimethylolpropane by adopting multi-tower series connection and reactive distillation impurity removal refining, and discloses a method for refining trimethylolpropane by adopting multi-tower series connection and extractive distillation impurity removal. In the production of trimethylolpropane by a calcium method, more high boiling point impurities (heavy components) are generated, a reaction catalytic distillation technology is adopted, and a proper catalyst is selected to remove part of the high boiling point impurities. High boiling point impurity is easy to dissolve in organic solvent, and multiple-tower series technology is adopted, so that the rectification separation efficiency is improved, and the rectification quality of trimethylolpropane is improved. The invention utilizes automatic control to reduce the fluctuation of the rectifying tower, and the quality of the trimethylolpropane obtained by the measures can reach 99.5 percent.
Drawings
FIG. 1 is a flow chart of a trimethylolpropane multi-tower series extraction rectification impurity removal refining method.
Detailed Description
The invention is described in detail below with reference to the figures and the detailed description.
Example 1: as shown in FIG. 1, the extracted organic phase (60 ℃) is firstly passed through a solvent recovery tower, the solvent is recovered at the top of the tower (110 ℃), and the solvent is removed at the bottom of the tower (180 ℃). According to materials, acidic catalyst =15:1 adding an acidic catalyst which is formic acid, acetic acid, phosphoric acid, hypophosphorous acid, methanesulfonic acid, cation exchange resin and the like, entering a TMP (trimethylolpropane) rectifying tower, separating light components in materials at the top of the TMP rectifying tower (at the temperature of 110 ℃) and entering the light component rectifying tower. And (3) decomposing heavy components by reaction at the tower kettle temperature of 180 ℃ in the TMP rectifying tower to obtain CTF, and feeding the CTF into a light component rectifying tower from the tower top for refining. The material reacted by the TMP rectifying tower enters a main tower to recover the trihydroxy products, the temperature at the top of the main tower is 110 ℃, TMP is extracted by the reflux of the lateral line of the main tower, and the quality of the obtained trihydroxy products reaches 99.5 percent. The temperature of the tower kettle of the main tower is 180 ℃, and the flash tower is removed. Heavy components are obtained at the bottom of the flash tower, and the top of the tower is recycled.
Example 2: as shown in fig. 1, the extracted organic phase (72 ℃) firstly passes through a solvent recovery tower, the solvent is recovered at the tower top (115 ℃), the materials are desolventized at the tower bottom (185 ℃), acidic catalysts (formic acid, acetic acid, phosphoric acid, hypophosphorous acid, methanesulfonic acid, cation exchange resin and the like) are added according to the ratio of the materials: acidic catalysts =18, the materials enter a TMP rectifying tower, and light components in the materials are separated at the tower top (125 ℃) and enter a light component rectifying tower. The temperature of the tower kettle is 185 ℃, heavy components are decomposed by reaction to obtain CTF, the CTF enters a light component rectifying tower from the top of the tower to be refined (65% of CTF is extracted from the top of the rectifying tower), the reacted materials enter a main tower to recover trihydroxy, the temperature of the top of the tower is 115 ℃, TMP is extracted from the lateral line of the main tower by reflux, the quality of the obtained trihydroxy product reaches 99.5%, the temperature of the tower kettle is 190 ℃, the TMP is removed from a flash tower to be flashed, the heavy components are obtained, and the top of the tower is recycled.
Example 3: as shown in FIG. 1, the extracted organic phase (90 ℃) is firstly passed through a solvent recovery tower, the solvent is recovered at the top of the tower (125 ℃), and the solvent is removed at the bottom of the tower (190 ℃). According to the material: 1 adding an acidic catalyst which is formic acid, acetic acid, phosphoric acid, hypophosphorous acid, methanesulfonic acid, cation exchange resin and the like, entering a TMP (trimethylolpropane) rectifying tower, separating light components in materials at the top of the TMP rectifying tower (at the temperature of 130 ℃) and entering the light component rectifying tower. And (3) decomposing heavy components by reaction at the tower kettle temperature of 190 ℃ in the TMP rectifying tower to obtain CTF, and feeding the CTF into a light component rectifying tower from the tower top for refining. The material reacted by the TMP rectifying tower enters a main tower to recover the trihydroxy products, the temperature at the top of the main tower is 130 ℃, TMP is extracted by the reflux of the lateral line of the main tower, and the quality of the obtained trihydroxy products reaches 99.5 percent. The temperature of the tower kettle of the main tower is 190 ℃, and the flash tower is removed. Heavy components are obtained at the bottom of the flash tower, and the top of the tower is recycled.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (7)
1. A trimethylolpropane multi-tower series extraction rectification impurity-removing refining method is characterized in that: in the production of trimethylolpropane by a calcium method, a plurality of towers are connected in series and subjected to negative pressure reaction, rectification, impurity removal and refining to separate light components, and meanwhile, the heat energy of a rectification system is utilized, and an acid catalyst is used for reaction treatment of heavy components, so that trimethylolpropane cyclic formal CTF with economic value is obtained;
the method for refining by extraction, rectification, impurity removal and refining specifically comprises the following steps:
(1) And (3) extraction:
concentrating the condensed liquid to separate calcium formate to obtain a refined raw material, adding a solvent into the refined raw material, and separating organic phases such as trimethylolpropane, ditrimethylolpropane and high-boiling-point impurities in the extracted material from a water phase;
(2) A solvent recovery tower:
the extracted organic phase enters a solvent recovery tower, the temperature of the tower kettle is 180-190 ℃, the temperature of the tower top is 115-125 ℃, and the solvent is recovered;
(3) TMP rectifying tower:
adding an acid catalyst into the material after the solvent is removed, feeding the material into a TMP rectifying tower, wherein the tower kettle temperature is 180-190 ℃, the tower top temperature is 110-130 ℃, treating high-boiling-point impurities at high temperature to obtain CTF, separating the CTF and light components in the material from the tower top, feeding the CTF and the light components in the material into a light component recovery tower, and feeding the material in the tower kettle into a TMP main tower;
(4) A main tower:
the temperature of the tower kettle is 180-190 ℃, the temperature of the tower top is 110-130 ℃, the material is basically trimethylolpropane, and the trimethylolpropane is refined by rectification, so that the content reaches 99.5%;
(5) Flash tower:
the material in the main tower is mainly high boiling point impurity and ditrimethylol, contains a small amount of trimethylolpropane, and part of trimethylolpropane is recovered by flash evaporation.
2. The method for purifying trimethylolpropane by multi-tower series extraction rectification according to claim 1 is characterized in that: in the extraction in the step (1), the ratio of the material after solvent removal to the acid catalyst is 15-20.
3. The trimethylolpropane multi-tower series extraction rectification impurity-removing refining method according to claim 1 or 2, characterized in that: the acidic catalyst is one or more of formic acid, acetic acid, phosphoric acid, hypophosphorous acid, methanesulfonic acid and cation exchange resin.
4. The trimethylolpropane multi-tower series extraction rectification impurity-removing refining method according to claim 1 or 2, characterized in that: the tower kettle enters a main tower to recover the trihydroxy, and TMP is extracted from the lateral line of the main tower by reflux; by the rectification mode, the quality of the trimethylolpropane product reaches 99.5 percent, and a small amount of heavy components are obtained by flash evaporation of the tower bottom of the main tower, so that a crude product of the ditrimethylolpropane is obtained.
5. The trimethylolpropane multi-tower series extraction rectification impurity-removing refining method according to claim 1 or 2, characterized in that: in the solvent recovery tower in the step (2), the temperature of a tower kettle is 185 ℃ and the temperature of a tower top is 120 ℃.
6. The trimethylolpropane multi-tower series extraction rectification impurity-removing refining method according to claim 1 or 2, characterized in that: in the TMP rectifying tower in the step (3), the tower kettle temperature is 185 ℃ and the tower top temperature is 120 ℃.
7. The method for purifying and refining trimethylolpropane by multi-tower series extraction and rectification according to claim 1 or 2 is characterized in that: in the main tower in the step (4), the temperature of the tower kettle is 185 ℃ and the temperature of the tower top is 120 ℃.
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