CN113372214A - Continuous rectification process of F112 - Google Patents
Continuous rectification process of F112 Download PDFInfo
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- CN113372214A CN113372214A CN202110617145.6A CN202110617145A CN113372214A CN 113372214 A CN113372214 A CN 113372214A CN 202110617145 A CN202110617145 A CN 202110617145A CN 113372214 A CN113372214 A CN 113372214A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
Abstract
The invention discloses a continuous rectification process of F112, which comprises the following preparation steps: s10), conveying the F112 coarse material into a continuous rectifying tower, wherein the F112 coarse material comprises Cl2HCl, F132b, F132a, F122b, F112; s20) and F112 coarse materials are subjected to mass transfer and heat transfer through vapor-liquid contact in a continuous rectifying tower to achieve the separation of light and heavy components; s30) and F112 are taken out as heavy phase components through a tower kettle, and Cl is obtained2HCl, F132b, F132a, F122b were withdrawn through the top of the column by the light phase component; the invention can completely replace the original batch rectification mode, obviously improve the productivity of F112, simultaneously improve the production automation degree and the production efficiency, and greatly reduce the energy consumption in the rectification process.
Description
Technical Field
The invention belongs to the field of synthesis and preparation of trifluoroacetic acid, and particularly relates to a continuous rectification process of F112.
Background
Trifluoroacetic acid is an important organic synthesis reagent from which various fluorine-containing compounds, pesticides and dyes can be synthesized, and is also a catalyst for esterification and condensation reactions. The commonly used synthesis route of trifluoroacetic acid in the prior art mainly adopts a technical route that trifluoropropene is oxidized by potassium permanganate or a technical route that acetic acid, hydrofluoric acid, sodium fluoride and the like are electrochemically fluorinated and then hydrolyzed, and the preparation cost of the trifluoroacetic acid is directly high due to the higher cost of the trifluoropropene. The traditional electrolysis process has high power consumption, is only suitable for small-scale production and is difficult to carry out industrial scale production.
The existing F142b high-boiling-point substance is taken as a raw material by our company, and trifluoroacetic acid is prepared by adopting a self-developed production process from the perspective of recycling economy, so that the product quality and the production cost both achieve excellent levels. Wherein, F112 is an important intermediate product in the production process of trifluoroacetic acid of our company, and the main process comprises the following steps: f142b high-boiling-point substance reacts after photochlorination to obtain F112 coarse material, the intermittent rectification mode is adopted to purify to 99.5% at present, F122 and F132 are purified firstly, and finally F112 distillation is carried out, the operation parameter control change is large, the automation degree is low, one-kettle distillation can be completed within 1 day, and the time is long; and because the boiling point of F112 is 91 ℃, the energy consumption in the rectification process is higher.
Therefore, the applicant wishes to seek a solution for the improved optimization of the rectification process of F112.
Disclosure of Invention
In view of this, the present invention provides a continuous rectification process for F112, which can completely replace the original batch rectification method, significantly improve the productivity of F112, simultaneously improve the production automation degree and production efficiency, and greatly reduce the energy consumption in the rectification process.
The technical scheme adopted by the invention is as follows:
a continuous rectification process of F112, wherein the F112 is 1, 1, 1-trichloro-22-difluoroethane, comprising the following preparation steps of:
s10), conveying the F112 coarse material into a continuous rectifying tower, wherein the F112 coarse material comprises Cl2、HCl、F132b、F132a、F122、F122b、F112；
S20) and F112 coarse materials are subjected to mass transfer and heat transfer through vapor-liquid contact in the continuous rectifying tower, so that the separation of light and heavy components is realized;
s30) and F112 are taken out as heavy phase components through a tower kettle, and Cl is obtained2HCl, F132b, F132a, F122b were withdrawn overhead by the light phase components.
Preferably, in the step S30), an overhead condenser is connected to the tower top, the overhead vapor is condensed by the overhead condenser to form a condensed liquid phase and a noncondensable gas phase, one path of the condensed liquid phase is refluxed to the tower top through a reflux tank, and the other path of the condensed liquid phase is taken out as the light phase component through the tower top.
Preferably, the heat exchange area of the overhead condenser ranges from 8 m to 10m2。
Preferably, in the step S20), a kettle reboiler is connected to the kettle, the kettle material is conveyed to the kettle reboiler through a kettle circulating pump, the kettle material is gasified and evaporated by the kettle reboiler to form a gas phase, and the gas phase is returned to the kettle.
Preferably, the heat exchange area of the tower kettle reboiler ranges from 3 m to 5m2。
Preferably, liquid phase distributors are respectively arranged above the feeding hole of the continuous rectifying tower, at the extraction hole of the tower bottom and at the joint of each section of tower section.
Preferably, a liquid phase distributor is arranged at the reflux position of the tower top.
Preferably, the continuous rectifying tower adopts 316L wire mesh corrugated packing, and the tower diameter is designed to be DN400 according to the packing factor.
Preferably, the number of the plates of the continuous rectifying tower is 48-52, the tower top temperature is set at 70 +/-3, the tower bottom temperature is set at 91 +/-4 ℃, and the tower top pressure is set at 100 +/-6 KPa.
Preferably, the F112 crude material is obtained by performing photochlorination synthesis reaction on the F142b high-boiling substance; f142b referred to throughout this application refers specifically to difluoromonochloroethane HCFC-142 b.
For the sake of reducing exposition, the components in the F112 crude material are denoted by reference numerals, and the proportional relationship, related features and the relationship between the components and the reference numerals in the F112 crude material are shown in the following table:
the invention provides a method for rectifying and purifying F112 coarse material by adopting a single set of continuous rectifying tower, and experimental verification proves that the method can completely replace the original batch rectifying mode, the productivity is increased from 1500t/a to 2100t/a, the productivity is improved by 40%, the production automation degree and the production efficiency are improved, and the energy consumption in the rectifying process is greatly reduced; therefore, the method also improves the treatment capacity of the F142b high-boiling-point substances, reduces the waste of fluorine resources, improves the recovery rate of the fluorine resources, reduces the environmental damage and pollution caused by the large volatilization of the fluorine resources in the atmosphere as a solvent, improves the yield of products, and reduces the consumption of raw materials and the production cost.
Drawings
FIG. 1 is a block diagram of the steps of a continuous rectification process for F112 in accordance with an embodiment of the present invention;
fig. 2 is a schematic structural view of a continuous rectification column T101 in the embodiment of the present invention.
Detailed Description
The embodiment of the invention discloses a continuous rectification process of F112, wherein the F112 is 1, 1, 1-trichloro-22-difluoroethane, and the continuous rectification process comprises the following preparation steps:
s10), conveying the F112 coarse material into a continuous rectifying tower, wherein the F112 coarse material comprises Cl2、HCl、F132b、F132a、F122、F122b、F112；
S20) and F112 coarse materials are subjected to mass transfer and heat transfer through vapor-liquid contact in a continuous rectifying tower to achieve the separation of light and heavy components;
s30) and F112 are taken out as heavy phase components through a tower kettle, and Cl is obtained2HCl, F132b, F132a, F122b are extracted from the light phase component through the top of the towerAnd (6) discharging.
In order to make those skilled in the art better understand the technical solution of the present invention, the technical solution in the embodiment of the present invention will be clearly and completely described below with reference to the drawings in the embodiment of the present invention, and it is obvious that the described embodiment is only a part of the embodiment of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1 in combination with fig. 2, a continuous rectification process for F112, wherein F112 is 1, 1, 1-trichloro-22-difluoroethane, includes the following steps:
s10), conveying the F112 coarse material into a continuous rectifying tower T101, preferably, in the embodiment, the F112 coarse material is obtained by photochlorination synthesis reaction of F142b high-boiling residues, and the F112 coarse material comprises C12、HCl、F132b、F132a、F122、F122b、F112；
Specifically, in the present embodiment, the photochlorination synthesis reaction is divided into addition photochlorination and hydrogen abstraction photochlorination, and the photochlorination of high boiling substances follows the hydrogen abstraction photochlorination mechanism. Chlorine radical first generates F142 radical by hydrogen atom on C-H, then chlorine gas and F142 radical generate F132 chain reaction, each element of the process is as follows:
Cl2→2Cl· (1)；
CH2ClCHF2+Cl·→CF2HCHCl…·H…Cl→CHCHF2·+HCl (2)；
CHClCHF2·+Cl2→C F2HCHCl…Cl…Cl→CF2HCHCl2+Cl· (3)。
followed by hydrogen abstraction photochlorination to yield F122.
S20) and F112 coarse materials are subjected to mass transfer and heat transfer through vapor-liquid contact in the continuous rectifying tower T101 to achieve the separation of light and heavy components; preferably, in the step S20), the tower V101 is connected to a tower reboiler E101, and the tower material is conveyed to the tower reboiler E101 by a tower circulating pump P102A/B (specifically, the tower circulating pump P102A/B)Adopting a falling film reboiler), gasifying and evaporating tower bottom materials through a tower bottom reboiler E101 to form a gas phase, and returning and conveying the gas phase to a tower bottom V101; the range of the heat exchange area of the tower kettle reboiler E101 is 3-5m2；
S30) and F112 as heavy phase components are extracted from a tower kettle V101 and are connected into an F112 finished product tank V103 and Cl2The HCl, F132b, F132a, F122 and F122b are extracted from the top of the tower through light phase components and are connected to a light component collecting tank; preferably, in the step S30), the tower top is connected with a tower top condenser E102, the tower top steam is condensed by the tower top condenser E102 to form a condensed liquid phase and an uncondensed gas phase respectively, one path of the condensed liquid phase is refluxed to the tower top by the reflux tank V102, and the other path is extracted as a light phase component through the tower top; the heat exchange area range of the overhead condenser E102 is 8-10m2。
Preferably, in the present embodiment, in order to facilitate vapor-liquid contact mass transfer and heat transfer effects, liquid phase distributors are respectively arranged above the feed inlet of the continuous rectification column T101, at the discharge outlet of the column bottom V101, at the connection of each section of the column, and at the reflux position of the column top.
Preferably, in the embodiment, the continuous rectification column T101 adopts 316L wire mesh corrugated packing, and the column diameter is designed to be DN400 according to the packing factor; the number of the trays of the continuous rectifying tower T101 is 48-52, the temperature of the tower top is set to be 70 +/-3, the temperature of the tower bottom V101 is set to be 91 +/-4 ℃, and the pressure of the tower top is set to be 100 +/-6 KPa.
More specifically, preferably, the parameters specifically adopted by the continuous rectification column T101 in this embodiment are shown in the following table:
further, the heat exchange area of the overhead condenser E102 was 9m2And the heat exchange area of the tower kettle reboiler E101 is 3.9m2。
In this embodiment, the separation principle of the F112 continuous rectification is a known rectification principle, and a known structure related to a continuous rectification column specifically adopted by the separation principle can be directly referred to as fig. 2, and the known structure shown in this embodiment is not described in an expanded text one by one; the specific idea of the embodiment is that different materials have different volatilities under the same pressure and temperature, so that when vapor-liquid equilibrium is realized, the gas phase and the liquid phase have different compositions, and the separation of light and heavy components is finally realized through multiple vapor-liquid contact mass transfer and heat transfer; through detection, the purity of the target product F112 extracted from the tower bottom reaches 99.5 wt%, and the purity of the F112 in the F112 coarse material is 60-80 wt%.
In the embodiment, a single set of continuous rectifying tower is adopted to carry out rectification and purification on the F112 coarse material, and experiments prove that the embodiment of the invention can completely replace the original intermittent rectification mode, the productivity is increased from 1500t/a to 2100t/a, the productivity is improved by 40%, the production automation degree and the production efficiency are improved, and the energy consumption in the rectification process is greatly reduced; therefore, the method also improves the treatment capacity of the F142b high-boiling-point substances, reduces the waste of fluorine resources, improves the recovery rate of the fluorine resources, reduces the environmental damage and pollution caused by the large volatilization of the fluorine resources in the atmosphere as a solvent, improves the yield of products, and reduces the consumption of raw materials and the production cost.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (10)
1. A continuous rectification process of F112, wherein the F112 is 1, 1, 1-trichloro-22-difluoroethane, which is characterized by comprising the following preparation steps:
s10), conveying the F112 coarse material into a continuous rectifying tower, wherein the F112 coarse material comprises Cl2、HCl、F132b、F132a、F122、F122b、F112；
S20) and F112 coarse materials are subjected to mass transfer and heat transfer through vapor-liquid contact in the continuous rectifying tower, so that the separation of light and heavy components is realized;
s30) and F112 are taken out as heavy phase components through a tower kettle, and Cl is obtained2HCl, F132b, F132a, F122b were withdrawn overhead by the light phase components.
2. The continuous rectification process as claimed in claim 1, wherein in the step S30), an overhead condenser is connected to the tower top, the overhead vapor is condensed by the overhead condenser to form a condensed liquid phase and a noncondensable gas phase, one path of the condensed liquid phase is refluxed to the tower top through a reflux tank, and the other path of the condensed liquid phase is taken out as the light phase component through the tower top.
3. The continuous rectification process as claimed in claim 2, wherein the heat exchange area of the overhead condenser is in the range of 8-10m2。
4. The continuous rectification process as claimed in claim 1, wherein in the step S20), a kettle reboiler is connected to the kettle, the kettle material is conveyed to the kettle reboiler through a kettle circulating pump, and the kettle material is gasified and evaporated by the kettle reboiler to form a gas phase and is conveyed back to the kettle.
5. The continuous rectification process as claimed in claim 4, wherein the heat exchange area of the kettle reboiler is in the range of 3-5m2。
6. The continuous rectification process as claimed in claim 1, wherein liquid phase distributors are respectively arranged above the feed inlet of the continuous rectification tower, at the outlet of the tower kettle and at the joint of each section of the tower section.
7. The continuous rectification process as claimed in claim 2, wherein a liquid phase distributor is provided at the top reflux.
8. The continuous rectification process as claimed in claim 1, wherein the continuous rectification column adopts 316L wire mesh corrugated packing, and the column diameter is designed to be DN400 according to the packing factor.
9. The continuous rectification process as claimed in claim 1 or 8, wherein the number of plates of the continuous rectification column is 48-52, the temperature of the top of the column is set at 70 plus or minus 3, the temperature of the bottom of the column is set at 91 plus or minus 4 ℃, and the pressure of the top of the column is set at 100 plus or minus 6 KPa.
10. The continuous rectification process as claimed in claim 1, wherein the F112 crude material is obtained from F142b high boiling substance after photochlorination synthesis reaction.
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| CN102766017A (en) * | 2012-07-31 | 2012-11-07 | 山东华安新材料有限公司 | Preparation method of tetrachloro-1,2-difluoroethane |
| CN103524325A (en) * | 2013-10-14 | 2014-01-22 | 常熟振氟新材料有限公司 | Preparation method of trifluoroacetic acid |
| CN107056581A (en) * | 2017-05-22 | 2017-08-18 | 山东东岳化工有限公司 | The separation method of the high-boiling components of the Difluoroethane production technology of 1 chlorine 1,1 |
| CN110963884A (en) * | 2019-12-16 | 2020-04-07 | 上海三爱富新材料科技有限公司 | Preparation method of 1,1,1, 2-tetrachloro-2, 2-difluoroethane |
| CN112537997A (en) * | 2020-12-09 | 2021-03-23 | 威海新元化工有限公司 | Method and device for co-production of 3,3, 3-trifluoropropene and 2-chloro-3, 3, 3-trifluoropropene |
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2021
- 2021-06-03 CN CN202110617145.6A patent/CN113372214A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102766017A (en) * | 2012-07-31 | 2012-11-07 | 山东华安新材料有限公司 | Preparation method of tetrachloro-1,2-difluoroethane |
| CN103524325A (en) * | 2013-10-14 | 2014-01-22 | 常熟振氟新材料有限公司 | Preparation method of trifluoroacetic acid |
| CN107056581A (en) * | 2017-05-22 | 2017-08-18 | 山东东岳化工有限公司 | The separation method of the high-boiling components of the Difluoroethane production technology of 1 chlorine 1,1 |
| CN110963884A (en) * | 2019-12-16 | 2020-04-07 | 上海三爱富新材料科技有限公司 | Preparation method of 1,1,1, 2-tetrachloro-2, 2-difluoroethane |
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