CN112499590B - Process and apparatus for producing anhydrous hydrogen fluoride - Google Patents
Process and apparatus for producing anhydrous hydrogen fluoride Download PDFInfo
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- CN112499590B CN112499590B CN202011344281.4A CN202011344281A CN112499590B CN 112499590 B CN112499590 B CN 112499590B CN 202011344281 A CN202011344281 A CN 202011344281A CN 112499590 B CN112499590 B CN 112499590B
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Abstract
The invention discloses a process and a device for producing anhydrous hydrogen fluoride, wherein the process comprises the following steps: 1) Extracting agent straight-chain primary alcohol C n H 2n+2 OH、H 2 Introducing the O-HF azeotrope into a continuous extraction tower, and extracting H by an extracting agent 2 O-HF azeotropyIn the product, hydrogen fluoride obtains an extract phase at the top of the continuous extraction tower, n is more than or equal to 8 and less than or equal to 10, and n is an integer; 2) Introducing the extract phase into a first-stage rectifying tower for rectification; 3) And introducing the first-stage tower top distillate into a second-stage rectifying tower for rectification to obtain a second-stage tower top distillate at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride. The invention utilizes the characteristics of extremely low solubility of the linear primary alcohol in water and the interaction between the linear primary alcohol and HF, and the extraction phase and the raffinate phase after extraction operation are easy to treat, so that the whole process flow has the advantages of simplicity, high efficiency, environmental protection, and reduction of investment and operation cost in the recycling process of producing anhydrous HF.
Description
Technical Field
The invention belongs to the technical field of HF separation and recycling, and particularly relates to a process and a device for producing anhydrous hydrogen fluoride.
Background
With the development of the production process in the electronics industry and the fluorine chemical industry, the demand for Anhydrous Hydrogen Fluoride (AHF) is increasing. The existing method for producing AHF by fluorite method has great environmental pollution and is an unsustainable process. Thus, how to derive H from industrial processes 2 The production of AHF in an O-HF azeotrope (or mixture) is a hot spot of current interest. The following methods are reported in the literature: concentrated sulfuric acid extractive distillation method and pressure swingRectification, n-hexane stripping, electrodialysis, etc. The concentrated sulfuric acid extractive distillation method has simple process, but has high corrosivity in long-term operation and high requirements on equipment materials; the principle of pressure swing distillation is based on the effect of pressure change on the azeotropic point of the system, but due to H 2 The O-HF system has low sensitivity to pressure change and can be realized only by needing larger pressure difference, so the operation cost is obviously increased; the n-hexane stripping method requires a large amount of n-hexane to be recycled, and the operation cost is too high; the electrodialysis method is simple to operate, but the quality standard of AHF is difficult to achieve at one time, and for H 2 The treatment efficiency of the O-HF azeotrope is low.
Several of the above-mentioned derivatives H 2 The process method for producing AHF in O-HF azeotrope has the defects of high operation cost, high operation difficulty and the like, and is not widely applied in the industrial production process.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process and a device for producing anhydrous hydrogen fluoride aiming at the defects in the prior art, wherein an extracting agent is easy to react with HF and H in the extraction and rectification processes 2 O is separated, so that the production process of Anhydrous Hydrogen Fluoride (AHF) with simple flow, convenient operation and low running cost is formed.
The technical scheme adopted for solving the technical problem of the invention is to provide a process for producing anhydrous hydrogen fluoride, which comprises the following steps:
1) Extracting agent straight-chain primary alcohol C n H 2n+2 OH、H 2 Introducing the O-HF azeotrope into a continuous extraction tower, and extracting H by an extracting agent 2 Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10 and is an integer;
2) Introducing the extract phase into a first-stage rectifying tower for rectification, and obtaining a first-stage tower top distillate at the tower top of the first-stage rectifying tower, wherein the first-stage tower top distillate comprises hydrogen fluoride and water, and obtaining a first-stage tower bottom at the tower bottom of the first-stage rectifying tower, wherein the first-stage tower bottom comprises linear primary alcohol C n H 2n+2 OH; this step is from H 2 Separating the extracting agent in an O-HF-extracting agent ternary system.
3) Introducing the primary tower top distillate into a secondary rectifying tower for rectification to obtain a secondary tower top distillate at the tower top of the secondary rectifying tower, wherein the secondary tower top distillate comprises anhydrous hydrogen fluoride, and a secondary tower bottom is obtained at the tower bottom of the secondary rectifying tower, wherein the secondary tower bottom comprises H 2 The O-HF azeotrope. This step separates hydrogen fluoride and water.
The extraction rate of HF in the extraction phase at the top of the continuous extraction tower in the step 1) is more than or equal to 99.5 percent. The content of HF in raffinate phase at the bottom of the continuous extraction tower is less than or equal to 0.2wt%, and the content of straight-chain primary alcohol is less than or equal to 0.05wt%, and the raffinate phase can be directly used as wastewater for treatment.
And 2) removing the linear primary alcohol of the extractant in the first-stage rectifying tower in the step 2) so as to recycle the extractant.
The second stage of the rectifying tower in the step 3) mainly processes H 2 Separating O and HF, and producing industrial AHF product at the tower top.
Preferably, the linear primary alcohols C n H 2n+2 OH is primary alcohol n-octanol, and n =8.
Preferably, the linear primary alcohols C n H 2n+2 OH is n-nonanol or n-decanol.
Preferably, the temperature in the continuous extraction tower in the step 1) is 5-35 ℃, and the pressure is 0.81325-1.21325 bar.
Preferably, the following step m) is further included after the step 2): and introducing the first-stage tower bottom into a continuous extraction tower for recycling.
In the step 2), the first-stage rectifying tower adopts a packed tower, the number of effective tower plates is 14-17, the position of a feed plate is 7-8, and the reflux ratio is 1.5-2.0.
In the step 3), the second-stage rectifying tower adopts a packed tower, the number of effective tower plates is 14-16, the position of a feed plate is 5-6, and the reflux ratio is 1.8-2.1.
Preferably, the following step n) is further included after the step 3): and (4) introducing the secondary tower bottom into a continuous extraction tower for retreatment.
Preferably, the extractant and H in the step 1) 2 O-HF azeotropes inCountercurrent contact is carried out in the continuous extraction tower.
The invention also provides a device for producing anhydrous hydrogen fluoride, which comprises:
a continuous extraction tower for introducing linear primary alcohol C of an extractant n H 2n+2 OH、H 2 O-HF azeotrope, extraction of H by extractant 2 Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10 and is an integer;
the first-stage rectifying tower is connected with the continuous extraction tower, the extract phase enters the first-stage rectifying tower for rectification, a first-stage tower top distillate is obtained at the tower top of the first-stage rectifying tower, the first-stage tower top distillate comprises hydrogen fluoride and water, a first-stage tower bottom is obtained at the tower bottom of the first-stage rectifying tower, and the first-stage tower bottom comprises linear primary alcohol C n H 2n+2 OH；
A second-stage rectifying tower connected with the tower top outlet of the first-stage rectifying tower, wherein the first-stage tower top distillate is introduced into the second-stage rectifying tower for rectification, and a second-stage tower top distillate is obtained at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride, and a second-stage tower bottom is obtained at the tower bottom of the second-stage rectifying tower, wherein the second-stage tower bottom comprises H 2 The O-HF azeotrope.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: the inlet of the first heat exchanger is connected with the outlet of the top of the continuous extraction tower, the outlet of the first heat exchanger is connected with the inlet of the first-stage rectifying tower, and the first heat exchanger is used for heating the extraction phase discharged from the top of the continuous extraction tower.
Preferably, in the device for producing anhydrous hydrogen fluoride, the outlet of the bottom of the first-stage rectifying tower is connected with the inlet of the continuous extraction tower.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: and the inlet of the second heat exchanger is connected with the outlet of the tower bottom of the first-stage rectifying tower, the outlet of the second heat exchanger is connected with the inlet of the continuous extraction tower, and the second heat exchanger is used for cooling the first-stage tower bottom discharged from the tower bottom of the first-stage rectifying tower.
Preferably, in the device for producing anhydrous hydrogen fluoride, the outlet of the second-stage rectifying tower is connected with the inlet of the continuous extraction tower.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: and an inlet of the third heat exchanger is connected with an outlet at the bottom of the second-stage rectifying tower, an outlet of the third heat exchanger is connected with an inlet of the continuous extraction tower, and the third heat exchanger is used for cooling a second-stage tower bottom discharged from the bottom of the second-stage rectifying tower.
The invention provides a process for producing Anhydrous Hydrogen Fluoride (AHF), which is characterized in that primary alcohol C based on linear chain is introduced n H 2n+2 OH (n is more than or equal to 8 and less than or equal to 10, n is an integer) is used as an extracting agent, and H is extracted by continuous extraction 2 HF in the O-HF azeotrope is transferred to the extraction phase and the extractant is removed in a rectification process to obtain AHF meeting the requirement of industrial first-grade product. With the existing various slaves H 2 Unlike the O-HF azeotrope process for AHF production, in the present invention linear primary alcohol C is used n H 2n+2 OH (n is more than or equal to 8 and less than or equal to 10, n is an integer) to H 2 The extraction of the O-HF azeotrope has the following characteristics: (1) Compared with sulfuric acid as extractant, linear primary alcohol C n H 2n+2 OH has no corrosiveness, low requirement on equipment materials, low toxicity and environmental friendliness; n-octanol has a very low hydroxyl activity compared to alcohols based on cycloalkanes or arenes, and does not react with HF during the whole process. (2) Compared with extracting agents such as sulfuric acid, benzyl alcohol and the like, the linear primary alcohol C n H 2n+2 The OH has extremely low solubility in water, and the solubility of n-octanol at 20 ℃ is only 0.05% (5 g/100 gH) 2 O) to facilitate reaction with HF and H during extraction and rectification 2 And O is separated, so that the AHF production process with simple flow, convenient operation and low running cost is formed.
The innovation of the invention is that: using linear primary alcohols C n H 2n+2 The characteristic that OH (n is an integer more than or equal to 8 and less than or equal to 10) has extremely low solubility in water and the characteristic that OH interacts with HF, the extraction and rectification are utilized to extract H 2 A process for producing AHF from an O-HF azeotrope. Due to the linear primary alcohols C n H 2n+2 OH (n is more than or equal to 8 and less than or equal to 10, n is an integer) is different from the characteristics of sulfuric acid and other naphthenic alcohol and aromatic alcohol, and an extraction phase and a raffinate phase after extraction operation are easy to treat, so that the whole process flow has the advantages of simplicity, high efficiency, environmental protection, and reduction of investment and operation cost in the recycling process of producing anhydrous HF.
Drawings
FIG. 1 is a schematic configuration diagram of an apparatus for producing anhydrous hydrogen fluoride according to example 2 of the present invention.
In the figure: 1-continuous extraction column; 2-a first stage rectification column; 3-a second-stage rectifying tower; 4-a first heat exchanger; 5-a second heat exchanger; 6-third heat exchanger.
Detailed Description
In order to make the technical solutions of the present invention better understood, the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Reference will now be made in detail to embodiments of the present patent, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative only for the purpose of explaining the present patent and are not to be construed as limiting the present patent.
Example 1
This example provides a process for producing anhydrous hydrogen fluoride, comprising the steps of:
1) Extracting agent straight-chain primary alcohol C n H 2n+2 OH、H 2 Introducing the O-HF azeotrope into a continuous extraction tower, and extracting H by an extracting agent 2 Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extraction phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10 and is an integer;
2) Introducing the extract phase into a first-stage rectifying tower for rectification to obtain a first-stage tower top distillate at the tower top of the first-stage rectifying tower, wherein the first-stage tower top distillate comprises hydrogen fluoride and water, and the first-stage tower top distillate is obtained at the first-stage rectifying towerObtaining primary tower bottom from the tower bottom, wherein the primary tower bottom comprises linear primary alcohol C n H 2n+2 OH; this step is from H 2 Separating the extracting agent in an O-HF-extracting agent ternary system.
3) Introducing the first-stage tower top distillate into a second-stage rectifying tower for rectification to obtain a second-stage tower top distillate at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride, and a second-stage tower bottom is obtained at the tower bottom of the second-stage rectifying tower, wherein the second-stage tower bottom comprises H 2 The O-HF azeotrope. This step separates hydrogen fluoride and water.
The extraction rate of HF in the extraction phase at the top of the continuous extraction tower in the step 1) is more than or equal to 99.5 percent. The content of HF in raffinate phase at the bottom of the continuous extraction tower is less than or equal to 0.2wt%, and the content of straight-chain primary alcohol is less than or equal to 0.05wt%, and the raffinate phase can be directly used as wastewater for treatment.
And 2) removing the linear primary alcohol of the extractant in the first-stage rectifying tower in the step 2) so as to recycle the extractant.
The second stage rectifying tower in the step 3) is mainly used for treating H 2 Separating O and HF, and producing industrial AHF product at the tower top.
The present embodiment also provides an apparatus for producing anhydrous hydrogen fluoride, which is used in the above method, including:
a continuous extraction tower for introducing linear primary alcohol C of an extractant n H 2n+2 OH、H 2 O-HF azeotrope, extraction of H by extractant 2 Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10 and is an integer;
the first-stage rectifying tower is connected with the continuous extraction tower, an extract phase enters the first-stage rectifying tower for rectification, first-stage tower top distillate is obtained at the tower top of the first-stage rectifying tower, the first-stage tower top distillate comprises hydrogen fluoride and water, first-stage tower bottom is obtained at the tower bottom of the first-stage rectifying tower, and the first-stage tower bottom comprises linear primary alcohol C n H 2n+2 OH；
A second stage rectification tower connected with the tower top outlet of the first stage rectification tower, wherein the distillate at the tower top of the first stage rectification tower is introduced into the second stage rectification towerRectifying in the tower to obtain secondary tower top distillate at the tower top of the second-stage rectifying tower, wherein the secondary tower top distillate comprises anhydrous hydrogen fluoride, and obtaining secondary tower bottom at the tower bottom of the second-stage rectifying tower, wherein the secondary tower bottom comprises H 2 The O-HF azeotrope.
The process for producing anhydrous hydrogen fluoride in this example utilizes a linear primary alcohol C n H 2n+2 The characteristic that OH (n is more than or equal to 8 and less than or equal to 10 and n is an integer) has extremely low solubility in water and the characteristic that OH interacts with HF, the extraction and rectification are utilized to extract H 2 A process for producing AHF from an O-HF azeotrope. Due to the linear primary alcohols C n H 2n+2 OH (n is more than or equal to 8 and less than or equal to 10, n is an integer) is different from the characteristics of sulfuric acid and other naphthenic alcohol and aromatic alcohol, and an extraction phase and a raffinate phase after extraction operation are easy to treat, so that the whole process flow has the advantages of simplicity, high efficiency, environmental protection, and reduction of investment and operation cost in the recycling process of producing anhydrous HF.
Example 2
As shown in fig. 1, the present embodiment provides an apparatus for producing anhydrous hydrogen fluoride, comprising:
a continuous extraction tower 1, and an S1 stream H is introduced through the top inlet of the continuous extraction tower 1 2 Introducing an O-HF azeotrope into a linear primary alcohol C of an S2 stream extractant through a tower bottom inlet of a continuous extraction tower 1 n H 2n+2 OH, extracting H by an extractant 2 Hydrogen fluoride in the O-HF azeotrope is used for obtaining an S3 stream raffinate phase at the bottom outlet of the continuous extraction tower 1 and an S4 stream extract phase at the top outlet of the continuous extraction tower 1, wherein n is more than or equal to 8 and less than or equal to 10 and is an integer;
the first-stage rectifying tower 2 is connected with the continuous extraction tower 1, an S4 stream extract phase enters the first-stage rectifying tower 2 for rectification, an S5 stream first-stage tower top distillate is obtained at the tower top outlet of the first-stage rectifying tower 2, the first-stage tower top distillate comprises hydrogen fluoride and water, an S6 stream first-stage tower bottom is obtained at the tower bottom outlet of the first-stage rectifying tower 2, and the first-stage tower bottom comprises linear primary alcohol C n H 2n+2 OH；
A second stage rectification column 3 and a top outlet of the first stage rectification column 2Connecting, introducing the S5 stream primary tower top distillate into a second-stage rectifying tower 3 for rectification, obtaining an S7 stream secondary tower top distillate at the tower top outlet of the second-stage rectifying tower 3, wherein the secondary tower top distillate comprises anhydrous hydrogen fluoride, obtaining an S8 stream secondary tower bottom at the tower bottom outlet of the second-stage rectifying tower 3, and the secondary tower bottom comprises H 2 The O-HF azeotrope.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: an inlet of the first heat exchanger 4 is connected with an outlet at the top of the continuous extraction tower 1, an outlet of the first heat exchanger 4 is connected with an inlet of the first-stage rectifying tower 2, and the first heat exchanger 4 is used for heating an extraction phase discharged from the top of the continuous extraction tower 1.
Preferably, in the device for producing anhydrous hydrogen fluoride, the bottom outlet of the first-stage rectifying tower 2 is connected with the inlet of the continuous extraction tower 1.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: and an inlet of the second heat exchanger 5 is connected with an outlet at the bottom of the first-stage rectifying tower 2, an outlet of the second heat exchanger 5 is connected with an inlet of the continuous extraction tower 1, and the second heat exchanger 5 is used for cooling a first-stage tower bottom discharged from the bottom of the first-stage rectifying tower 2.
Preferably, in the apparatus for producing anhydrous hydrogen fluoride, the outlet of the second-stage rectifying column 3 is connected to the inlet of the continuous extraction column 1.
Preferably, the apparatus for producing anhydrous hydrogen fluoride further comprises: and an inlet of the third heat exchanger 6 is connected with an outlet at the bottom of the second-stage rectifying tower 3, an outlet of the third heat exchanger 6 is connected with an inlet of the continuous extraction tower 1, and the third heat exchanger 6 is used for cooling a second-stage tower bottom discharged from the bottom of the second-stage rectifying tower 3.
The embodiment provides a process for producing anhydrous hydrogen fluoride by using the device, which comprises the following steps:
1) Extracting linear primary alcohol C of an S2 stream extractant under the conditions of normal temperature and normal pressure n H 2n+2 OH, S1 stream H 2 Introducing the O-HF azeotrope into a continuous extraction tower 1, and extracting with linear primary alcohol C n H 2n+2 OH is formed by continuousThe top of the extraction tower 1 enters into the extraction tower H 2 The O-HF azeotrope enters from the bottom of a continuous extraction tower 1, wherein n =8, and the extracting agent is n-octanol.
The stream S1 of material is H 2 O-HF azeotrope with a treatment capacity of 1100kg/hr, HF content of 37.2wt%, temperature of 20 ℃ and pressure of 1.1bar.
The stream S2 was an extractant, n-octanol, at a flow rate of 1500kg/hr, a temperature of 20 ℃ and a pressure of 1.1bar.
Extraction of H by means of an extractant 2 Hydrogen fluoride in the O-HF azeotrope, streams S1 and S2 are in countercurrent contact in a continuous extraction tower 1, an extract phase (an alcohol phase) is obtained at the top of the continuous extraction tower 1, and a raffinate phase (a water phase) is obtained at the bottom of the continuous extraction tower 1. The continuous extraction tower 1 adopts a sieve plate tower, the number of tower plates is 22, and the operation is carried out under the conditions of normal temperature and normal pressure. In stream S4 extracted from the top of the continuous extraction tower 1, the n-octanol content is 1499.7kg/hr, the HF content is 407.5kg/hr, and the H content is 2 O was 103.5kg/hr. H in stream S3 extracted from the bottom of the continuous extraction column 1 2 587.3kg/hr of O, 1.751kg/hr of HF and 0.257kg/hr of n-octanol.
The extraction rate of HF in the extraction phase at the top of the continuous extraction column 1 is not less than 99.5%, wherein the content of n-octanol is about 74.6wt%, the content of HF is about 20.3wt%, and H is 2 The O content was about 5.1wt%. Water content in raffinate phase at the bottom of continuous extraction column 1>99.7wt%, HF content less than or equal to 0.2wt%, and n-octanol content less than or equal to 0.05wt%, and can be directly discharged to downstream waste water treatment section as waste water for treatment.
2) And heating the stream S4 to a bubble point, specifically 47 ℃, through a first heat exchanger 4, and allowing the stream to enter a first-stage rectifying tower 2 for removing n-octanol. Obtaining a first-stage overhead distillate at the top of the first-stage rectifying tower 2, wherein the first-stage overhead distillate comprises a large amount of hydrogen fluoride and a small amount of water, and obtaining a first-stage bottom at the bottom of the first-stage rectifying tower 2, wherein the first-stage bottom comprises linear primary alcohol C n H 2n+2 OH, and also comprises a small amount of hydrogen fluoride and water; this step is from H 2 Separating the extracting agent in an O-HF-extracting agent ternary system. The first-stage rectifying tower 2 removes the straight-chain primary alcohol of the extracting agent so as to recycle the extracting agent.
In particular toThe first-stage rectifying tower 2 adopts a packed tower, the number of effective tower plates is 16, the position of a feed plate is 7, the reflux ratio is 1.8, the heat load at the top of the first-stage rectifying tower 2 is-321.9 kW, and the heat load at the bottom of the first-stage rectifying tower 2 is 424.4kW. A stream S5 is extracted from the top of the first-stage rectifying tower 2 at the temperature of 26.3 ℃ and the pressure of 1.001bar, wherein HF is 400.9kg/hr and H is 2 O is 78.4kg/hr, and n-octanol is 0.644kg/hr. A stream S6 is extracted from the bottom of the first-stage rectifying tower 2 at the temperature of 130.0 ℃ and the pressure of 1.010bar, wherein n-octanol is 1499.1kg/hr, HF is 6.501kg/hr, and H is 2 O was 25.09kg/hr.
3) And cooling the stream S6 to 20 ℃ through a second heat exchanger 5, and mixing the stream S6 with the stream S2 to realize the recycling of the extractant. And cooling the primary tower bottom by a second heat exchanger 5, and then circulating the primary tower bottom to the continuous extraction tower 1 for recycling.
4) Introducing the primary tower top distillate into a second-stage rectifying tower 3 for rectification to obtain a secondary tower top distillate at the tower top of the second-stage rectifying tower 3, wherein the secondary tower top distillate comprises anhydrous hydrogen fluoride, and a secondary tower bottom is obtained at the tower bottom of the second-stage rectifying tower 3, wherein the secondary tower bottom comprises H 2 The O-HF azeotrope. The step of separating hydrogen fluoride and water, and the second-stage rectifying tower 3 mainly processes H 2 Separating O and HF, and producing industrial AHF product at the tower top.
Specifically, stream S5 enters second stage rectifier 3 at bubble point. The second-stage rectifying tower 3 adopts a packed tower, the number of effective tower plates is 15, the position of a feed plate is 5, the reflux ratio is 2, the heat load at the top of the tower is 110.9kW, and the heat load at the bottom of the tower is 116.1kW. The stream S7 extracted from the top of the second-stage rectifying tower 3 is an AHF product, the temperature is 19.3 ℃, the pressure is 1.001bar, wherein the HF is 360.0kg/hr, and the H is 2 The content of O and n-octanol is less than 0.288kg/hr. The stream S8 is obtained at the bottom of the second-stage rectifying tower 3 at the temperature of 112.2 ℃ and the pressure of 1.010bar, wherein n-octanol is 0.644kg/hr, HF is 40.94kg/hr, and H is 2 O was 78.42kg/hr.
5) And cooling the stream S8 to 20 ℃ through a third heat exchanger 6, mixing the stream S with the stream S1, and feeding the stream S into a raw material inlet of the continuous extraction tower 1.
The process for producing anhydrous hydrogen fluoride in this example utilizes a linear primary alcohol C n H 2n+2 OH(8≤n≤10，nIs an integer) has very low solubility in water and its interaction with HF, and extraction and rectification have been developed for extracting H 2 A process for producing AHF from an O-HF azeotrope. Due to linear primary alcohols C n H 2n+2 OH (n is more than or equal to 8 and less than or equal to 10, n is an integer) is different from the characteristics of sulfuric acid and other naphthenic alcohol and aromatic alcohol, and an extraction phase and a raffinate phase after extraction operation are easy to treat, so that the whole process flow has the advantages of simplicity, high efficiency, environmental protection, and reduction of investment and operation cost in the recycling process of producing anhydrous HF.
Example 3
This example provides a process using the apparatus for producing anhydrous hydrogen fluoride of example 2, which differs from the process of example 2 in that:
the temperature in the continuous extraction tower is 5-35 ℃, and the pressure is 0.81325-1.21325 bar.
Extractant straight-chain primary alcohol C n H 2n+2 OH (n is more than or equal to 8 and less than or equal to 10, n is an integer), specifically, n =9, and the extracting agent is straight-chain n-nonanol.
The first stage of the rectifying tower adopts a packed tower, the number of effective tower plates is 14, the position of a feed plate is 8, and the reflux ratio is 1.5.
The second-stage rectifying tower adopts a packed tower, the number of effective tower plates is 14, the position of a feed plate is 6, and the reflux ratio is 1.8.
Example 4
This example provides a process using the apparatus for producing anhydrous hydrogen fluoride of example 2, which differs from the process of example 2 in that:
the temperature in the continuous extraction tower is 5-35 ℃, and the pressure is 0.81325-1.21325 bar.
Extractant straight-chain primary alcohol C n H 2n+2 OH (n is more than or equal to 8 and less than or equal to 10, n is an integer), specifically, n =10, and the extracting agent is straight-chain n-decanol.
The first stage of rectifying tower adopts a packed tower, 17 effective tower plates are arranged, the position of a feed plate is 7, and the reflux ratio is 2.0.
The second-stage rectifying tower adopts a packed tower, the number of effective tower plates is 16, the position of a feed plate is 5, and the reflux ratio is 2.1.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (7)
1. A process for producing anhydrous hydrogen fluoride comprising the steps of:
1) Extracting agent straight-chain primary alcohol C n H 2n+2 OH、H 2 Introducing the O-HF azeotrope into a continuous extraction tower, and extracting H by an extracting agent 2 Hydrogen fluoride in the O-HF azeotrope is used for obtaining an extract phase at the top of the continuous extraction tower and a raffinate phase at the bottom of the continuous extraction tower, wherein n is more than or equal to 8 and less than or equal to 10 and is an integer, the content of HF in the raffinate phase at the bottom of the continuous extraction tower is less than or equal to 0.2wt%, the content of straight-chain primary alcohol is less than or equal to 0.05wt%, and the balance is water;
2) Introducing the extract phase into a first-stage rectifying tower for rectification, and obtaining a first-stage tower top distillate at the tower top of the first-stage rectifying tower, wherein the first-stage tower top distillate comprises hydrogen fluoride and water, and obtaining a first-stage tower bottom at the tower bottom of the first-stage rectifying tower, wherein the first-stage tower bottom comprises linear primary alcohol C n H 2n+2 OH；
3) Introducing the first-stage tower top distillate into a second-stage rectifying tower for rectification to obtain a second-stage tower top distillate at the tower top of the second-stage rectifying tower, wherein the second-stage tower top distillate comprises anhydrous hydrogen fluoride, and a second-stage tower bottom is obtained at the tower bottom of the second-stage rectifying tower, wherein the second-stage tower bottom comprises H 2 The O-HF azeotrope.
2. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the linear primary alcohol C is n H 2n+2 OH is primary alcohol n-octanol, and n =8.
3. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the temperature in the continuous extraction column in the step 1) is 5 to 35 ℃ and the pressure is 0.81325 to 1.21325bar.
4. The process for producing anhydrous hydrogen fluoride according to claim 1, further comprising the following step m) after the step 2): and introducing the first-stage tower bottom into a continuous extraction tower for recycling.
5. The process for producing anhydrous hydrogen fluoride according to claim 1, wherein the first-stage rectifying tower in the step 2) is a packed tower, the number of effective plates is 14 to 17, the position of a feed plate is 7 to 8, and the reflux ratio is 1.5 to 2.0.
6. The process for producing anhydrous hydrogen fluoride according to claim 1, further characterized in that the second-stage rectification column in the step 3) is a packed column, the effective number of the trays is 14-16, the position of the feed plate is 5-6, and the reflux ratio is 1.8-2.1.
7. The process for producing anhydrous hydrogen fluoride according to claim 1, further comprising the following step n) after the step 3): and (4) introducing the secondary tower bottom into a continuous extraction tower for retreatment.
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| FR2977584B1 (en) * | 2011-07-08 | 2014-12-05 | Arkema France | PROCESS FOR SEPARATING AND RECOVERING 2,3,3,3-TETRAFLUOROPROPENE AND FLUORHYDRIC ACID |
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