CN111847382B - Reaction system for removing hydrogen fluoride in hydrogen chloride - Google Patents
Reaction system for removing hydrogen fluoride in hydrogen chloride Download PDFInfo
- Publication number
- CN111847382B CN111847382B CN202010768302.9A CN202010768302A CN111847382B CN 111847382 B CN111847382 B CN 111847382B CN 202010768302 A CN202010768302 A CN 202010768302A CN 111847382 B CN111847382 B CN 111847382B
- Authority
- CN
- China
- Prior art keywords
- chloride
- external circulation
- gas
- circulation system
- concentration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
Abstract
The invention provides a reaction system for removing hydrogen fluoride in hydrogen chloride, which comprises the following components: the invention applies the hypergravity separator to the removal of hydrogen fluoride in hydrogen chloride, can make gas-liquid contact more fully, improves the removal rate of hydrogen fluoride, in the external circulation system, a three-stage isolation system is used, avoids the influence of precipitation of metal fluoride on a feed pump, and the fluorine removal agent component can be maintained at the minimum limit value by adopting the regular monitoring and the feed system, thereby effectively improving the fluorine removal effect; after the pressure is released through the gas holder, the moisture carried by the gas and the fluorine removing agent after the gas contacts can be effectively removed, and the desorption regeneration of the absorption tower is facilitated; the invention carries out graded removal and adsorption on the hydrogen fluoride, can realize the effective removal of hydrogen fluoride with different concentrations, and has wider application range.
Description
Technical Field
The invention relates to the field of chemical industry, in particular to a reaction system for removing hydrogen fluoride in hydrogen chloride.
Background
Common methods of introducing fluorine atoms include: addition reactions, substitution reactions, electrochemical reactions, telomerization reactions, and the like. In the refrigerant and foaming industry, the most mature technology for introducing fluorine atoms is to prepare fluorinated alkane by replacing chlorinated hydrocarbon with hydrogen fluoride. The process generally adopts an excessive hydrogen fluoride method to reduce the content of byproducts in the production process, so that the entrainment phenomenon of hydrogen fluoride along with reaction products and byproducts hydrogen chloride exists, and the hydrogen fluoride must be treated in the subsequent process of the reaction. The treatment is generally carried out by the method of water alkali washing in industry, so that a large amount of fluorine-containing hydrochloric acid is generated. The fluorine-containing hydrochloric acid has the advantages of small application range, low selling price, sometimes even being capable of being used for waste liquid treatment, seriously affecting economic benefit and causing potential environmental hazard. The hydrogen fluoride in the byproduct hydrogen chloride is removed, and the byproduct hydrogen chloride is processed into high-purity hydrogen chloride with high added value and small environmental hazard, so that the method is an effective way for realizing sustainable development of economic cycle.
In the prior published data, most of the defluorination is carried out by adopting a fixed adsorption bed loaded with metal salt or an adsorption tower loaded with metal salt, mainly comprising ferric salt, calcium salt, aluminum salt, magnesium salt, chromium salt and the like, and no defluorination is reported by adopting zirconium salt and yttrium salt. Because it is mostly the load of solid metal salt, contact the back with hydrogen fluoride and arouse the top layer fluoridation easily and lose the defluorination effect, actual defluorination effect can be along with live time decline greatly, and the solid sample of high pressure adsorption bed layer or adsorption tower is higher in the liquid operation degree of difficulty, and its change is also comparatively loaded down with trivial details.
Disclosure of Invention
The invention provides a reaction system for removing hydrogen fluoride in hydrogen chloride, which aims to solve the problems of poor fluorine removal effect, high solid sampling difficulty and the like in the prior art.
The invention takes the above factors into consideration, creatively applies the hypergravity separator to the fluorine removal of hydrogen chloride, so that the detection is more convenient, and the concentration of the effective components in the hypergravity separator is easier to control. After being connected with an external circulation system, the metal fluoride salt formed in the external circulation system can be separated more conveniently, and the metal fluoride salt is prevented from entering the defluorination separation system again. The fluorine ion concentration in the fluorine ion-containing wastewater can be treated to ppb level by the method.
The technical scheme of the invention is as follows:
a reaction system for removing hydrogen fluoride from hydrogen chloride, comprising: the device comprises a supergravity separator, an external circulation system, a gas holder, a feeding system and an absorption tower; the hypergravity separator is provided with: a liquid inlet, a liquid outlet, an air inlet and an air outlet; the liquid inlet and the liquid outlet are connected with the external circulation system; the external circulation system is connected with the feeding system; the air outlet is connected with the gas holder and the absorption tower.
Preferably, a multi-component active fluorine removal solution is arranged in the external circulation system and the feeding system, wherein the concentration of the multi-component active fluorine removal solution in the external circulation system is 0.01mol/L to 10mol/L.
Further, the multi-component active defluorination solution in the external circulation system is periodically detected, and when the concentration of the multi-component active defluorination solution is lower than 0.01mol/L, the solid metal salt or the multi-component active defluorination solution with the concentration higher than 0.01mol/L is supplemented by the feeding system.
Further, the multi-component active defluorination solution or the solid metal salt is composed of two or more metal chlorides, oxychlorides, hydroxides, oxides.
Further, the metal chloride includes: calcium chloride, aluminum chloride, zirconium chloride, magnesium chloride, ferric chloride, sodium chloride, potassium chloride, yttrium chloride; the oxychloride comprises: zirconium oxychloride; the hydroxide comprises: calcium hydroxide, aluminum hydroxide, iron hydroxide, magnesium hydroxide; the oxide includes: alumina, calcium oxide, yttrium oxide.
Further, the external circulation system is a three-stage isolation system.
Preferably, a metering pump is arranged between the super-gravity separator and the external circulation system.
Further, the supergravity separator is provided with a pressure sensor; the feeding speed of the liquid inlet is 2-30 m 3 And/h, the gas inlet gas feeding speed is 0.5-20 m 3 And/h, wherein the gas inlet is filled with hydrogen chloride gas containing hydrogen fluoride.
Further, the high-volume ratio of the super-gravity separator is 1:1-10:1, the filler is fluorine-containing polymer or chlorine-containing polymer, the operating pressure is 0.1-2.5 MPa, and the rotating speed is 200-2000 r/min.
Preferably, the adsorbate within the absorber column comprises: spherical sodium fluoride and spherical potassium fluoride.
The invention has the following beneficial effects:
1. the hypergravity separator is applied to the removal of hydrogen fluoride in hydrogen chloride, so that the gas-liquid contact is more sufficient; the outlet of the reaction kettle reflux tower is directly connected with the hypergravity separator, the pressure of the reaction kettle reflux tower is fully utilized, the concentration of the hydrogen fluoride in the hydrogen chloride is improved, the removal rate of the hydrogen fluoride is improved, and the utilization rate of energy is also improved;
2. in the external circulation system, a three-stage isolation system is used, so that the influence of precipitation of metal fluoride on a feed pump is avoided, the metal fluoride can be effectively separated, and the fluorine removal agent component can be maintained at the minimum limit value by adopting the periodic monitoring and feeding system for the first time, so that the fluorine removal effect is effectively improved;
3. after the pressure is released through the gas holder, the moisture carried by the gas and the fluorine removing agent after the contact can be effectively removed, the spherical sodium fluoride can be effectively prevented from absorbing water and dissolving, and the desorption and regeneration of the absorption tower are facilitated; the invention carries out graded removal and adsorption on the hydrogen fluoride, can realize the effective removal of hydrogen fluoride with different concentrations, and has wider application range.
Drawings
FIG. 1 is a schematic diagram of a reaction system for removing hydrogen fluoride from hydrogen chloride according to the present invention.
Reference numerals: 1. the device comprises a supergravity separator 2, an external circulation system 3, a metering pump, 4, a gas holder 5, a feeding system 6, a liquid inlet 7, a liquid outlet 8, a gas inlet 9, a gas outlet 10, a pressure sensor 11, a first stage 12, a third stage 13, an absorption tower 14 and a gas outlet.
Detailed Description
In order to make the technical problems, technical solutions and advantages to be solved more apparent, the following detailed description will be given with reference to the accompanying drawings and specific embodiments. In the following description, feature details such as specific configurations and components are provided merely to aid in a thorough understanding of embodiments of the invention. It will therefore be apparent to those skilled in the art that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of the invention. In addition, descriptions of well-known functions and constructions are omitted for clarity and conciseness.
It should be appreciated that reference throughout this specification to "one embodiment" or "an embodiment" means that a particular feature, structure or characteristic described in connection with the embodiment is included in at least one embodiment of the present invention. Thus, the appearances of the phrases "in one embodiment" or "in an embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In various embodiments of the present invention, it should be understood that the sequence numbers of the following processes do not mean the order of execution, and the order of execution of the processes should be determined by the functions and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present invention.
It should be understood that the term "and/or" is merely an association relationship describing the associated object, and means that three relationships may exist, for example, a and/or B may mean: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
In the examples provided herein, it should be understood that "B corresponding to a" means that B is associated with a from which B may be determined. It should also be understood that determining B from a does not mean determining B from a alone, but may also determine B from a and/or other information.
With reference to the schematic structural diagram of fig. 1, the invention comprises: the device comprises a supergravity separator 1, an external circulation system 2, a metering pump 3, a gas holder 4, a feeding system 5 and an absorption tower 13; the supergravity separator 1 is provided with: a liquid inlet 6, a liquid outlet 7, an air inlet 8 and an air outlet 9; the feeding system 5 is connected with a first stage 11 in the external circulation system 2; the third stage 12 of the external circulation system 2 is connected with the liquid inlet 6, the multicomponent active defluorination solution in the external circulation system 2 is introduced into the super-gravity separator 1 through the metering pump 3, and the multicomponent active defluorination solution after the reaction of the super-gravity separator 1 is discharged from the liquid outlet 7 and is introduced into the first stage of the external circulation system 2 again; the gas inlet 8 is directly connected with the outlet of the reaction kettle reflux tower, hydrogen chloride gas containing hydrogen fluoride in the reaction kettle reflux tower enters the hypergravity separator 1 from the gas inlet 8, is discharged from the gas outlet and is introduced into the gas holder 4 after reaction, and is introduced into the adsorption tower 13 after pressure release of the gas holder 4.
In one embodiment, the multicomponent active defluorination solution is configured in the external circulation system 2 and the feeding system 5, wherein the concentration of the multicomponent active defluorination solution in the external circulation system 2 is 0.01mol/L to 10mol/L, the multicomponent active defluorination solution in the external circulation system 2 needs to be detected periodically, and when the concentration of the multicomponent active defluorination solution is lower than 0.01mol/L, the solid metal salt or the multicomponent active defluorination solution with the concentration higher than 0.01mol/L is fed through the feeding system 5;
further, the multi-component active defluorination solution or the solid metal salt is composed of two or more metal chlorides, oxychlorides, hydroxides, oxides, wherein the metal chlorides comprise: calcium chloride, aluminum chloride, zirconium chloride, magnesium chloride, ferric chloride, sodium chloride, potassium chloride, yttrium chloride; the oxychloride includes: zirconium oxychloride; the hydroxide includes: calcium hydroxide, aluminum hydroxide, iron hydroxide, magnesium hydroxide; the oxide includes: alumina, calcium oxide, yttrium oxide.
Further, the external circulation system 2 is a three-stage isolation system, wherein the first stage 11 is connected with the feeding system 5 and the liquid outlet 7, and the third stage 12 is connected with the liquid inlet 6; the first stage 11 is connected with the liquid outlet 7, and the third stage 12 is connected with the liquid inlet 6, so that the supergravity separator 1 and the external circulation system 2 form a complete circulation system, and the multicomponent active defluorination solution is fully utilized. The feeding system 5 is connected with the external circulation system 2, and can timely supplement the multi-component active fluorine removal solution or the solid metal salt, so that the concentration of the multi-component active fluorine removal solution in the external circulation system 2 is ensured to be more than 0.01mol/L.
In one embodiment, the supergravity separator 1 is provided with a pressure sensor 10; the feeding speed of the liquid inlet 6 is 2-30 m 3 And/h, the gas feeding speed of the gas inlet 8 is 0.5-20 m 3 And/h, wherein the high-volume ratio of the super gravity separator (1) is 1:1-10:1, the filler is fluorine-containing polymer or chlorine-containing polymer, the operating pressure is 0.1-2.5 MPa, and the rotating speed is 200-2000 r/min.
Further preferably, the hypergravity separator 1 has a height-to-volume ratio of 1.5:1-3:1, the filler is annular structured filler of chlorine-containing polymer, the operating pressure is 1-1.5 MPa, and the rotating speed is 200-600 r/min.
Further, the adsorbates within the absorber column 13 include: spherical sodium fluoride and spherical potassium fluoride.
The implementation steps of the invention are as follows:
step 1, preparing and preparing 0.01-10 mol/L multicomponent active defluorination solution in an external circulation system 2. Preparing 0.1 mol-10 mol/L high-concentration defluorination solution in the feeding system 5.
And 3, returning the reacted multicomponent active defluorination solution to an external circulation system through a liquid outlet, introducing gas into a gas holder 4, decompressing and removing water, controlling the pressure of the gas holder to be about 1-100 kPa, and sampling and detecting the content of hydrogen fluoride from the gas and 4.
And 4, enabling the gas to enter an absorption tower from an outlet of the gas holder, filling spherical sodium fluoride in the tower, finally removing fluorine, entering a hydrogen chloride separation system, and sampling and detecting the hydrogen fluoride content of the gas outlet.
And 5, periodically sampling and detecting the concentration of the active components in the multi-component active defluorination solution in the external circulation system 2, and supplementing the mixed solution to the external circulation system 2 by the feeding system 5 until the concentration of the active components is 0.1mol/L when the concentration is lower than 0.01mol/L.
The following are different metal chlorides, oxychlorides, hydroxides and oxides, hydrogen fluoride with different concentrations, different feeding speeds of the liquid inlet 8, different air inlet speeds of the air inlet 9, different pressures and different rotating speeds in the hypergravity separator 1, and the content of the hydrogen fluoride in the hydrogen chloride gas obtained through the steps.
Example 1
Preparing 0.1mol/L magnesium chloride solution in an external circulation system, and adding calcium hydroxide to make the concentration of the magnesium chloride solution be 0.1mol/L. 5mol/L magnesium chloride solution is prepared in a feeding system, and calcium hydroxide is added at the same time, so that the concentration of the magnesium chloride solution is 5mol/L. The metering pump was started at 10m 3 Pumping the multicomponent active defluorination solution in the external circulation system into a supergravity separator at a speed of/h and at the same time making the concentration of the solution 5m 3 Introducing hydrogen chloride gas flow containing fluorinated product at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotorThe rotation speed is 300r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And (3) periodically sampling and detecting the concentration of calcium ions and the concentration of magnesium ions in the multi-component active defluorination solution, and when the concentration of the calcium ions and the concentration of the magnesium ions are lower than 0.01mol/L, replenishing the mixed solution from a feeding system to the inside until the concentration of the calcium ions and the concentration of the magnesium ions are 0.1mol/L.
Example 2
Preparing 0.1mol/L ferric chloride solution in an external circulation system, and adding calcium hydroxide to make the concentration of the solution be 0.1mol/L. 5mol/L ferric chloride solution is prepared in a feeding system, and calcium hydroxide is added at the same time, so that the concentration of the ferric chloride solution is 5mol/L. The metering pump was started at 10m 3 Pumping the multicomponent active defluorination solution in the external circulation system into a supergravity separator at a speed of/h and at the same time making the concentration of the solution 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotating speed of the rotor to be 300r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And (3) periodically sampling and detecting the concentration of calcium ions and the concentration of iron ions in the multi-component active defluorination solution, and when the concentration of the calcium ions and the concentration of the iron ions are lower than 0.01mol/L, replenishing the mixed solution from a feeding system to the inside until the concentration of the calcium ions and the concentration of the iron ions are 0.1mol/L.
Example 3
Preparing 0.1mol/L aluminum chloride solution in an external circulation system, and adding calcium hydroxide to make the concentration of the solution be 0.1mol/L. 3mol/L aluminum chloride solution is prepared in a feeding system, and calcium hydroxide is added at the same time, so that the concentration of the aluminum chloride solution is 3mol/L. The metering pump was started at 10m 3 The speed of/h will be externalPumping the multicomponent active defluorination solution into supergravity separator at the same time using 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotating speed of the rotor to be 300r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And (3) periodically sampling and detecting the concentration of calcium ions and the concentration of aluminum ions in the multi-component active defluorination solution, and when the concentration of the calcium ions and the concentration of the aluminum ions are lower than 0.01mol/L, replenishing the mixed solution from a feeding system to the inside until the concentration of the aluminum ions and the concentration of the calcium ions are 0.1mol/L.
Example 4
Preparing 0.1mol/L yttrium chloride solution in an external circulation system, and adding calcium hydroxide to make the concentration of the solution be 0.1mol/L. And preparing a 3mol/L yttrium chloride solution in a feeding system, and simultaneously adding calcium hydroxide to ensure that the concentration of the solution is 3mol/L. The metering pump was started at 10m 3 Pumping the multicomponent active defluorination solution in the external circulation system into a supergravity separator at a speed of/h and at the same time making the concentration of the solution 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotating speed of the rotor to be 300r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And (3) periodically sampling and detecting the concentration of calcium ions and yttrium ions in the multi-component active defluorination solution, and when the concentration of the calcium ions and the concentration of the yttrium ions are lower than 0.01mol/L, replenishing the mixed solution from a feeding system to the inside until the concentration of the calcium ions and the concentration of the yttrium ions are 0.1mol/L.
Example 5
In an external circulation system0.1mol/L zirconium oxychloride solution is prepared, and calcium hydroxide is added to make the concentration of the solution be 0.1mol/L. 1mol/L zirconium oxychloride solution is prepared in a feeding system, and calcium hydroxide is added at the same time, so that the concentration of the zirconium oxychloride solution is 1mol/L. The metering pump was started at 10m 3 Pumping the multicomponent active defluorination solution in the external circulation system into a supergravity separator at a speed of/h and at the same time making the concentration of the solution 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotating speed of the rotor to be 300r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And (3) periodically sampling and detecting the concentration of calcium ions and the concentration of zirconium ions in the multi-component active defluorination solution, and when the concentration of calcium ions and the concentration of zirconium ions are lower than 0.01mol/L, supplementing the mixed solution from a feeding system to the inside until the concentration of calcium ions and the concentration of zirconium ions are 0.1mol/L.
Example 6
Preparing 0.1mol/L zirconium oxychloride solution in an external circulation system, and adding sodium chloride to ensure that the concentration is 0.1mol/L. 1mol/L zirconium oxychloride solution is prepared in a feeding system, and sodium chloride is added at the same time, so that the concentration of the zirconium oxychloride solution is 1mol/L. The metering pump was started at 10m 3 Pumping the multicomponent active defluorination solution in the external circulation system into a supergravity separator at a speed of/h and at the same time making the concentration of the solution 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotating speed of the rotor to be 300r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. Periodic sampling detection of zirconium ion concentration in multicomponent active defluorination solutionAnd when the concentration of the zirconium ions and the sodium ions is lower than 0.01mol/L, the mixed solution is fed in from the feeding system until the concentration of the zirconium ions and the sodium ions is 0.1mol/L.
Example 7
Preparing 0.1mol/L zirconium oxychloride solution in an external circulation system, adding sodium chloride to the concentration of 0.05mol/L zirconium oxychloride solution, and adding potassium chloride to the concentration of 0.15mol/L zirconium oxychloride solution. 1mol/L zirconium oxychloride solution is prepared in a feeding system, and sodium chloride and potassium chloride are added simultaneously, so that the concentration of the solution is 0.5mol/L. The metering pump was started at 10m 3 Pumping the multicomponent active defluorination solution in the external circulation system into a supergravity separator at a speed of/h and at the same time making the concentration of the solution 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotating speed of the rotor to be 300r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And periodically sampling and detecting the concentration of zirconium ions, sodium ions and potassium ions in the multi-component active defluorination solution, and when the concentration of the zirconium ions, the sodium ions and the potassium ions is lower than 0.01mol/L, replenishing the mixed solution from a feeding system to the inside until the concentration of the zirconium ions, the sodium ions and the potassium ions are 0.05mol/L and 0.15mol/L.
Example 8
Preparing 0.1mol/L aluminum chloride solution in an external circulation system, and adding sodium chloride to make the concentration of the solution be 0.3mol/L. 1mol/L aluminum chloride solution is prepared in a feeding system, and sodium chloride is added at the same time, so that the concentration of the aluminum chloride solution is 3mol/L. The metering pump was started at 10m 3 Pumping the multicomponent active defluorination solution in the external circulation system into a supergravity separator at a speed of/h and at the same time making the concentration of the solution 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotating speed of the rotor to be 300r/min. The reacted multicomponent active defluorination solution is returned to the external circulation system through the liquid outletAnd (3) introducing the gas into a gas holder, decompressing and removing water, controlling the pressure of the gas holder to be about 10kPa, and sampling and detecting the content of hydrogen fluoride in the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical potassium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system, and the gas is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And (3) periodically sampling and detecting the concentration of aluminum ions and the concentration of sodium ions in the multi-component active defluorination solution, and when the concentration of the aluminum ions and the concentration of the sodium ions are lower than 0.01mol/L, supplementing the mixed solution to the inside by a feeding system until the concentration of the zirconium ions is 0.1mol/L and the concentration of the sodium ions is 0.3mol/L.
Example 9
Preparing 0.1mol/L zirconium oxychloride solution in an external circulation system, and adding sodium chloride to ensure that the concentration is 0.3mol/L. 1mol/L zirconium oxychloride solution is prepared in a feeding system, and sodium chloride is added at the same time, so that the concentration of the zirconium oxychloride solution is 3mol/L. The metering pump was started at 20m 3 Pumping the multicomponent active defluorination solution in the external circulation system into a supergravity separator at a speed of/h and at the same time making the concentration of the solution 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotating speed of the rotor to be 300r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And periodically sampling and detecting the concentration of zirconium ions, sodium ions and potassium ions in the multi-component active defluorination solution, and when the concentration of the zirconium ions, the sodium ions and the potassium ions is lower than 0.01mol/L, supplementing the mixed solution into the mixed solution by a feeding system until the concentration of the zirconium ions is 0.1mol/L and the concentration of the sodium ions is 0.3mol/L.
Example 10
Preparing 0.1mol/L zirconium oxychloride solution in an external circulation system, and adding sodium chloride to ensure that the concentration is 0.3mol/L. 1mol/L zirconium oxychloride solution is prepared in a feeding system, and sodium chloride is added at the same time, so that the concentration of the zirconium oxychloride solution is 3mol/L. The metering pump was started at 10m 3 Pumping the multi-component active defluorination solution in the external circulation system into the ultrasonic reactor at the speed of/hGravity separator at the same time at 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 1.3MPa, and controlling the rotating speed of the rotor to be 600r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And periodically sampling and detecting the concentration of zirconium ions, sodium ions and potassium ions in the multi-component active defluorination solution, and when the concentration of the zirconium ions, the sodium ions and the potassium ions is lower than 0.01mol/L, supplementing the mixed solution into the mixed solution by a feeding system until the concentration of the zirconium ions is 0.1mol/L and the concentration of the sodium ions is 0.3mol/L.
Example 11
Preparing 0.1mol/L zirconium oxychloride solution in an external circulation system, and adding sodium chloride to ensure that the concentration is 0.3mol/L. 1mol/L zirconium oxychloride solution is prepared in a feeding system, and sodium chloride is added at the same time, so that the concentration of the zirconium oxychloride solution is 3mol/L. The metering pump was started at 10m 3 Pumping the multicomponent active defluorination solution in the external circulation system into a supergravity separator at a speed of/h and at the same time making the concentration of the solution 5m 3 And introducing hydrogen chloride gas flow containing fluorinated products at the speed of/h, sampling and detecting the hydrogen fluoride content of the gas inlet, controlling the internal pressure of the super-gravity separator to be 0.6MPa, and controlling the rotating speed of the rotor to be 300r/min. The reacted multicomponent active defluorination solution returns to the external circulation system through a liquid outlet, gas enters a gas holder, decompression and dehydration are carried out, the pressure of the gas holder is controlled to be about 10kPa, and the content of hydrogen fluoride is detected by sampling from the gas holder. The gas enters an absorption tower from a gas holder outlet, spherical sodium fluoride is filled in the tower, and after final defluorination, the gas enters a hydrogen chloride separation system and is sampled and detected to obtain the hydrogen fluoride content of a gas outlet. And periodically sampling and detecting the concentration of zirconium ions, sodium ions and potassium ions in the multi-component active defluorination solution, and when the concentration of the zirconium ions, the sodium ions and the potassium ions is lower than 0.01mol/L, supplementing the mixed solution into the mixed solution by a feeding system until the concentration of the zirconium ions is 0.1mol/L and the concentration of the sodium ions is 0.3mol/L.
Table 1 results for examples 1-11
From the results in table 1, we can see that the reaction system can effectively remove hydrogen fluoride in hydrogen chloride, the effective removal rate of hydrogen fluoride exceeds 98%, and the reaction system has a wider application range, so that the condition that the hydrogen fluoride in the treated hydrogen chloride is out of standard due to unstable working conditions can be avoided.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; while the invention has been described in detail with reference to the above-described embodiments, those skilled in the art will appreciate that modifications may be made to the embodiments described in the foregoing description, or that certain features may be substituted for those illustrated in the drawings; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A reaction system for removing hydrogen fluoride from hydrogen chloride, comprising: the device comprises a hypergravity separator (1), an external circulation system (2), a gas holder (4), a feeding system (5) and an absorption tower (13); the hypergravity separator (1) is provided with: a liquid inlet (6), a liquid outlet (7), an air inlet (8) and an air outlet (9); the liquid inlet (6) and the liquid outlet (7) are connected with the external circulation system (2); the external circulation system (2) is connected with the feeding system (5); the air outlet (9) is connected with the gas holder (4) and the absorption tower (13);
the multi-component active defluorination solution is configured in the external circulation system (2) and the feeding system (5), wherein the concentration of the multi-component active defluorination solution in the external circulation system (2) is 0.01 mol/L-10 mol/L;
the multi-component active defluorination solution in the external circulation system (2) is periodically detected, and when the concentration of the multi-component active defluorination solution is lower than 0.01mol/L, solid metal salt is supplemented by the feeding system (5);
the solid metal salt consists of more than two metal chlorides; the metal chloride comprises: calcium chloride, aluminum chloride, zirconium chloride, magnesium chloride, ferric chloride, sodium chloride, potassium chloride, yttrium chloride;
the external circulation system (2) is a three-stage isolation system, wherein a first stage (11) is connected with the feeding system (5) and the liquid outlet (7), and a third stage (12) is connected with the liquid inlet (6); the first stage (11) is connected with the liquid outlet (7), the third stage (12) is connected with the liquid inlet (6), so that the supergravity separator (1) and the external circulation system (2) form a complete circulation system, the multicomponent active defluorination solution is fully utilized, the feeding system (5) is connected with the external circulation system (2), the solid metal salt can be timely supplemented, and the concentration of the multicomponent active defluorination solution in the external circulation system (2) is ensured to be more than 0.01mol/L.
2. A reaction system for removing hydrogen fluoride from hydrogen chloride according to claim 1, characterized in that a metering pump (3) is arranged between the supergravity separator (1) and the external circulation system (2).
3. A reaction system for removing hydrogen fluoride from hydrogen chloride according to claim 2, characterized in that the supergravity separator (1) is provided with a pressure sensor (10); the feeding speed of the liquid inlet (6) is 2-30 m 3 And/h, wherein the gas feeding speed of the gas inlet (8) is 0.5-20 m 3 And/h, wherein the gas inlet (8) is filled with hydrogen chloride gas containing hydrogen fluoride.
4. A reaction system for removing hydrogen fluoride from hydrogen chloride according to claim 3, wherein the high volume ratio of the super gravity separator (1) is 1:1-10:1, the filler is fluorine-containing polymer or chlorine-containing polymer, the operating pressure is 0.1-2.5 MPa, and the rotating speed is 200-2000 r/min.
5. A reaction system for removing hydrogen fluoride from hydrogen chloride according to claim 1, wherein the adsorbate in the absorber (13) comprises: spherical sodium fluoride and spherical potassium fluoride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010768302.9A CN111847382B (en) | 2020-08-03 | 2020-08-03 | Reaction system for removing hydrogen fluoride in hydrogen chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010768302.9A CN111847382B (en) | 2020-08-03 | 2020-08-03 | Reaction system for removing hydrogen fluoride in hydrogen chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111847382A CN111847382A (en) | 2020-10-30 |
| CN111847382B true CN111847382B (en) | 2023-05-30 |
Family
ID=72952925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010768302.9A Active CN111847382B (en) | 2020-08-03 | 2020-08-03 | Reaction system for removing hydrogen fluoride in hydrogen chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111847382B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788457A (en) * | 2021-10-25 | 2021-12-14 | 江苏三美化工有限公司 | Method for separating hydrogen chloride in R134a by using supergravity dry method |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE841011A (en) * | 1975-04-25 | 1976-08-16 | PROCESS FOR SEPARATING HYDROFLUORIC ACID AND / OR SILICUM TETRA-FLUORIDE FROM HYDROCHLORIC GAS | |
| DE19535716A1 (en) * | 1995-09-26 | 1997-03-27 | Bayer Ag | Process for working up the reaction gases in the oxidation of HCl to chlorine |
| CN101495403A (en) * | 2006-05-23 | 2009-07-29 | 拜尔材料科学股份公司 | Method for oxidizing hydrogen chloride with oxygen |
| CA2764278A1 (en) * | 2009-06-26 | 2010-12-29 | Michael Lee Trippeer | Selective dehydrohalogenation of tertiary halogenated hydrocarbons and removal of tertiary halogenated hydrocarbon impurities |
| CN102874756A (en) * | 2012-09-24 | 2013-01-16 | 巨化集团技术中心 | Method for removing hydrogen fluoride from hydrogen chloride gas |
| CN203639145U (en) * | 2013-10-29 | 2014-06-11 | 洛阳万基金属钠有限公司 | Device for removing nitrogen trichloride from chlorine |
| CN105377751A (en) * | 2013-05-15 | 2016-03-02 | 旭硝子株式会社 | Method for purifying hydrogen chloride |
| CN106495100A (en) * | 2016-11-09 | 2017-03-15 | 中南大学 | A kind of removing fluohydric acid gas from hydrogen chloride gas the method for reclaiming fluohydric acid gas |
| CN106744688A (en) * | 2016-12-28 | 2017-05-31 | 兰州大学淮安高新技术研究院 | A kind of method for removing hydrogen fluoride gas in hydrogen chloride gas |
| CN109850848A (en) * | 2019-04-04 | 2019-06-07 | 南京工业大学 | The method of hydrogen fluoride is removed in hydrogen chloride gas |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN203346070U (en) * | 2012-12-31 | 2013-12-18 | 江苏梅兰化工有限公司 | Device for removing hydrogen fluoride in by-product hydrogen chloride in fluorine chemical engineering |
| CN105289032B (en) * | 2014-06-09 | 2019-05-31 | 张天德 | Highly volatile organic matter enfleurage method recovery process |
| CN106927423A (en) * | 2017-03-03 | 2017-07-07 | 巨化集团技术中心 | A kind of defluorination method of hydrofluoric acid containing acidic aqueous solution |
| CN107754495B (en) * | 2017-10-16 | 2019-05-03 | 北京化工大学 | A kind of system and device of gas cleaning and its application |
| CN107998827B (en) * | 2017-12-22 | 2019-11-01 | 江苏天楹环保能源成套设备有限公司 | A kind of high temperature gas containing acid fume hydrogen chloride recovery system |
| CN109966889A (en) * | 2017-12-28 | 2019-07-05 | 中国石油天然气集团公司 | The removing process of hydrogen sulfide in a kind of refinery gas |
-
2020
- 2020-08-03 CN CN202010768302.9A patent/CN111847382B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE841011A (en) * | 1975-04-25 | 1976-08-16 | PROCESS FOR SEPARATING HYDROFLUORIC ACID AND / OR SILICUM TETRA-FLUORIDE FROM HYDROCHLORIC GAS | |
| DE19535716A1 (en) * | 1995-09-26 | 1997-03-27 | Bayer Ag | Process for working up the reaction gases in the oxidation of HCl to chlorine |
| CN101495403A (en) * | 2006-05-23 | 2009-07-29 | 拜尔材料科学股份公司 | Method for oxidizing hydrogen chloride with oxygen |
| CA2764278A1 (en) * | 2009-06-26 | 2010-12-29 | Michael Lee Trippeer | Selective dehydrohalogenation of tertiary halogenated hydrocarbons and removal of tertiary halogenated hydrocarbon impurities |
| CN102874756A (en) * | 2012-09-24 | 2013-01-16 | 巨化集团技术中心 | Method for removing hydrogen fluoride from hydrogen chloride gas |
| CN105377751A (en) * | 2013-05-15 | 2016-03-02 | 旭硝子株式会社 | Method for purifying hydrogen chloride |
| EP2998270A1 (en) * | 2013-05-15 | 2016-03-23 | Asahi Glass Company, Limited | Method for purifying hydrogen chloride |
| CN203639145U (en) * | 2013-10-29 | 2014-06-11 | 洛阳万基金属钠有限公司 | Device for removing nitrogen trichloride from chlorine |
| CN106495100A (en) * | 2016-11-09 | 2017-03-15 | 中南大学 | A kind of removing fluohydric acid gas from hydrogen chloride gas the method for reclaiming fluohydric acid gas |
| CN106744688A (en) * | 2016-12-28 | 2017-05-31 | 兰州大学淮安高新技术研究院 | A kind of method for removing hydrogen fluoride gas in hydrogen chloride gas |
| CN109850848A (en) * | 2019-04-04 | 2019-06-07 | 南京工业大学 | The method of hydrogen fluoride is removed in hydrogen chloride gas |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111847382A (en) | 2020-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101648104B (en) | Technology for reclaiming hydrogen chloride tail gas in chemical production | |
| CN108212114A (en) | A kind of copper ion trace composite adsorbing material and preparation method thereof | |
| CN111847382B (en) | Reaction system for removing hydrogen fluoride in hydrogen chloride | |
| CN113072468B (en) | System and method for efficiently preparing taurine | |
| CN110157921A (en) | A method of rapidly extracting osmium in material containing osmium | |
| CN106702184A (en) | Clear water desorption process of alkalescence anion resin | |
| CN103028309A (en) | Absorption method of chlorinated tail gas | |
| CN105521697B (en) | Remove the absorbent and removal methods of monoxone sulfur dioxide in tail gas | |
| CN110465279A (en) | Catalyst without mercury carrier active carbon and preparation method thereof for PVC production | |
| CN103962107B (en) | A kind of preparation method of metal-modified humic acid defluorination absorbing material | |
| CN107019997A (en) | A kind of carbon tetrachloride hydrogen reducing solvent recovery technology from vent gas | |
| CN101428773A (en) | Purifying method for nitric oxide gas with 3N purity | |
| CN105480948A (en) | Method and system for recycling by-product hydrogen chloride in fatty acid or fatty acyl chloride chlorination production process | |
| CN204079524U (en) | A kind of high salt high ammonia-nitrogen sewage treatment system | |
| CN104324691B (en) | Preparation method of carbon adsorbent with high CO2 adsorption property | |
| CN209771794U (en) | Device for preparing liquid sulfur dioxide | |
| CN113929058A (en) | Catalyst carrier for preparing chlorine by catalytic oxidation of fluorine-containing HCl gas and preparation method and application thereof | |
| CN102923662A (en) | Method for separating hydrogen fluoride and hydrogen chloride in chloropyridine derivative fluorination process | |
| CN103083941B (en) | Method for increasing alcohol concentration in low carbon alcohol water system | |
| CN217410318U (en) | Carbon dioxide recovery system | |
| CN101549855A (en) | Alkali-removing method used for hydrogen production by borohydride | |
| CN111036065B (en) | Device for removing hydrogen fluoride and using method thereof | |
| CN117797786A (en) | Impregnating resin and preparation method thereof and method for separating tungsten and molybdenum | |
| CN215691759U (en) | System for hydrochloric acid removes free chlorine in succession | |
| CN104529006A (en) | Device capable of reducing acidity and moisture of dichloromethane waste liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |