CN113830828A - Preparation method of high-purity arsenic trichloride - Google Patents
Preparation method of high-purity arsenic trichloride Download PDFInfo
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- CN113830828A CN113830828A CN202111200952.4A CN202111200952A CN113830828A CN 113830828 A CN113830828 A CN 113830828A CN 202111200952 A CN202111200952 A CN 202111200952A CN 113830828 A CN113830828 A CN 113830828A
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- arsenic
- sulfuric acid
- trichloride
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- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 146
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 101
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 101
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 22
- 239000000460 chlorine Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 5
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000012074 organic phase Substances 0.000 claims description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000003513 alkali Substances 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 10
- 238000005507 spraying Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229960002594 arsenic trioxide Drugs 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 7
- 229910000413 arsenic oxide Inorganic materials 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000003350 kerosene Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- KTTMEOWBIWLMSE-UHFFFAOYSA-N diarsenic trioxide Chemical compound O1[As](O2)O[As]3O[As]1O[As]2O3 KTTMEOWBIWLMSE-UHFFFAOYSA-N 0.000 claims 1
- 239000012535 impurity Substances 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 53
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000005191 phase separation Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DKWUBXHBESRXMO-UHFFFAOYSA-N [Cl].[As] Chemical class [Cl].[As] DKWUBXHBESRXMO-UHFFFAOYSA-N 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/007—Halides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of high-purity arsenic trichloride, which comprises the following steps: (1) mixing and stirring arsenic powder and sulfuric acid in a reactor; (2) then introducing chlorine into the reactor, stopping introducing the chlorine when the reaction is carried out until no solid exists, continuing stirring for 2-3 hours, and then obtaining crude arsenic trichloride liquid and an arsenic-containing sulfuric acid solution; (3) and distilling the crude arsenic trichloride solution, and collecting 130-140 ℃ fractions to obtain high-purity arsenic trichloride. The preparation method comprises the steps of premixing a sulfuric acid solution and an arsenic raw material in a reactor, introducing chlorine gas into the reactor to react with arsenic, covering the sulfuric acid solution on the surface of the arsenic, controlling the reaction rate well, absorbing impurities of the generated arsenic trichloride by sulfuric acid, and removing impurities. In addition, the method does not need to sublimate the arsenic powder and then react with the chlorine, so that the energy consumption can be reduced, and the obtained arsenic trichloride has good purity and high yield.
Description
Technical Field
The invention relates to the technical field of inorganic chemical industry, in particular to a preparation method of high-purity arsenic trichloride.
Background
Arsenic trichloride is an inorganic compound, is colorless or light yellow fuming oily liquid, is mainly used for ceramic preparation, synthesis of arsenic-chlorine derivatives and the like, and is mainly applied to epitaxy and diffusion processes in the semiconductor preparation process and the preparation aspect of high-purity arsenic.
At present, the methods for producing arsenic trichloride mainly comprise a hydrochloric acid method and a gas phase chlorination method. The hydrochloric acid method for preparing the arsenic trichloride mainly comprises the following steps: adding arsenic trioxide into a reactor, adding concentrated hydrochloric acid, slowly adding concentrated sulfuric acid dropwise under stirring, removing water generated by reaction due to dropwise addition of the concentrated sulfuric acid, and precipitating the generated arsenic trichloride at the bottom of the reactor after two-phase separation. After the concentrated sulfuric acid is dripped, heating and distilling are carried out, and fractions at 90-107 ℃ are collected. And cooling the distillate, and separating the arsenic trichloride and the acid layer by using a separating funnel to obtain the arsenic trichloride product. Arsenic trichloride generated by the method is easy to hydrolyze in the reaction process to form arsenous acid, so that the yield is not high, the waste acid yield is high, and the treatment cost is high.
The gas phase chlorination method for preparing high-purity arsenic trichloride mainly comprises the following steps: taking crude arsenic containing 95-99% of arsenic as a raw material, sublimating to remove impurities such as iron, zinc and the like, introducing chlorine gas into the purified arsenic, reacting to generate arsenic trichloride, and distilling to obtain high-purity arsenic trichloride. In the method, crude arsenic needs to be sublimated firstly, and residues left in a sublimation furnace are easy to agglomerate, so that the operation is inconvenient. And the reaction is violent when the arsenic is initially reacted with the chlorine, and the reaction rate is difficult to control. The absorption of the arsenic-containing tail gas usually adopts sodium hydroxide lye for spraying, the arsenic-containing lye is directly used as waste liquid for treatment, the used reagents are more in the treatment process, the generated arsenic-containing hazardous waste amount is large, and the treatment cost is high.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of high-purity arsenic trichloride.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of high-purity arsenic trichloride comprises the following steps:
(1) mixing and stirring arsenic powder and sulfuric acid in a reactor;
(2) and then introducing chlorine into the reactor, stopping introducing the chlorine when no obvious solid exists in the reaction, and continuing stirring for 2-3 hours to ensure that the sulfuric acid is fully contacted with the crude arsenic trichloride solution, so as to wash away impurities in the arsenic trichloride. The method is characterized in that a sulfuric acid solution and arsenic trichloride are insoluble, impurities such as Se, Sb, Fe, Bi and the like have different solubilities in the arsenic trichloride and the sulfuric acid solution, the arsenic trichloride is washed by the sulfuric acid solution to remove impurities, and the impurities such as Se, Sb, Fe, Bi and the like in the arsenic trichloride enter the sulfuric acid solution to achieve the effect of removing the impurities. Then crude arsenic trichloride solution and arsenic-containing sulfuric acid solution are obtained.
(3) And distilling the crude arsenic trichloride solution, and collecting 130-140 ℃ fractions to obtain high-purity arsenic trichloride.
The inventor finds that the preparation method adopts the sulfuric acid solution and the arsenic raw material to be mixed in advance in the reactor, then chlorine is introduced into the reactor to react with arsenic, the sulfuric acid solution covers the surface of the arsenic, the reaction rate can be controlled better, and the sulfuric acid can absorb impurities of the generated arsenic trichloride to play a role in removing impurities. In addition, the method does not need to sublimate the arsenic powder and then react with the chlorine, so that the energy consumption can be reduced, and the obtained arsenic trichloride has good purity and high yield.
Preferably, in the step (1), the mass fraction of the sulfuric acid is 98%, and the arsenic powder and the sulfuric acid are fed according to the mass ratio of 1: 5-1: 10.
The inventor discovers through research that when the concentration of the sulfuric acid solution is low, the sulfuric acid solution contains more water, the introduced chlorine and water are used for forming the hydrochloric acid solution, the arsenic trichloride is dissolved in the hydrochloric acid solution, the hydrochloric acid and the sulfuric acid solution are mutually soluble, the three solutions are mutually soluble, the arsenic trichloride is difficult to separate, and therefore the mass fraction of the sulfuric acid solution is selected to be 98%. The sulfuric acid solution mainly has the following functions in the reaction system: firstly, covering the surface of arsenic to control the reaction rate; secondly, absorbing impurities of the generated arsenic trichloride, and simultaneously, a small amount of arsenic is dissolved in sulfuric acid to cause arsenic loss, so that the arsenic powder and the sulfuric acid are fed according to the mass ratio of 1: 5-1: 10, because the mass of the sulfuric acid is low when the mass of the sulfuric acid is too low, the impurity removal effect of the arsenic trichloride is negatively influenced, the mass of the sulfuric acid is high when the mass of the sulfuric acid is too high, the arsenic loss is large, the feeding ratio is controlled to be 1: 5-1: 10, and the three aspects of comprehensive reaction rate, impurity removal effect and arsenic loss rate are relatively suitable.
Preferably, the introduction amount of the chlorine gas in the step (2) is 40-100L/h. The inventor discovers through research that the reaction rate is influenced by the introduction amount of chlorine, the reaction rate is reduced due to the excessively low introduction rate of chlorine, the reaction time is prolonged, the introduction rate of chlorine is excessively high, excessive chlorine cannot participate in the reaction, and chlorine loss is caused, and when the introduction amount is selected to be 40-100L/h, the reaction rate is optimal.
Preferably, the preparation method of the high-purity arsenic trichloride further comprises the recovery treatment of an arsenic-containing sulfuric acid solution, and specifically comprises the following steps:
(a) diluting the arsenic-containing sulfuric acid solution obtained in the step (2) with water, wherein the arsenic-containing sulfuric acid solution and the water are diluted according to the volume ratio of 1: 1-1: 3; the inventor finds that if the phase separation speed is low without dilution, the phase separation speed can be accelerated by diluting the arsenic-containing sulfuric acid solution with water.
(b) Performing five-stage extraction on the arsenic-extracted organic phase and the arsenic-containing sulfuric acid solution diluted in the step (a), and extracting the arsenic-extracted organic phase and the arsenic-containing sulfuric acid solution diluted in the step (a) according to the volume ratio of 1: 1-1: 3 to obtain an arsenic-rich organic phase;
(c) carrying out four-stage water washing on the arsenic-rich organic phase by using water at the temperature of 60-100 ℃, wherein the volume ratio of the water to the arsenic-rich organic phase is 1: 3-1: 6, and obtaining an arsenic-rich water phase after water washing;
(d) and evaporating, concentrating and crystallizing the arsenic-rich water phase to obtain an arsenic oxide byproduct.
Preferably, in the step (a), the arsenic-containing sulfuric acid solution is diluted with water in a volume ratio of 1: 1.
Preferably, in the step (b), the arsenic extraction organic phase consists of 30 volume percent of TBP and 70 volume percent of kerosene; and (c) extracting the arsenic organic phase with the arsenic-containing sulfuric acid solution diluted in the step (a) according to the volume ratio of 1: 1.
Preferably, in the step (c), the arsenic-rich organic phase is washed with water at 70 ℃, and the volume ratio of the water to the arsenic-rich organic phase is 1: 3. The inventor finds that backwashing the arsenic-rich organic phase by using water with the temperature of 70 ℃ can accelerate phase separation.
The method for recycling the arsenic-containing sulfuric acid solution carries out resource treatment on the arsenic-containing sulfuric acid solution instead of simply treating the arsenic-containing sulfuric acid solution as wastewater, and compared with the prior art, the method not only recycles reaction byproducts, but also reduces the discharge of pollutants, and is green and environment-friendly.
Preferably, the preparation method of the high-purity arsenic trichloride further comprises tail gas treatment, wherein the tail gas mainly contains chlorine and arsenic trichloride, the original arsenic-containing tail gas absorption is realized by adopting two-stage sodium hydroxide alkali liquor for spraying absorption, the arsenic-containing alkali liquor is directly used as wastewater for treatment, more reagents are added in the treatment engineering, the generated arsenic-containing hazardous waste amount is large, and the treatment cost is high. The tail gas treatment step of the invention is to introduce the tail gas into a sulfuric acid solution and then introduce the tail gas into a sodium hydroxide alkali liquor spraying system.
Preferably, the sulfuric acid solution is sulfuric acid with the mass fraction of 98% at the temperature of 0-5 ℃. The inventor finds that part of arsenic trichloride in the tail gas can be condensed and precipitated to the bottom of concentrated sulfuric acid by introducing the tail gas into cold concentrated sulfuric acid solution. The arsenic-containing tail gas is pretreated by cold concentrated sulfuric acid and then enters the original alkali liquor spraying system, so that the arsenic content in the alkali liquor can be effectively reduced, and arsenic trichloride condensed from the cold concentrated sulfuric acid can be used as a raw material for reutilization.
The invention has the beneficial effects that: the invention provides a preparation method of high-purity arsenic trichloride, when arsenic reacts with chlorine, sulfuric acid solution is adopted for covering, the reaction rate is controlled, the sulfuric acid solution absorbs impurities in the arsenic trichloride, a crude arsenic sublimation step is not needed, the energy consumption is low, and then the high-purity arsenic trichloride obtained by distilling the obtained crude arsenic trichloride is high in yield. And the sulfuric acid solution can be recycled after being treated, and the concentrated sulfuric acid is used as a raw material after condensing arsenic trichloride in the tail gas, so that the arsenic content in the alkali liquor of the spray tower is effectively reduced, and the problems of large arsenic-containing hazardous waste amount, high treatment cost and the like caused by arsenic-containing waste liquid treatment are solved.
Detailed Description
To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to specific examples.
Example 1
The embodiment of the invention provides a preparation method of high-purity arsenic trichloride, which comprises the following steps: 200g of arsenic powder (with the As content of 99.5%) is taken, 1L of 98% sulfuric acid solution is added, chlorine is introduced at the flow rate of 60L/h, when no obvious solid exists in the container, the chlorine is stopped to be introduced, the solution is stirred for 2h and then separated to obtain 461 crude arsenic trichloride solution (containing impurities of Fe:2mg/L, Bi:5mg/L, Sb:221mg/L, Se:11mg/L and S:166mg/L) and arsenious sulfuric acid solution, then the crude arsenic trichloride solution is distilled, 130-plus-140 ℃ fractions are collected to obtain 443g of high-purity arsenic trichloride solution, the yield is 91.5%, and the purity is more than 99.99%.
The method comprises the following steps of treating the arsenic-containing sulfuric acid solution: diluting concentrated sulfuric acid containing arsenic with water according to the ratio of 1: 1; extracting an arsenic-extracting organic phase (composed of 30% of TBP and 70% of kerosene by volume fraction) and a diluted arsenic-containing sulfuric acid solution according to the volume ratio of 1:1, and performing five-stage extraction to obtain an arsenic-rich organic phase; washing the arsenic-rich organic phase by pure water at 70 ℃, wherein the volume ratio of water to the arsenic-rich organic phase is 1:3, and washing the arsenic-rich organic phase by four stages to obtain an arsenic-rich water phase; the arsenic-rich water phase is evaporated, concentrated and crystallized to obtain an arsenic oxide byproduct, and the arsenic oxide byproduct is recycled by qualified factories.
The tail gas treatment step specifically comprises the following steps: introducing the tail gas into concentrated sulfuric acid solution at 0 ℃ to condense and precipitate part of arsenic trichloride in the tail gas to the bottom of concentrated sulfuric acid. Then introducing the tail gas into the original sodium hydroxide alkali liquor spraying system. The arsenic content in the arsenic-containing waste liquid is 1236mg/L.
Example 2
The embodiment of the invention provides a preparation method of high-purity arsenic trichloride, which comprises the following steps: 200g of arsenic powder (with the As content of 99.5%) is taken, 1L of 98% sulfuric acid solution is added, chlorine is introduced at the flow rate of 80L/h, when no obvious solid exists in the container, the chlorine is stopped to be introduced, the container is stirred for 2h and then subjected to liquid separation to obtain 467g of crude arsenic trichloride solution (containing impurities of 1mg/L Fe, 2mg/L Bi, 156mg/L Sb, 9mg/L Se and 96mg/L S), the crude arsenic trichloride solution is distilled, and the fraction at 140 ℃ of 130-.
The method comprises the following steps of treating the arsenic-containing sulfuric acid solution: diluting concentrated sulfuric acid containing arsenic with water according to the ratio of 1: 3; extracting an arsenic-extracting organic phase (composed of 30% of TBP and 70% of kerosene by volume fraction) and a diluted arsenic-containing sulfuric acid solution according to the volume ratio of 1:3, and performing five-stage extraction to obtain an arsenic-rich organic phase; washing the arsenic-rich organic phase by pure water at 90 ℃, wherein the volume ratio of water to the arsenic-rich organic phase is 1:6, and washing the arsenic-rich organic phase by four stages to obtain an arsenic-rich water phase; the arsenic-rich water phase is evaporated, concentrated and crystallized to obtain an arsenic oxide byproduct, and the arsenic oxide byproduct is recycled by qualified factories.
The tail gas treatment step specifically comprises the following steps: introducing the tail gas into concentrated sulfuric acid solution at 5 ℃ to condense and precipitate part of arsenic trichloride in the tail gas to the bottom of concentrated sulfuric acid. Then introducing the tail gas into the original sodium hydroxide alkali liquor spraying system. The arsenic content in the arsenic-containing waste liquid is 1162 mg/L.
Comparative example 1
The preparation method of the high-purity arsenic trichloride as the comparative example of the invention is basically the same as the preparation method of the example 1, and the only difference is that: and (3) tail gas treatment, namely spraying and absorbing by adopting a secondary sodium hydroxide alkali liquor in the comparative example 1, wherein the arsenic content in the arsenic-containing waste liquid is 6329 mg/L.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (9)
1. The preparation method of high-purity arsenic trichloride is characterized by comprising the following steps:
(1) mixing and stirring arsenic powder and sulfuric acid in a reactor;
(2) then introducing chlorine into the reactor, stopping introducing the chlorine when the reaction is carried out until no solid exists, continuing stirring for 2-3 hours, and then obtaining crude arsenic trichloride liquid and an arsenic-containing sulfuric acid solution;
(3) and distilling the crude arsenic trichloride solution, and collecting 130-140 ℃ fractions to obtain high-purity arsenic trichloride.
2. The preparation method of high-purity arsenic trichloride according to claim 1, wherein the mass fraction of sulfuric acid in the step (1) is 98%, and the arsenic powder and the sulfuric acid are fed in a mass ratio of 1: 5-1: 10.
3. The method for preparing high-purity arsenic trichloride according to claim 1, wherein the amount of chlorine gas introduced in the step (2) is 40-100L/h.
4. The method for preparing high-purity arsenic trichloride according to any one of claims 1 to 3, further comprising a recovery treatment of the arsenic-containing sulfuric acid solution, comprising the steps of:
(a) diluting the arsenic-containing sulfuric acid solution obtained in the step (2) with water, wherein the arsenic-containing sulfuric acid solution and the water are diluted according to the volume ratio of 1: 1-1: 3;
(b) extracting with an arsenic-extracting organic phase relative to the arsenic-containing sulfuric acid solution diluted in the step (a), and extracting with the arsenic-extracting organic phase and the arsenic-containing sulfuric acid solution diluted in the step (a) according to a volume ratio of 1: 1-1: 3 to obtain an arsenic-rich organic phase;
(c) washing the arsenic-rich organic phase with water at the temperature of 60-100 ℃, wherein the volume ratio of the water to the arsenic-rich organic phase is 1: 3-1: 6, and obtaining an arsenic-rich water phase after washing;
(d) and evaporating, concentrating and crystallizing the arsenic-rich water phase to obtain an arsenic oxide byproduct.
5. The method of producing high-purity arsenic trichloride as claimed in claim 4, wherein in the step (a), the arsenic-containing sulfuric acid solution is diluted with water in a volume ratio of 1: 1.
6. The method for preparing high-purity arsenic trichloride as claimed in claim 4, wherein in the step (b), the arsenic extraction organic phase is composed of 30% by volume of TBP and 70% by volume of kerosene; and (c) extracting the arsenic organic phase with the arsenic-containing sulfuric acid solution diluted in the step (a) according to the volume ratio of 1: 1.
7. The method for preparing high-purity arsenic trichloride as claimed in claim 4, wherein in the step (c), the arsenic-rich organic phase is washed with water at 70 ℃, and the volume ratio of the water to the arsenic-rich organic phase is 1: 3.
8. The method for preparing high-purity arsenic trichloride according to any one of claims 1 to 3, further comprising a tail gas treatment step, wherein the tail gas is introduced into a sulfuric acid solution, and then the tail gas is introduced into a sodium hydroxide alkali liquor spraying system.
9. The method for preparing high-purity arsenic trichloride according to claim 8, wherein the sulfuric acid solution is sulfuric acid with a mass fraction of 98% at 0-5 ℃.
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| CN114105195A (en) * | 2021-12-31 | 2022-03-01 | 红河砷业有限责任公司 | Method for reducing tin content in arsenic trichloride |
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| CN103184354A (en) * | 2011-12-29 | 2013-07-03 | 广东先导稀材股份有限公司 | Preparation method of high-purity arsenic |
| CN107963663A (en) * | 2017-12-27 | 2018-04-27 | 清远先导材料有限公司 | The synthetic method of arsenic trichloride |
| CN111471874A (en) * | 2020-04-07 | 2020-07-31 | 中南大学 | Method for extracting and separating arsenic and iron by chloride system |
| CN113184905A (en) * | 2021-05-12 | 2021-07-30 | 广东先导稀材股份有限公司 | Impurity removing method for arsenic trichloride high-boiling residue |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114105195A (en) * | 2021-12-31 | 2022-03-01 | 红河砷业有限责任公司 | Method for reducing tin content in arsenic trichloride |
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