CN111377478A - Purification method of arsenic trioxide - Google Patents
Purification method of arsenic trioxide Download PDFInfo
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- CN111377478A CN111377478A CN201811643631.XA CN201811643631A CN111377478A CN 111377478 A CN111377478 A CN 111377478A CN 201811643631 A CN201811643631 A CN 201811643631A CN 111377478 A CN111377478 A CN 111377478A
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- GOLCXWYRSKYTSP-UHFFFAOYSA-N arsenic trioxide Inorganic materials O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 title claims abstract description 118
- HJTAZXHBEBIQQX-UHFFFAOYSA-N 1,5-bis(chloromethyl)naphthalene Chemical compound C1=CC=C2C(CCl)=CC=CC2=C1CCl HJTAZXHBEBIQQX-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000000746 purification Methods 0.000 title claims abstract description 34
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims abstract description 44
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 31
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000013014 purified material Substances 0.000 claims abstract description 18
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000009833 condensation Methods 0.000 claims description 17
- 230000005494 condensation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 26
- 230000008569 process Effects 0.000 abstract description 25
- 230000003647 oxidation Effects 0.000 abstract description 21
- 239000012535 impurity Substances 0.000 abstract description 17
- 238000009835 boiling Methods 0.000 abstract description 7
- 238000005092 sublimation method Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 66
- 238000000859 sublimation Methods 0.000 description 23
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 17
- 230000008022 sublimation Effects 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 13
- 229910052717 sulfur Inorganic materials 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 229910052732 germanium Inorganic materials 0.000 description 7
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 7
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000005019 vapor deposition process Methods 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000005922 Phosphane Substances 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- -1 arsenic trioxide compound Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910000078 germane Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000064 phosphane Inorganic materials 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G28/00—Compounds of arsenic
- C01G28/005—Oxides; Hydroxides; Oxyacids
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a method for purifying arsenic trioxide. The purification method comprises the following steps: step S1, oxidizing the crude arsenic trioxide to be purified by ozone to obtain an oxidized material; step S2, heating the oxidized material to enable sulfur trioxide and phosphorus pentoxide in the oxidized material to sublime and escape and separate from arsenic trioxide to obtain a primary purified material; and step S3, heating the primary purified material to enable the arsenic trioxide therein to sublimate and escape, and then condensing to obtain the purified arsenic trioxide. Oxidizing each impurity of the crude arsenic trioxide into oxides by an oxidation process, then separating low-boiling-point oxides from the arsenic trioxide by the difference of boiling points and heating temperatures, and then sublimating the arsenic trioxide to separate the arsenic trioxide from high-boiling-point impurities, thereby obtaining the purified arsenic trioxide. Ozone oxidation in the above-mentioned flow is easily realized, and the sublimation process all is that the physical process is easily controlled, therefore the purification method of this application is easily controlled and easy realization efficiency is higher.
Description
Technical Field
The invention relates to the field of preparation of arsenic trioxide, and particularly relates to a purification method of arsenic trioxide.
Background
Arsine is an important raw material for the production of semiconductor devices, thin film solar cells, and the like. For example, arsine is an important special gas for producing gallium arsenide, and gallium arsenide thin-film solar cells generally require a gas source with the purity reaching 6N level. The method for preparing arsine by electrolysis can realize the on-line production of arsine and avoid the safety risk brought by the storage and transportation of arsine. Because the purification of gas has high requirements on the process and the process is difficult to control, the raw material arsenic trioxide for electrolysis is sought to be purified to remove compounds which can generate impurity gases in the electrolysis process so as to prepare higher-purity arsine.
The impurity gases in the arsine gas, which have a large influence on the subsequent vapor deposition process, mainly comprise germane, phosphane, silane, hydrogen sulfide, carbonyl sulfide and the like, and the gases have a large influence on the vapor deposition process and are difficult to detect, so the method is mainly designed for removing the arsenic trioxide compound containing phosphorus, silicon, germanium and sulfur.
Disclosure of Invention
The invention mainly aims to provide a method for purifying arsenic trioxide, which solves the problem of low efficiency of the method for purifying arsenic trioxide in the prior art.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for purifying arsenic trioxide, comprising: step S1, oxidizing the crude arsenic trioxide to be purified by ozone to obtain an oxidized material; step S2, heating the oxidized material to enable sulfur trioxide and phosphorus pentoxide in the oxidized material to sublime and escape and separate from arsenic trioxide to obtain a primary purified material; and step S3, heating the primary purified material to enable the arsenic trioxide therein to sublimate and escape, and then condensing to obtain the purified arsenic trioxide.
Further, the step S1 includes: oxidizing the crude arsenic trioxide by ozone at 50-100 ℃, wherein the ozone is continuously introduced into the crude arsenic trioxide at a flow rate of 0.1-2L/min.
Further, the step S2 includes: controlling the temperature of the oxidized material to be 50-100 ℃, so that sulfur trioxide is sublimated and escaped to obtain a first separated material; and heating the first separated material to 300-400 ℃ to enable phosphorus pentoxide to sublimate and escape, thereby obtaining a primary purified material.
Further, the escaped sulfur trioxide is absorbed by water, and the temperature of the water for absorbing the sulfur trioxide is preferably between 5 and 50 ℃.
Further, the sulfur trioxide is introduced into the water at a flow rate of 0.003L/min or less.
Further, the temperature of the water used for absorbing the escaped phosphorus pentoxide is preferably 1-30 ℃.
Further, the phosphorus pentoxide is introduced into the water at a flow rate of 0.0001L/min or less.
Further, the step S3 includes: heating the primary purified material to 460-600 ℃ to enable the arsenic trioxide therein to sublimate and escape; the gaseous arsenic trioxide is condensed to obtain purified arsenic trioxide, preferably in a different apparatus than the apparatus in which step S2 and step S3 are performed.
Further, the gaseous arsenic trioxide is condensed by the steam condensing device, wherein the gaseous arsenic trioxide is controlled to enter the steam condensing device for condensation at the flow rate of 0.0001L/min-0.5L/min.
Further, the condensation temperature of the gaseous arsenic trioxide is 0-10 ℃.
By applying the technical scheme of the invention, impurities such as phosphorus, silicon, germanium, sulfur and the like in the crude arsenic trioxide are oxidized into oxides by an oxidation process, then the low-boiling-point oxides are separated from the arsenic trioxide by utilizing the boiling point difference between each oxide and the arsenic trioxide and the heating temperature is different, and then the arsenic trioxide is sublimated and separated from the high-boiling-point impurities, thereby obtaining the purified arsenic trioxide. Ozone oxidation in the above-mentioned flow is easily realized, and the sublimation process all is that the physical process is easily controlled, therefore the purification method of this application is easily controlled and easy realization efficiency is higher.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows a schematic diagram of a purification system for carrying out the arsenic trioxide purification process according to the present invention.
Wherein the figures include the following reference numerals:
1. a constant temperature water tank; 2. an ozone generating device; 3. a first reaction tank; 4. a second reaction tank; 5. a steam condensing device.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
As analyzed by the background art of the present application, the prior art has a high requirement on the purity of arsine gas, and needs to purify arsenic trioxide, which is a raw material for preparing arsine by electrolysis, in order to provide high-purity arsine gas. In order to solve the problem, the application provides a method for purifying arsenic trioxide. The purification method comprises the following steps: step S1, oxidizing the crude arsenic trioxide to be purified by ozone to obtain an oxidized material; step S2, heating the oxidized material to enable sulfur trioxide and phosphorus pentoxide in the oxidized material to sublime and escape and separate from arsenic trioxide to obtain a primary purified material; and step S3, heating the primary purified material to enable the arsenic trioxide therein to sublimate and escape, and then condensing to obtain the purified arsenic trioxide.
The method has the advantages that impurities such as phosphorus, silicon, germanium, sulfur and the like in the crude arsenic trioxide product are oxidized into high-valence oxides (the oxides of phosphorus, silicon, germanium and sulfur are determined by detecting and separating materials) through an oxidation process, namely, the ozone oxidation can oxidize the phosphorus into the high-valence phosphorus pentoxide, oxidize the sulfur into the high-valence sulfur trioxide, oxidize the germanium into the germanium dioxide and oxidize the silicon into the silicon dioxide. Then, by utilizing the boiling point difference between each oxide and the arsenic trioxide and the difference of heating temperature, the low boiling point oxide is firstly separated from the arsenic trioxide, and then the arsenic trioxide is sublimated and separated from high boiling point impurities, thereby obtaining the purified arsenic trioxide. Ozone oxidation in the above-mentioned flow is easily realized, and the sublimation process all is that the physical process is easily controlled, therefore the purification method of this application is easily controlled and easy realization efficiency is higher. The crude arsenic trioxide product is the crude arsenic trioxide product with the main impurities of phosphorus, silicon, germanium and sulfur.
In order to improve the oxidation efficiency, it is preferable that the step S1 includes: oxidizing the crude arsenic trioxide by ozone at 50-100 ℃, wherein the ozone is continuously introduced into the crude arsenic trioxide at a flow rate of 0.1-2L/min. Placing the crude arsenic trioxide product in a reaction tank, continuously introducing ozone, wherein the continuously introduced ozone has a spraying effect on the arsenic trioxide, so that the contact effect of two reactants is improved, and the reaction efficiency is accelerated; meanwhile, the oxidation is controlled to occur at 50-100 ℃, so that the reaction efficiency is further improved.
In a preferred embodiment, the step S2 includes: controlling the temperature of the oxidized material to be 50-100 ℃, so that sulfur trioxide is sublimated and escaped to obtain a first separated material; and heating the first separated material to 300-400 ℃ to enable phosphorus pentoxide to sublimate and escape, thereby obtaining a primary purified material. Because the temperature of the oxidized material is 50-100 ℃, the sulfur trioxide in the oxidized material can escape to obtain a first separated material without the sulfur trioxide after the reaction tank is opened, and then the first separated material is heated to raise the temperature to 300-400 ℃ so as to sublimate and escape the phosphorus pentoxide, thereby obtaining the initially purified material without the sulfur trioxide and the phosphorus pentoxide. Through the control of the temperature, the sulfur trioxide and the phosphorus pentoxide can quickly escape without causing the loss of arsenic trioxide. The above-mentioned process of sulfur trioxide sublimation evolution can also take place simultaneously in the ozone oxidation process.
The above-mentioned escaped sulfur trioxide can be collected and stored after condensation, preferably by absorbing the escaped sulfur trioxide with water to form a sulfuric acid by-product, improving the economic effect of the purification process of the present application. In order to improve the absorption efficiency, the temperature of the water for absorbing sulfur trioxide is preferably between 5 and 50 ℃. In order to avoid the loss of sulfur trioxide, the sulfur trioxide is preferably introduced into water at a flow rate of 0.003L/min or less.
The escaped phosphorus pentoxide can be condensed and collected for storage, and preferably the escaped phosphorus pentoxide is absorbed by water to form a phosphoric acid byproduct, thereby improving the economic efficiency of the purification method of the present application. In order to improve the absorption efficiency, the temperature of the water for absorbing the phosphorus pentoxide is preferably between 1 and 30 ℃. In order to avoid loss of phosphorus pentoxide, the phosphorus pentoxide is preferably introduced into water at a flow rate of 0.0001L/min or less.
In an embodiment of the present application, the step S3 includes: heating the primary purified material to 460-600 ℃ to enable the arsenic trioxide therein to sublimate and escape; condensing the gaseous arsenic trioxide to obtain the purified arsenic trioxide. Through the control of the temperature, arsenic trioxide rapidly escapes, and germanium dioxide and silicon dioxide with high boiling points are not sublimated basically. Preferably, the step S2 and the step S3 are performed in different devices, and different devices are used for sublimating sulfur trioxide, phosphorus pentoxide and arsenic trioxide, so that the overall efficiency of the process is improved, and the primary purification of the next group of materials can be performed while the arsenic trioxide is sublimated; p which can also avoid sublimation2O5、SO3Gas remains in the apparatus and affects As2O3The purity of (2); conveniently cleaning germanium oxide and SiO without sublimation2。
In order to accelerate the condensation of arsenic trioxide, gaseous arsenic trioxide is preferably condensed by means of a steam condensation device, wherein the gaseous arsenic trioxide is fed into the steam condensation device for condensation at a flow rate of 0.0001L/min to 0.5L/min. Further, the condensation temperature of the gaseous arsenic trioxide is controlled to be 0-10 ℃.
The following illustrates the implementation of the above purification method:
the purification method is carried out by using the device shown in FIG. 1, and ozone is fed into the As-containing chamber from the ozone generating device 2 at a certain flow rate2O3In a first reaction tank 3 of the crude product, the first reaction tank 3 is adjusted to a certain temperature, and after a certain time, the impurity compounds are completely converted into corresponding oxides under the action of ozone, and the conversion rate is 95.99-99.99%; in which the sulfur element is SO3Is introduced into the constant-temperature water bath 1 from the first reaction tank 3 at a constant flow rate to absorb water, the water in the constant-temperature water bath 1 has a constant temperature to ensure that absorption can be rapidly performed, and the absorption is performed in the first reaction tank 3SO3SO detected in the outlet line3When the concentration of (B) is lower than a certain level, the SO is judged3Sublimating to obtain a first separated material, and adjusting the temperature of the first reaction tank 3 to a certain temperature to allow phosphorus oxide P to be obtained2O5Sublimating rapidly when detecting P in the outlet line2O5When the concentration of (B) is lower than a certain level, P is judged2O5Obtaining a primary purified material after sublimation; transferring the primary purified material in the first reaction tank 3 to a second reaction tank 4, adjusting the temperature of the second reaction tank 4 to a certain temperature, simultaneously switching an outlet pipeline of the second reaction tank 4 to be connected to a steam condensing device 5, As2O3Sublimating rapidly at the temperature, entering the steam condensing device 5 at a certain gas flow rate, and As after a certain time2O3Sublimation is finished by 98-99 percent, and germanium oxide and SiO2Sublimation at this temperature is slower, As2O3The steam is condensed in a steam condensing device 5 to obtain high-purity As2O3Powder with purity of 98.9-99.9%. After the first reaction tank 3 is used for sublimating sulfur trioxide and phosphorus pentoxide, the second reaction tank 4 is used for sublimating arsenic trioxide, so that the overall efficiency of the process is improved, and the primary purification of the next group of materials in the first reaction tank 3 can be carried out while the arsenic trioxide is sublimed in the second reaction tank 4; p which can also avoid sublimation2O5、SO3The gas is still inIn the first reaction tank 3, in turn, As2O3The purity of (2); conveniently clean the germanium oxide and SiO which are not sublimated in the second reaction tank 42。
The advantageous effects of the present application will be further described below with reference to examples and comparative examples.
The content of each element before and after purification is detected by an element analyzer, and then the removal proportion of impurities, the sublimation rate of the arsenic trioxide and the purity of the arsenic trioxide before and after purification are calculated.
Example 1
The following procedure was carried out using the purification apparatus shown in FIG. 1:
the ozone generating device 2 feeds ozone with the volume flow rate of 0.5L/min into the first reaction tank 3, and the temperature of the first reaction tank 3 is adjusted to 80 ℃; 10Kg of As with a mass fraction of 90%2O3The materials are subjected to oxidation reaction in the first reaction tank 3, and the weight of the materials is not increased after 5 hours, which indicates that the oxidation is complete; in which the sulfur element is SO3The mixture is absorbed by flowing into a constant temperature water tank 1 with a temperature of 40 ℃ from a first reaction tank 3 at a flow rate of 0.003L/min and 99.99% SO3Is removed in this process; the temperature of the first reaction tank 3 is adjusted to 400 ℃ so that P is2O5Fast sublimation; p2O5The steam enters a constant temperature water tank 1 with the temperature of 20 ℃ for absorption at the flow rate of 0.0001L/min, and P is obtained after 2h2O5After sublimation, 99% of P2O5Is removed in the process; as is2O3Transferring the material to a second reaction tank 4, raising the temperature of the second reaction tank 4 to 460 ℃, simultaneously switching an outlet pipeline of the second reaction tank 4 to be connected to a steam condensing device 5, condensing arsenic trioxide in the steam condensing device 5 at the flow rate of 0.5L/min, controlling the temperature of the steam condensing device 5 to be 5 ℃, and after 8h, adding As2O3Sublimation was completed 98.79%; as after completion of condensation2O3The purity of (2) was 99.5%.
Example 2
The following procedure was carried out using the purification apparatus shown in FIG. 1:
the ozone generating device 2 feeds volume flow into the first reaction tank 3Ozone with the speed of 1L/min, and the temperature of the first reaction tank 3 is adjusted to be 100 ℃; 10Kg of As with a mass fraction of 95%2O3The materials are subjected to oxidation reaction in the first reaction tank 3, the weight of the materials is not increased any more after 1 hour, so that the oxidation is complete, and the oxidation conversion rate of impurities is about 99.99 percent; in which the sulfur element is SO3Flows into a constant temperature water tank 1 with the temperature of 50 ℃ from a first reaction tank 3 for absorption, and has the flow rate of 0.001L/min and 99.99 percent of SO3Is removed in this process; the temperature of the first reaction tank 3 is adjusted to 370 ℃ so that P is2O5Fast sublimation; p2O5The steam enters a constant temperature water tank 1 with the temperature of 30 ℃ for absorption at the flow rate of 0.0001L/min, and P is obtained after 3h2O5After sublimation, 97.99% of P was present in the process2O5Is removed in the process; as is2O3Transferring the material to a second reaction tank 4, raising the temperature of the second reaction tank 4 to 500 ℃, simultaneously switching an outlet pipeline of the second reaction tank 4 to be connected to a steam condensing device 5, condensing arsenic trioxide in the condensing device at the flow rate of 0.1L/min, wherein the temperature of the condensing device is 10 ℃, and after 3 hours, the As is2O3The sublimation is finished by 99.99 percent; as after completion of condensation2O3The purity of (2) was 99.1%.
Example 3
The following procedure was carried out using the purification apparatus shown in FIG. 1:
the ozone generating device 2 feeds ozone with the volume flow rate of 0.1L/min into the first reaction tank 3, and the temperature of the first reaction tank 3 is adjusted to 50 ℃; 10Kg of As with a mass fraction of 95%2O3The materials are subjected to oxidation reaction in the first reaction tank 3, the weight of the materials is not increased any more after 3 hours, so that the oxidation is complete, and the oxidation conversion rate of impurities is about 99.99 percent; in which the sulfur element is SO3The solution is absorbed by flowing into a constant temperature water tank 1 with a temperature of 5 ℃ from a first reaction tank 3 at a flow rate of 0.001L/min and 99.99% SO3Is removed in this process; the temperature of the first reaction tank 34 is adjusted to 400 ℃ so that P is2O5Fast sublimation; p2O5The steam enters a constant temperature water tank 1 with the temperature of 5 ℃ at the flow rate of 0.0001L/minAbsorption, P after 3h2O5After sublimation, 98.99% of P2O5Is removed in the process; as is2O3Transferring the material to a second reaction tank 4, raising the temperature of the second reaction tank 4 to 600 ℃, simultaneously switching an outlet pipeline of the reaction tank to be connected to a steam condensing device 5, feeding arsenic trioxide into the steam condensing device 5 at the flow rate of 0.0005L/min for condensation, controlling the temperature of the steam condensing device 5 to be 10 ℃, and after 5h, adding As2O3The sublimation is finished by 99.99 percent; as after completion of condensation2O3The purity of (2) was 99.99%.
Example 4
The following procedure was carried out using the purification apparatus shown in FIG. 1:
the ozone generating device 2 feeds ozone with the volume flow rate of 2L/min into the first reaction tank 3, and the temperature of the first reaction tank 3 is adjusted to be 100 ℃; 10Kg of As with a mass fraction of 90%2O3The material is subjected to oxidation reaction in the first reaction tank 3, the material weight is not increased after 3 hours, the oxidation is complete, and the oxidation conversion rate of impurities is 98.99 percent; in which the sulfur element is SO3Flows into a constant temperature water tank 1 with the temperature of 50 ℃ from a first reaction tank 3 for absorption, and has the flow rate of 0.003L/min and 99.99 percent of SO3Is removed in this process; the temperature of the first reaction tank 3 is adjusted to 400 ℃ so that P is2O5Fast sublimation; p2O5The steam enters a constant temperature water tank 1 with the temperature of 30 ℃ for absorption at the flow rate of 0.0001L/min, and P is obtained after 3h2O5After sublimation, 99.99% P in the process2O5Is removed in the process; as is2O3Transferring the material to a second reaction tank 4, raising the temperature of the second reaction tank 4 to 500 ℃, simultaneously switching an outlet pipeline of the reaction tank to be connected into a steam condensing device 5, condensing arsenic trioxide in the steam condensing device 5 at the flow rate of 0.1L/min, controlling the temperature of the steam condensing device 5 to be 0 ℃, and after 10 hours, adding As2O3The sublimation is finished by 99.99 percent; as after completion of condensation2O3The purity of (2) was 99.99%.
Example 5
The following procedure was carried out using the purification apparatus shown in FIG. 1:
the ozone generating device 2 feeds ozone with the volume flow rate of 2L/min into the first reaction tank 3, and the temperature of the first reaction tank 3 is adjusted to be 100 ℃; 10Kg of As with a mass fraction of 90%2O3The material is subjected to oxidation reaction in the first reaction tank 3, the material weight is not increased after 3 hours, the oxidation is complete, and the oxidation conversion rate of impurities is 98.99 percent; in which the sulfur element is SO3Flows into a constant temperature water tank 1 with the temperature of 50 ℃ from a first reaction tank 3 for absorption, and has the flow rate of 0.003L/min and 99.99 percent of SO3Is removed in this process; the temperature of the first reaction tank 3 is adjusted to 350 ℃ so that P is2O5Fast sublimation; p2O5The steam enters a constant temperature water tank 1 with the temperature of 30 ℃ for absorption at the flow rate of 0.0001L/min, and P is obtained after 5h2O5After sublimation, 99.0% P in the process2O5Is removed in the process; as is2O3Transferring the material to a second reaction tank 4, raising the temperature of the second reaction tank 4 to 450 ℃, simultaneously switching an outlet pipeline of the reaction tank to be connected to a steam condensing device 5, feeding arsenic trioxide into the steam condensing device 5 at the flow rate of 0.0001L/min for condensation, controlling the temperature of the steam condensing device 5 to be 0 ℃, and after 20 hours, adding As2O3Sublimation was completed 98.43%; as after completion of condensation2O3The purity of (A) was 99.07%.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
according to the method, impurities such as phosphorus, silicon, germanium and sulfur in the crude arsenic trioxide product are oxidized into oxides through an oxidation process, then the low-boiling-point oxides are separated from the arsenic trioxide by utilizing the boiling point difference between each oxide and the arsenic trioxide through the difference of heating temperatures, then the arsenic trioxide is sublimated and separated from the high-boiling-point impurities, and thus the purified arsenic trioxide is obtained. Ozone oxidation in the above-mentioned flow is easily realized, and the sublimation process all is that the physical process is easily controlled, therefore the purification method of this application easily controls and realizes higher efficiency easily.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for purifying arsenic trioxide, which is characterized by comprising the following steps:
step S1, oxidizing the crude arsenic trioxide to be purified by ozone to obtain an oxidized material;
step S2, heating the oxidized material to enable sulfur trioxide and phosphorus pentoxide in the oxidized material to sublimate and escape to be separated from arsenic trioxide, and obtaining a primary purified material; and
and step S3, heating the primary purified material to enable the arsenic trioxide therein to sublimate and escape, and then condensing to obtain the purified arsenic trioxide.
2. The purification method according to claim 1, wherein the step S1 includes:
and oxidizing the crude arsenic trioxide by using the ozone at the temperature of 50-100 ℃, wherein the ozone is continuously introduced into the crude arsenic trioxide at the flow rate of 0.1-2L/min.
3. The purification method according to claim 1, wherein the step S2 includes:
controlling the temperature of the oxidized material to be 50-100 ℃, so that the sulfur trioxide is sublimated and escaped to obtain a first separated material;
and heating the first separated material to 300-400 ℃ to enable the phosphorus pentoxide to sublimate and escape, so as to obtain a primary purified material.
4. The purification process according to claim 1, characterized in that the sulphur trioxide escaping is absorbed with water, preferably the temperature of the water used for absorbing the sulphur trioxide is between 5 and 50 ℃.
5. The purification process according to claim 4, wherein the sulfur trioxide is introduced into the water at a flow rate of 0.003L/min or less.
6. The purification method according to claim 1, wherein the phosphorus pentoxide escaping is absorbed by water, preferably the temperature of the water used for absorbing the phosphorus pentoxide is between 1 and 30 ℃.
7. The purification method according to claim 6, wherein the phosphorus pentoxide is introduced into the water at a flow rate of 0.0001L/min or less.
8. The purification method according to claim 1, wherein the step S3 includes:
heating the primary purified material to 460-600 ℃ to enable the arsenic trioxide in the primary purified material to sublimate and escape;
condensing the gaseous arsenic trioxide to obtain purified arsenic trioxide, preferably wherein said step S2 and said step S3 are performed in different apparatuses.
9. The purification method according to claim 8, wherein the gaseous arsenic trioxide is condensed by a steam condensing device, wherein the gaseous arsenic trioxide is controlled to enter the steam condensing device for condensation at a flow rate of 0.0001L/min to 0.5L/min.
10. The purification process according to claim 8, wherein the gaseous arsenic trioxide has a condensation temperature of 0 to 10 ℃.
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| CN114314657A (en) * | 2022-02-18 | 2022-04-12 | 郑州德凯科技有限公司 | Production device and method for continuously preparing arsenic trioxide |
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