CN111829850B - Method for directly synthesizing high-purity sulfur-arsenic-copper ore by solid-phase reaction - Google Patents
Method for directly synthesizing high-purity sulfur-arsenic-copper ore by solid-phase reaction Download PDFInfo
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- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- VWZXPOSFVRUORB-UHFFFAOYSA-N [As].[S].[Cu] Chemical compound [As].[S].[Cu] VWZXPOSFVRUORB-UHFFFAOYSA-N 0.000 title description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 41
- 239000010439 graphite Substances 0.000 claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000010949 copper Substances 0.000 claims abstract description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 16
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 12
- 229910052785 arsenic Inorganic materials 0.000 claims abstract description 11
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 239000012071 phase Substances 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 7
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000005540 biological transmission Effects 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 238000007605 air drying Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000005498 polishing Methods 0.000 claims abstract description 4
- 238000003860 storage Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052697 platinum Inorganic materials 0.000 claims description 18
- 235000012431 wafers Nutrition 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 229910052683 pyrite Inorganic materials 0.000 claims description 6
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011028 pyrite Substances 0.000 claims description 6
- 229910052971 enargite Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007858 starting material Substances 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 150000001495 arsenic compounds Chemical class 0.000 claims 1
- 229940093920 gynecological arsenic compound Drugs 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 229910052964 arsenopyrite Inorganic materials 0.000 abstract description 9
- MJLGNAGLHAQFHV-UHFFFAOYSA-N arsenopyrite Chemical compound [S-2].[Fe+3].[As-] MJLGNAGLHAQFHV-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 11
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 238000005245 sintering Methods 0.000 description 9
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 6
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052948 bornite Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- LRVADRRXFCBAMY-UHFFFAOYSA-N [Cu].[As].[Cu] Chemical compound [Cu].[As].[Cu] LRVADRRXFCBAMY-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052951 chalcopyrite Inorganic materials 0.000 description 2
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910052569 sulfide mineral Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- JEMGLEPMXOIVNS-UHFFFAOYSA-N arsenic copper Chemical compound [Cu].[As] JEMGLEPMXOIVNS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 chalcopyrite Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- BPQWCZKMOKHAJF-UHFFFAOYSA-N scheele's green Chemical compound [Cu+2].O[As]([O-])[O-] BPQWCZKMOKHAJF-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- G01N1/32—Polishing; Etching
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N1/34—Purifying; Cleaning
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Abstract
The invention discloses a method for directly synthesizing high-purity copper arsenopyrite through solid-phase reaction, wherein analytically pure copper sulfide and analytically pure arsenic disulfide are weighed according to a molar ratio of 6:1, and are uniformly ground and mixed to serve as initial raw materials; pressing the mixture powder into a cylinder, covering the end face with a sulfur powder wafer, sequentially filling the sulfur powder wafer, the mixture cylinder and the sulfur powder wafer into a platinum-graphite double-sample cavity, sealing to prepare a sample, placing the sample into an h-BN tube, and taking the h-BN as a pressure transmission medium; carrying out high-temperature high-pressure reaction on a cubic apparatus press, taking out a reacted cylindrical sample, polishing, ultrasonically cleaning, air-drying, and then placing in an inert gas atmosphere for storage. The obtained copper arsenopyrite is a single phase and has no impurities.
Description
Technical Field
The invention relates to a method for directly synthesizing high-purity sulfur-arsenic-copper ore by solid-phase reaction, belonging to the field of mineralogy research.
Background
The copper-arsenic-copper ore is a common copper-arsenic sulfide mineral, and is usually a columnar, platy or granular aggregate, and sulfides such as chalcopyrite, bornite and the like are enriched in the bornite with hydrothermal formation, so that the copper-arsenic-copper ore is one of important mineral raw materials for extracting copper and arsenic. The copper arsenopyrite is one of the most difficult sulfide minerals to treat because it is chemically stable and forms a protective film of oxides and complex sulfides on its surface in air to prevent its internal oxidation. The natural copper pyrite has very complex components and often contains microscopic inclusions of symbiotic minerals such as chalcopyrite, bornite and the like. Due to the lack of the standard sample of the high-purity atacamite, quantitative research on the atacamite cannot be carried out. The artificial synthesis of copper-containing sulfide mainly adopts a hydrothermal method, but the copper arsenopyrite belongs to the sulfide containing arsenic, has high toxicity and is difficult to control experimental operation. Therefore, exploring the standard sample synthesis of the copper pyrite is the basis for quantitatively researching the porphyritic copper mine.
The solid phase reaction method is the most basic synthesis method in the field of materials, and means that a target product is generated by sintering a starting material at a high temperature and performing a solid phase diffusion reaction. Most commonly, two oxides are formed into the desired product by a solid phase reaction method, for example, copper oxide CuO and strontium oxide SrO (strontium oxide SrO is obtained by decomposing strontium carbonate) are mixed at a molar ratio of 1:1, and directly sintered at 980 ℃ for 12 hours by a solid phase reaction method to form copper oxide SrCuO2. We can think about whether we can go through analogy with SrCuO2By solid phase reaction of copper sulfide CuS and arsenic disulfide As2S2Mixing the materials according to a molar ratio of 6:1, and directly sintering the mixture by utilizing a solid-phase reaction to generate the copper arsenopyrite Cu3AsS4Is there a In fact, this reaction is very difficult to control experimentally due to the poor chemical stability of the sulfide, since (1) it is completely distinguished from the solid-phase reaction of oxides, CuS and As2S2Sintering in air can directly oxidize to generate oxide and can not generate Cu3AsS4. (2) The problem that part of materials are easy to oxidize can be effectively solved by using a quartz vacuum tube sealing technology, for example, iron-based superconducting 111-type LiFeAs can be obtained by directly sintering lithium powder Li, iron powder Fe and arsenic powder As in a vacuum tube. However, elemental sulfur S is very volatile compared to heavier arsenic As. During the high-temperature sintering process, sulfide can undergo auto-oxidation reduction to carry out desulfurization reaction, and sulfur is extremely easy to volatilize to cause loss. The higher the sintering temperature and the longer the sintering time, the more severe the desulfurization reaction. Therefore, although the vacuum tube can avoid the oxidation of sulfide, the open system can not solve the problems of desulfurization reaction and elemental sulfur volatilization, so that the solid-phase reaction is difficult to be carried out according to the stoichiometric proportion of the copper arsenopyrite, and the purity of the product can not be ensured.
Disclosure of Invention
The invention aims to solve the problems and provide a method for directly synthesizing high-purity atacamite by solid-phase reaction so as to solve the technical problem of quantitative research on porphyrite copper ore at present.
The purpose of the invention is realized by the following technical scheme: a method for directly synthesizing high-purity atacamite by solid-phase reaction comprises the following steps:
step 1, use of analytically pure copper sulfide CuS and analytically pure arsenic disulfide As2S2Weighing according to the molar ratio of 6:1, grinding and uniformly mixing to obtain a starting material;
step 2, pressing the mixture powder in the step 1 into a cylinder with phi 5mm multiplied by 5mm by using a powder tablet press, pressing analytically pure sulfur powder S into wafers with phi 5mm multiplied by 0.5mm by using the powder tablet press, and preparing two sulfur powder wafers;
step 3, putting the mixture cylinder and the sulfur powder wafer pre-pressed in the step 2 into a platinum-graphite double-sample cavity, sealing to prepare a sample, wherein the sample cavity is a sulfur powder wafer-mixture cylinder-sulfur powder wafer in the sequence from top to bottom, preparing the sample, and putting the prepared sample into an h-BN pipe, wherein h-BN is used as a pressure transmission medium;
step 4, assembling the h-BN pipe provided with the sample in the step 3 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction;
step 5, taking out the sample reacted in the step 4, cutting platinum by using a diamond cutter, stripping a platinum-graphite double-sample cavity, and taking out a cylindrical bulk sample of the enargite;
and 6, grinding and polishing the upper bottom surface, the lower bottom surface and the side surface of the cylindrical bulk sample of the copper pyrite, placing the sample in acetone for ultrasonic cleaning for 5 minutes, and placing the sample in an inert gas atmosphere for storage after air drying.
Further, steps 1, 2 and 3 are all carried out in a glove box protected by argon gas, so that direct contact with arsenic-containing sulfide is avoided.
Further, the manufacturing of the platinum-graphite double-sample cavity in the step 3 specifically comprises the following steps: the hollow graphite tube and the graphite sheets at the pipe orifices at the two ends form a graphite inner cavity, and the graphite inner cavity is fastened by a platinum snap fastener.
Further, the sample loading process in step 3 specifically comprises: placing a sulfur powder wafer-mixture cylinder-sulfur powder wafer sample in a graphite inner cavity, sealing by using an outer sample cavity platinum snap fastener to form double sample cavities, placing the double sample cavities in an h-BN tube, sealing by using an h-BN sheet, and finally assembling the h-BN tube in a high-pressure synthesis assembly block.
Further, the temperature of the high-temperature high-pressure reaction in the step 4 is 400 ℃, the pressure is 0.2GPa, and the reaction time is 15 minutes.
Further, the copper arsenopyrite obtained in the step 6 is a single phase and has no impurity phase.
The invention has the beneficial effects that:
1. the fully-closed double-sample-cavity assembly is designed, and the problems of poor chemical stability of sulfide and extremely difficult control of solid-phase reaction on experiments are solved by controlling high-temperature and high-pressure reaction conditions. Specifically, the graphite-platinum double-sample cavity is assembled to form a completely closed system under the conditions of high temperature and high pressure, and the functions of the system are as follows: (1) the graphite sample cavity is an inner sample cavity, and has strong adsorbability and lubricity at high temperature and high pressure. The device can completely adsorb residual oxygen in the sample cavity, control the oxygen loss degree and the reducibility of the sample cavity and ensure that sulfides are not oxidized. Meanwhile, the sulfur sheets added on the upper bottom surface and the lower bottom surface of the sample can volatilize at high temperature, the inner wall of the graphite cavity can adsorb volatilized sulfur, a layer of sulfur protective film is formed on the whole graphite-sample interface to control the sulfur loss, and the sulfur desulfurization reaction of sulfide is inhibited by utilizing the environment saturated by sulfur volatile matters. In addition, the graphite sample cavity has strong lubricity, can be well attached to the outer wall of the sample, effectively separates the sample from the platinum outer sample cavity, and avoids direct contact of sulfide and corrosion of platinum. (2) The platinum sample cavity is an outer sample cavity, and has extremely strong ductility and plasticity under high temperature and high pressure. The graphite sample cavity is wrapped by the sulfur diffusion-proof device to form a completely closed system, and sulfur in the cavity cannot diffuse to the outside. Meanwhile, the graphite sample cavity is easy to generate irregular deformation under the influence of temperature and pressure gradient, and the plasticity of the platinum sample cavity ensures that the sample cavity is cylindrical, so that the irregular deformation is avoided. In addition, the platinum sample cavity effectively separates the graphite sample cavity from the pressure transmission medium h-BN, and the graphite is prevented from diffusing on an h-BN interface at high temperature. Combining the above (1) and (2), we designed a graphite-platinum dual sample chamber assembly to control oxygen and sulfur evolutionOn the premise of high temperature and high pressure, the stability of the sulfide is ensured by avoiding oxidation and desulfurization reaction, so that CuS and As2S2Can react to generate Cu according to a molar ratio of 6:13AsS4。
2. Besides the design of double sample cavities, the control of high-temperature and high-pressure reaction conditions is also a key factor for synthesizing the copper-arsenic-sulfide ore by a solid phase method. We found through a lot of experiments that the pressure of 0.2GPa, the temperature of 400 ℃, the reaction time of 15min are the best reaction conditions, because: (1) the copper pyrite belongs to a submarine hydrothermal fluid formation mineral and can be stable under the pressure of hundreds of megapascals MPa. Therefore, the reaction pressure is set to be 0.2GPa, which is close to the hydrothermal formation pressure of the copper arsenopyrite seabed, and the pressure is the lowest pressure which can be set by the cubic press. (2) The cubic press reaction temperature is generally set at intervals of at least 50 ℃ due to the temperature gradient. We have found that by setting the reaction temperature to 350 ℃ the solid phase reaction is incomplete and the product has a small amount of starting phase remaining in addition to the atacamite. The reaction temperature is set to be 450 ℃, and the product has extremely small amount of Cu besides the sulfur-copper-arsenic ore2And S. The reaction temperature is set to be 400 ℃, the solid phase reaction is ideal, and the product is pure copper arsenite without impurity phase. (3) The pressure can greatly reduce the activation energy of the reaction and promote the reaction rate, so that the CuS and As2S2The solid phase of the method can be quickly carried out within 15min, and the factors of unstable chemical properties caused by long-time sintering of the copper-arsenic-sulphide ore can be prevented. Compared with the prior art, the solid-phase reaction rate under normal pressure is much slower, and the sintering time is generally not less than 12 h.
The invention is further illustrated by the following specific examples.
Detailed Description
Examples
A method for directly synthesizing high-purity atacamite by solid-phase reaction comprises the following steps:
step 1, use of analytically pure copper sulfide CuS and analytically pure arsenic disulfide As2S2Weighing according to the molar ratio of 6:1, grinding and uniformly mixing to obtain a starting material;
step 2, pressing the mixture powder in the step 1 into a cylinder with phi 5mm multiplied by 5mm by using a powder tablet press, pressing analytically pure sulfur powder S into wafers with phi 5mm multiplied by 0.5mm by using the powder tablet press, and preparing two sulfur powder wafers;
step 3, putting the mixture cylinder and the sulfur powder wafer pre-pressed in the step 2 into a platinum-graphite double-sample cavity, sealing to prepare a sample, wherein the sample cavity is a sulfur powder wafer-mixture cylinder-sulfur powder wafer in the sequence from top to bottom, preparing the sample, and putting the prepared sample into an h-BN pipe, wherein h-BN is used as a pressure transmission medium;
step 4, assembling the h-BN pipe provided with the sample in the step 3 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, wherein the temperature is 400 ℃, the pressure is 0.2GPa, and the reaction time is 15 minutes;
step 5, taking out the sample reacted in the step 4, cutting platinum by using a diamond cutter, stripping a platinum-graphite double-sample cavity, and taking out a cylindrical bulk sample of the enargite;
and 6, grinding and polishing the upper bottom surface, the lower bottom surface and the side surface of the cylindrical bulk sample of the copper pyrite, placing the sample in acetone for ultrasonic cleaning for 5 minutes, and placing the sample in an inert gas atmosphere for storage after air drying.
Further, steps 1, 2 and 3 are all carried out in a glove box protected by argon gas, so that direct contact with arsenic-containing sulfide is avoided.
Further, the assembling process of the sulfur powder wafer-mixture cylinder-sulfur powder wafer sample in the platinum-graphite double-sample cavity in the step 3 specifically comprises the following steps:
step (1): and machining a graphite tube with the inner diameter phi of 5mm, the outer diameter phi of 7mm and the height of 8mm on a lathe. Processing two graphite sheets with the thickness of phi 5mm and the thickness of 1mm on a lathe, wherein a graphite sample inner cavity with the thickness of 1mm is formed by a graphite tube and a pair of graphite sheets;
step (2): processing a platinum snap fastener, wherein the sizes of the secondary opening are phi 7mm, phi 7.2mm and 8.1mm in height, and the sizes of the primary opening are phi 7.2mm, phi 7.4mm and 8.1mm in height;
and (3): a graphite sample cavity is formed by the graphite tube and the graphite sheet, and a platinum-graphite sample cavity is formed by the platinum snap fastener. Two sulfur powder original sheets are placed on the upper bottom surface and the lower bottom surface of the cylindrical sample, placed in a graphite inner sample cavity, and then integrally sealed by a platinum snap fastener;
and (4): drilling a phi 7.4mm hole in the center of a phi 12mm h-BN rod on a lathe to form an h-BN tube, inserting a platinum-graphite sample cavity filled with a sulfur powder wafer-mixture cylinder-sulfur powder wafer sample into the tube, sealing two ends with phi 7.4mm h-BN pieces with the thickness of 2mm, and assembling the h-BN tube in a high-pressure synthesis assembly block.
The specific process of assembling the h-BN pipe in the high-pressure synthesis assembly block in the step (5) is as follows: selecting a pyrophyllite block, and drilling a phi 14mm circular through hole in the center of the pyrophyllite block; a circular graphite heating pipe with the outer diameter phi of 14mm and the inner diameter phi of 12mm is sleeved in the circular through hole; a sample sealed by an h-BN pipe with the diameter of phi 12mm is placed in the middle of the graphite heating pipe; the upper end and the lower end of the round graphite heating furnace are sealed by pyrophyllite plugs.
Further, the copper arsenopyrite obtained in the step 6 is a single phase and has no impurity phase. Is stable in air and easy to store.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A method for directly synthesizing high-purity atacamite through solid-phase reaction is characterized by comprising the following steps:
step 1, use of analytically pure copper sulfide CuS and analytically pure arsenic disulfide As2S2Weighing according to the molar ratio of 6:1, grinding and uniformly mixing to obtain a starting material;
step 2, pressing the mixture powder in the step 1 into a cylinder with phi 5mm multiplied by 5mm by using a powder tablet press, pressing analytically pure sulfur powder S into wafers with phi 5mm multiplied by 0.5mm by using the powder tablet press, and preparing two sulfur powder wafers;
step 3, putting the mixture cylinder and the sulfur powder wafer pre-pressed in the step 2 into a platinum-graphite double-sample cavity, sealing to prepare a sample, putting the sulfur powder wafer-the mixture cylinder-the sulfur powder wafer in the sample cavity from top to bottom in sequence to prepare the sample, putting the prepared sample into an h-BN pipe, and taking the h-BN as a pressure transmission medium, wherein the preparation of the platinum-graphite double-sample cavity in the step 3 specifically comprises the following steps: the hollow graphite pipe and the graphite sheets at the pipe orifices at the two ends form a graphite inner cavity, and the graphite inner cavity is fastened by a platinum snap fastener to form a platinum outer cavity;
step 4, assembling the h-BN pipe provided with the sample in the step 3 in a high-pressure synthesis assembly block and placing the h-BN pipe in a cubic apparatus large press for high-temperature high-pressure reaction, wherein the temperature of the high-temperature high-pressure reaction is 400 ℃, the pressure of the high-temperature high-pressure reaction is 0.2GPa, and the reaction time is 15 minutes;
step 5, taking out the sample reacted in the step 4, cutting platinum by using a diamond cutter, stripping a platinum-graphite double-sample cavity, and taking out a cylindrical bulk sample of the enargite;
and 6, grinding and polishing the upper bottom surface, the lower bottom surface and the side surface of the cylindrical bulk sample of the copper pyrite, placing the sample in acetone for ultrasonic cleaning for 5 minutes, and placing the sample in an inert gas atmosphere for storage after air drying.
2. The method for direct synthesis of high-purity atacamite by solid-phase reaction according to claim 1, wherein steps 1, 2 and 3 are performed in an argon-protected glove box, avoiding direct contact with arsenic compounds.
3. The method for directly synthesizing the high-purity atacamite through the solid-phase reaction according to claim 1, wherein the sample loading process in the step 3 is specifically as follows: placing a sulfur powder wafer-mixture cylinder-sulfur powder wafer sample in a graphite inner cavity, sealing with an outer sample cavity platinum snap fastener to form double sample cavities, and placing the double sample cavities inhin-BN tubes, withh-BN sheet sealing, finallyhThe BN tubes are assembled in a high pressure synthesis assembly block.
4. According to claim 1The method for directly synthesizing the high-purity atacamite through the solid-phase reaction is characterized in that the atacamite Cu obtained in the step 63AsS4Is a single phase and has no impurity phase.
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