CN111675540A - Method for directly synthesizing high-purity bornite through solid-phase reaction - Google Patents
Method for directly synthesizing high-purity bornite through solid-phase reaction Download PDFInfo
- Publication number
- CN111675540A CN111675540A CN202010725178.8A CN202010725178A CN111675540A CN 111675540 A CN111675540 A CN 111675540A CN 202010725178 A CN202010725178 A CN 202010725178A CN 111675540 A CN111675540 A CN 111675540A
- Authority
- CN
- China
- Prior art keywords
- sample
- bornite
- graphite
- platinum
- sulfur powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052948 bornite Inorganic materials 0.000 title claims abstract description 41
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 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 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 16
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 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
- 238000007789 sealing Methods 0.000 claims abstract description 10
- 239000012071 phase Substances 0.000 claims abstract description 8
- 238000003825 pressing Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 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
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005303 weighing Methods 0.000 claims abstract description 3
- 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 14
- 239000010949 copper Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000035484 reaction time Effects 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
- 238000011068 loading method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 abstract 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052951 chalcopyrite Inorganic materials 0.000 description 8
- 238000005245 sintering Methods 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052683 pyrite Inorganic materials 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 229910001779 copper mineral Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- 229910052903 pyrophyllite Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052947 chalcocite Inorganic materials 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
- 230000001788 irregular Effects 0.000 description 2
- 229910052960 marcasite Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241000907663 Siproeta stelenes Species 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 chalcopyrite Chemical class 0.000 description 1
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 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
- 230000007774 longterm Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001681 protective effect Effects 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
- 238000007086 side reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 229910052569 sulfide mineral Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/547—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on sulfides or selenides or tellurides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
- C04B35/645—Pressure sintering
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/446—Sulfides, tellurides or selenides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a method for directly synthesizing high-purity bornite through solid-phase reaction, which comprises the steps of weighing analytically pure cuprous sulfide, copper sulfide and analytically pure ferrous sulfide according to a molar ratio of 2:1:1, and uniformly grinding and mixing the raw materials 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 bornite is a single phase and has no impurities.
Description
Technical Field
The invention relates to a method for directly synthesizing high-purity bornite through solid-phase reaction, belonging to the field of mineralogy research.
Background
The porphyrite is a common copper-iron sulfide mineral, and is often enriched in the porphyrite copper minerals with hydrothermal causes with sulfides such as chalcopyrite, chalcocite and the like in a compact block or a dispersed granule, the copper content of the porphyrite copper minerals reaches 63.3 percent, and the porphyrite copper minerals are one of main mineral raw materials for extracting copper. Because of high copper content, the chalcopyrite is relatively unstable in chemical property compared with chalcopyrite, and is easily weathered and oxidized on the ground surface to generate malachite and chalcopyrite. In addition, the formation of bornite strongly depends on the ambient temperature, and chalcopyrite and other sulfides are easily decomposed at a high temperature. Therefore, the natural bornite has very complex components and often contains microscopic inclusions of symbiotic minerals such as chalcocite and chalcopyrite. Due to the lack of the standard sample of the high-purity bornite, the quantitative research of the bornite cannot be carried out. The artificially synthesized copper-iron sulfide mainly adopts a hydrothermal method, but the bornite belongs to Cu2+/Cu+The complex valence sulfide has difficult control of experimental conditions. Therefore, exploring the standard sample synthesis of the porphyrite is the basis for quantitatively researching the porphyrite.
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 (II) sulphide (Cu)2S, copper sulfide CuS and ferrous sulfide FeS are mixed according to the mol ratio of 2:1:1, and the mixture is directly sintered by utilizing solid phase reaction to generate the bornite Cu5FeS4Is there a In fact, due to the poor chemical stability of the sulfides, the reaction is very difficult to control experimentally, for the reasonIn that (1) Cu is completely distinguished from the solid-phase reaction of oxides2S, CuS and FeS are directly oxidized to generate CuO and Fe when being sintered in air2O3And SO2No formation of bornite Cu5FeS4. (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 carry out according to the stoichiometric proportion of the bornite in practice, 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 bornite through solid-phase reaction so as to solve the technical problem of quantitative research on bornite at present.
The purpose of the invention is realized by the following technical scheme: a method for directly synthesizing high-purity bornite by solid-phase reaction comprises the following steps:
step 1, using analytically pure cuprous sulfide Cu2S, weighing analytically pure copper sulfide (CuS) and analytically pure ferrous sulfide (FeS) according to a molar ratio of 2:1:1, and grinding and uniformly mixing to obtain an initial raw 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 the platinum by using a diamond cutter, stripping off a platinum-graphite double-sample cavity, and taking out the bornite cylindrical block sample;
and 6, grinding and polishing the upper bottom surface, the lower bottom surface and the side surface of the sample of the columniform block material of the bornite, 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, 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 bornite 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. At the same time, we added sulfur to the upper and lower surfaces of the sampleThe sheet 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 degree, and the sulfur desulfurization reaction 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. By combining the above (1) and (2), the graphite-platinum double-sample cavity assembly designed by us is based on the premise of controlling oxygen fugacity and sulfur fugacity, and oxidation and desulfurization reactions are avoided to ensure the stability of sulfide under the completely closed environment of high temperature and high pressure, so that Cu is ensured2S, CuS and FeS can react to generate Cu according to the molar ratio of 2:1:15FeS4。
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 bornite 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 bornite belongs to submarine hydrothermal fluid formation mineral and can be stable under the pressure of hundreds of megapascals MPa, but the high-pressure stability of the bornite is far less than that of pyrite FeS2It is now reported that pyrite can remain structurally stable at pressures of hundreds of gigapascals GPa, which makes pyrite prone to formation at higher pressures. If the pressure is too high, side reactions can occur: 2CuS + FeS → Cu2S+FeS2No formation of bornite Cu5FeS4. Therefore, the reaction pressure is set to be 0.2GPa, which is close to the hydrothermal formation pressure of the bornite 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 found that the solid phase reaction was incomplete by setting the reaction temperature to 350 ℃. The reaction temperature is set to be 450 ℃, and the product has very little FeS besides the bornite2And chalcopyrite CuFeS2. The reaction temperature is set to be 400 ℃, the solid phase reaction is ideal, and the product is pure bornite and has no impurity phase. (3) The pressure can greatly reduce the activation energy of the reaction and promote the reaction rate, so that the Cu2S, CuS and FeS should be able to rapidly proceed within 15min to prevent unstable chemical properties caused by long-term sintering of bornite. 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 bornite by solid-phase reaction comprises the following steps:
step 1, using analytically pure cuprous sulfide Cu2S, copper sulfide CuS and analytically pure ferrous sulfide FeS are weighed according to the molar ratio of 2:1:1, and are ground and uniformly mixed to serve as initial raw materials;
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 the platinum by using a diamond cutter, stripping off a platinum-graphite double-sample cavity, and taking out the bornite cylindrical block sample;
and 6, grinding and polishing the upper bottom surface, the lower bottom surface and the side surface of the sample of the columniform block material of the bornite, 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, 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 (4) 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 bornite obtained in the step 6 is a single phase and has no impurity phase.
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 (5)
1. A method for directly synthesizing high-purity bornite by solid-phase reaction is characterized by comprising the following steps:
step 1, using analytically pure cuprous sulfide Cu2S, weighing analytically pure copper sulfide (CuS) and analytically pure ferrous sulfide (FeS) according to a molar ratio of 2:1:1, and grinding and uniformly mixing to obtain an initial raw 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 the platinum by using a diamond cutter, stripping off a platinum-graphite double-sample cavity, and taking out the bornite cylindrical block sample;
and 6, grinding and polishing the upper bottom surface, the lower bottom surface and the side surface of the sample of the columniform block material of the bornite, 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 directly synthesizing the high-purity bornite through the solid-phase reaction according to claim 1, wherein the manufacturing of the platinum-graphite double-sample cavity in the step 3 is specifically as follows: the hollow graphite pipe and the graphite sheets with pipe orifices at 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.
3. The method for directly synthesizing the high-purity bornite 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 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.
4. The method for directly synthesizing the high-purity bornite through the solid-phase reaction according to claim 1, wherein 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.
5. The method for directly synthesizing high-purity bornite by solid-phase reaction according to claim 1, wherein the bornite obtained in step 6 is a single phase and has no impurity phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010725178.8A CN111675540B (en) | 2020-07-24 | 2020-07-24 | Method for directly synthesizing high-purity bornite through solid-phase reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010725178.8A CN111675540B (en) | 2020-07-24 | 2020-07-24 | Method for directly synthesizing high-purity bornite through solid-phase reaction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111675540A true CN111675540A (en) | 2020-09-18 |
| CN111675540B CN111675540B (en) | 2021-05-14 |
Family
ID=72457996
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010725178.8A Expired - Fee Related CN111675540B (en) | 2020-07-24 | 2020-07-24 | Method for directly synthesizing high-purity bornite through solid-phase reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111675540B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130171056A1 (en) * | 2012-01-04 | 2013-07-04 | Franklin And Marshall College | Development of Earth-Abundant Mixed-Metal Sulfide Nanoparticles For Use In Solar Energy Conversion |
| US20160114336A1 (en) * | 2011-09-13 | 2016-04-28 | Cidra Minerals Processing Inc. | Mineral processing |
| CN105973796A (en) * | 2016-06-24 | 2016-09-28 | 中国科学院地球化学研究所 | Method for preparing chalcopyrite electrode |
| CN107675255A (en) * | 2017-09-04 | 2018-02-09 | 中国科学院地球化学研究所 | A kind of method for growing siderite monocrystalline at high temperature under high pressure |
| CN108793259A (en) * | 2018-06-15 | 2018-11-13 | 中国科学院地球化学研究所 | A method of synthesizing nemalite at high temperature under high pressure |
-
2020
- 2020-07-24 CN CN202010725178.8A patent/CN111675540B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160114336A1 (en) * | 2011-09-13 | 2016-04-28 | Cidra Minerals Processing Inc. | Mineral processing |
| US20130171056A1 (en) * | 2012-01-04 | 2013-07-04 | Franklin And Marshall College | Development of Earth-Abundant Mixed-Metal Sulfide Nanoparticles For Use In Solar Energy Conversion |
| CN105973796A (en) * | 2016-06-24 | 2016-09-28 | 中国科学院地球化学研究所 | Method for preparing chalcopyrite electrode |
| CN107675255A (en) * | 2017-09-04 | 2018-02-09 | 中国科学院地球化学研究所 | A kind of method for growing siderite monocrystalline at high temperature under high pressure |
| CN108793259A (en) * | 2018-06-15 | 2018-11-13 | 中国科学院地球化学研究所 | A method of synthesizing nemalite at high temperature under high pressure |
Non-Patent Citations (2)
| Title |
|---|
| AIJUAN ZHANG .ET AL: "Twin Engineering in Solution-Synthesized Nonstoichiometric Cu5FeS4 Icosahedral Nanoparticles for Enhanced Thermoelectric Performance", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| 方啸虎: "《超硬材料科学与技术》", 30 April 1998 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111675540B (en) | 2021-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Richardson | Latter-day origin of diamonds of eclogitic paragenesis | |
| CN111829849B (en) | Method for directly synthesizing high-purity and high-density chalcopyrite block material by solid-phase reaction | |
| CN106830082B (en) | A kind of method that controllable magnanimity prepares molybdenum disulfide nano band | |
| WO2002020143A1 (en) | Ceramic/metal composite article, composite structure for transporting oxide ion, and composite article having sealing property | |
| CN112851351B (en) | Method for directly synthesizing iron-doped zinc sulfide block through solid-phase reaction | |
| CN111675540B (en) | Method for directly synthesizing high-purity bornite through solid-phase reaction | |
| CN1263791A (en) | Mixing conducting cubic perofskite for ceramic ion transmission membrane | |
| CN111829850B (en) | Method for directly synthesizing high-purity sulfur-arsenic-copper ore by solid-phase reaction | |
| CN111825122B (en) | Method for directly synthesizing high-density magnesium sulfide iron block through solid-phase reaction | |
| CN111646513B (en) | Method for directly synthesizing manganese-doped zinc sulfide block through solid-phase reaction | |
| CN113148960B (en) | Method for preparing high-purity sulfur-containing product from molybdenum concentrate in short process | |
| Arenberg et al. | Steam Sintering of Uranium Dioxide | |
| CN113481598B (en) | Zn-P-As crystal material and preparation method and application thereof | |
| Sakka et al. | Surface chemistry and sintering characteristics of nickel ultrafine powders | |
| HU204244B (en) | Process for producing ceramic and ceramic-metal products containing filling materials | |
| Varela et al. | Effect of atmosphere and dopants on sintering of SnO2 | |
| Shah et al. | Kinetics and mechanism of the conversion of covellite (CuS) to digenite (Cu 1.8 S) | |
| CN112299835A (en) | Preparation method of A-site part doped alkali metal ion perovskite oxygen-permeable membrane material | |
| CN113493929A (en) | Preparation method of black phosphorus single crystal wafer | |
| CN112062107A (en) | Activated porous boron nitride adsorbent and preparation method and application thereof | |
| CA1083336A (en) | Sintered ceramics having controlled density and porosity | |
| US4929572A (en) | Dopant of arsenic, method for the preparation thereof and method for doping of semiconductor therewith | |
| JPS6448326A (en) | Metal added ceramic superconductor and its manufacture | |
| Wang et al. | Phase development in the formation of CaLa2S4 powder and pellet | |
| CN113234940B (en) | Method for preparing molybdenum metal product from molybdenum concentrate in short process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210514 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |