CN1460726A - Process for extracting metal calcium by thermal reduction - Google Patents
Process for extracting metal calcium by thermal reduction Download PDFInfo
- Publication number
- CN1460726A CN1460726A CN 03117996 CN03117996A CN1460726A CN 1460726 A CN1460726 A CN 1460726A CN 03117996 CN03117996 CN 03117996 CN 03117996 A CN03117996 A CN 03117996A CN 1460726 A CN1460726 A CN 1460726A
- Authority
- CN
- China
- Prior art keywords
- reduction
- calcium
- thermal reduction
- tank
- prepared
- 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
Images
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides a heat reduction process for extracting metal calcium. It is implemented by successively using the steps of preparing material, ball-grinding, blending, briquetting, heat reduction and desublimation. It utilizes the strong reduction characteristics of aluminium powder, in the specific vacuum reduction tank the aluminium powder can be heated to make heat reduction reaction, the reduced gas calcium can be absorbed by crystallizing box with coiled cooling tube and desublimated to obtain metal calcium ingot, and the industrial waste slag resulted after heat reduction reaction can be used as ingredient for producing cement, so that said process has no waste gas and waste slag discharge.
Description
The technical field is as follows:
the invention relates to the technical field of metallurgical industry, in particular to a method for preparing elemental metal by adopting a vacuum thermal reduction method, and specifically relates to a process for extracting calcium metal by thermal reduction.
Background art:
as we know, pure elemental metal calcium is a very important industrial raw material, the elemental metal calcium is a silver-white light metal, has active chemical properties and a plurality of important application characteristics, and has very wide application prospects in the industries of metallurgical chemical industry, medical biochemistry, nuclear energy, electrical appliances and the like: in the metallurgical industry, precious nuclear metal uranium and other rare earth metals of yttrium, erbium, holmium, dysprosium and the like are prepared by calcium-thermal reduction; the metal calcium is added into the steel-making ladle, so that harmful substances such as nitrogen, sulfur, phosphorus and the like in the molten steel can be effectively removed, and the microstructure of the steel can be effectively improved; the calcium metal can also be used as an important stabilizer and foaming agent in the plastic industry, so that the performance of the plastic is effectively improved; can be used as a dehydrating agent of an organic solvent in organic chemical engineering; can be used for manufacturing calcium batteries and lead-calcium storage batteries in the energy industry; in particular, calcium metal is used in the pharmaceutical industry to produce important pharmaceuticals such as vitamins. Therefore, the scientific, reasonable, economic and efficient development and utilization of precious calcium resources have important significance for the high-speed development of national economy in China. Although the calcium resource of China is rich, the calcium resource exists in a chemical combination state in nature, the elemental metal calcium which can be directly utilized is still poor in practice, the production level of the existing metal calcium of China is still low, and the requirement of industries such as metallurgical chemical engineering, medical biochemistry, nuclear energy, electrical appliances and the like on the elemental metal calcium can not be met, so far, the calcium production industry of China always uses the traditional calcium chloride molten salt electrolysis method to produce the metal calcium product, although the traditional calcium chloride molten salt electrolysis method can produce the high-quality metal calcium product, the electrolysis method has the disadvantages of long process, complex process, troublesome maintenance and management, high power consumption in the operation process causes extreme increase of the production cost, a small amount of chlorine is often escaped in the electrolysis operation process, the environment is polluted, and the operation environment of workers is relatively bad.
The invention content is as follows:
the invention provides a process for extracting metallic calcium by thermal reduction, which is short in process, simple in used equipment, extremely convenient to operate, maintain and manage, low in production and operation cost and free of polluting ecological environment, and is realized by the following technical scheme:
the method comprises the following steps of:
(1) preparing materials: feeding a limestone raw material into a kiln, and calcining at high temperature of 1073-1373K to prepare quick lime;
(2) ball milling: the prepared quicklime is subjected to moisture isolation and cooling and then sent into a ball mill for crushing and ball milling to prepare quicklime powder, and the granularity of the quicklime powder is controlled to be 80-200 meshes;
(3) preparing materials: (by weight):
1 part of quicklime powder (80-200 meshes)
Reducing agent: 0.15 to 0.35 portion of (30 to 150 meshes)
Respectively weighing quicklime powder and a reducing agent by metering, adding into a mixing tank, and fully mixing by stirring to obtain a mixture;
the reducing agent is aluminum powder material, silicon or other reducing material can be selected as the reducing agent, and the extracted calcium metal can also be produced;
(4) briquetting: feeding the prepared mixture into a ball making machine to be pressed into a spherical lump material, wherein the lump size is controlled to be 1.5-5 cm;
(5) thermal reduction: adding the prepared pellet block material into a reduction tank, arranging a crystallization box with a cooling pipe in the cover body of the reduction tank, covering the reduction tank, sealing, vacuumizing, and controlling the vacuum degree to be 1 × 10-3～1×10-2Pa; heating the reduction tank, controlling the temperature of the spherical lump materials in the reduction tank to be 1323-1573K, and carrying out thermal reduction reaction for 14-16 hours, wherein the chemical reaction equation of the thermal reduction is as follows:
(6) desublimation: the metallic calcium vapor that the thermal reduction reaction sublimation was made, it absorbs by the crystallization box that reduction jar internal installation coiled the cooling tube, the temperature of desublimation in the regulation control crystallization box by the cooling tube that coils is between 523 ~ 673K, the gaseous calcium vapor of sublimating becomes the metallic calcium spindle in the sublimation box, still can be with the temperature control of desublimation in the crystallization box between 873 ~ 1023K, also can be with sublimating into gaseous calcium vapor in the crystallization box and desublimate into the metallic calcium spindle, it can to take out metallic calcium spindle form product from the crystallization box to open the lid after cooling. The calcium metal ingot can be further treated by vacuum argon-filling smelting, and a high-purity calcium metal ingot-shaped product with the purity of more than 99.5 percent can be obtained; or further chipping the calcium metal ingot to obtain a calcium metal flake product.
The present invention uses aluminium powder as reducing agent, and heats it in a specific vacuum reduction tank to make thermal reduction reaction, and uses the crystallization box coiled with cooling tube to absorb and desublimate it into calcium metal ingot, and the industrial waste residue after thermal reduction reaction can be used as adjuvant material for producing cement, and has no waste gas and waste residue discharge, and has no pollution to ecological environment. The invention has simple, scientific and reasonable process, simple used equipment, easy operation, extremely convenient maintenance and management, safe and stable production and operation, and can greatly reduce the production cost of the calcium metal.
The attached drawing is a process flow schematic diagram of the invention.
The specific implementation mode is as follows:
the first embodiment is as follows:
the method comprises the following steps of:
(1) preparing materials: feeding a limestone raw material into a kiln, and calcining at high temperature at 1073K to prepare quick lime;
(2) ball milling: the prepared quicklime is sent into a ball mill for crushing and ball milling after moisture insulation and cooling to prepare quicklime powder, and the granularity of the quicklime powder is controlled to be 80 meshes;
(3) preparing materials: (by weight):
1 portion of quicklime powder (80 meshes)
Reducing agent: 0.15 part of aluminum powder (30 meshes)
Respectively weighing quicklime powder and aluminum powder by metering, adding into a mixing tank, and fully mixing by stirring to obtain a mixture;
(4) briquetting: the prepared mixture is sent into a ball making machine to be pressed into spherical lump materials, and the lump size is controlled to be 1.5 cm;
(5) thermal reduction: adding the prepared pellet block material into a reduction tank, arranging a crystallization box with a cooling pipe in the cover body of the reduction tank, covering the reduction tank, sealing, vacuumizing, and controlling the vacuum degree to be 1 × 10-3Pa; heating the reduction pot, controlling the temperature of the spherical lump materials in the reduction pot to be 1323K, carrying out thermal reduction reaction for 14 hours, sublimating to prepare metal calcium vapor, wherein the chemical reaction equation of the thermal reduction is as follows:
(6) desublimation: the metallic calcium vapor which is preparedby sublimation of the thermal reduction reaction is absorbed by a crystallization box which is arranged in the cover body of the reduction tank and is wound with a cooling pipe, the desublimation temperature in the crystallization box is adjusted to be 523K by the wound cooling pipe, the calcium vapor which is sublimated into gaseous state is desublimated into a metallic calcium ingot in the crystallization box, and the cover body is opened after cooling to take out the metallic calcium ingot-shaped product from the crystallization box. The calcium metal ingot can be further treated by vacuum argon-filling smelting, and a high-purity calcium metal ingot-shaped product with the purity of more than 99.5 percent can be obtained.
The industrial waste residue after the thermal reduction reaction is used as an ingredient for producing cement, and the ecological environment is not polluted.
Example two:
the method comprises the following steps of:
(1) preparing materials: feeding a limestone raw material into a kiln, and carrying out high-temperature calcination at the temperature of 1373K to prepare quick lime;
(2) ball milling: the prepared quicklime is sent into a ball mill for crushing and ball milling after moisture insulation and cooling to prepare quicklime powder, and the granularity of the quicklime powder is controlled to be 200 meshes;
(3) preparing materials: (by weight):
1 portion of quicklime powder (200 meshes)
Reducing agent: 0.35 part of aluminum powder (150 meshes)
Respectively weighing quicklime powder and aluminum powder by metering, adding into a mixing tank, and fully mixing by stirring to obtain a mixture;
(4) briquetting: the prepared mixture is sent into a ball making machine to be pressed into spherical lump materials, and the lump size is controlled to be 5 cm;
(5) thermal reduction: adding the prepared pellet block material into a reduction tank, arranging a crystallization box with a cooling pipe in the cover body of the reduction tank, covering the reduction tank, sealing, vacuumizing, and controlling the vacuum degree to be 1 × 10-2Pa; heating the reduction tank, controlling the temperature of the spherical lump materials in the reduction tank to 1573K, and carrying out thermal reduction reaction for 16 hours, wherein the chemical reaction equation of the thermal reduction is as follows:
(6) desublimation: the metallic calcium vapor which is prepared by sublimation of thermal reduction reaction is absorbed by a crystallization box which is arranged in the cover body of the reduction tank and is coiled with a cooling pipe, the desublimation temperature in the crystallization box is adjusted and controlled to be 673K by the coiled cooling pipe, the calcium vapor which is sublimated into gaseous state is desublimated into a metallic calcium ingot in the crystallization box, and the cover body is opened after cooling to take out the metallic calcium ingot-shaped product from the crystallization box. The prepared calcium metal ingot can be further sliced and processed into calcium metal sheet products.
The industrial waste residue after thermal reduction reaction is centrally stockpiled and used as a material for producing cement, and no waste gas and waste residue are discharged, so that the ecological environment is not polluted.
Example three:
the method comprises the following steps of:
(1) preparing materials: feeding a limestone raw material into a kiln, and calcining at 1220K at high temperature to prepare quicklime;
(2) ball milling: the prepared quicklime is sent into a ball mill for crushing and ball milling after moisture insulation and cooling to prepare quicklime powder, and the granularity of the quicklime powder is controlled to be 140 meshes;
(3) preparing materials: (by weight):
1 portion of quicklime powder (140 meshes)
Reducing agent: 0.22 portion of aluminum powder (90 meshes)
Respectively weighing quicklime powder and aluminum powder by metering, adding into a mixing tank, and fully mixing by stirring to obtain a mixture;
(4) briquetting: the prepared mixture is sent into a ball making machine to be pressed into spherical lump materials, and the lump size is controlled to be 3.5 cm;
(5) thermal reduction: adding the prepared pellet block material into a reduction tank, arranging a crystallization box with a cooling pipe in the cover body of the reduction tank, covering the reduction tank, vacuumizing, and controlling the vacuum degree to be 0.5 multiplied by 10-2Pa; heating the reduction pot, controlling the temperature of the spherical lump materials in the reduction pot to 1450K, and carrying out thermal reduction reaction for 15 hours, wherein the chemical reaction equation of the thermal reduction is as follows:
(6) desublimation: the metallic calcium vapor which is prepared by sublimation of the thermal reduction reaction is absorbed by a crystallization box which is arranged in the cover body of the reduction tank and is wound with a cooling pipe, the desublimation temperature in the crystallization box is regulated and controlled to be 950K by the wound cooling pipe, the calcium vapor which is sublimated into a gaseous state is desublimated into a metallic calcium ingot in the crystallization box, and the cover body is opened after cooling to take out the metallic calcium ingot-shaped product from the crystallization box. The prepared calcium metal ingot can be further treated by vacuum argon-filling smelting to obtain a high-purity calcium metal ingot-shaped product with the purity of more than 99.5 percent; the industrial waste residue after thermal reduction reaction can be collected and stored in a centralized way and supplied to a cement factory as a material for cement production, and the process for extracting metallic calcium by thermal reduction provided by the invention has no waste gas and waste residue discharge and no pollution to the ecological environment.
Claims (3)
1. The process for extracting metallic calcium by thermal reduction sequentially comprises the following steps of:
(1) preparing materials: feeding a limestone raw material into a kiln, and calcining at high temperature of 1073-1373K to prepare quick lime;
(2) ball milling: the prepared quicklime is subjected to moisture isolation and cooling and then sent into a ball mill for crushing and ball milling to prepare quicklime powder, and the granularity of the quicklime powder is controlled to be 80-200 meshes;
the method is characterized by also comprising the following steps in sequence:
(3) preparing materials: (by weight):
1 part of quicklime powder (80-200 meshes)
0.15 to 0.35 portion of reducing agent (30 to 150 meshes)
Respectively weighing quicklime powder and a reducing agent by metering, adding into a mixing tank, and fully mixing by stirring to obtain a mixture;
(4) briquetting: feeding the prepared mixture into a ball making machine to be pressed into a spherical lump material, wherein the lump size is controlled to be 1.5-5 cm;
(5) thermal reduction: adding the prepared pellet-shaped lump material into a reduction tank, covering and sealing the reduction tank, vacuumizing the reduction tank, and controlling the vacuum degree to be 1 multiplied by 10-3～1×10-2Pa; heating the reduction tank, controlling the temperature of the spherical lump materials in the reduction tank to be 1323-1573K, and carrying out thermal reduction reaction for 14-16 hours;
(6) desublimation: and absorbing and desublimating the metallic calcium vapor prepared by sublimation of the thermal reduction reaction by a crystallization box in the reduction tank cover body to form a metallic calcium spindle-shaped product, and controlling the desublimating temperature in the crystallization box to be 523-673K.
2. The process for the thermal reductive extraction of metallic calcium according to claim 1, wherein: the reducing agent is an aluminum powder material.
3. The process for the thermal reduction extraction of metallic calcium according to claim 1 or 2, characterized in that: the desublimation temperature in the crystallization box can be controlled to be 873-1023K.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117996 CN1253590C (en) | 2003-06-02 | 2003-06-02 | Process for extracting metal calcium by thermal reduction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03117996 CN1253590C (en) | 2003-06-02 | 2003-06-02 | Process for extracting metal calcium by thermal reduction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1460726A true CN1460726A (en) | 2003-12-10 |
| CN1253590C CN1253590C (en) | 2006-04-26 |
Family
ID=29591050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03117996 Expired - Fee Related CN1253590C (en) | 2003-06-02 | 2003-06-02 | Process for extracting metal calcium by thermal reduction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1253590C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205573A (en) * | 2013-05-06 | 2013-07-17 | 重庆大学 | Method for preparing magnesium and calcium through carbon thermal reduction |
| CN104607635A (en) * | 2015-02-06 | 2015-05-13 | 池州博瑞德钙业有限公司 | Calcium metal ingot pressing device |
| CN104668557A (en) * | 2015-02-06 | 2015-06-03 | 池州博瑞德钙业有限公司 | Calcium metal ingot press-forming device |
| CN105803189A (en) * | 2016-05-16 | 2016-07-27 | 贵州大学 | Method for efficiently removing phosphorus from high-phosphorus oolitic hematite |
| CN111893301A (en) * | 2019-05-06 | 2020-11-06 | 北京事竟成有色金属研究所 | Clean and environment-friendly method for preparing reduced metal calcium (coarse calcium) |
-
2003
- 2003-06-02 CN CN 03117996 patent/CN1253590C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205573A (en) * | 2013-05-06 | 2013-07-17 | 重庆大学 | Method for preparing magnesium and calcium through carbon thermal reduction |
| CN104607635A (en) * | 2015-02-06 | 2015-05-13 | 池州博瑞德钙业有限公司 | Calcium metal ingot pressing device |
| CN104668557A (en) * | 2015-02-06 | 2015-06-03 | 池州博瑞德钙业有限公司 | Calcium metal ingot press-forming device |
| CN104668557B (en) * | 2015-02-06 | 2018-12-28 | 安徽腾拓新材料科技有限公司 | A kind of calcium metal briquetting molding equipment |
| CN105803189A (en) * | 2016-05-16 | 2016-07-27 | 贵州大学 | Method for efficiently removing phosphorus from high-phosphorus oolitic hematite |
| CN105803189B (en) * | 2016-05-16 | 2018-06-29 | 贵州大学 | A kind of method of phosphorus in efficient removal high-phosphor oolitic hematite |
| CN111893301A (en) * | 2019-05-06 | 2020-11-06 | 北京事竟成有色金属研究所 | Clean and environment-friendly method for preparing reduced metal calcium (coarse calcium) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1253590C (en) | 2006-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1194888C (en) | Method for producing vanadium nitride | |
| CN112978777B (en) | Method for treating waste material containing electrolyte | |
| CN102502722A (en) | Preparation method of high-purity magnesium oxide | |
| CN1895802A (en) | Treatment of aluminum electrolytic cell waste refractory materials | |
| CN1699168A (en) | Combustion synthesis method of zirconium diboride micro-powder | |
| CN1253590C (en) | Process for extracting metal calcium by thermal reduction | |
| CN102001661A (en) | Method for slagging, boron removal and purification of metalluragical silicon | |
| CN1704337A (en) | Process for producing high purity magnesia | |
| CN101066872A (en) | Composite Sialon ceramic material and its prepn process | |
| CN1850596A (en) | Method for preparing SiC complex-phase material utilizing iron ore tailings | |
| Yang et al. | A new strategy for de-oxidation of diamond-wire sawing silicon waste via the synergistic effect of magnesium thermal reduction and hydrochloric acid leaching | |
| CN108516565B (en) | Method for preparing P-type zeolite molecular sieve by using aluminum calcium powder reaction slag | |
| CN1299992C (en) | High purity magnesium oxide cleaning production method | |
| CN115807171A (en) | Green and environment-friendly production method for reducing magnesium by thermit process | |
| CN104961138A (en) | Preparation method of <10>B-enriched zirconium diboride powder | |
| Ji et al. | Preparation of Li4SiO4 from lithium-ion battery cathode waste and diamond wire saw silicon powder using a two-step process | |
| CN102011021A (en) | Method for reduction preparation of Mg-Li-Sr alloy by vacuum heat | |
| CN1195086C (en) | Preparation method of metal lithium | |
| CN1213158C (en) | Lithium preparing process with lithium carbonate | |
| CN1408904A (en) | Process for producing high purity magnesium oxide monocrystal using waste magnesite ore | |
| CN108862301B (en) | High purity Ti3B2Preparation method of N material | |
| CN1189580C (en) | Vanadium-base solid solution hydrogen-storing alloy and its prepn process | |
| CN113957269B (en) | Can stabilize beta-C in magnesium slag 2 S magnesium smelting pellet and magnesium smelting method | |
| CN102583480A (en) | Method utilizing witherite to prepare barium hydroxide octahydrate | |
| JIANG et al. | Synthesis of (Ca, Mg)–α′-Sialon–AlN–BN powders from boron-rich blast furnace slag by microwave carbothermal reduction-nitridation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Process for extracting metal calcium by thermal reduction Effective date of registration: 20100908 Granted publication date: 20060426 Pledgee: Leshan SME investment Company limited by guarantee Pledgor: Zhang Xianfu Registration number: 2010990000875 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20101228 Granted publication date: 20060426 Pledgee: Leshan SME investment Company limited by guarantee Pledgor: Zhang Xianfu Registration number: 2010990000875 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20101228 Granted publication date: 20060426 Pledgee: Leshan SME investment Company limited by guarantee Pledgor: Zhang Xianfu Registration number: 2010990000875 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060426 Termination date: 20160602 |