CN103030312B - Treatment method of magnesium metal smelting waste slag - Google Patents
Treatment method of magnesium metal smelting waste slag Download PDFInfo
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- CN103030312B CN103030312B CN201310008204.5A CN201310008204A CN103030312B CN 103030312 B CN103030312 B CN 103030312B CN 201310008204 A CN201310008204 A CN 201310008204A CN 103030312 B CN103030312 B CN 103030312B
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- slag
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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Abstract
The invention relates to a method for treating and using magnesium metal smelting waste slag as a raw material for producing cements, and belongs to the field of magnesium smelting industry waste recycle. Massive gas furnace slag, refining slag and reducing slag are discharged generally in the magnesium metal smelting process, wherein the main components of the slag are also used for producing cements, and the content ratio of the main components also approaches the ratio of cement producing component, so that the environmental pollution caused by wastes in the magnesium smelting process can be removed, and increasingly exhausted natural petrochemical resources can be further replaced massively by making good use of the magnesium smelting waste slag. The treatment method specifically comprises the following steps: (1) crushing; (2) leaching with hot water; (3) filtering; (4) obtaining mixed slag from the reducing slag; (5) pulping; (6) carbonizing; and (7) filtering to obtain a supernatant and filter residues, wherein the obtained supernatant is used for manufacturing a magnesium salt, and the filter residues are used as the raw materials of cements.
Description
Technical field
The invention belongs to magnesium melting waste slag and industrial waste resource utilization and recycle field.Relate generally to production of magnesium by pidgeonprocess solid slag and industrial gaseous waste in conjunction with the method for recycling.
Background technology
In Pidgeon process magnesium metal smelting process, one ton of MAGNESIUM METAL of every production is discharged 1-1.5 ton coal gas slag, 0.2-0.35 ton left and right refining slag, 7-8 ton reducing slag.In these slags, coal gas slag is mainly silicon-dioxide and aluminium sesquioxide, also has a small amount of ferric oxide and carbon slag; In refining slag, mainly contain more water soluble chloride, as magnesium chloride, Repone K, sodium-chlor and bariumchloride, also have the Calcium Fluoride (Fluorspan) of magnesium oxide and 15-20%; In reducing slag, mainly contain calcium oxide, silicon-dioxide, ferric oxide and Calcium Fluoride (Fluorspan), also have unreacted magnesium oxide.These slags have independent discharge, also there is dual disposal, calcium oxide in these slags, silicon-dioxide, aluminium sesquioxide, ferric oxide and Calcium Fluoride (Fluorspan) are all the main components of manufacture of cement, content wherein substantially meets or approaches several main batching parameters such as silico-calcium ratio in manufacture of cement batching, silica alumina ratio, can become the substitute of the fossil feedstock such as Wingdale, clay, powdered iron ore and fluorite in manufacture of cement completely.But owing to containing water soluble chloride and magnesium oxide in production of magnesium by pidgeonprocess refining slag, in reducing slag, remaining magnesium oxide is the objectionable impurities of manufacture of cement in addition, is during it is produced, to need the strict index of controlling.
Subordinate list one, gas furnace slag ingredient
Subordinate list two, refining slag composition
Subordinate list three, reducing slag composition
For above magnesium metal smelting slag, process and have at present following several method:
For gas furnace slag, be mainly used as at present the raw material of clay brick and manufacture of cement.
For refining slag, utilize Waste Sulfuric Acid to process the slag that contains water soluble chloride, extract magnesium sulfate and produce magnesium smelting flux.But its system is complicated, and muriate and sulfate radical separation difficulty, also likely generate the complex materials such as hydrofluoric acid and magnesium fluoride, and concrete operations are more difficult.Not yet utilize at present, all by random discharge, serious environment pollution and underground water.
For reducing slag, independent utilization has following several method at present:
1, as magnesium slag cement, produce
The method technique is simple, reduced investment, but because content of magnesia in reducing slag surpasses silicate cement production standard, the magnesium oxide in slag and silicon-dioxide produce and easily turns brilliant Magnesium Silicate q-agent, cause late strength of concrete low, poor stability.In addition because magnesium reduction process Raw processing fineness is on the low side, cause insufficient, the low conversion rate of contact, free magnesium and calcium oxide are higher, reducing roasting temperature reaches more than 1200 ℃, causes calcium oxide, magnesium oxide burning, hydrability variation, hydration time extends to a couple of days, during cement products blanks and moulding and conserving, this part free calcium oxide, magnesium oxide generation aquation, produce defeated and dispersedly, cause concrete stability poor.Therefore, cement product quality is poor, slack market, and the performance of enterprises is not good.
2, make steamed brick
Due to the characteristic of slag, made steam-cured slag brick is cracking and frost resistance variation easily, is difficult to introduce to the market equally.
3, as carbonated lime brick building block, produce.See Zhu Guangdong ZL02135468.5 < < method for making brick with slag form smelting magnesium by Pidgeon process on January 26th, 2005 > >.This method is mainly utilized slag Free CaO and magnesium oxide and magnesium to produce flue gas under certain humidity, to carry out carbonization solidifying and setting principle and make brick or building block, and this product becomes again carbonatite product because of carbonization, and density is larger, and single brick quality is overweight, is also difficult to introduce to the market.
4, as low grade masonry cement
Present method technique is simple, reduced investment, but production marketing radius is little, is worth lowly, also cannot extensively promote.
5, for acid soil improving agent
Owing to containing alkaline oxygenated calcium and magnesium oxide, can be used as acid soil improving agent.Because China's acid soil is mainly distributed in the south of the lower reaches of the Yangtze River, and MAGNESIUM METAL factory owner will be distributed in the ground such as Shanxi, Shaanxi, Inner Mongol, Ningxia, Xinjiang, and shipment distance is excessively far away, does not also promote the use of.
Due to current not effectively a large amount of utilization of MAGNESIUM METAL factory metallurgical slag, on the spot stacking, landfill, fill out ditch etc., take a large amount of soils, cause severe environmental pollution, alkalization of soils, atmospheric dust severe overweight.Simultaneously, because magnesium metal smelting and other are as Ammonia Production, biological fermentation and other chemical industry, metallurgy industry give off again a large amount of carbon dioxides, atmosphere is caused to severe contamination.
Summary of the invention
For the problem of above-mentioned existence, we seek a kind ofly magnesium metal smelting waste residue and industrial gaseous waste can be combined and carry out comprehensive treating process, and the resource utilization that can reach refuse reclaims and recycle, turn harm into good, and bring benefit to the people.
For this purpose, we propose a kind of hot water lixiviate middle water soluble chloride of slagging tap that utilizes, with the carbonic acid gas in industrial gaseous waste and water, under condition of high voltage, generate carbonic acid again, insoluble magnesium oxide in leaching slag, make it generate water-soluble grand hydrocarbonate, from slag, separate, thereby except the magnesium oxide in removing slag.Remove the magnesian metallurgical slag of water soluble chloride and water-insoluble again with magnesium production process in gas furnace slag (containing a large amount of silicon-dioxide and aluminum oxide and ferric oxide) be mixed for manufacture of cement.We select most economical extraction process, and its technical process is as follows:
A treatment process for magnesium metal smelting slag, is characterized in that, comprises the following steps:
(1) pulverize: get metallic magnesium refining ground-slag and be broken to 10-30 order;
(2) hot water leaching: will be crushed to 10-30 object slag and add in leaching groove, and add slag volume 4-5 75 ℃ of above hot water doubly to stir molten soaking, turn/Min of rotating speed of agitator 2-30, leaching time 1-2 hour, obtains leaching mixed solution;
(3) filter: the leaching mixed solution after leaching is filtered to filter residue;
(4) filter residue excessively of gained in step (3) is sneaked into the reducing slag being crushed to more than 80 orders and must mix slag;
(5) to the water that adds 4-5 times of volume in the mixing slag in step (4), making beating, obtains slurries;
(6) slurries in step (5) are pumped in carbonating tower, add leaching agent to carry out scale pressure carbonization, intake pressure is 0.45-0.6Mpa, controlling quiet liquid level is 3/5 place of tower, tower top pressure is controlled at 0.25-0.35MPa, and temperature is controlled at 25-35 ℃, react to PH be below 6;
(7) filter: obtain clear liquid and filter residue.
In step (7), gained clear liquid is used for making magnesium salts, and filter residue is used as cement raw material.
The leaching agent that carburising step adopts is unnecessary CO in water and synthetic ammonia urea production
2or the dense CO of height of biological fermentation generation
2or the above CO of purification concentrate to 50%
2the carbonic acid soln that the waste gas of pressure content under high pressure forms.
Specific embodiment
Concrete technology flow process is divided into the two-stage:
The extraction of water soluble chloride in first stage slag
(1) pulverize: get metallic magnesium refining ground-slag and be broken to 10-30 order.
(2) reaction leaching, will be crushed to 10-30 object slag particle and add in reactive tank, add 75 ℃ of above hot water of volume 4-5 temperature doubly to stir leaching, and stirring velocity is turn/min of 2-30.
(3) filter, react and filter after 1-2 hour, filter residue is delivered to subordinate phase and is extracted wherein insoluble magnesium oxide, and clear liquid is processed into through evaporation the refining flux that magnesium is smelted.
The magnesian extraction in the insoluble danger of water in subordinate phase slag
(1) ground-slag is broken, and ground-slag is broken to 100 orders.
(2) slag mixes, and mixes with the filter residue that the first stage is sent here.
(3) making beating, adds troughing by mixing slag, adds slag volume 4-5 normal temperature clear water doubly to stir, and mixes, and stirrer rotating speed is turn/Min of 2-3.
(4) compressive reaction, slag slurry is added in reaction tower with slush pump, start gas compressor industrial gaseous waste (waste gas of the dense CO2 of height that the CO2 that synthetic ammonia urea production is unnecessary or biological fermentation produce or the above CO2 content of purification concentrate to 50%) is forced into 0.5-0.8MPa, control tower pressure on top surface 0.25-0.35MPa, reaction 4-6 hour, sampling at the bottom of tower, in slag, MgO < is qualified below 5% goes out.
(5) filter, by reacting feed liquid in reaction tower, put reaction liquid bath into, with pump, add in filter and filter, after filter residue and first stage extraction, filter residue is put together and is allowed it continue seasoning dehydration, and cement mill to be transported to produces use.Clear liquid flow to clear liquid storage tank and is then processed into magnesium salts.
Claims (3)
1. a treatment process for magnesium metal smelting slag, is characterized in that, comprises the following steps;
(1) pulverize: get metallic magnesium refining ground-slag and be broken to 10-30 order;
(2) hot water leaching: will be crushed to 10-30 object refining slag and add in leaching groove, and add slag volume 4-5 75 ℃ of above hot water doubly to stir molten soaking, turn/min of rotating speed of agitator 2-30, leaching time 1-2 hour, obtains leaching mixed solution;
(3) filter: the leaching mixed solution after leaching is filtered to filter residue;
(4) filter residue excessively of gained in step (3) is sneaked into the reducing slag being crushed to more than 80 orders and must mix slag;
(5) to the water that adds 4-5 times of volume in the mixing slag in step (4), making beating, obtains slurries;
(6) slurries in step (5) are pumped in carbonating tower, with gas compressor, add CO unnecessary in synthetic ammonia urea production
2or the dense CO of height of biological fermentation generation
2, or purify the above CO of concentrate to 50%
2the waste gas of content carries out carbonating leaching, carbonating tower intake pressure 0.45-0.6Mpa, controlling quiet liquid level is 3/5 place of tower, tower top pressure is controlled at 0.25-0.35Mpa, temperature is controlled at 25-35 ℃, react to PH be below 6;
(7) the carbonization mixed solution of step (6) gained is filtered, must contain the clear liquid and the slag that is insoluble to carbodiimide solution of magnesium salts.
2. the treatment process of magnesium metal smelting slag as described in claim 1, is characterized in that in step (7), gained clear liquid is used for making magnesium salts.
3. the treatment process of magnesium metal smelting slag as described in claim 1, is characterized in that in step (7) that gained filter residue is as cement raw material.
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| CN201310008204.5A CN103030312B (en) | 2013-01-10 | 2013-01-10 | Treatment method of magnesium metal smelting waste slag |
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| CN201310008204.5A CN103030312B (en) | 2013-01-10 | 2013-01-10 | Treatment method of magnesium metal smelting waste slag |
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| CN103030312B true CN103030312B (en) | 2014-07-30 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103553109B (en) * | 2013-10-11 | 2015-07-01 | 银川能源学院 | Comprehensive utilization method of magnesium-smelting slag from Pidgeon process |
| CN105218110B (en) * | 2015-08-21 | 2017-12-26 | 山西八达镁业有限公司 | Waste refractory materials recoverying and utilizing method in a kind of magnesium metal smelting |
| CN106241842B (en) * | 2016-08-30 | 2018-01-09 | 闻喜县远华冶金材料有限公司 | The production method of light magnesium carbonate |
| CN107723485B (en) * | 2017-10-24 | 2019-08-30 | 闻喜县远华冶金材料有限公司 | The recycling method of manganese in magnesium alloy flux waste residue |
| CN113136490A (en) * | 2017-10-24 | 2021-07-20 | 山西宝盛远华新材料股份有限公司 | Method for recovering residual rare earth in rare earth magnesium alloy flux slag |
| CN114250366A (en) * | 2019-09-10 | 2022-03-29 | 山西宝盛远华新材料股份有限公司 | Method and equipment for recovering magnesium refining flux waste residue by using boiling point difference |
| CN112811448A (en) * | 2021-01-18 | 2021-05-18 | 朱广东 | Recovery process of magnesium oxide reducing slag |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1140765A (en) * | 1995-07-15 | 1997-01-22 | 兰州大学 | Treating method for waste slag of smelting magnesium |
| CN1401605A (en) * | 2002-09-07 | 2003-03-12 | 朱广东 | Method for making brick with slag form smelting magnesium by Pidgeon process |
| CN1410352A (en) * | 2001-10-08 | 2003-04-16 | 中国科学院过程工程研究所 | Comprehensive utilization method of converting chromium slag totally into light magnesium carbonate and fine iron breeze |
| CN101417867A (en) * | 2008-10-31 | 2009-04-29 | 仝仲盛 | Method for preparing silicate magnesium slag concrete by using magnesium slag |
| CN101704010A (en) * | 2009-08-31 | 2010-05-12 | 张伟 | Method for stepwise preparing coarse magnesium grains, fusing agent and magnesium bricks from refined magnesium slag |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6709509B2 (en) * | 2001-06-05 | 2004-03-23 | Ernest John Taylor-Smith | Portland cement manufacture from slag from the production of magnesium metal |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1140765A (en) * | 1995-07-15 | 1997-01-22 | 兰州大学 | Treating method for waste slag of smelting magnesium |
| CN1410352A (en) * | 2001-10-08 | 2003-04-16 | 中国科学院过程工程研究所 | Comprehensive utilization method of converting chromium slag totally into light magnesium carbonate and fine iron breeze |
| CN1401605A (en) * | 2002-09-07 | 2003-03-12 | 朱广东 | Method for making brick with slag form smelting magnesium by Pidgeon process |
| CN101417867A (en) * | 2008-10-31 | 2009-04-29 | 仝仲盛 | Method for preparing silicate magnesium slag concrete by using magnesium slag |
| CN101704010A (en) * | 2009-08-31 | 2010-05-12 | 张伟 | Method for stepwise preparing coarse magnesium grains, fusing agent and magnesium bricks from refined magnesium slag |
Non-Patent Citations (2)
| Title |
|---|
| 徐祥斌 等.镁合金冶炼过程中污染物的无公害处理.《铸造技术》.2009,第30卷(第12期),1566-1568. |
| 镁合金冶炼过程中污染物的无公害处理;徐祥斌 等;《铸造技术》;20091231;第30卷(第12期);1566-1568 * |
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Owner name: SHANXI BADA MAGNESIUM CO., LTD. LIU YINGJIE ZHANG Free format text: FORMER OWNER: ZHANG WEIXING Effective date: 20130510 |
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Effective date of registration: 20130510 Address after: 043800 No. 538, west square, county square, Shanxi County, Wenxi Province Applicant after: Zhu Guangdong Applicant after: SHANXI BADA MAGNESIUM CO., LTD. Applicant after: Liu Yingjie Applicant after: Zhang Weixing Address before: 043800 No. 538, west square, county square, Shanxi County, Wenxi Province Applicant before: Zhu Guangdong Applicant before: Zhang Weixing |
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