CN103553109B - Comprehensive utilization method of magnesium-smelting slag from Pidgeon process - Google Patents
Comprehensive utilization method of magnesium-smelting slag from Pidgeon process Download PDFInfo
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- CN103553109B CN103553109B CN201310472586.7A CN201310472586A CN103553109B CN 103553109 B CN103553109 B CN 103553109B CN 201310472586 A CN201310472586 A CN 201310472586A CN 103553109 B CN103553109 B CN 103553109B
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- Prior art keywords
- magnesium
- slag
- production
- pidgeonprocess
- comprehensive utilization
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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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
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a comprehensive utilization method of magnesium-smelting slag from a Pidgeon process. The comprehensive utilization method comprises the following steps of smashing the magnesium-smelting slag from the Pidgeon process; dissolving the smashed magnesium-smelting slag with an acid; adding a precipitant in a first filtered solution after the acid solution is filtered for a first time so as to make CaCl2 in the first filtered solution generate a CaSO4.2H2O precipitate; then carrying out a secondary filtration; and making the obtained CaSO4.2H2O precipitate into paste powder. The secondary filtered solution is used as a liquid nitrogen fertilizer. Aiming at chemical components of the magnesium-smelting slag from the Pidgeon process, in the comprehensive utilization method of the magnesium-smelting slag from the Pidgeon process, various chemical components in a reducing slag are separated, extracted and utilized successively according to an idea of circular economy and a conception of making the best use of everything, the magnesium-smelting slag from the Pidgeon process is turned into wealth and utilized comprehensively; pollutions of the magnesium-smelting slag to the environment is effectively treated and some economic benefits are created for enterprises.
Description
Technical field
The present invention relates to nonferrous metallurgy industry technology field, particularly relate to a kind of method of comprehensive utilization of production of magnesium by pidgeonprocess slag.
Background technology
Know in the industry, Pidgeon process belongs to the silicothermic process in vacuum metallurgy, and be called for short silicothermic process, being invented by Canadian Toronto college professor L.M.Pidgeon, is the main method of production MAGNESIUM METAL.With calcination (or calcining) rhombspar (be commonly called as forge white), for raw material, ferrosilicon (ferrosilicon containing 75 ~ 80%Si) is reductive agent to the method, adds appropriate fluorite (CaF
2), be pressed into pelletizing feed after batching, combined grinding.A material is put into refractory alloy steel vacuum reducing tank (inside is evacuated to the vacuum tightness of 13.3 ~ 1.33Pa or higher), be heated to 1200 ± 10 DEG C (boiling point Tb.p.=1107 DEG C of magnesium), the magnesium oxide forged in white (CaO+MgO) is reduced by Si, generation magnesium vapor is overflowed, with calcium silicate slag (2CaOSiO
2) enter reductive jar front end after separation condenser in separate out crude magnesium (Crystalline Magnesium), highly purified MAGNESIUM METAL can be obtained through refining again after coming out of the stove.
Production of magnesium by pidgeonprocess technique is simple, and small investment of production equipment, adds that China has the good source condition of production of magnesium by pidgeonprocess, and therefore the magnesium of China's refining at present industry mostly adopts Pidgeon process, and 2011 yearly capacities have reached 1,580,000 tons, belong to the big producing country of world's MAGNESIUM METAL.But the maximum shortcoming of production of magnesium by pidgeonprocess is that its solid slag quantity discharged is large, generally produces 1 ton of MAGNESIUM METAL and about have 8 ~ 10 tons of slag emissions.At present, each manufacturer is mostly it directly toppled over as solid waste for the process of this solid slag, so not only occupies soil, and its efflorescence thing one chance is blown, white dust flies upward all over the sky, and causing environmental pollution, is also objectively the waste of Nonrenewable resources.In prior art, also have some reducing slags utilizing production of magnesium by pidgeonprocess to produce the bibliographical information of air-entrained concrete building block and novel wall material aspect, but these can not adapt far away with the amplification of Smelting magnesium throughput.Therefore, the comprehensive utilization mode of seeking a kind of production of magnesium by pidgeonprocess slag becomes China's refining magnesium industry urgent problem.
Summary of the invention
The present invention is directed to existing production of magnesium by pidgeonprocess process slag quantity discharged large, be difficult to the problem fully utilized, propose the method for comprehensive utilization of production of magnesium by pidgeonprocess slag.
The technical solution used in the present invention is:
A method of comprehensive utilization for production of magnesium by pidgeonprocess slag, is characterized in that its technique comprises following processing step: pulverized by production of magnesium by pidgeonprocess slag, with acid dissolve, adds the CaCl that precipitation agent makes wherein after once filtering in a filtered liquid
2generate CaSO
42H
2o precipitates, and then carries out secondary filtration, the CaSO of gained
42H
2o precipitation makes terra alba, and secondary filtrate is as liquid nitrogenous fertilizer.
Grinding particle size 3 ~ the 0.1mm of described production of magnesium by pidgeonprocess slag.
Described acid dissolve refers to that the hydrochloric acid with mass concentration is 3% ~ 7% dissolves.
A described filtered filtration residue and ferroalloy production waste coke fines, binding agent proportioning are pressed into smelting duriron and roll into a ball and expect.
Described binding agent is tar, starch or polyvinyl alcohol, and addition is 4 ~ 8% of raw material total amount.
Described precipitation agent is (NH
4)
2sO
4.
The method of comprehensive utilization of production of magnesium by pidgeonprocess slag of the present invention is for the Chemical Composition of production of magnesium by pidgeonprocess slag, according to circular economy concept and the conception of making the best use of everything, successively separation and Extraction utilization is carried out to the various chemical composition of reducing slag, thus make production of magnesium by pidgeonprocess slag turn waste into wealth, be fully utilized, the environmental pollution that it causes effectively is administered simultaneously, certain economic benefit can also be created for enterprise.
Accompanying drawing explanation
Fig. 1 is basic flowsheet of coal preparation of the present invention.In figure, the meaning of each numbering representative is as follows:
1: production of magnesium by pidgeonprocess slag; 2: the hot furnace gas of reduction furnace or the hot furnace gas of rotary kiln; 3: fine terra alba; 4: secondary filtrate (liquid nitrogenous fertilizer); 5: ferroalloy works give up coke fines; 6: tackiness agent; 7: smelting duriron group's material.
1-1: milling equipment; 1-2: stirred tank; 1-3: filtration unit; 1-4: reactive tank; 1-5: filtration unit; 1-6: drying plant; 1-7: mixing equipment; 1-8: suppress agglomerating equipment.
Embodiment
(1) pulverize: production of magnesium by pidgeonprocess slag 1 milling equipment 1-1 is pulverized, is crushed to granularity 3 ~ 0.1mm.
(2) acid-soluble: the Mg-smelting furnace slag pulverized to be sent into stirred tank 1-2, adds 3% ~ 7% hydrochloric acid, with hydrochloric acid, the solvend in slag is dissolved.Principal reaction: CaO+2HCl==CaCl
2+ H
2o.Also have MgO, Al
2o
3and K, Na oxide compound also dissolves in wherein.
(3) once filter: the reaction solution after acid-soluble after filtration device 1-3 filters, indissoluble and not soluble oxide Fe
2o
3, SiO
2be filtered out Deng as filter residue.Collect first-time filtrate.
(4) first-time filtrate terra alba: first-time filtrate is put into reactive tank 1-4, adds sulfate precipitation agent, makes the CaCl in filtrate
2react with precipitation agent and generate CaSO
42H
2o precipitates.
Conventional Ca
2+precipitation agent has: carbonate, sulfate radical, phosphate radical, oxalate, MnO4 etc.Consider in the present invention that filtrate will continue comprehensive utilization, therefore select with (NH
4)
2sO
4as Ca
2+precipitation agent.
Principal reaction is as follows:
CaCl
2＋(NH
4)
2SO
4+2H
2O＝＝Ca SO
4·2H
2O↓＋2NH
4Cl
(5) secondary filtration: with filtration unit 1-5 by CaSO
42H
2o sedimentation and filtration out, utilizes reduction furnace or the hot furnace gas 2 of rotary kiln to dry at drying plant 1-6, make use of the heat energy of furnace gas, obtained terra alba 3.Secondary filtrate 4 is collected, except NH in filtrate
4cl, also has Mg
2+, Fe
3+, Al
3+, Na
+, K
+plasma, can be used as liquid nitrogenous fertilizer.(drip irrigation and spray irrigation formula is applied fertilizer, wherein Mg
2+the impact that magnesium deficiency causes can be made up, and the Fe of other trace
3+, Al
3+, K
+, Na
+plasma belongs to security element/ion.）
(6) one times filter residue is pressed into smelting duriron group material: the waste material produced in being produced with ferroalloy works by a waste residue---coke fines 5, tackiness agent 6 mix in mixing equipment 1-7, in the agglomerating equipment 1-8 of compacting, suppress agglomerating material 7.By SiO in recrement
2and Fe
2o
3the actual content of (or amounting to FeO) allocates required reductive agent and coke fines (by coke fines fixed carbon content and be converted into butt) into.The smelting FeSi75 that then presses as on the low side in ferriferous oxide content in recrement wants supplement to adjust refined iron mine powder, can give balanced adjustment as higher in total furnace charge to silica.Described tackiness agent is tar, starch, polyvinyl alcohol etc., and addition is 4 ~ 8% of raw material total amount.
Claims (3)
1. the method for comprehensive utilization of a production of magnesium by pidgeonprocess slag, it is characterized in that its technique comprises following processing step: pulverized by production of magnesium by pidgeonprocess slag, dissolve with the hydrochloric acid that mass concentration is 3% ~ 7%, after once filtering, in a filtered liquid, add precipitation agent (NH
4)
2sO
4make CaCl wherein
2generate CaSO
42H
2o precipitates, and then carries out secondary filtration, the CaSO of gained
42H
2o precipitation makes terra alba, and secondary filtrate is as liquid nitrogenous fertilizer;
A described filtered filtration residue and ferroalloy production waste coke fines, binding agent proportioning are pressed into smelting duriron and roll into a ball and expect.
2., according to the method for comprehensive utilization of claim 1 production of magnesium by pidgeonprocess slag, it is characterized in that the grinding particle size 3 ~ 0.1mm of described production of magnesium by pidgeonprocess slag.
3., according to the method for comprehensive utilization of claim 1 production of magnesium by pidgeonprocess slag, it is characterized in that described binding agent is tar, starch or polyvinyl alcohol, addition is 4 ~ 8% of raw material total amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310472586.7A CN103553109B (en) | 2013-10-11 | 2013-10-11 | Comprehensive utilization method of magnesium-smelting slag from Pidgeon process |
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|---|---|---|---|
| CN201310472586.7A CN103553109B (en) | 2013-10-11 | 2013-10-11 | Comprehensive utilization method of magnesium-smelting slag from Pidgeon process |
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|---|---|
| CN103553109A CN103553109A (en) | 2014-02-05 |
| CN103553109B true CN103553109B (en) | 2015-07-01 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106032331A (en) * | 2015-03-16 | 2016-10-19 | 大地亮环保服务有限公司 | Method for producing liquid fertilizer containing secondary trace elements by water washing treatment of blast furnace slag |
| CN110734349B (en) * | 2019-10-31 | 2022-06-07 | 西安交通大学 | Calcium-magnesium-phosphorus compound fertilizer prepared from waste residues generated in magnesium smelting by Pidgeon process and method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1044137C (en) * | 1995-07-15 | 1999-07-14 | 兰州大学 | Treating method for waste slag of smelting magnesium |
| CN102030566B (en) * | 2010-11-22 | 2012-08-22 | 北京科技大学 | New process for producing efficient calcium magnesium sulphur silicon fertilizer by utilizing slag from magnesium reduction furnace |
| CN102115084A (en) * | 2010-12-31 | 2011-07-06 | 张胜勇 | Method for producing silicon dioxide and calcium sulfate from phosphorous slag |
| CN102899516A (en) * | 2012-11-08 | 2013-01-30 | 石嘴山市学礼工贸有限公司 | Zero-emission recycling technology for refined waste residues of magnesium alloys |
| CN103030312B (en) * | 2013-01-10 | 2014-07-30 | 朱广东 | Treatment method of magnesium metal smelting waste slag |
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