CN106676287B - A kind of utilization method of boron mud - Google Patents

A kind of utilization method of boron mud Download PDF

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Publication number
CN106676287B
CN106676287B CN201710020858.8A CN201710020858A CN106676287B CN 106676287 B CN106676287 B CN 106676287B CN 201710020858 A CN201710020858 A CN 201710020858A CN 106676287 B CN106676287 B CN 106676287B
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boron mud
reducing agent
calcirm
fluoride
quick lime
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CN106676287A (en
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于洪翔
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Beris Engineering and Research Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/20—Obtaining alkaline earth metals or magnesium
    • C22B26/22—Obtaining magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/16—Sintering; Agglomerating
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/242—Binding; Briquetting ; Granulating with binders
    • C22B1/244—Binding; Briquetting ; Granulating with binders organic
    • C22B1/245—Binding; Briquetting ; Granulating with binders organic with carbonaceous material for the production of coked agglomerates
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)
  • Treatment Of Sludge (AREA)

Abstract

The present invention provides a kind of utilization methods of boron mud, including：(1) boron mud is dried, be subsequently sent to rotary kiln or heat the boron mud after kiln roasting is roasted；(2) boron mud, quick lime, carbonaceous reducing agent and the calcirm-fluoride after roasting is broken and levigate respectively, it is then uniformly mixed by preset ratio and obtains mixture；(3) mixture is heated and is pressed into pelletizing and obtain hot pressing pelletizing；(4) hot pressing pelletizing is placed in the reduction furnace with magnesium crystallizer and is restored, reduction is cooled down after terminating, and obtains magnesium metal.The method of the present invention, which realizes boron mud, to be efficiently used, and reduces pollution of the boron mud to environment, and obtain high value added product magnesium metal.

Description

A kind of utilization method of boron mud
Technical field
The invention belongs to Metallurgical resources field of comprehensive utilization, in particular it relates to a kind of utilization method of boron mud.
Background technology
Boron mud is the residue of chemical industry station-service boromagnesite or ludwigite standby borax made of stones.Boron mud color is light brown, Belong to indissoluble substance, newly generated boron mud is interior containing 30% or so Free water, and boron mud is in alkalinity.Boron mud main component is MgO And SiO2, and contain a certain amount of Fe2O3、B2O3With a small amount of CaO, Al2O3Deng.
If not dealing carefully with boron mud, the alkaline matter in boron mud can influence environment, polluted source, lead to that not even a blade of grass grows； Boron mud particle racks to finish the meeting and be polluted to air.
1 ton of borax of production needs 4 tons or so B2O3The boromagnesite that grade is 12% about generates 4 tons of boron mud.Reform is opened After putting, as borax is in the extensive use of industry-by-industry, the annual output of borax increases considerably, and the yield of boron mud also increases therewith Add.Liaoning Province's boron mud total amount is more than 20,000,000 tons.Especially in recent years, with the increase year by year of borax annual output and raw ore The total amount of the reduction of grade, boron mud is being continuously increased, and sufficient raw material guarantee is provided to large-scale develop and utilize boron mud.
The research paid much attention to boron mud and utilize technology domestic at present such as produces concrete, prepares foam glass, prepares foam Viscous brick etc..Boron mud is used as to the raw material of agglomerates of sintered pellets, improves the intensity and yield of pelletizing.Using boron mud as flocculant process dirt Water.
The extraction of magnesium elements has following two methods in boron mud at present：
A kind of method is to use borax production equipment, is operated using boron mud-carbonatation process technique, after boron mud is pre-processed It is digested, carburizing reagent, aqueous 70% or so semi-finished product is obtained after filtering, pyrolysis, press filtration, are obtained after 150 DEG C of dryings Magnesium carbonate.Magnesium carbonate drying and calcining at 800 DEG C obtains magnesia, and the overall recovery of magnesium is 65%.
Another method is to make boron mud leaching agent using industrial sulphuric acid, by leaching, cohesion, vacuum filter, flotation, wadding Solidifying, vacuum filter obtains Adlerika.It uses sodium carbonate as precipitating reagent, purified Adlerika is precipitated, filter, is washed It washs, dry, calcination processing obtains magnesia.
The product of both the above method is magnesia, and in practical applications, often based on applied metal magnesium, therefore also It needs the product to both the above method to be further processed, there is a problem of complex for operation step.
Invention content
The goal of the invention of the present invention is in view of the drawbacks of the prior art, to provide a kind of utilization method of boron mud.
The utilization method of the boron mud of the present invention, includes the following steps：
(1) boron mud is dried, be subsequently sent to rotary kiln or heat the boron mud after kiln roasting is roasted；
(2) boron mud, quick lime, carbonaceous reducing agent and the calcirm-fluoride after roasting is broken and levigate respectively, then by default Ratio is uniformly mixed and obtains mixture；
(3) mixture is heated and is pressed into pelletizing and obtain hot pressing pelletizing；
(4) hot pressing pelletizing is put into the reduction furnace with magnesium crystallizer and is restored, reduction is cooled down after terminating, and is obtained Obtain magnesium metal.
Method above-mentioned, in step (1), calcination temperature is 700-920 DEG C.
In step (2), boron mud, quick lime, carbonaceous reducing agent and the calcirm-fluoride after roasting are crushed respectively for method above-mentioned And it is levigate to grain size in 0.1mm or less.
Method above-mentioned, in step (2), preset ratio is as follows：
The proportioning of quick lime and boron mud is：(calcium oxide gross mass in quick lime and boron mud)/it is (siliceous in boron mud Amount) it is 1-2；
Carbonaceous reducing agent amount of allocating is：(fixed carbon quality in carbonaceous reducing agent)/(quality+iron oxide of oxygen in magnesia The quality of middle oxygen) it is 0.825-1.65；
The amount of allocating of calcirm-fluoride is：The quality of calcirm-fluoride/(boron mud, total matter of carbonaceous reducing agent, quick lime and calcirm-fluoride Amount) it is 0.02-0.05.
Method above-mentioned in step (3), heats the mixture to 430-530 DEG C and maintains 3-5 minutes, later will mixing Object is pressed into pelletizing.
Method above-mentioned in step (4), is restored under conditions of pressure≤500Pa and temperature are 1150-1500 DEG C 40-240 minutes.
Method above-mentioned in step (4), after reduction terminates, argon gas is passed through into reduction furnace and furnace temperature is cooled to 600 DEG C or less.
Method above-mentioned, the carbonaceous reducing agent are coke or coal.
Method above-mentioned, the hot pressing pelletizing is elliposoidal.
Compared with the existing technology, method of the invention, which realizes boron mud, efficiently uses, and reduces boron mud to environment Pollution, and obtain high value added product magnesium metal.
Description of the drawings
Fig. 1 is the process flow chart of the method for the present invention.
Specific implementation mode
In order to fully understand the purpose of the present invention, feature and effect, by following specific implementation modes, the present invention is made detailed It describes in detail bright.For the process of the present invention in addition to following the description, remaining is all made of the conventional method or device of this field.
The method of the present invention is directed to boron mud caused by chemical industry station-service boromagnesite or ludwigite standby borax made of stones Residue, color are light browns, belong to indissoluble substance.According to chemical analysis, the composition of boron mud is mainly：Content of MgO is in 20- Between 45% (weight), SiO2Content is between 5-35%, B2O3Content is between 0.5-6%, Fe2O3Content 3-18% it Between, CaO content is between 1-5%, Al2O3Content is between 0-5%.According to XRD analysis, mainly by Mg in boron mud2SiO4With MgCO3Composition.
With reference to Fig. 1, the method for the present invention is described in detail.The boron mud of the present invention includes following step using method Suddenly：
The first step is dried boron mud and roasts.
Boron mud is dried first, then boron mud is sent into rotary kiln or heating furnace, at a temperature of 700-920 DEG C It is roasted.By high-temperature roasting, Free water and the crystallization water in boron mud are divested, also, in roasting, in boron mud MgCO3It decomposes and generates MgO and CO2。
Second step, it is material is broken, levigate and uniformly mixed obtain mixture.
Boron mud, quick lime, carbonaceous reducing agent and calcirm-fluoride after roasting is crushed respectively and levigate.Specifically, it will roast Rear boron mud is broken, it is levigate to grain size in 0.1mm or less；By quick lime (i.e. calcium oxide) it is broken, levigate to grain size in 0.1mm； By carbonaceous reducing agent (for example, coke or coal) it is broken, levigate to grain size in 0.1mm or less；By calcirm-fluoride it is broken, levigate extremely 0.1mm or less.
Above-mentioned quick lime, carbonaceous reducing agent and calcirm-fluoride can be obtained by regular market purchase.
After being crushed by material and is levigate, each material is uniformly mixed according to preset ratio and obtains mixture.Wherein, it presets Ratio is specific as follows：
The proportioning of quick lime and boron mud is：(calcium oxide gross mass in quick lime and boron mud)/it is (siliceous in boron mud Amount) it is 1-2；
Carbonaceous reducing agent amount of allocating is：(fixed carbon quality in carbonaceous reducing agent)/(quality+iron oxide of oxygen in magnesia The quality of middle oxygen) it is 0.825-1.65；
The amount of allocating of calcirm-fluoride is：The quality of calcirm-fluoride/(boron mud, total matter of carbonaceous reducing agent, quick lime and calcirm-fluoride Amount) it is 0.02-0.05.
Above-mentioned preset ratio is conducive to the progress reacted in subsequent reduction step.
Third walks, and prepares hot pressing pelletizing.
The mixture that second step obtains is heated to 430-530 DEG C, carbonaceous reducing agent occurs fierce within this temperature range Depolymerization reaction, generate the smaller gaseous component of a large amount of molecular weight and the larger sticky liquid phase component of molecular weight.In the temperature It is maintained 3-5 minutes in range, mixture is then pressed into pelletizing and obtains hot pressing pelletizing.Have using hot pressing pelletizing process following Advantage：Without using binder, low temperature intensity is high, elevated temperature strength is high, increases the contact area between each material, and reproducibility It is good.
Obtained hot pressing pelletizing is preferably elliposoidal, is conducive to the abundant progress of sequential reduction reaction.
4th step, reduction and acquisition product.
Hot pressing pelletizing is put into the reduction furnace with magnesium crystallizer, is 1150-1500 DEG C in pressure≤500Pa and temperature Under the conditions of carry out reduction 40-240 minutes.Reduction terminate after, be passed through into reduction furnace argon gas and by furnace temperature be cooled to 600 DEG C with Under, magnesium crystallizer is taken out, magnesium metal is obtained.
In reduction furnace, under vacuum and hot conditions, carbonaceous reducing agent magnesia forms magnesium steam and carbon monoxide. Carbon monoxide is removed into reaction system by vacuum environment, while magnesium steam being allowed to condense into magnesium metal at crystallizer, is ensured anti- It should be carried out towards the direction for generating magnesium.
In 2MgOSiO present in boron mud2Because the presence of CaO can occur to react as follows under high temperature：
2MgO·SiO2(s)+2CaO (s)=2MgO (s)+2CaOSiO2(s) ΔGθ=-51600-15.61T
The reaction is conducive to constantly form free magnesia in system, and magnesia continues by carbonaceous reducing agent, shape At magnesium steam, magnesium steam condensation is on crystallizer.
Existing small amounts boron can form stable slag system with calcium oxide, silica in pelletizing, and reaction is promoted to carry out.Body Existing calcirm-fluoride is conducive to increase the mobility of slag in system, to having reacted catalytic action.
As a result of above mentioned preset ratio so that each reaction of reduction step fully carries out, and ensures to generate Waste minimization.
Above-mentioned magnesium crystallizer is the conventional equipment of this field.
After 4th the end of the step, waste residue is discharged, continues to add raw material, is that reaction continues.
Embodiment
It is further illustrated the present invention below by the mode of embodiment, but does not therefore limit the present invention to the reality It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient Product specification selects.
The boron mud used in following embodiments comes from waste caused by certain borax production plant, and composition is：MgO contains Measure 35.94wt%, SiO2Content 24.41wt%, B2O3Content 3.8%, Fe2O3Content 7.7wt%, CaO content 4.4wt%, Al2O3Content 2.73wt%, Na2O content 0.89wt%, K2O content 0.63wt%, scaling loss content 19.5wt%.
The carbonaceous reducing agent used in following embodiments is cheap coal dust purchased in market.
Embodiment 1：
(1) boron mud is dried, is sent into rotary kiln or heating furnace roasting, 700 DEG C of calcination temperature sloughs wherein moisture and gas Body.
(2) boron mud after roasting is broken, levigate to 0.1mm or less；Quick lime is broken, levigate to 0.1mm；By carbonaceous Reducing agent is broken, levigate to 0.1mm or less；Calcirm-fluoride is broken, levigate to 0.1mm or less；
Levigate boron mud, quick lime, carbonaceous reducing agent, calcirm-fluoride are uniformly mixed according to following ratios：
The proportioning of quick lime and boron mud is：(calcium oxide total amount in quick lime and boron mud)/(silica quality in boron mud) It is 1.8；Carbonaceous reducing agent amount of allocating is：(fixed carbon quality in carbonaceous reducing agent)/(in magnesia in quality+iron oxide of oxygen The quality of oxygen) it is 1.3；The amount of allocating of calcirm-fluoride is：The quality of calcirm-fluoride/(boron mud, carbonaceous reducing agent, quick lime, calcirm-fluoride Gross mass and) be 0.04.
(3) mixed material of step (2) is heated to 430 DEG C, and maintains 5min at such a temperature, it is interior at such a temperature to incite somebody to action Mixed material is pressed into pelletizing.
(4) by reduction furnace of the hot pressing pelletizing merging with magnesium crystallizer, under the conditions of 1500 DEG C of pressure≤500Pa and temperature Reduction, time 40min；Reduction terminate backward with magnesium crystallizer reduction furnace in be passed through argon gas, be cooled to 600 DEG C hereinafter, Magnesium crystallizer is taken out, magnesium metal is obtained；Waste residue is discharged；Continue to add raw material, reaction is made to continue.
Embodiment 2：
(1) boron mud is dried, is sent into rotary kiln or heating furnace roasting, 750 DEG C of calcination temperature sloughs wherein moisture and gas Body.
(2) boron mud after roasting is broken, levigate to 0.1mm or less；Quick lime is broken, levigate to 0.1mm；By carbonaceous Reducing agent is broken, levigate to 0.1mm or less；Calcirm-fluoride is broken, levigate to 0.1mm or less；
Levigate boron mud, quick lime, carbonaceous reducing agent, calcirm-fluoride are uniformly mixed according to following ratios：
The proportioning of quick lime and boron mud is：(calcium oxide total amount in quick lime and boron mud)/(silica quality in boron mud) It is 2；Carbonaceous reducing agent amount of allocating is：(fixed carbon quality in carbonaceous reducing agent)/(oxygen in quality+iron oxide of oxygen in magnesia Quality) be 1.65；The amount of allocating of calcirm-fluoride is：The quality of calcirm-fluoride/(boron mud, carbonaceous reducing agent, quick lime, calcirm-fluoride Gross mass and) be 0.05.
(3) mixed material of step (2) is heated to 530 DEG C, and maintains 3min at such a temperature, it is interior at such a temperature to incite somebody to action Mixed material is pressed into pelletizing.
(4) by reduction furnace of the hot pressing pelletizing merging with magnesium crystallizer, under the conditions of 1300 DEG C of pressure≤500Pa and temperature Reduction, time 100min；Reduction terminate backward with magnesium crystallizer reduction furnace in be passed through argon gas, be cooled to 600 DEG C hereinafter, Magnesium crystallizer is taken out, magnesium metal is obtained；Waste residue is discharged；Continue to add raw material, reaction is made to continue.
Embodiment 3：
(1) boron mud is dried, is sent into rotary kiln or heating furnace roasting, 860 DEG C of calcination temperature sloughs wherein moisture and gas Body.
(2) boron mud after roasting is broken, levigate to 0.1mm or less；Quick lime is broken, levigate to 0.1mm；By carbonaceous Reducing agent is broken, levigate to 0.1mm or less；Calcirm-fluoride is broken, levigate to 0.1mm or less；
Levigate boron mud, quick lime, carbonaceous reducing agent, calcirm-fluoride are uniformly mixed according to following ratios：
The proportioning of quick lime and boron mud is：(calcium oxide total amount in quick lime and boron mud)/(silica quality in boron mud) It is 1.4；Carbonaceous reducing agent amount of allocating is：(fixed carbon quality in carbonaceous reducing agent)/(in magnesia in quality+iron oxide of oxygen The quality of oxygen) it is 1；The amount of allocating of calcirm-fluoride is：The quality of calcirm-fluoride/(boron mud, carbonaceous reducing agent, quick lime, calcirm-fluoride it is total Quality and) be 0.03.
(3) mixed material of step (2) is heated to 460 DEG C, and maintains 3min at such a temperature, it is interior at such a temperature to incite somebody to action Mixed material is pressed into pelletizing.
(4) by reduction furnace of the hot pressing pelletizing merging with magnesium crystallizer, under the conditions of 1200 DEG C of pressure≤500Pa and temperature Reduction, time 160min；Reduction terminate backward with magnesium crystallizer reduction furnace in be passed through argon gas, be cooled to 600 DEG C hereinafter, Magnesium crystallizer is taken out, magnesium metal is obtained；Waste residue is discharged；Continue to add raw material, reaction is made to continue.
Embodiment 4：
(1) boron mud is dried, is sent into rotary kiln or heating furnace roasting, 920 DEG C of calcination temperature sloughs wherein moisture and gas Body.
(2) boron mud after roasting is broken, levigate to 0.1mm or less；Quick lime is broken, levigate to 0.1mm；By carbonaceous Reducing agent is broken, levigate to 0.1mm or less；Calcirm-fluoride is broken, levigate to 0.1mm or less；
Levigate boron mud, quick lime, carbonaceous reducing agent, calcirm-fluoride are uniformly mixed according to following ratios：
The proportioning of quick lime and boron mud is：(calcium oxide total amount in quick lime and boron mud)/(silica quality in boron mud) It is 1；Carbonaceous reducing agent amount of allocating is：(fixed carbon quality in carbonaceous reducing agent)/(oxygen in quality+iron oxide of oxygen in magnesia Quality) be 0.83：The amount of allocating of calcirm-fluoride is：The quality of calcirm-fluoride/(boron mud, carbonaceous reducing agent, quick lime, calcirm-fluoride Gross mass and) be 0.02.
(3) mixed material of step (2) is heated to 490 DEG C, and maintains 4min at such a temperature, it is interior at such a temperature to incite somebody to action Mixed material is pressed into pelletizing.
(4) by reduction furnace of the hot pressing pelletizing merging with magnesium crystallizer, under the conditions of 1150 DEG C of pressure≤500Pa and temperature Reduction, time 240min；Reduction terminate backward with magnesium crystallizer reduction furnace in be passed through argon gas, be cooled to 600 DEG C hereinafter, Magnesium crystallizer is taken out, magnesium metal is obtained；Waste residue is discharged；Continue to add raw material, reaction is made to continue.

Claims (8)

1. a kind of utilization method of boron mud, which is characterized in that include the following steps：
(1) boron mud is dried, be subsequently sent to rotary kiln or heat the boron mud after kiln roasting is roasted；
(2) boron mud, quick lime, carbonaceous reducing agent and the calcirm-fluoride after roasting is broken and levigate respectively, then press preset ratio It is uniformly mixed and obtains mixture；
(3) mixture is heated and is pressed into pelletizing and obtain hot pressing pelletizing；
(4) hot pressing pelletizing is put into the reduction furnace with magnesium crystallizer and is restored, reduction is cooled down after terminating, and obtains gold Belong to magnesium；
Wherein, the proportioning of quick lime and boron mud is：(calcium oxide gross mass in quick lime and boron mud)/it is (siliceous in boron mud Amount) it is 1-2；
Carbonaceous reducing agent amount of allocating is：(fixed carbon quality in carbonaceous reducing agent)/(oxygen in quality+iron oxide of oxygen in magnesia Quality) be 0.825-1.65；
The amount of allocating of calcirm-fluoride is：The quality of calcirm-fluoride/(boron mud, the gross mass of carbonaceous reducing agent, quick lime and calcirm-fluoride) be 0.02-0.05。
2. according to the method described in claim 1, it is characterized in that, in step (1), calcination temperature is 700-920 DEG C.
3. according to the method described in claim 1, it is characterized in that, in step (2), by boron mud, quick lime, the carbonaceous after roasting Reducing agent and calcirm-fluoride be crushed respectively and it is levigate to grain size in 0.1mm or less.
4. according to the method described in claim 1, it is characterized in that, in step (3), 430-530 DEG C is heated the mixture to simultaneously It maintains 3-5 minutes, mixture is pressed into pelletizing later.
It is 1150- in pressure≤500Pa and temperature 5. according to the method described in claim 1, it is characterized in that, in step (4) Reduction 40-240 minutes is carried out under conditions of 1500 DEG C.
6. according to the method described in claim 1, it is characterized in that, in step (4), after reduction terminates, lead into reduction furnace Enter argon gas and furnace temperature is cooled to 600 DEG C or less.
7. according to the method described in claim 1, it is characterized in that, the carbonaceous reducing agent is coke or coal.
8. according to the method described in claim 1, it is characterized in that, the hot pressing pelletizing is elliposoidal.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1071967A (en) * 1992-10-19 1993-05-12 清华大学 With silicothermic process extraction of metal magnesium from boron mud
CN103667705A (en) * 2013-11-27 2014-03-26 山东理工大学 Comprehensive utilization method for boric sludge waste

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103572044B (en) * 2013-10-12 2015-03-04 酒泉钢铁(集团)有限责任公司 Method for producing iron hot-pressed carbon-containing pellets through direction reduction on metallized iron powder

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1071967A (en) * 1992-10-19 1993-05-12 清华大学 With silicothermic process extraction of metal magnesium from boron mud
CN103667705A (en) * 2013-11-27 2014-03-26 山东理工大学 Comprehensive utilization method for boric sludge waste

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