CN102653814B - Processing method for boron mud reutilization - Google Patents
Processing method for boron mud reutilization Download PDFInfo
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- CN102653814B CN102653814B CN2012101430760A CN201210143076A CN102653814B CN 102653814 B CN102653814 B CN 102653814B CN 2012101430760 A CN2012101430760 A CN 2012101430760A CN 201210143076 A CN201210143076 A CN 201210143076A CN 102653814 B CN102653814 B CN 102653814B
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- boron mud
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- boron
- carbon
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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
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- Y02P10/00—Technologies related to metal processing
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Abstract
The invention relates to the technical field of waste boron mud reutilization, and particularly relates to a processing method for reutilization of boron mud as a metallurgy slag marking material through removing harmful impurities. The processing method is characterized in that a method comprising the steps of drying, carbon blending, pellet formation and reduction roasting is adopted, and hazardous materials including water, phosphorus and sulfur and the like in the boron mud are removed. The processing method provided by the invention reduces phosphorus oxide in the boron mud through carbon blending and roasting, the phosphorus oxide is reduced into phosphorus steam, the boron mud dephosphorization is realized, thus the harmless treatment for boron mud used for steelmaking slag forming is realized, and the phosphorus steam is also used for recovering simple substance phosphorus; and therefore, the processing method provided by the invention realizes the waste boron mud harmless reutilization, and has many technical and economy advantages.
Description
Technical field
The present invention relates to discarded boron mud recycling processing technology field, particularly a kind of boron mud, for metallurgical slag making materials, is removed detrimental impurity, realizes the treatment process of recycling.
Background technology
China's boron resource is abundant, and proven reserve surpass 100,000,000 tons (with B
2o
3meter), be in the world boron resource big country few in number; But the grade of the most crude boron stones of China is low, and mostly is the mixed type ores such as szaibelyite, boron magnesium iron, after extracting borax with the carbon alkaline process, produce a large amount of discarded boron mud (annotate: by current production technique, 1 ton of borax of every production, will produce 3-4 ton boron mud); The main component of boron mud is MgO, CaO, Fe
2o
3, B
2o
3deng, the research fully utilized about boron mud also has to be carried out, as utilizes boron mud to produce boric magnesium fertilizer and Magnesium Carbonate Light 41-45 etc., but because the boron in boron mud, iron, magnesium etc. all belong to assorted lean ore, extraction cost is too high, complex treatment process; Therefore, China still lacks the industrial method of realizing the high added value comprehensive utilization for discarded boron mud at present, pile up and process as waste always, not only take a large amount of land resources, and the boron mud of carrying after boron due to the carbon alkaline process has than strong basicity, a large amount of outdoor accumulations of boron mud form serious pollution to soil and water resources, if things go on like this will jeopardize the mankind's health and even survive; China is with carbon alkali method for producing borax over more than 40 years, nearly hundred million tons, the boron mud that fixed point is piled up, and the pollution brought and occupation of land problem are day by day serious, and therefore, boron mud problem of complex utilization is anxious to be resolved.
In prior art, the report using boron mud as metallurgical slag-making addition is more; As Chinese invention patent (application number: 200910012692.0) ironmaking additive and preparation method thereof; Chinese invention patent (application number: 201010505931.9) a kind of boron-containing fluorine-free fluxing slag-melting agent for electric steelmaking; Chinese invention patent (application number: 201110037710.8) a kind of boron-containing fluoride-free covering slag for steel continuous-casting crystallizer and preparation method thereof, etc., these existing inventions all propose in boron mud with addition of metallurgical slag making materialses of preparation such as lime, wollastonites, this is to utilize boron mud to have the advantages such as fusing point is low, activity is high, easy slagging, can substitute steelmaking slagging fluxing agent fluorite, iron oxide pellet, red bauxite etc.; But it is higher that existing boron rock is carried in the boron mud that the boron technology produces harmful substance contents, particularly the harmful elements such as the phosphorus in boron mud, sulphur can increase p and s in steel, pollute molten steel, have limited usage quantity and the use range of boron mud in metallurgical slag making.
Therefore, the high problems of foreign matter content such as phosphorus sulphur that exist for metallurgical slag making materials for solving current boron mud, the present invention proposes a kind of boron mud and realizes the material processing of recycling for metallurgical slag making materials.
Summary of the invention
The objective of the invention is: provide a kind of boron mud for metallurgical slag making materials, remove detrimental impurity, realize the treatment process of recycling, solve the high problems of harmful element content such as phosphorus sulphur that boron mud exists for metallurgical slag making, improve application quantity and the range of application of boron mud.
Technology imagination principle of the present invention is: boron mud is MgO, CaO, B for the main valuable constituent of metallurgical slag making
2o
3deng, its objectionable constituent are mainly P
2o
5, sulphur and crystal water etc., by adding thermal bake-out, the organosulfur in boron mud and crystal water can effectively be removed, inorganic sulfur is by roasting, sulfide can change SO into
2gas is removed; Phosphorus in boron mud is mainly phosphoric acid salt, and by reducing roasting, the temperature of the hierarchy of control, mixed carbon comtent, make the P in phosphoric acid salt
2o
5be reduced into P
2steam is with removal, MgO, CaO, B in boron mud
2o
3the boron mud after roasting Deng at roasting process, is not reduced, so can be used as metallurgical slag making materials.
Based on above-mentioned principle, realize that technical scheme of the present invention is:
Invent a kind of boron mud for metallurgical slag making materials, remove detrimental impurity, realize the treatment process of recycling, it is characterized in that drying → joining by employing the method for carbon → pelletizing → reducing roasting, remove the objectionable impuritiess such as water in boron mud, p and s; The feature of concrete treatment process is as follows:
A) drying course is mainly removed crystal water and the organosulfur in boron mud, bake out temperature is controlled at 200-300 ℃, drying time was controlled at more than 0.5 hour, if bake out temperature is too low, can't effectively remove crystal water, otherwise bake out temperature is too high, can cause sintering, be unfavorable for joining carbon and mixing and pelletizing of postorder;
B) boron mud should become finely powdered after drying, and through conventional crushing and screening, makes its granularity be less than 0.075mm, is then joined carbon, and because the phosphorus in boron mud mainly exists with phos-phate forms, the difficulty of its reduction is greater than P freely
2o
5, the ferric oxide in boron mud has precedence over P
2o
5reduction, therefore, want the phosphoric acid salt in reducing slag, the ferric oxide in necessary first reducing slag, so mixed carbon comtent calculates according to the ferric oxide in boron mud, phosphorus element content and required excess quantity, calculation formula is:
Mixed carbon comtent [C] %=0.3 * [Fe
2o
3] %+1.0 * [P] %+ excess quantity
In formula: mixed carbon comtent [C] % is the massfraction of joining carbon; [Fe
2o
3] the % massfraction that is ferric oxide in boron mud; The massfraction that [P] % is phosphoric in boron mud; Surplus measures 2-3%;
C) adopt pressure ball pelletizing method, the boron mud powder pressure ball that will join carbon and mix, the size range of pelletizing is 10-30mm;
D) the boron mud ball adopts rotary hearth furnace or the roasting apparatuss such as tunnel furnace or rotary kiln to carry out roasting, and maturing temperature is controlled at 700-1200 ℃, if maturing temperature is low, the phosphorus in phosphoric acid salt is difficult to reduction, but maturing temperature is too high, and other oxide compounds in boron mud are as B
2o
3, SiO
2deng also, can be reduced, in addition, high temperature causes the adhesion of boron mud ball serious, and even fusing, adhere to roasting apparatus, and these are all disadvantageous; Roasting time 20-30 minute determines that according to the diameter of ball, when the mean diameter of ball is less than 20mm, roasting time removes the limit 20 minutes, when mean diameter of a ball is greater than 25mm, and roasting time capping 30 minutes; When the diameter of ball is 20 ~ 25 mm, roasting time is got and is greater than 20 minutes and is less than 30 minutes, is generally 23 ~ 28 minutes.
E) flue gas that roasting process produces makes phosphorus simple substance after by water-cooled;
F) the boron mud ball after roasting is packed after cooling, can be used as metallurgical slag making materials.
Main creativeness of the present invention is: the control of mixed carbon comtent and reducing roasting system temperature in the present invention, make it to occur the selective reduction reaction, mixed carbon comtent need to meet and will the phosphorous oxides in phosphoric acid salt be reduced fully after the reduction such as ferric oxide, manganese oxide again, simultaneously, select to control the roasting reduction temperature, control the phosphoric acid salt reduction and other oxide compounds are not reduced, therefore, although what the present invention adopted is the conventional reduction reaction, it is main creative place of the present invention that method of reducing, reduction are controlled.
Compared with prior art major advantage of the present invention is as follows:
(1), boron mud piles up as waste at present, contaminate environment, the present invention can effectively reduce harmful element P in boron mud, S content, P≤0.03 wherein, S≤0.03, reach the standard of the metallurgical slag making materials of high-quality, realized the high added value recycling of boron mud as the metallurgical slag material of high-quality;
(2), after method of the present invention processes boron mud, the fusing point of boron mud ball is low, at 1200-1400 ℃, can substitute traditional slag-making fluxing agents such as fluorite, has eliminated fluoride pollution, realizes floride-free slag making;
(3), after method of the present invention processes boron mud, the boron mud ball is difficult for efflorescence, water resisting property is strong, can be directly used in metallurgical slag making, also can be used as raw material production pre-melted slag product, suitability is wider;
(4) method processing cost of the present invention is low, and because low, the of the present invention processing cost of the price of boron mud own is not high, the boron mud ball that adopts the present invention to produce is lower than the price of fluorite, red bauxite etc. on market, can bring significant economic benefit.
Embodiment
embodiment 1:
A, raw material are processed and calcination process
The boron mud that China factory production borax of take produces is raw material, and boron mud is dried the composition of caustic soda after 0.5 hour following (massfraction %): B by analysis under 200 ℃
2o
32.5%, CaO 17.5%, Fe
2o
35%, SiO
215%, MgO 38%, Al
2o
38%, P 1.6%, and S 0.8%, and all the other are the insoluble impurity of Determining Micro Acid;
B, grind, join carbon, mix
By the boron mud grind up after roasting, through conventional crushing and screening, making its granularity is 0.075mm, is then joined carbon, and mixed carbon comtent is according to formula: [C] %=0.3 * [Fe
2o
3] %+1.0 * [P] %+ excess quantity calculating, excess carbon measures 2%, so mixed carbon comtent is: [C] %=0.3 * 5%+1.0 * 1.6%+2%=5.1%;
C, employing pressure ball pelletizing method, the boron mud powder pressure ball that will join carbon and mix, the granularity of finished ball is controlled at 26 ~ 27mm;
D, boron mud ball are through the rotary hearth furnace roasting, and maturing temperature is controlled at 1180 ℃, roasting 30 minutes; Boron mud ball after roasting is packed and be can be used as metallurgical slag making materials after cooling, and the phosphorous flue gas that roasting process produces reclaims phosphorus simple substance after water-cooled.
The composition of the boron mud ball that by analysis, the present embodiment obtains is:
B
2o
32.4%, CaO 17.3%, SiO
214.8%, MgO 37.8%, Al
2o
38.9%, Fe 3.1%, and P 0.03%, and S 0.03%, and all the other are the insoluble impurity of Determining Micro Acid, and its harmful element foreign matter content is low, and physical property research shows, 1283 ℃ of its fusing points, be suitable as metallurgical slag making materials, can substitute fluorite as metallurgical slag-making fluxing agent.
embodiment 2:
A, raw material are processed and calcination process
The boron mud that China Liaoning factory production borax of take produces is raw material, and boron mud is dried the composition of caustic soda after 1 hour following (massfraction %): B by analysis under 300 ℃
2o
31.5%, CaO 12.5%, Fe
2o
37%, SiO
215%, MgO 48%, Al
2o
39%, P 1.2%, and S 0.9%, and all the other are the insoluble impurity of Determining Micro Acid;
B, grind, join carbon, mix
By the boron mud grind up after roasting, through conventional crushing and screening, making its granularity is 0.05mm, is then joined carbon, and mixed carbon comtent is according to formula: [C] %=0.3 * [Fe
2o
3] %+1.0 * [P] %+ excess quantity calculating, excess carbon measures 3%, so mixed carbon comtent is: [C] %=0.3 * 7%+1.0 * 1.2%+3%=6.3%;
C, employing pressure ball pelletizing method, the boron mud powder pressure ball that will join carbon and mix, the granularity of finished ball is controlled at 18 ~ 19mm;
D, boron mud ball are through the rotary hearth furnace roasting, and maturing temperature is controlled at 1080 ℃, roasting 20 minutes; Boron mud ball after roasting is packed and be can be used as metallurgical slag making materials after cooling, and the phosphorous flue gas that roasting process produces reclaims phosphorus simple substance after water-cooled.
The composition of the boron mud ball that by analysis, the present embodiment obtains is:
B
2o
31.5%, CaO 15.3%, SiO
214.7%, MgO 47.8%, Al
2o
38.6%, Fe 4.1%, P 0.02%, S 0.02%, all the other are the insoluble impurity of Determining Micro Acid, and its harmful element foreign matter content is low, and physical property research shows, 1373 ℃ of its fusing points, be suitable as metallurgical slag making materials, facts have proved and can substitute fluorite as metallurgical slag-making fluxing agent, also can be for external refining slag making etc.
Claims (2)
1. the treatment process of a boron mud recycling, is characterized in that: dry → join the method for carbon → pelletizing → reducing roasting by employing, remove objectionable impurities in boron mud; Be specially:
A) dry to remove crystal water and the organosulfur in boron mud, bake out temperature is controlled at 200-300 ℃, and drying time was controlled at more than 0.5 hour;
B) boron mud should become finely powdered after drying, and through conventional crushing and screening, makes its granularity be less than 0.075mm, is then joined carbon, and mixed carbon comtent calculates according to the ferric oxide in boron mud, phosphorus element content and required excess quantity, and calculation formula is:
Mixed carbon comtent [C] %=0.3 * [Fe
2o
3] %+1.0 * [P] %+ excess quantity;
In formula: mixed carbon comtent [C] % is the massfraction of joining carbon; [Fe
2o
3] the % massfraction that is ferric oxide in boron mud; The massfraction that [P] % is phosphoric in boron mud; Surplus measures 2-3%;
C) adopt pressure ball pelletizing method, the boron mud powder pressure ball that will join carbon and mix, the size range of pelletizing is 10-30mm;
D) the boron mud ball adopts rotary hearth furnace or tunnel furnace or rotary kiln to carry out roasting, and maturing temperature is controlled at 700-1200 ℃; Roasting time is 20-30 minute, and boron mud ball diameter is larger, and roasting time is longer;
E) flue gas that roasting process produces makes phosphorus simple substance after by water-cooled;
F) the boron mud ball after roasting is packed after cooling, can be used as metallurgical slag making materials.
2. the treatment process that a kind of boron mud as claimed in claim 1 recycles, it is characterized in that: when the mean diameter of ball is less than 20mm, roasting time removes the limit 20 minutes, when mean diameter of a ball is greater than 25mm, roasting time capping 30 minutes; When the diameter of ball is 20 ~ 25 mm, roasting time is got and is greater than 20 minutes and is less than 30 minutes.
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| CN102653814B true CN102653814B (en) | 2013-12-11 |
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2012
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| CN1245219A (en) * | 1998-08-18 | 2000-02-23 | 李绍兵 | Technology for making compound B-Mg balls and its usage |
| CN1962891A (en) * | 2006-11-24 | 2007-05-16 | 辽宁中兴矿业集团有限公司 | Boron composite fluxing agent for making steel |
| CN101033496A (en) * | 2007-04-03 | 2007-09-12 | 江苏大学 | Alkaline oxygen converter steelmaking slagging fluxing agent and its preparing method and slagging method |
| CN101560583A (en) * | 2009-05-16 | 2009-10-21 | 鞍钢股份有限公司 | Converter coolant taking metallurgical waste as raw material and manufacturing method thereof |
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