CN102344981A - Separation and direct reduction process of iron and boron in boron-containing iron ore concentrate - Google Patents
Separation and direct reduction process of iron and boron in boron-containing iron ore concentrate Download PDFInfo
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- CN102344981A CN102344981A CN2011102828978A CN201110282897A CN102344981A CN 102344981 A CN102344981 A CN 102344981A CN 2011102828978 A CN2011102828978 A CN 2011102828978A CN 201110282897 A CN201110282897 A CN 201110282897A CN 102344981 A CN102344981 A CN 102344981A
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Abstract
The invention provides a separation and direct reduction process of iron and boron in boron-containing iron ore concentrate. The process comprises the following steps of: adding an external reducing agent and a desulfurizing agent in the boron-containing iron ore concentrate powder, and drying the furnace material with high-temperature flue gas; adding the dried furnace material in an SiC roasting tank according to the proportion and a charging method, closing the material tank with the reducing agent, and putting the material tank in a trolley and pushing into a tunnel kiln; operating for about 30 hours at a preheating section, a reduction section and a heat-insulation slow cooling section so as to complete the reduction process; and discharging the reduced roasted material. According to the invention, clean gas is used as a heat source, preheated air is adopted for combustion supporting, a computer is adopted to control the furnace temperature so that reduced atmosphere in the furnace is maintained and the stable reduction section temperature is maintained to be 1050-1180 DEG C, thereby effectively preventing secondary oxidation; and after the discharged reduced roasted material is smashed, magnetic separation or submerged arc electric furnace smelting separation is carried out so as to produce two products namely metal iron and boron-rich slag. By using the process in the invention, the problems that in the prior art, the separation of iron and boron in the boron-containing iron ore concentrate is difficult and a boron resource is not recycled so as to cause great resource waste are solved, thereby promoting the development and utilization of rich boron-iron type mineral resources.
Description
Technical field
The present invention relates to a kind of technology of direct-reduced iron, particularly relate to a kind of boron-containing iron concentrate direct-reduced iron that utilizes and realize the isolating production technique of iron boron.
Background technology
Domestic boron resource rich is compared with external economic usable reserves with proven reserve and to be occupied the 4th in the world.The Liaoning in northeast, Jilin Area boron resource reserves account for 65% of national total amount, are China main places of production of boron in this century resource.Boron rock mainly contains boron magnesium type and ferro-boron type, and for many years, boron magnesium type boron rock supports for the boron industrial expansion provides resource always, has brought into play important effect to promoting China's Economic development.But boron magnesium type boron resource is closely exhausted at present, and the contradiction of boron resource worsening shortages is very outstanding, has been difficult to satisfy the needs of growing national economy and boron industrial development.And abundant 58% of the national reserves that account for of ferro-boron type ore reserves, wherein the father-in-law of Fengcheng City, Liaoning spring ditch paigeite is the maximum paigeite in Asia, proven reserve are 2.8 hundred million tons, are the most potential boron resource in China's boron industry future.But its ore complex structure, washability is poor, and iron boron separating difficulty is big, and is still under test to its development and use, do not go on the suitability for industrialized production of technology maturation.
The development and use of Liaoning paigeite resource obtain national high degree of attention and support always.Through tackling of key scientific and technical problems for many years, there are some gordian techniquies to make a breakthrough, like the paigeite technique of preparing, choose B
2O
36.34%, TFe27.3% sample ore adopts discarding coarse tailing stage grading technology, because the ore washability is poor, only adopts the single one physical beneficiation method, can not make that boron is separated with iron preferably in the ore, can only obtain boron concentrate (B
2O
3About 12%) and the ferro-boron concentrate (about TFe50%, B
2O
3About 6%) two kinds of products.Boron concentrate just can be used to produce borax after improving activity; Paigeite separates deep process technology owing to lack ferro-boron; Each manufacturing enterprise is many to be undersold the boron-containing iron concentrate powder to iron work as the ironmaking additive; Can only reclaim iron wherein out with the regular pig form through blast furnace; And valuable boron resource can not get recycling, and causes the significant wastage of resource.Ongoing pyrogenic process separates the ferro-boron test like blast furnace process and ore-smelting furnace method; On Technology, have than quantum jump; But still have some outstanding problems to need to improve; As will be with addition of the tackiness agent agglomeration; Want the high temperature oxidation roasting desulfurization, the ash content of pyrometallurgical smelting process coke and sludging flux etc. can pollute the boron slag and reduce B in the slag
2O
3Content makes B in the slag
2O
312-16% can only be used to produce borax and be difficult to single stage method production boric acid; Therefore the pyrogenic process Technology of the separating ferro-boron improvement of still needing.
Summary of the invention
The technical problem that the present invention will solve; Provide a kind of production process, equipment is simple, technological process is controlled easily, uniform in quality; Steady quality, thus can realize that the boron-containing iron concentrate iron boron that iron, boron high efficiency separation make full use of limited boron resource separates direct reducing process.
The technical scheme that adopts is:
Boron-containing iron concentrate iron boron separates direct reducing process, is to be that raw material and outer is joined solid reductant and sweetening agent and melted minute to process through drying, roasting, abrasive material or fragmentation, magnetic separation or electric furnace and contain B with the boron-containing iron concentrate powder
2O
3Rich boron rock slag of 20-22% higher-grade and iron yield are greater than 95% briquetting or shrend particulate state reduced iron.Processing step is:
1. get-200 purpose boron-containing iron concentrate powder and join the solid reductant and the sweetening agent mixture of granularity outward less than 3mm by proportioning, in the drum-type drying stove with 350-450 ℃ high temperature flue gas drying to moisture less than 2%;
2. will pack in the Sie system roasting pot by proportioning blended mineral material, tunnel furnace 1050-1180 ℃ with the condition that keeps reducing atmosphere under reducing roasting at least 30 hours;
3. with the reducing roasting material through ball mill abrasive material to 140 order or with crusher in crushing to subsequent use less than 100mm;
4. 140 order abrasive materials are carried out magnetic separation and separate maybe will to be crushed to and send less than 100mm reducing roasting material that electric furnace is molten to be divided, make the iron yield greater than 95% reduced iron with contain B
2O
3The rich boron rock slag of 20-22% higher-grade.
-200 above-mentioned purpose boron-containing iron concentrate powder are: TFe50-52%, B
2O
36% ± 0.2%, MgO14%, SiO
24-6%, the fine ore of S＜0.3%.
Above-mentioned granularity less than the solid reductant of 3mm be fixed carbon greater than 82%, sulphur less than 0.6% coke powder or fixed carbon greater than 65%, ash content less than 10%, sulphur is less than 0.6% pulverized anthracite.
Above-mentioned granularity is to contain CaO greater than 50% Wingdale less than the solid desulfurating agent of 3mm.
The dosage of above-mentioned reductive agent is extraordinarily to go into by 2 of the theoretical mixed carbon comtent of FeO+C=Fe+CO reaction formula, and the amount of allocating into of sweetening agent is by 10% adding of allocating reduction dosage into.
Above-mentioned magnetic separation separation or electric furnace be molten to be divided and makes that the iron yield is pressed into bulk greater than 95% reduced iron or shrend becomes particulate state, higher-grade B
2O
3Rich boron slag greater than 20% can be used for sulfuric acid and leaches single stage method production boric acid and magnesium sulfate heptahydrate, realizes boron, iron, magnesium resource comprehensive reutilization in the paigeite.
The beneficial effect that the present invention obtains is:
1, raw material, reductive agent, fuel solve easily
With the boron-containing iron concentrate powder of Liaoning paigeite after ore dressing is raw material, B
2O
3About 6%, about TFe50%, SiO
24-6%, MgO14.0%, S0.31%, P0.02%, granularity-200 order, fusing point 1300-1450 ℃; With producer gas or other inflammable gass is thermal source, and reductive agent is hard coal or coke powder; The sweetening agent Wingdale, CaO>=50%.
2, production process is simple: needn't add binding agent and make ball, not need roasting to become acid pellet to improve intensity, also need not carry out the oxidizing roasting desulfurization.Reduzate is not contaminated, the high B of rich boron cinder grade
2O
3Can reach 20-22%, can be used as sulfuric acid and leach the raw material that single stage method is produced boric acid and magnesium sulfate heptahydrate.
3, simple, the production technique easy master of equipment, production process are controlled easily, have prevented recurrent knot kiln fault in the kiln process explained hereafter.
Tunnel furnace technology generally is made up of reduction furnace, chassis, transition car, kiln car pusher, temperature instrumentation, chimney etc.Adopt the coal gas type of heating; Temperature-stable ground in the stove is controlled in 1050-1180 ℃ the scope, for the SiC matter on the tunnel kiln car fuse jar pack kiln into from kiln hood continuously in, be incubated the slow cooling section through the preheating section reduction section and amount to about about 30 hours; Accomplish reduction process, get into the discharging operation.The ratio of fine ore and coal dust and loading method are easy to grasp, and maturing temperature and roasting time also are not difficult to realize, so tunnel furnace technology easy master, and process is controlled easily.
The tunnel kiln direct reduced iron process procedure is few, and equipment is simple, and is very long in the following life-span of above-mentioned maturing temperature, almost do not have fault to go out, and the special construction of bar shaped tunnel furnace has guaranteed stable and reliable operation.Loading and unloading material system and briquetting system adopt mechanize to control automatically, increase work efficiency and the accuracy of equipment operation.
4, uniform in quality, steady quality
Owing to adopt closed batch can reductive method in reduction furnace, the concentration of reducing atmosphere in the batch can and pressure are improved, and adopt the computer control furnace temperature, have a narrow range of temperature, be prone to keep reducing atmosphere, so be easy to guarantee the requirement of reducing process.Because furnace charge is all packed into according to same ratio and loading method in each batch can; All be under same atmosphere, accomplish reduction process under the condition of same maturing temperature, same roasting time, therefore must obtain certain degree of metalization; Certain C, Si, S, P foreign matter content, certain B
2O
3The final product of content, quality product must be uniformly stable.
5, can realize iron, boron high efficiency separation
The reduction with carbon under standard state of boron, ferriferous oxide is reacted as follows in the boron-containing iron concentrate powder:
G °=147763-150.07T of FeO+C=Fe+CO Δ T
Beginning=985K
B
2O
3G °=858363-473.80T of+3C=2B+3CO Δ T
Beginning=1812K
About desulphurization reaction:
CaO+FeS→CaS+FeO；CaO+COS→CaS+CO
2
In direct reducing process temperature range, make reductive agent with carbon, FeO can realize degree of metalization about 98%, and B
2O
3Be difficult to realize reduction, B
2O
3100% be retained in the slag almost, this is the principle that can realize boron and iron high efficiency separation.
From the reducing roasting material that tunnel furnace unloads out, take two kinds of technologies to carry out iron, boron mask work:
Adopt that a kind of separating technology by the plant produced conditional decision.
6, waste heat effectively utilizes, environmental friendliness
Energy-conservation aspect: the using waste heat from tail gas of tunnel furnace is effectively utilized, as making combustion air after the waste heat heat exchange; With the dry furnace charge of waste heat; Useless reductive agent recuperation utilizes; Adopt the low heat-storing material of high thermal resistance to make kiln body building materials etc., after the employing abovementioned technology, the about 350kg mark of reduction sintered material operation power consumption per ton coal.
The environmental protection aspect: adopt clean gas to make fuel, the reduction reaction product mainly is CO
2And metallic iron, exhaust gas emission is up to standard fully; Adopt material sealing conveying and multiple dedusting means dust discharge up to standard fully; No sewage pollution and sound pollution; The recyclable utilization of solid waste (like useless retort and useless reductive agent).Therefore this art production process environment is friendly.
Description of drawings
Fig. 1 is magnetic separation ferro-boron separation process scheme figure of the present invention.
Fig. 2 is the molten ferro-boron separation process scheme figure that divides of electric furnace of the present invention.
Embodiment
Embodiment 1: with tunnel kiln direct reduced iron magnetic separation separation of iron boron technology is the example (see figure 1); A kind of technology of utilizing boron-containing iron concentrate powder direct-reduced iron; May further comprise the steps :-200 purpose boron-containing iron concentrate powder; Take outer mixture of joining coke powder and Wingdale; With high-temperature flue gas oven dry (moisture content is less than 2%); Be respectively charged in the SiC jar according to proportion scale and loading method; With reductive agent sealing batch can; Be contained in and push in the tunnel furnace on the chassis; At kiln hood the sealing gland air curtain is set, prevents that the outer cold wind of kiln from getting into and the interior hot gas of kiln is excessive.Reducing roasting is 30 hours under 1050-1180 ℃ of hot conditions, and discharging cools; Reducing roasting material abrasive material to 140 order after the cooling sand removal carries out magnetic separation, obtains metal iron powder and two kinds of products of rich boron rock slag.Metal iron powder is according to the bulk or the pelletizing shape of customer requirements compacting different size, and rich boron rock slag supplies the chemical plant to produce boric acid and produces magnesium sulfate heptahydrate with paying.
Embodiment 2: with the molten branch of tunnel kiln direct reduced iron electric furnace iron boron technology is the example (see figure 2); May further comprise the steps; Boron-containing iron concentrate powder (200 order) is taked outer anthracite powder (fixed carbon＞65%; Ash content＜10%; Sulphur＜0.6%; Granularity-3mm) and limestone powder (＜3mm) mixture; With high temperature flue gas drying furnace charge (water＜2%); Be respectively charged in the SiC jar according to proportioning and loading method; With reductive agent sealing batch can; Be contained in and push in the tunnel furnace on the chassis; At kiln hood the sealing gland air curtain is set, reducing roasting is 30 hours under 1150 ℃ of hot conditionss, and discharging cools; Reducing roasting material after the cooling sand removal is crushed to less than 100mm; Send ore-smelting furnace to melt and isolate metallic iron and rich boron slag; Metallic iron carries out the shrend granulation or is cast into bulk by customer need, and rich boron slag also becomes highly active Water Quenching Slag to be used to produce boric acid and recovery magnesium sulfate heptahydrate through shrend.
Claims (6)
1. boron-containing iron concentrate iron boron separates direct reducing process, it is characterized in that with the boron-containing iron concentrate powder being that raw material and outer is joined solid reductant and sweetening agent and melted minute to process through drying, roasting, abrasive material or fragmentation, magnetic separation or electric furnace and contain B
2O
3Rich boron rock slag of 20-22% higher-grade and iron yield are greater than 95% briquetting or shrend particulate state reduced iron, and processing step is:
1. get-200 purpose boron-containing iron concentrate powder and join the solid reductant and the sweetening agent mixture of granularity outward less than 3mm by proportioning, in the drum-type drying stove with 350-450 ℃ high temperature flue gas drying to moisture less than 2%;
2. will pack in the Sie system roasting pot by proportioning blended mineral material, tunnel furnace 1050-1180 ℃ with the condition that keeps reducing atmosphere under reducing roasting at least 30 hours;
3. with the reducing roasting material through ball mill abrasive material to 140 order or with crusher in crushing to subsequent use less than 100mm;
4. 140 order abrasive materials are carried out magnetic separation and separate maybe will to be crushed to and send less than 100mm reducing roasting material that electric furnace is molten to be divided, make the iron yield greater than 95% reduced iron with contain B
2O
3The rich boron rock slag of 20-22% higher-grade.
2. above-mentioned boron-containing iron concentrate iron boron according to claim 1 separates direct reducing process, it is characterized in that with-200 purpose boron-containing iron concentrate powder being: TFe50-52%, B
2O
36% ± 0.2%, MgO14%, SiO
24-6%, the fine ore of S＜0.3%.
3. above-mentioned boron-containing iron concentrate iron boron according to claim 1 separates direct reducing process, it is characterized in that described granularity less than the solid reductant of 3mm be fixed carbon greater than 82%, sulphur less than 0.6% coke powder or fixed carbon greater than 65%, ash content less than 10%, sulphur is less than 0.6% pulverized anthracite.
4. above-mentioned boron-containing iron concentrate iron boron according to claim 1 separates direct reducing process, it is characterized in that described granularity is to contain CaO greater than 50% Wingdale less than the solid desulfurating agent of 3mm.
5. above-mentioned boron-containing iron concentrate iron boron according to claim 1 separates direct reducing process; The dosage that it is characterized in that described reductive agent is extraordinarily to go into by 2 of the theoretical mixed carbon comtent of FeO+C=Fe+CO reaction formula, and the amount of allocating into of sweetening agent is by 10% adding of allocating reduction dosage into.
6. above-mentioned boron-containing iron concentrate iron boron according to claim 1 separates direct reducing process, it is characterized in that described magnetic separation separation or electric furnace make the iron yield greater than 95% molten the branch, and reduced iron is pressed into bulk or shrend becomes particulate state, higher-grade B
2O
3, the rich boron slag greater than 20% can be used for sulfuric acid and leaches single stage method production boric acid and magnesium sulfate heptahydrate, realizes boron, iron, magnesium resource comprehensive reutilization in the paigeite.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103074483A (en) * | 2013-01-10 | 2013-05-01 | 东北大学 | Comprehensive utilization method for ferroboron concentrates by virtue of selective reduction |
| CN103602773A (en) * | 2013-11-27 | 2014-02-26 | 北京科技大学 | Method for comprehensive utilization of paigeite through direct reduction-electric furnace melting separation of rotary hearth furnace |
| CN103667688A (en) * | 2012-12-29 | 2014-03-26 | 北京神雾环境能源科技集团股份有限公司 | Method for performing boron and iron separation on paigeite |
| CN103937960A (en) * | 2014-04-08 | 2014-07-23 | 东北大学 | Staged reduction method of boron-containing iron ore concentrate |
| CN106978530A (en) * | 2017-03-21 | 2017-07-25 | 江苏省冶金设计院有限公司 | Boron-magnesium compound additives and its production and use |
| WO2017153634A1 (en) * | 2016-03-11 | 2017-09-14 | Global Ecoprocess Services Oy | Method for separating metals |
| CN108893572A (en) * | 2018-06-15 | 2018-11-27 | 河北工程大学 | A kind of method of valuable constituent element comprehensive reutilization in paigeite |
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| CN1374150A (en) * | 2002-01-28 | 2002-10-16 | 赵庆杰 | Magnetic and gravitational separation and comprehensive utilization of vonsenite |
| CN101157977A (en) * | 2007-11-27 | 2008-04-09 | 北京科技大学 | Concentration method for iron and boron in low-grade paigeite |
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2011
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| CN1374150A (en) * | 2002-01-28 | 2002-10-16 | 赵庆杰 | Magnetic and gravitational separation and comprehensive utilization of vonsenite |
| CN101157977A (en) * | 2007-11-27 | 2008-04-09 | 北京科技大学 | Concentration method for iron and boron in low-grade paigeite |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103667688A (en) * | 2012-12-29 | 2014-03-26 | 北京神雾环境能源科技集团股份有限公司 | Method for performing boron and iron separation on paigeite |
| CN103667688B (en) * | 2012-12-29 | 2015-07-08 | 北京神雾环境能源科技集团股份有限公司 | Method for performing boron and iron separation on paigeite |
| CN103074483A (en) * | 2013-01-10 | 2013-05-01 | 东北大学 | Comprehensive utilization method for ferroboron concentrates by virtue of selective reduction |
| CN103602773A (en) * | 2013-11-27 | 2014-02-26 | 北京科技大学 | Method for comprehensive utilization of paigeite through direct reduction-electric furnace melting separation of rotary hearth furnace |
| CN103937960A (en) * | 2014-04-08 | 2014-07-23 | 东北大学 | Staged reduction method of boron-containing iron ore concentrate |
| WO2017153634A1 (en) * | 2016-03-11 | 2017-09-14 | Global Ecoprocess Services Oy | Method for separating metals |
| CN106978530A (en) * | 2017-03-21 | 2017-07-25 | 江苏省冶金设计院有限公司 | Boron-magnesium compound additives and its production and use |
| CN108893572A (en) * | 2018-06-15 | 2018-11-27 | 河北工程大学 | A kind of method of valuable constituent element comprehensive reutilization in paigeite |
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Application publication date: 20120208 |