CN103667687A - Method for preventing pellets from high temperature reduction bonding in high phosphorus oolitic hematite treatment shaft furnace - Google Patents
Method for preventing pellets from high temperature reduction bonding in high phosphorus oolitic hematite treatment shaft furnace Download PDFInfo
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- 230000009467 reduction Effects 0.000 title claims abstract description 58
- 239000008188 pellet Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 38
- 229910052595 hematite Inorganic materials 0.000 title claims abstract description 33
- 239000011019 hematite Substances 0.000 title claims abstract description 33
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 29
- 239000011574 phosphorus Substances 0.000 title claims abstract description 27
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003245 coal Substances 0.000 claims abstract description 33
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000011946 reduction process Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 12
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- 235000012255 calcium oxide Nutrition 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000005453 pelletization Methods 0.000 description 20
- 229910000831 Steel Inorganic materials 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 235000010755 mineral Nutrition 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
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- 229910052782 aluminium Inorganic materials 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 2
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- 238000007599 discharging Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
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- 238000000280 densification Methods 0.000 description 1
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- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000009628 steelmaking Methods 0.000 description 1
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Abstract
一种处理高磷鲕状赤铁矿竖炉防球团高温还原黏结的方法，属于直接还原炼铁技术领域。将高磷鲕状赤铁矿粉与煤粉、脱磷剂和粘接剂按合适的比例进行配料、混碾、压球，制成冷固结球团，该固结球团经过烘干或养生处理，进入直接还原竖炉；球团在直接还原竖炉内，将自上而下地经历热煤气焙烧及气基预还原、煤基直接还原和冷却过程，固结球团经历的气基预还原、煤基直接还原温度范围850-1200℃，在竖炉内的停留时间为1-5h；还原气组成：为H2/CO=1.2-4，经还原后的球团密封冷却，在冷却段出口处，固结球团温度控制在100～200℃，再将固结球团破碎、磁选和压块，得到的铁产品中TFe≥88%，磷含量<0.3%。优点在于，降低竖炉还原过程的能源消耗。
The invention discloses a method for treating high-phosphorus oolitic hematite shaft furnace anti-pellet high-temperature reduction bonding method, which belongs to the technical field of direct reduction ironmaking. The high-phosphorus oolitic hematite powder is mixed with coal powder, dephosphorization agent and binder in an appropriate proportion, mixed and rolled, and pelletized to make cold-consolidated pellets. The consolidated pellets are dried or In the direct reduction shaft furnace, the pellets will undergo hot gas roasting, gas-based pre-reduction, coal-based direct reduction and cooling from top to bottom, and the gas-based pre-reduction process experienced by the consolidated pellets Reduction, coal-based direct reduction temperature range 850-1200 ℃, residence time in the shaft furnace is 1-5h; reduction gas composition: H 2 /CO=1.2-4, the reduced pellets are sealed and cooled, after cooling At the outlet of the section, the temperature of the consolidated pellets is controlled at 100-200°C, and then the consolidated pellets are crushed, magnetically separated and briquetting, and the obtained iron products have TFe≥88% and phosphorus content<0.3%. The advantage is that the energy consumption of the shaft furnace reduction process is reduced.
Description
Technical field
The invention belongs to direct reduction processes of Iron ores field, relate to a kind of method that the anti-pelletizing high temperature reduction of high-phosphor oolitic hematite shaft furnace coheres of processing, utilize gas base+coal-based shaft furnace to process the technique of oolitic hematite.
Background technology
For domestic a large amount of existence, be difficult to the roe shape high-phosphorus hematite resource utilized again, domesticly attempt to solve gordian technique bottleneck always, get through technical process, accomplish scale production, make domestic iron and steel enterprises break away from gradually the dependency to external high price iron ore deposit.But from existing achievement in research, the utilisation technology Recent Progresses In The Development of this direction is slower.Though carrying out a large amount of research work aspect the optimization of roe shape high-phosphorus hematite technique of preparing in the past, particularly ore dressing aspect, as Central South University's (patent: a kind of method of smelting iron with iron ore concentrate of being prepared by phosphorous oolitic hematite, application number: CN200710034838.2), Guizhou University's (patent: a kind of beneficiation method of oolitic hematite, application number: CN200910309207.6).But due to the special nested mineral phase structure of densification of roe shape high-phosphorus hematite, ferric oxide with ore deposit phase distributed dimension such as phosphatic rock at 10 μ m, cause the metallic iron in these mineral very difficult effectively separated with impurity element phosphorus, still can not meet the restriction requirement of existing Steel Production Flow Chart to phosphorus content in finished product ore deposit.And current relatively ripe coal-based direct reduction method (as rotary hearth furnace, rotary kiln etc.), no matter aspect industrial scale, production stability and technico-economical comparison, still process this special mineral structure of roe shape high-phosphorus hematite, all also there is no successful story.At present a large amount of Basic Experiment Study relevant to coal-based direct reduction, a lot of achievements only limit to carry out for concrete technology link, apart from real through engineering approaches, also have certain distance.
For the recycling of this special mineral of roe shape high-phosphorus hematite, reach the required source of iron requirement of current steel-making, must select favourable technological approaches, the efficient technical bottleneck problem of carrying iron, falling phosphorus that solves.The present invention attempts reaching by the compound direct reduction process of gas base+coal-based shaft furnace that combines the object of carrying iron, falling phosphorus, make the contained ferric oxide of these mineral be efficiently reduced into the metallic iron with certain magnetic, simultaneously, make its contained impurity substances such as phosphorus oxide be deposited in as far as possible nonmagnetic gangue mutually in, reduzate passes through the crushing-magnetic selection of less expensive again, realizes the effectively separated of iron and phosphorus.
The maximum difficult point that restricts gas base+coal-based shaft furnace through engineering approaches that this technique proposes is how to solve burden direct motion and loading softening phenomenon and the adhesion problems of nodulizing in high temperature (850 ℃-1200 ℃) reduction process.Current correlative study is less, particularly for the research that prevents nodulizing high temperature reduction bonding of the shaft furnace of coal-based+gas base.Patent utilization of the present invention has the shaft furnace device of large-scale production potentiality and processes roe shape high-phosphorus hematite resource, solves the pelletizing high temperature reduction adhesion problems that coal-based shaft furnace exists, thereby obtains direct-reduction product low-phosphorous, high Fe content.
Summary of the invention
The object of the present invention is to provide a kind of method and device that the anti-pelletizing high temperature reduction of high-phosphor oolitic hematite shaft furnace coheres of processing; solved the problem that pelletizing high temperature reduction coheres; once this processing technology routine is got through; be expected to become the effective means that roe shape high-phosphorus hematite resource is processed in the most potential mass-producing of steel industry; for steel industry provides new source of iron; both can be used as the substitute of a large amount of steel scraps that use in bof process, can become again the main source of steel scrap in the short flow process of electric furnace.Therefore, getting through of this processing technology routine, is apparent to the pushing effect of steel industry technical progress.
Operational path of the present invention is to adopt gas base+coal-based compound direct reduction shaft furnace combining to process high-phosphor oolitic hematite, produce direct-reduction iron product.By high-phosphor oolitic hematite powder and coal dust, dephosphorizing agent and caking agent in suitable ratio prepare burden, mixed grind, pressure ball, make cold bound pellet, this agglomerated pellet, through drying or health is processed, enters direct-reduction shaft furnace; Pelletizing is in direct-reduction shaft furnace, from top to down is experienced to heating gas roasting and the prereduction of gas base, coal-based direct reduction and process of cooling, the prereduction of gas base, the coal-based direct reduction temperature range 850-1200 ℃ of agglomerated pellet experience, the residence time in shaft furnace is 1-5h; Reducing gas forms: be H
2/ CO=1.2-4, (CO+H
2>90%, N
2<10%), the pelletizing sealing after reduction is cooling, in cooling section exit, agglomerated pellet temperature is controlled at 100～200 ℃, again by agglomerated pellet fragmentation, magnetic separation and briquetting, TFe>=88% in the iron product obtaining, phosphorus content <0.3%.
Described agglomerated pellet ultimate compression strength >1500N;
Described reduction shaft furnace adopts the shaft furnace structure of syllogic: shaft furnace is followed successively by pellet roasting and gas base prereduction section, coal-based direct reduction section and cooling section from top to bottom, and the space of shaft furnace and short transverse can guarantee that the blanking velocity of pelletizing is controlled within the scope of 2-8m/h;
In roasting and gas base prereduction section, in shaft furnace, temperature is controlled at 850～950 ℃ of scopes; In coal-based direct reduction section, in shaft furnace, temperature is controlled at 950～1200 ℃ of scopes.
Described oolitic hematite weight percentage TFe:>40%, SiO
2: 4-15%, Al
2o
3: >5%, P:0.4-1.0%.
Described cold bound pellet dual alkalinity is 0.7-1.3; Oolitic hematite weight percentage is 65-85%; Coal blending: 5-20%; Binding agent: 3-7%.
The material of the raising pellet strength adding in described agglomerated pellet is siliceous binding agent, prevent agglomerated pellet surface high-temp reduction cohere institute with addition of material, aluminum oxide calcareous for being oxidized or magnesia material.
Shaft furnace tail gas is carried out to the processing of dedusting and carbon dioxide removal, the shaft furnace tail gas after processing heats up through heated by gas device, then enters place, shaft furnace coal gas air port, forms the closed-loop control that shaft furnace circulation of tail gas utilizes, and reduces the energy consumption of reduction shaft furnace process.
In order to realize aforesaid method, shaft furnace of the present invention has following features:
(1) in order to guarantee the effective reduction of pelletizing in shaft furnace and to prevent gluing, by controlling air port place's gas flow and the temperature of blanking velocity and different heights in shaft furnace, guarantee that top pellet roasting and gas base prereduction section, middle part pelletizing coal-based direct reduction section and bottom pelletizing cooling section are all the time in the temperature controlling range in expection.
(2) whole shaft furnace at least designs three row's coal gas air ports on different heights position, and the gas flow that every exhaust outlet place blasts and temperature can need to control according to technique;
(3) heating gas that blasts shaft furnace need be heated to through heated by gas device temperature required, then enters shaft furnace; For guaranteeing that the coal gas that enters shaft furnace makes different positions in corresponding shaft furnace obtain temperature field relatively uniformly, can become can enter shaft furnace central position radially by coal gas air port design;
(4) by controlling the discharging speed of shaft furnace, the blanking velocity of furnace charge in shaft furnace is controlled to the scope of 2～8m/h, alleviates the problem of the bonding of furnace charge under high temperature reduction;
(5) adopt pair roller type or disc type drawing mechanism.
In order to prevent that stove pelletizing from producing high temperature reduction and cohering in shaft furnace, the method for employing is:
(1) in pelletizing, add the intensity (ultimate compression strength >1500N) that binding agent improves pelletizing;
(2) in shaft furnace, prevent the structure design that pelletizing coheres: adopt shaft furnace to comprise pellet roasting and gas base prereduction section, high-temperature coal base directly reducing section and cooling section; By controlling discharging speed, controlling the blanking velocity of pelletizing in shaft furnace is 2-8m/h; By the control to different air ports place's gas flow and temperature, strict pellet roasting and gas base prereduction section and the high-temperature coal base directly reducing section temperature controlled, roasting and gas base prereduction section temperature are 850～950 ℃, and high-temperature coal base directly reducing section temperature is 950～1200 ℃.
(3) on pelletizing surface with addition of a certain amount of anti-cakingagent.
The present invention compares tool of the present invention and has the following advantages with additive method:
(1) in attempted gas base+coal-based composite reduction process, the highest reduction temperature can reach 1200 ℃, is conducive to the efficient reduction of iron-bearing mineral; And current shaft furnace gas base is at 850-900 ℃.By improving stove pellet strength, adopt in unique shaft furnace structure design and pelletizing method with addition of tack reducing material to solve the adhesion problems of pelletizing high temperature reduction.
(2) consider the selective reduction of oolitic hematite institute's containing metal iron and impurity element phosphorus in reduction process and carry iron, fall phosphorus problem, the present invention utilizes alkaline matters such as adding lime to suppress the reduction of phosphorus, causes in ore ferric oxide to have precedence over phosphorus oxide and is reduced into the metallic iron iron crystalline phase microscopic dimensions requirement separated with being conducive to magnetic separation with certain magnetic.
(3) utilize producer gas generator to produce reduction shaft furnace coal gas used; Utilize heated by gas that heated by gas device produces producer gas generator to the temperature required scope of reduction shaft furnace; By shaft furnace tail gas being deviate to the processing of carbonic acid gas, guarantee to enter active principle CO+H in the coal gas of reduction shaft furnace
2>90%, realizes efficient, less energy-consumption reduction.
Accompanying drawing explanation
Fig. 1 is the technical process that coal-based+gas-based shaft kiln is processed oolitic hematite.
Fig. 2 is the anti-pelletizing high temperature reduction bonding of gas base+coal-based shaft furnace schematic diagram.
Embodiment
Embodiment 1
Raw material is quality percentage composition TFe45.27%, SiO
28.21%, Al
2o
35.61%, the oolitic hematite of P0.58%.Proportionally: weight percentage is that 80% oolitic hematite, 8% coal, slaked lime 7% and binding agent 5% mix, pressure ball.By reduction shaft furnace, reduction temperature is 1130 ℃, and the recovery time is 1.5h, and reducing gas consists of (H
2: 50%; CO:42%; N
2: 8%), sealing cool to room temperature.Reduced ore is broken, carry out low intensity magnetic separation, the product weight percentage composition TFe92% obtaining, phosphorus content 0.10% after grinding.
Embodiment 2
Raw material is quality percentage composition TFe42.1%, SiO
212.4%, Al
2o
36.5%, the oolitic hematite of P0.82%.Proportionally: weight percentage is that 78% oolitic hematite, 10% coal, slaked lime 5% and binding agent 7% mix, pressure ball.By reduction shaft furnace, reduction temperature is 1200 ℃, and the recovery time is 1.2h, and reducing gas consists of (H
2: 52%; CO:40%; N
2: 8%), sealing cool to room temperature.Reduced ore is broken, carry out low intensity magnetic separation, the product weight percentage composition TFe94% obtaining, phosphorus content 0.13% after grinding.
Embodiment 3
Raw material is quality percentage composition TFe40.7%, SiO
214.4%, Al
2o
37.5%, the oolitic hematite of P0.98%.Proportionally: weight percentage is that 82% oolitic hematite, 7% coal, slaked lime 6% and binding agent 5% mix, pressure ball.By reduction shaft furnace, reduction temperature is 1150 ℃, and the recovery time is 1.0h, and reducing gas consists of (H
2: 50%; CO:40%; N
2: 10%), sealing cool to room temperature.Reduced ore is broken, carry out low intensity magnetic separation, the product weight percentage composition TFe90% obtaining, phosphorus content 0.16 after grinding.
Claims (8)
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| CN104212929A (en) * | 2014-08-19 | 2014-12-17 | 北京神雾环境能源科技集团股份有限公司 | Iron making method for treating high-phosphorus ore through direct reduction of gas-based shaft furnace and magnetic separation |
| CN104313229A (en) * | 2014-10-30 | 2015-01-28 | 武汉钢铁(集团)公司 | Method for manufacturing high-phosphorus iron by using shaft furnace to directly reduce high phosphorus ore |
| CN104404246A (en) * | 2014-11-24 | 2015-03-11 | 北京神雾环境能源科技集团股份有限公司 | Method for improving metallization rate of metallurgical slag pellet |
| CN104404245A (en) * | 2014-11-19 | 2015-03-11 | 武汉钢铁(集团)公司 | Method for producing abrasion-resistant material by utilizing high-phosphorus oolitic hematite |
| CN105219907A (en) * | 2015-10-14 | 2016-01-06 | 钢铁研究总院 | The iron-smelting process of high-phosphor oolitic hematite gas base directly reducing-mill ore magnetic selection |
| CN105695734A (en) * | 2016-02-24 | 2016-06-22 | 武汉科技大学 | Industrial production method for conducting iron increase and phosphorous reduction on high-phosphorus oolitic hematite |
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| CN110066915A (en) * | 2019-04-25 | 2019-07-30 | 西安建筑科技大学 | A kind of method that calcining magnetic separation removes phosphorus in high-phosphor oolitic hematite |
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| CN117265258A (en) * | 2023-09-20 | 2023-12-22 | 攀钢集团研究院有限公司 | Method for reducing adhesion of vanadium titano-magnetite gas-based shaft furnace smelting pellets |
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