CN102864265A - Method for recycling gas-base direct reducted tail gas - Google Patents
Method for recycling gas-base direct reducted tail gas Download PDFInfo
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- CN102864265A CN102864265A CN2012103570722A CN201210357072A CN102864265A CN 102864265 A CN102864265 A CN 102864265A CN 2012103570722 A CN2012103570722 A CN 2012103570722A CN 201210357072 A CN201210357072 A CN 201210357072A CN 102864265 A CN102864265 A CN 102864265A
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Abstract
The invention discloses a method for recycling gas-base direct reduced tail gas. Firstly the gas-base direct reduced tail gas is used for conducting pre-heating and pre-reduction treatment on iron ore pellets, CO in the tail gas has a reaction that two COs are reacted to generate CO2 and C in the above treatment process, separated carbon black is deposited in holes and on surfaces of pre-reduced pellets where gaps are rich, and the pre-reduced pellets containing fine carbon black are formed. The pre-reduced carbon separated pellets are mixed with certain quantity of a reducing agent, and then added into an industrial microwave oven to conduct deep reduction, and then magnetic separating is carried out to obtain direct reduced iron. The method can effectively use tail gas in traditional gas-base direct reduction process and secondary heat reducing gas produced in a metallurgy process to conduct prereduction and carbon separation, and use high-efficient and rapid characteristics of microwave heating and excellent absorbing properties of carbon black to conduct direct reduction on the iron ore pellets so as to achieve a purpose of energy conservation and environmental protection production.
Description
Technical field
The present invention relates to the method that a kind of tail gas recycle is utilized, particularly relate to a kind of direct-reduction tail gas that utilizes and analyse the method that charcoal-microwave reduction is produced sponge iron.
Background technology
Direct-reduced iron (DRI) is pure because of quality, stable components, is the desirable feedstock of a kind of alternative steel scrap, smelting high-quality steel and special steel, much can both produce with sponge iron with the special steel that steel scrap can not be produced.In recent years, along with the rise of " the short flow process of Electric furnace steel making ", rapid as the direct-reduced iron development of steel scrap substitute and the indispensable raw material of the excellent special steel of production.At present the direct-reduced iron 75% or more is by the production of gas-based shaft kiln method in the world, and wherein typical process is Midrex and HYL-III method (2010 account for respectively direct-reduced iron output 59.7% and 14.1%).
Make a general survey of at present all in the world gas-based shaft kiln reducing process, all after washing, purifying, small portion acts as a fuel its stock gas, and most of the mixing with Sweet natural gas carries out catalytic cracking reaction and change into reducing gas participation shaft furnace and circulate.Yet stock gas causes a large amount of calorific losss on the one hand behind washing, scavenging process, remain on the other hand the objectionable constituent that are difficult in the coal gas thoroughly remove and also build up along with the increase of cycle index, thereby affect the conversion (poisoning of catalyst) of Sweet natural gas and the normal operation of shaft furnace.
Micro-wave energy is as a kind of cleaning, efficient novel energy; have advantages of that other heating means such as selectivity, homogeneity, instantaneity are incomparable; the aspect has clear superiority improving working condition and enhance productivity etc., thereby has obtained using more and more widely in fields such as metallurgy, chemical industry, environment protection.
Summary of the invention
Technical problem to be solved by this invention provides a kind of efficient utilization to reduction shaft furnace tail gas, strengthens the method for the gas base directly reducing tail gas recycle utilization of iron ore pellets microwave reduction.
In order to solve the problems of the technologies described above, the method that gas base directly reducing tail gas recycle provided by the invention is utilized, carry out according to the following steps:
(1), the iron ore acid pellet is carried out preheating, prereduction 10min～60min in 400 ℃～700 ℃ direct-reduction tail gas, in pelletizing surface and hole, analyse charcoal and form the pre-reduced pellet that contains a certain amount of particulate carbon black;
(2), will through prereduction, analyse charcoal pelletizing with add that to be heated to 800 ℃～1100 ℃, time in the industrial microwave oven be that 10min～60min continues dark reduction after reductive agent mixes, the consumption of described reductive agent accounts for 1%～10% of compound total mass;
(3), the magnetic separation separation after the protection cooling of the product behind the microwave reduction obtains nonmagnetics and direct-reduced iron.
Described iron ore acid pellet, its TFe content are 64%～69%, granularity is that 8mm～16mm, ultimate compression strength are 1800N/～3500N/.
Described direct-reduction exhaust gas component and volume ratio are (CO+H
2): (CO
2+ H
2O): (CH
4+ N
2)=(40～70): (50～20): (0～10).
Pelletizing prereduction rate reaches 20%～60% described in the step (1), and pelletizing is analysed charcoal and accounted for total mass 1%～10%.
Reductive agent described in the above-mentioned steps (2) is one or more mixture of bituminous coal, hard coal, brown coal, coke, biomass and plastics.
Described microwave oven frequency is 2.45GHz and adjustable powerful industrial microwave oven.
Adopt the method for the gas base directly reducing tail gas recycle utilization of technique scheme, at first utilize gas base directly reducing tail gas that iron ore pellets is carried out preheating, prereduction processing, CO reacts in the tail gas in this process: 2CO → CO
2+ C, the carbon black of separating out form the pre-reduced pellet that contains the particulate carbon black at pre-reduced pellet hole and the surface deposition of hole prosperity.The charcoal pelletizing of analysing of prereduction is mixed with an amount of reductive agent and adds industrial microwave oven and deeply reduce, and then magnetic separation separates the acquisition direct-reduced iron.The beneficial effect that it brings:
(1), can effectively utilize in the reduction shaft furnace tail gas remaining physical thermal and chemical energy, saved simultaneously washing and the purge segment of reduction tail gas.
(2), avoided because objectionable constituent residual in the tail gas enter the poisoning of catalyst problem that the natural gas pyrolysis system causes and the enrichment that in follow-up shaft furnace working cycle, causes.
(3), utilize reduction tail gas that the pre-reduced pellet of hole prosperity is analysed charcoal, can make the particulate carbon black be evenly distributed on the various piece of pelletizing, improved the dynamic conditions of back segment reduction, strengthened the dark reduction process of follow-up microwave.
(4), utilize the good microwave absorbing property of the characteristics such as microwave heating is efficient, environmental protection and charcoal, but the reduction process of efficient hardening pelletizing (comprise and reduce reduction temperature, Accelerating reduction process, raising pellet strength), thereby for promoting efficient, the energy-conservation reduction of iron ore pellets to create condition.
The present invention is by directly utilizing the second heat reducing gas that produces in the direct-reduction that the iron ore acid pellet is carried out preheating, prereduction, and finishes the charcoal of analysing to pelletizing in this process.Utilize simultaneously strong suction ripple (microwave) performance of carbon black to realize analysing further deeply reducing of charcoal pre-reduced pellet.Thereby be the efficient utilization of reduction shaft furnace tail gas, and the reinforcement of iron ore pellets microwave reduction provides a feasible approach.
In sum, the present invention is by utilizing reduction shaft furnace tail gas that the iron ore acid pellet is carried out preheating, prereduction, and finish simultaneously the charcoal of analysing to pelletizing, then utilize the advantages such as microwave heating is efficient, environmental protection to realize analysing the dark reduction process of charcoal pre-reduced pellet, a kind of efficient utilization to reduction shaft furnace tail gas, and the method for strengthening the gas base directly reducing tail gas recycle utilization of iron ore pellets microwave reduction.
Embodiment
Following embodiment is to further specifying of inventing, rather than the restriction scope of invention.
The iron ore acid pellet that adopts among the embodiment is from domestic certain large-scale pelletizing plant, and its main chemical compositions sees the following form 1.Test adopts hard coal and biomass charcoal as reductive agent, and anthracitic technical analysis sees the following form 2, and size composition sees Table 3.The mean particle size of biomass charcoal is 10mm, and its technical analysis sees the following form 4.
Table 1 iron ore acid pellet main chemical compositions/%
| Composition | TFe | FeO | SiO 2 | Al 2O 3 | MgO | CaO | LOI |
| Content | 64.24 | 0.24 | 5.31 | 1.55 | 0.61 | 0.56 | 0.04 |
Technical analysis/the % of table 2 pulverized anthracite
| Fixed carbon | Ash content | Volatile matter | S |
| 79.57 | 11.29 | 9.14 | 0.48 |
Size composition/the % of table 3 pulverized anthracite
| Granularity | >1mm | 0.5～1mm | 0.3～0.5mm | 0.075～0.3mm | <0.075mm |
| Content | 11.51 | 35.30 | 3.26 | 34.24 | 15.69 |
The technical analysis of table 4 biomass charcoal and physical properties
| Component | Ash content/% | Fugitive constituent/% | Fixed carbon/% | Calorific value/MJkg -1 | Porosity/% | Granularity/mm |
| Content | 5.10 | 7.55 | 87.34 | 30.77 | 46 | 2～30 |
Reference examples 1: (12mm～16mm) and 25g pulverized anthracite (account for total mass 20%) are put into industrial microwave oven after mixing and are reduced, and microwave power is set as 1.5kW to get 100g iron ore acid pellet.It is 75min that pelletizing and coal dust intermixture are warming up to 1000 ℃ of required times, and this moment, the pelletizing degree of metalization was 77.29%, and mean compressive strength is 1032N/.
Reference examples 2: (12mm～16mm) 100g adds reduction shaft furnace, is 60%CO, 30%H in 1000 ℃ of temperature, atmosphere to get above-mentioned acid pellet
2, 2%CO
2, 8%N
2Under (percent by volume) condition behind the reductase 12 0min reduction ratio of gained pre-reduced pellet sample be 65.38%.The gained pre-reduced pellet with put into microwave oven reduction (power is 1.5kW) after 20% coal dust mixes, to 1000 ℃ of required times be 71min, this moment, the pelletizing degree of metalization was 83.06%, mean compressive strength is 1075N/.
Reference examples 3: (12mm～16mm) 100g adds reduction shaft furnace, is 60%CO, 30%H in 1000 ℃ of temperature, atmosphere to get above-mentioned acid pellet
2, 2%CO
2, 8%N
2Under (percent by volume) condition behind the reduction 60min degree of metalization of gained pelletizing sample be 92.32%, mean compressive strength is 726N/.
Embodiment 1: (12mm～16mm) 100g adds reduction shaft furnace, is 60%CO, 10%H in 700 ℃ of temperature, atmosphere to get acid pellet
2, 20%CO
2, 10%N
2Behind the reduction 30min, gained pre-reduced pellet reduction ratio is 40.31%, analyse the charcoal amount is 5.82% of total mass under (percent by volume) condition.The gained pre-reduced pellet with put into microwave oven reduction (power is 1.5kW) after 10% the coal dust that accounts for the compound total mass mixes, temperature is 1000 ℃, required time is 37min, this moment, the pelletizing degree of metalization was 95.34%, mean compressive strength is 1725N/.With reference examples 1,2 more as can be known, its heating-up time in microwave oven nearly shortens half, degree of metalization improves 12%～18% than not analysing the charcoal pelletizing, and more than the pelletizing ultimate compression strength increase 700N.With reference examples 3 gas base reduction ratios, degree of metalization slightly is improved and ultimate compression strength is significantly increased.
Embodiment 2: (8mm～12mm) 100g adds reduction shaft furnace, is 40%CO, 30%H in 500 ℃ of temperature, atmosphere to get acid pellet
2, 10%CO
2, 10%H
2O, 10%N
2Behind the reduction 60min, gained pre-reduced pellet reduction ratio is 42.01%, analyse the charcoal amount is 5.56% of total mass under (percent by volume) condition.The gained pre-reduced pellet with put into microwave oven reduction (power is 1.5kW) after 8% the coal dust that accounts for the compound total mass mixes, temperature is 1000 ℃, required time is 36min, this moment, the pelletizing degree of metalization was 97.13%, mean compressive strength is 1885N/.With reference examples 1,2 more as can be known, its heating-up time in microwave oven nearly shortens half, degree of metalization improves 14%～20% than not analysing the charcoal pelletizing, and more than the pelletizing ultimate compression strength increase 800N.With reference examples 3 gas base reduction ratios, degree of metalization and ultimate compression strength are significantly improved.
Embodiment 3:
(12mm～16mm) 100g adds reduction shaft furnace, is 70%CO, 20%CO in 450 ℃ of temperature, atmosphere to get acid pellet
2, 10%N
2After processing 60min under (percent by volume) condition, gained pre-reduced pellet reduction ratio is 28.98%, analyse the charcoal amount is 4.62% of total mass.The gained pre-reduced pellet with put into microwave oven reduction (power is 1.5kW) after 15% the hard coal that accounts for the compound total mass mixes, temperature is 1000 ℃, required time is 39min, this moment, the pelletizing degree of metalization was 93.21%, mean compressive strength is 1522N/.With reference examples 1,2 more as can be known, its heating-up time in microwave oven nearly shortens half, degree of metalization is not than analysing charcoal pelletizing raising 10%～15%, pelletizing ultimate compression strength increases approximately 500N.With reference examples 3 gas base reduction ratios, degree of metalization is basic quite and ultimate compression strength is significantly increased.
Embodiment 4: (12mm～16mm) 100g adds reduction shaft furnace, is 60%CO, 10%H in 600 ℃ of temperature, atmosphere to get acid pellet
2, 20%CO
2, 10%N
2After processing 50min under (percent by volume) condition, gained pre-reduced pellet reduction ratio is 40.31%, analyse the charcoal amount is 5.82% of total mass.The gained pre-reduced pellet with put into microwave oven reduction (power is 1.5kW) after 10% the biomass charcoal that accounts for the compound total mass mixes, temperature is 1000 ℃, required time is 45min, this moment, the pelletizing degree of metalization was 97.64%, mean compressive strength is 1956N/.With reference examples 1,2 more as can be known, its heating-up time in microwave oven shortens 30min, degree of metalization improves 14%～20% than not analysing the charcoal pelletizing, and more than the pelletizing ultimate compression strength increase 900N.With reference examples 3 gas base reduction ratios, degree of metalization and ultimate compression strength all obviously improve.
Embodiment 5: (12mm～16mm) 100g adds reduction shaft furnace, is 50%CO, 10%H in 600 ℃ of temperature, atmosphere to get acid pellet
2, 20%CO
2, 10%H2
O, 10%N
2Behind the reduction 50min, gained pre-reduced pellet reduction ratio is 40.31%, analyse the charcoal amount is 5.82% of total mass under (percent by volume) condition.The gained pre-reduced pellet with put into microwave oven reduction (power is 1.5kW) after 6% the bituminous coal that accounts for the compound total mass mixes, temperature is 1100 ℃, required time is 42min, this moment, the pelletizing degree of metalization was 97.62%, mean compressive strength is 1905N/.With reference examples 1,2 more as can be known, its heating-up time in microwave oven obviously shortens, degree of metalization improves 14%～20% than not analysing the charcoal pelletizing, and pelletizing ultimate compression strength increases approximately 900N.With reference examples 3 gas base reduction ratios, degree of metalization and ultimate compression strength all obviously improve.
Embodiment 6: (12mm～16mm) 100g adds reduction shaft furnace, is 50%CO, 20%H in 650 ℃ of temperature, atmosphere to get acid pellet
2, 20%CO
2, 10%N
2Behind the reduction 40min, gained pre-reduced pellet reduction ratio is 37.31%, analyse the charcoal amount is 5.82% of total mass under (percent by volume) condition.Gained pre-reduced pellet and 7.28% the coal dust that accounts for the compound total mass (analyse charcoal and outer coal blending account for total mass 13%) put into microwave oven reduction (power is 1.5kW) after mixing, temperature is 900 ℃, required time is 20min, this moment, the pelletizing degree of metalization was 89.58%, and mean compressive strength is 1400N/.With reference examples 1,2 more as can be known, its heating-up time in microwave oven shortens approximately 50min, degree of metalization improves 6%～12% than not analysing the charcoal pelletizing, and pelletizing ultimate compression strength increases approximately 400N.With reference examples 3 gas base reduction ratios, degree of metalization slightly reduces, but ultimate compression strength obviously improves.
Embodiment 7: (12mm～16mm) 100g adds reduction shaft furnace, is 60%CO, 30%CO in 600 ℃ of temperature, atmosphere to get acid pellet
2, 10%N
2After processing 60min under (percent by volume) condition, gained pre-reduced pellet reduction ratio is 23.54%, analyse the charcoal amount is 1.71% of total mass.The gained pre-reduced pellet with put into microwave oven reduction (power is 1.5kW) after 10% the biomass charcoal that accounts for the compound total mass mixes, temperature is 900 ℃, required time is 50min, this moment, the pelletizing degree of metalization was 88.69%, mean compressive strength is 1368N/.With reference examples 1,2 more as can be known, its heating-up time in microwave oven shortens approximately 20min, degree of metalization improves 8%～10% than not analysing the charcoal pelletizing, pelletizing ultimate compression strength increases approximately 300N.With reference examples 3 gas base reduction ratios, degree of metalization slightly reduces, but ultimate compression strength obviously increases.
Embodiment 8: (12mm～16mm) 100g adds reduction shaft furnace, is 60%CO, 10%H in 400 ℃ of temperature, atmosphere to get acid pellet
2, 20%CO
2, 10%N
2After processing 60min under (percent by volume) condition, gained pre-reduced pellet reduction ratio is 32.68%, analyse the charcoal amount is 2.83% of total mass.The gained pre-reduced pellet with put into microwave oven reduction (power is 1.5kW) after 10% the hard coal that accounts for the compound total mass mixes, temperature is 1100 ℃, required time is 43min, this moment, the pelletizing degree of metalization was 92.51%, mean compressive strength is 1543N/.With reference examples 1,2 more as can be known, its heating-up time in microwave oven shortens approximately 30min, degree of metalization improves more than 10% than not analysing the charcoal pelletizing, pelletizing ultimate compression strength increases 500N.With reference examples 3 gas base reduction ratios, degree of metalization is basic quite and ultimate compression strength is significantly increased.
Claims (5)
1. the method utilized of a gas base directly reducing tail gas recycle is characterized in that: carry out according to the following steps:
(1), the iron ore acid pellet is carried out preheating, prereduction 10min～60min in 400 ℃～700 ℃ direct-reduction tail gas, in pelletizing surface and hole, analyse charcoal and form the pre-reduced pellet that contains a certain amount of particulate carbon black;
(2), will through prereduction, analyse charcoal pelletizing with add that to be heated to 800 ℃～1100 ℃, time in the industrial microwave oven be that 10min～60min continues dark reduction after reductive agent mixes, the consumption of described reductive agent accounts for 1%～10% of compound total mass;
(3), the magnetic separation separation after the protection cooling of the product behind the microwave reduction obtains nonmagnetics and direct-reduced iron.
2. the method utilized of gas base directly reducing tail gas recycle according to claim 1, it is characterized in that: the iron ore acid pellet described in the above-mentioned steps (1), its TFe content are 64%～69%, granularity is that 8mm～16mm, mean compressive strength are 1800N/～3500N/.
3. the method utilized of gas base directly reducing tail gas recycle according to claim 1, it is characterized in that: the direct-reduction exhaust gas component described in the above-mentioned steps (1) and volume ratio are (CO+H
2): (CO
2+ H
2O): (CH
4+ N
2)=(40～70): (50～20): (0～10).
4. the method utilized of gas base directly reducing tail gas recycle according to claim 1 is characterized in that: the reductive agent described in the above-mentioned steps (2) is one or more mixture of bituminous coal, hard coal, brown coal, coke, biomass and plastics.
5. the method utilized of gas base directly reducing tail gas recycle according to claim 1, it is characterized in that: microwave oven frequency described in the above-mentioned steps (2) is 2.45GHz and adjustable powerful industrial microwave oven.
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Cited By (5)
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| CN106367647A (en) * | 2016-09-05 | 2017-02-01 | 中南大学 | Method for preparing high-carbon ferromanganese through gas-based reduction of ferromanganese oxide |
| CN106430196A (en) * | 2016-09-05 | 2017-02-22 | 中南大学 | Method for preparing manganese carbide by gas-based reduction of manganese oxides |
| CN107119166A (en) * | 2017-05-19 | 2017-09-01 | 安徽工业大学 | A kind of biomass iron content agglomerate mini-mill steelmaking and the method for producing stainless steel |
| CN110062812A (en) * | 2016-10-24 | 2019-07-26 | 技术资源有限公司 | The production of iron |
| US11959153B2 (en) | 2016-10-24 | 2024-04-16 | Technological Resources Pty Limited | Production of iron |
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|---|---|---|---|---|
| CN106367647A (en) * | 2016-09-05 | 2017-02-01 | 中南大学 | Method for preparing high-carbon ferromanganese through gas-based reduction of ferromanganese oxide |
| CN106430196A (en) * | 2016-09-05 | 2017-02-22 | 中南大学 | Method for preparing manganese carbide by gas-based reduction of manganese oxides |
| CN106367647B (en) * | 2016-09-05 | 2018-06-01 | 中南大学 | A kind of method that gas-based reduction manganese iron axinite prepares high carbon ferromanganese |
| CN110062812A (en) * | 2016-10-24 | 2019-07-26 | 技术资源有限公司 | The production of iron |
| US11479829B2 (en) | 2016-10-24 | 2022-10-25 | Technological Resources Pty. Limited | Production of iron |
| US11959153B2 (en) | 2016-10-24 | 2024-04-16 | Technological Resources Pty Limited | Production of iron |
| CN107119166A (en) * | 2017-05-19 | 2017-09-01 | 安徽工业大学 | A kind of biomass iron content agglomerate mini-mill steelmaking and the method for producing stainless steel |
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