CN102864265B - 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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- CN102864265B CN102864265B CN201210357072.2A CN201210357072A CN102864265B CN 102864265 B CN102864265 B CN 102864265B CN 201210357072 A CN201210357072 A CN 201210357072A CN 102864265 B CN102864265 B CN 102864265B
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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 a kind of method that tail gas recycle is utilized, particularly relate to one and utilize direct-reduction tail gas to analyse the method for charcoal-microwave reduction production sponge iron.
Background technology
Direct-reduced iron (DRI), because quality is pure, stable components, is the desirable feedstock of a kind of alternative steel scrap, smelting high-quality steel and special steel, much can produce with sponge iron with the not fertile special steel of steel scrap.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.More than 75% direct-reduced iron is produced by gas-based shaft kiln method in the world at present, and wherein typical process is Midrex and HYL-III method (accounting for respectively direct-reduced iron output 59.7% and 14.1% for 2010).
Make a general survey of at present all in the world gas-based shaft kiln reducing process, its stock gas is all after washing, purifying, and small portion is as fuel, and most of mixing with Sweet natural gas carries out catalytic cracking reaction and change into reducing gas participation shaft furnace and circulate.But stock gas causes on the one hand a large amount of calorific losss after washing, scavenging process, remain on the other hand the objectionable constituent that are difficult in coal gas thoroughly to 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 clean, the efficient novel energy of one; have advantages of that other heating means such as selectivity, homogeneity, instantaneity are incomparable; improving working condition and enhance productivity etc., aspect has clear superiority, thereby has obtained application 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 is to provide a kind of efficient utilization to reduction shaft furnace tail gas, the method that the gas base directly reducing tail gas recycle of strengthening iron ore pellets microwave reduction is utilized.
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), iron ore acid pellet is carried out in the direct-reduction tail gas of 400 ℃～700 ℃ to preheating, prereduction 10min～60min, in pelletizing surface and hole, analyse charcoal and form containing the pre-reduced pellet of a certain amount of particulate carbon black;
(2), by adding after prereduction, the pelletizing of analysing charcoal mix with reductive agent, in industrial microwave oven, to be heated to 800 ℃～1100 ℃, time be that 10min～60min continues dark reduction, the consumption of described reductive agent accounts for 1%～10% of compound total mass;
(3), the product after microwave reduction through protect cooling after magnetic separation separate and obtain nonmagnetics and direct-reduced iron.
Described iron ore acid pellet, its TFe content is 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).
Described in step (1), pelletizing prereduction rate reaches 20%～60%, and pelletizing is analysed charcoal and accounted for total mass 1%～10%.
Reductive agent described in 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.
The method that adopts the gas base directly reducing tail gas recycle of technique scheme to utilize, first utilizes gas base directly reducing tail gas to carry out preheating, prereduction processing to iron ore pellets, and in this process, in tail gas, CO reacts: 2CO → CO
2+ C, the carbon black of separating out, at pre-reduced pellet hole and the surface deposition of hole prosperity, forms the pre-reduced pellet containing particulate carbon black.The charcoal pelletizing of analysing of prereduction is mixed and adds industrial microwave oven deeply to reduce with appropriate reductive agent, and then magnetic separation separates and obtains direct-reduced iron.The beneficial effect that it brings:
(1), can effectively utilize in reduction shaft furnace tail gas remaining physical thermal and chemical energy, saved washing and the purge segment of reduction tail gas simultaneously.
(2), avoided because objectionable constituent residual in tail gas enter the poisoning of catalyst problem that natural gas pyrolysis system causes and the enrichment causing in follow-up shaft furnace working cycle.
(3), utilize reduction tail gas to analyse charcoal to the pre-reduced pellet of hole prosperity, can make 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 features such as microwave heating is efficient, environmental protection and charcoal, reduction process that can efficient hardening pelletizing (comprise reduce reduction temperature, Accelerating reduction process, improve 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 producing in direct-reduction to carry out preheating, prereduction to iron ore acid pellet, and in this process, completes the charcoal of analysing to pelletizing.Utilize strong suction ripple (microwave) performance of carbon black to realize the further dark reduction of analysing charcoal pre-reduced pellet simultaneously.Thereby be the efficient utilization of reduction shaft furnace tail gas, and the strengthening of iron ore pellets microwave reduction provides a feasible approach.
In sum, the present invention is by utilizing reduction shaft furnace tail gas to carry out preheating, prereduction to iron ore acid pellet, and complete the charcoal of analysing to pelletizing simultaneously, then utilize the advantages such as microwave heating is efficient, environmental protection to realize the dark reduction process of analysing charcoal pre-reduced pellet, a kind of efficient utilization to reduction shaft furnace tail gas, and the method for the gas base directly reducing tail gas recycle utilization of strengthening iron ore pellets microwave reduction.
Embodiment
Embodiment is to further illustrating of inventing below, rather than restriction scope of invention.
The iron ore acid pellet adopting in 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 is in 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: get and put into industrial microwave oven after 100g iron ore acid pellet (12mm～16mm) and 25g pulverized anthracite (account for total mass 20%) mix and reduce, microwave power is set as 1.5kW.It is 75min that pelletizing and coal dust intermixture are warming up to 1000 ℃ of required times, and now pelletizing degree of metalization is 77.29%, and mean compressive strength is 1032N/.
Reference examples 2: getting above-mentioned acid pellet (12mm～16mm) 100g and add reduction shaft furnace, is 60%CO, 30%H in 1000 ℃ of temperature, atmosphere
2, 2%CO
2, 8%N
2under (percent by volume) condition, after reductase 12 0min, the reduction ratio of gained pre-reduced pellet sample is 65.38%.Gained pre-reduced pellet is put into microwave oven reduction (power is 1.5kW) after mixing with 20% coal dust, to 1000 ℃ of required times be 71min, now pelletizing degree of metalization is 83.06%, mean compressive strength is 1075N/.
Reference examples 3: getting above-mentioned acid pellet (12mm～16mm) 100g and add reduction shaft furnace, is 60%CO, 30%H in 1000 ℃ of temperature, atmosphere
2, 2%CO
2, 8%N
2the degree of metalization of gained pelletizing sample after 60min that reduces under (percent by volume) condition is 92.32%, and mean compressive strength is 726N/.
Embodiment 1: getting acid pellet (12mm～16mm) 100g and add reduction shaft furnace, is 60%CO, 10%H in 700 ℃ of temperature, atmosphere
2, 20%CO
2, 10%N
2under (percent by volume) condition, reduce after 30min, gained pre-reduced pellet reduction ratio is 40.31%, analyse charcoal amount is 5.82% of total mass.Gained pre-reduced pellet is put into microwave oven reduction (power is 1.5kW) after mixing with 10% the coal dust that accounts for compound total mass, and temperature is 1000 ℃, and required time is 37min, and now pelletizing degree of metalization is 95.34%, and mean compressive strength is 1725N/.More known with reference examples 1,2, its heating-up time in microwave oven shortens half nearly, and degree of metalization improves 12%～18% than not analysing charcoal pelletizing, and more than pelletizing ultimate compression strength increase 700N.With reference examples 3 gas base reduction ratios, degree of metalization is slightly improved and ultimate compression strength is significantly increased.
Embodiment 2: getting acid pellet (8mm～12mm) 100g and add reduction shaft furnace, is 40%CO, 30%H in 500 ℃ of temperature, atmosphere
2, 10%CO
2, 10%H
2o, 10%N
2under (percent by volume) condition, reduce after 60min, gained pre-reduced pellet reduction ratio is 42.01%, analyse charcoal amount is 5.56% of total mass.Gained pre-reduced pellet is put into microwave oven reduction (power is 1.5kW) after mixing with 8% the coal dust that accounts for compound total mass, and temperature is 1000 ℃, and required time is 36min, and now pelletizing degree of metalization is 97.13%, and mean compressive strength is 1885N/.More known with reference examples 1,2, its heating-up time in microwave oven shortens half nearly, and degree of metalization improves 14%～20% than not analysing charcoal pelletizing, and more than 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:
Getting acid pellet (12mm～16mm) 100g and add reduction shaft furnace, is 70%CO, 20%CO in 450 ℃ of temperature, atmosphere
2, 10%N
2under (percent by volume) condition, process after 60min, gained pre-reduced pellet reduction ratio is 28.98%, analyse charcoal amount is 4.62% of total mass.Gained pre-reduced pellet is put into microwave oven reduction (power is 1.5kW) after mixing with 15% the hard coal that accounts for compound total mass, and temperature is 1000 ℃, and required time is 39min, and now pelletizing degree of metalization is 93.21%, and mean compressive strength is 1522N/.More known with reference examples 1,2, its heating-up time in microwave oven shortens half nearly, and degree of metalization improves 10%～15% than not analysing charcoal pelletizing, and pelletizing ultimate compression strength increases about 500N.With reference examples 3 gas base reduction ratios, degree of metalization is basic quite and ultimate compression strength is significantly increased.
Embodiment 4: getting acid pellet (12mm～16mm) 100g and add reduction shaft furnace, is 60%CO, 10%H in 600 ℃ of temperature, atmosphere
2, 20%CO
2, 10%N
2under (percent by volume) condition, process after 50min, gained pre-reduced pellet reduction ratio is 40.31%, analyse charcoal amount is 5.82% of total mass.Gained pre-reduced pellet is put into microwave oven reduction (power is 1.5kW) after mixing with 10% the biomass charcoal that accounts for compound total mass, and temperature is 1000 ℃, and required time is 45min, and now pelletizing degree of metalization is 97.64%, and mean compressive strength is 1956N/.More known with reference examples 1,2, its heating-up time in microwave oven shortens 30min, and degree of metalization improves 14%～20% than not analysing charcoal pelletizing, and more than 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: getting acid pellet (12mm～16mm) 100g and add reduction shaft furnace, is 50%CO, 10%H in 600 ℃ of temperature, atmosphere
2, 20%CO
2, 10%H2
o, 10%N
2under (percent by volume) condition, reduce after 50min, gained pre-reduced pellet reduction ratio is 40.31%, analyse charcoal amount is 5.82% of total mass.Gained pre-reduced pellet is put into microwave oven reduction (power is 1.5kW) after mixing with 6% the bituminous coal that accounts for compound total mass, and temperature is 1100 ℃, and required time is 42min, and now pelletizing degree of metalization is 97.62%, and mean compressive strength is 1905N/.More known with reference examples 1,2, its heating-up time in microwave oven obviously shortens, and degree of metalization improves 14%～20% than not analysing charcoal pelletizing, and pelletizing ultimate compression strength increases about 900N.With reference examples 3 gas base reduction ratios, degree of metalization and ultimate compression strength all obviously improve.
Embodiment 6: getting acid pellet (12mm～16mm) 100g and add reduction shaft furnace, is 50%CO, 20%H in 650 ℃ of temperature, atmosphere
2, 20%CO
2, 10%N
2under (percent by volume) condition, reduce after 40min, gained pre-reduced pellet reduction ratio is 37.31%, analyse charcoal amount is 5.82% of total mass.Gained pre-reduced pellet with account for compound total mass 7.28% coal dust (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, now pelletizing degree of metalization is 89.58%, and mean compressive strength is 1400N/.More known with reference examples 1,2, its heating-up time in microwave oven shortens about 50min, and degree of metalization improves 6%～12% than not analysing charcoal pelletizing, and pelletizing ultimate compression strength increases about 400N.With reference examples 3 gas base reduction ratios, degree of metalization slightly reduces, but ultimate compression strength obviously improves.
Embodiment 7: getting acid pellet (12mm～16mm) 100g and add reduction shaft furnace, is 60%CO, 30%CO in 600 ℃ of temperature, atmosphere
2, 10%N
2under (percent by volume) condition, process after 60min, gained pre-reduced pellet reduction ratio is 23.54%, analyse charcoal amount is 1.71% of total mass.Gained pre-reduced pellet is put into microwave oven reduction (power is 1.5kW) after mixing with 10% the biomass charcoal that accounts for compound total mass, and temperature is 900 ℃, and required time is 50min, and now pelletizing degree of metalization is 88.69%, and mean compressive strength is 1368N/.More known with reference examples 1,2, its heating-up time in microwave oven shortens about 20min, and degree of metalization improves 8%～10% than not analysing charcoal pelletizing, and pelletizing ultimate compression strength increases about 300N.With reference examples 3 gas base reduction ratios, degree of metalization slightly reduces, but ultimate compression strength obviously increases.
Embodiment 8: getting acid pellet (12mm～16mm) 100g and add reduction shaft furnace, is 60%CO, 10%H in 400 ℃ of temperature, atmosphere
2, 20%CO
2, 10%N
2under (percent by volume) condition, process after 60min, gained pre-reduced pellet reduction ratio is 32.68%, analyse charcoal amount is 2.83% of total mass.Gained pre-reduced pellet is put into microwave oven reduction (power is 1.5kW) after mixing with 10% the hard coal that accounts for compound total mass, and temperature is 1100 ℃, and required time is 43min, and now pelletizing degree of metalization is 92.51%, and mean compressive strength is 1543N/.More known with reference examples 1,2, its heating-up time in microwave oven shortens about 30min, and degree of metalization improves more than 10% than not analysing charcoal pelletizing, and 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 (4)
1. the method that gas base directly reducing tail gas recycle is utilized, is characterized in that: carry out according to the following steps:
(1), iron ore acid pellet is carried out in the direct-reduction tail gas of 400 ℃～700 ℃ to preheating, prereduction 10min～60min, in pelletizing surface and hole, analyse charcoal and form containing the pre-reduced pellet of a certain amount of particulate carbon black; 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);
(2), by adding after prereduction, the pelletizing of analysing charcoal mix with reductive agent, in industrial microwave oven, to be heated to 800 ℃～1100 ℃, time be that 10min～60min continues dark reduction, the consumption of described reductive agent accounts for 1%～10% of compound total mass;
(3), the product after microwave reduction through protect cooling after magnetic separation separate and obtain nonmagnetics and direct-reduced iron.
2. the method that gas base directly reducing tail gas recycle according to claim 1 is utilized, it is characterized in that: the iron ore acid pellet described in above-mentioned steps (1), its TFe content is 64%～69%, granularity is that 8mm～16mm, mean compressive strength are 1800N/～3500N/.
3. the method that gas base directly reducing tail gas recycle according to claim 1 is utilized, is characterized in that: the reductive agent described in above-mentioned steps (2) is one or more mixture of bituminous coal, hard coal, brown coal, coke, biomass and plastics.
4. the method that gas base directly reducing tail gas recycle according to claim 1 is utilized, is characterized in that: the industrial microwave oven described in above-mentioned steps (2) is that frequency is 2.45GHz and adjustable powerful industrial microwave oven.
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| CN106430196B (en) * | 2016-09-05 | 2018-06-29 | 中南大学 | A kind of method that Mn oxide gas-based reduction prepares manganess carbide |
| 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 |
| ES2910989T3 (en) | 2016-10-24 | 2022-05-17 | Tech Resources Pty Ltd | Process and apparatus for the continuous reduction of iron ore through the use of biomass |
| CN107119166B (en) * | 2017-05-19 | 2019-05-07 | 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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