CN102766718A - Method for producing sponge iron and zinc-rich materials by blast furnace zinc-containing ash - Google Patents
Method for producing sponge iron and zinc-rich materials by blast furnace zinc-containing ash Download PDFInfo
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Abstract
A method for producing sponge iron and zinc-rich materials by blast furnace zinc-containing ash belongs to the technical field of the comprehensive utilization of steel mill wastes. The method comprises the preparation process: reducing blast furnace zinc-containing ash in a rotary kiln so as to obtain the zinc-rich materials, synchronously crushing the cooled iron slag, and then separating the iron-rich materials from the slag by magnetic separation, wherein the CO volume concentration in the gas of the rotary kiln meets the condition that CO/(CO2+CO) is more than 70%, and the temperature of the gas in the kiln is 1150 DEG C to 1300 DEG C; the water content when the blast furnace zinc-containing ash is fed in the kiln is 10wt% to 30wt%; the mass content of carbon in the furnace material component fed into the rotary kiln is not less than 20wt%; in the slag ion mixture obtained by the reducing in the rotary kiln, the reducing rate of iron is not lower than 85% and the metal iron particle size is not less than 0.1mm; the average particle size of the slag iron mixture before being fed into the magnetic separator is 0.05mm-0.2mm; and the full iron content in the separated metal ion product is not lower than 85wt%, and the metalizing rate is not less than 85wt%. The method has the following advantages: the valuable metals and dangerous heavy metals in the blast furnace ash are used effectively, and the high-quality sponge iron and zinc-rich materials are obtained.
Description
Technical field
The invention belongs to steel mill's waste ' s reclamation technical field, particularly provide a kind of blast furnace that utilizes to contain the method that zinc gray is produced sponge iron and rich zinc material, be applicable to that blast furnace contains the comprehensive treating process of zinc gray.
Background technology
The annual blast-furnace dust that produces about ten-million-ton scale of China's steel industry; Blast-furnace dust contains harmful elements such as zinc, lead, arsenic; Simply blast-furnace dust is poured onto field or landfill, these heavy metal elements can little by little leach under the effect of rainwater, pollute peripheral soil, river, underground water; Bring disaster to farm crop and animal, finally the mankind are produced harm.Blast furnace contains zinc gray has caused people and government to the influence of environment attention at present.
It is directly blast furnace to be contained zinc gray to use at Iron And Steel Plant's internal recycle that China's blast furnace the earliest contains the zinc gray method of resource; Promptly use it as a kind of raw materials for sintering; But the circulation enrichment meeting of zinc in blast furnace shortened the life-span of furnace lining and caused furnace nodulation, influences the normal running of blast furnace.
Existing physics method is handled blast furnace and is contained the various combination technology that zinc gray technology mainly contains magnetic method, gravity separation method, flotation process, hydrocyclone staging and this several method.Shortcoming is that the iron ore grade of selecting yield lower, iron is lower.
There is following problem in wet processing process: the plumbous leaching yield of zinc is lower, and leached mud both had been difficult to as raw material also to have satisfied not the stacking requirement that environmental law proposes in Iron And Steel Plant's recycle; Unit operation is too much, and leaching agent consumes more, and cost is higher; Equipment corrosion is serious, and most of operational conditions are more abominable; Responsive to raw material ratio, make difficult technique to optimize; The sulphur of introducing in the treating processes, chlorine etc. are prone to cause new environmental pollution.
The method that the blast furnace of employing pyrogenic attack at present contains zinc gray is mainly from Japan, and a kind of is early stage rotary kiln technology, and more representational is SPM (the Sumitomo Pre-reduction Method) technology of SUMITOMO CHEMICAL metal exploitation; Traditional smelting in rotary kiln high-grad iron ore deposit being produced the main thought succession of sponge iron technology comes; At first, mix, again compound is joined in the rotary drying kiln with various dust and reductive agent with after the various slurry dewaterings; Through drying, produce original pelletizing; Then original pelletizing is joined in the rotary kiln, through preheating and reduction, dezincification, obtain prereduced burden, prereduced burden is again through the rotary kiln cooling, will be greater than the product of 7 ㎜ as the blast furnace feeding material through sieving; Powder less than 7 ㎜ needs sintering again.
The rotary kiln of Japan's exploitation is handled blast furnace and is contained zinc gray, focus on removing the zinc in the blast-furnace dust, and iron product is of poor quality, shows that slag iron mixes, and degree of metalization is lower, can only use as blast furnace burden.Just the zinc in the blast-furnace dust is removed through rotary kiln technology, and then as the raw material of blast furnace.Certainly with directly blast furnace is contained zinc gray as blast furnace raw material, technical progress is still arranged.
Along with the development of technology, the rotary kiln of Japan processing blast furnace contains the zinc gray technology and is replaced by the rotary hearth furnace of exploitation afterwards.Rotary hearth furnace can separate zinc preferably from blast-furnace dust, obtain the iron content pelletizing of certain degree of metalization simultaneously.Ma Gang has introduced 1 cover processing blast furnace from Japan several years ago and has contained the rotary hearth furnace that zinc gray is used.Rotary hearth furnace contains in the zinc gray practice at the processing blast furnace and has some outstanding problems, and show: (1) rotary hearth furnace process dust is big, though through pressure ball and drying treatment; But there is a certain amount of water in the carbonaceous pelletizing, it is added the condition of high temperature, explosion easily suddenly; Practice shows that Dust Capacity can reach 30% level; Need to handle, both increased energy consumption, worsen the technology direct motion again; (2) high-temperature heat-exchanging easy blocking because Dust Capacity is big, particularly contains dust such as zinc, lead and is easy to be bonded on the heat exchanger wall, influences heat exchange efficiency, and the time has been grown, and influences the technology direct motion; (3) iron product is of poor quality; Reclaim zinc at the rotary hearth furnace that adopts oxidizing atmosphere, influence the reduction of iron, practice shows that degree of metalization is lower; Between 50～70%; Simultaneously a large amount of gangues and metallic iron mix, and product is not a sponge iron, can only be added in converter or the blast furnace as refrigerant or common furnace charge.
China also contains the comprehensive utilization technique of zinc gray at the research blast furnace in this century; Application number 200710193281.7 and 201110040852.X apply for a patent; Adopt Japan's rotary kiln reduction technique in last century, with the zinc enrichment of blast-furnace dust, ferric charge is as the raw material of blast furnace simultaneously; Here it is Japan last century way, by afterwards the exploitation the rotary hearth furnace technology generation replace.
Visible by above-mentioned analysis, to contain the utilization of zinc gray mainly be dezincify to blast furnace at present, and utilizing of iron is relatively poor, and its main difficult point is that the iron that blast furnace contains in the zinc gray is lower, normally is lower than 40%, and so low iron content and slag mixture separation difficulty is very big,
Application number is 200810058950.4 applies for a patent, and the way that adopts the method slag iron reduzate that reduction obtains to rotary kiln of ultra-fine mill to carry out magnetic separation obtains iron content and be 50%～70% fine ore; But because the iron crystal grain after the reduction is trickle, be difficult to effectively separate, cause the yield of iron to have only 50% left and right horizontal with slag; And part iron is secondary oxidation in the process of selective grinding; Iron product also can only be a fine ore, is not sponge iron, causes the wasting of resources.
Except the low reason of iron level, second major reason is that the iron reduction needs reducing atmosphere, and rotary hearth furnace is a weak oxide property atmosphere, and the degree of metalization of iron is low in the slag iron mixture.Rotary kiln reduction blast furnace contains zinc gray, applies for a patent from both domestic and external, only controls reduction temperature, the reducing atmosphere of not mentioned control kiln hood, so the degree of metalization of iron also is difficult to guarantee.
It is low that blast furnace contains in the zinc gray iron level, and the reducing atmosphere of smelting equipment simultaneously at present is difficult to guarantee, is the major reason that present blast furnace contains fe source utilization difference in the zinc gray.
Summary of the invention
The object of the present invention is to provide a kind of blast furnace that utilizes to contain the method that zinc gray is produced sponge iron and rich zinc material, can make sponge iron, make all iron content greater than 85%, degree of metalization is greater than 85%.
Core difficult point of the present invention is to improve blast furnace to contain the smelting parameter that zinc gray is produced the iron product degree of metalization, guarantees the abundant isolating favourable condition of follow-up metallic iron and slag simultaneously.
Preparation flow of the present invention is that the reduction blast furnace contains zinc gray and obtains rich zinc material in rotary kiln, simultaneously cooled slag iron is carried out fragmentation, again through magnetic separation separation slag and rich iron substance.The technical parameter of in technology, controlling is:
The CO volumetric concentration satisfies CO/ (CO in the revolution kiln hood coal gas
2+ CO)>70% and the kiln hood gas temperature be 1150 ℃～1300 ℃; The water cut that blast furnace contains zinc gray when going into stove is at 10～30wt%; Carbonaceous amount content is not less than 20% in the charge composition of entering rotary kiln; In the slag iron mixture that the rotary kiln reduction obtains, the reduction ratio of iron is not less than 85wt% and the metallic iron particle size is not less than 0.1mm; Go into the mean particle size 0.08mm-0.2mm of the preceding slag iron mixture of magnetic separator; All iron content is not less than 85wt% in the metallic iron product after the separation, and degree of metalization is not less than 85wt%.
Method of the present invention; The carbon content that contains in the zinc gray when blast furnace is lower than 20 wt%; Can be with addition of carbonaceous fuels such as part coal dust or coke powders; Guarantee that carbonaceous amount content reaches more than 20 wt% (calculating to go into charge composition) in the feed stock for blast furnace, the carbonaceous fuel of adding can contain zinc gray with blast furnace and mix the back in kiln tail adding kiln, also can spray into the kiln internal combustion from kiln hood.
Method of the present invention; The shrend type of cooling is adopted in hot metal iron that the rotary kiln reduction obtains and the cooling of slag mixture; Or the type of cooling (is that water coolant does not directly contact with furnace charge indirectly; But utilize mode such as cylinder that the furnace charge heat is passed to water coolant through the contact wall), these two kinds of methods can effectively be cooled off hot metal iron and the slag mixture that present method obtains
Method of the present invention; Method according to claim 1; It is characterized in that: described slag iron mixture is milled down to 0.08mm-0.2mm through ball mill with the mean particle size of this slag iron mixture, or the mode that adds ball milling through fragmentation is milled down to 0.08mm-0.2mm with the mean particle size of slag iron mixture.
Method of the present invention adopts wet magnetic separator that the slag iron mixture is separated into metal iron powder and slag.
Method of the present invention, it is dry that magnetic separation is separated the moisture metal iron powder that obtains, and water-content is less than 2 wt %.
Method of the present invention is directly used dried metal iron powder, or uses through being cold-pressed into sponge iron blocks or ball.
Down the principle of the invention is further set forth:
In order to improve the degree of metalization of iron product, the selection of reactor drum is very important, and from present reactor drum, rotary hearth furnace is difficult to guarantee reducing atmosphere, so the present invention selects rotary kiln as smelting equipment.In order to prevent the secondary oxidation in rotary kiln, applicant's research shows that the CO volumetric concentration satisfies CO/ (CO in the coal gas of rotary kiln end
2+ CO)>70%, can guarantee that blast furnace contains the abundant reduction of red stone in the zinc gray, obtain high degree of metalization, surpass 85%.
Except the reducing atmosphere of control kiln hood, it is tiny that blast furnace contains the granularity of materials such as carbon and the red stone in the zinc gray, and fully contact has simultaneously guaranteed that blast furnace contains the fast restore of zinc gray.
Normal rotary kiln end reduction temperature is lower than 1100 ℃, and the iron crystal grain that obtains after the reduction is very tiny, and is active high; Secondary oxidation also is difficult to separate simultaneously easily, causes the later separation difficulty; Need degree of depth ball milling (need be milled down to 200 orders even 300 orders or 400 orders), cause the secondary oxidation of trickle abrasive grit on the other hand, the present poor product quality of final body; Can not get the high sponge iron of iron level, the yield of iron is on the low side simultaneously.In order to obtain the high sponge iron of iron level; Need adjust the smelting temperature of traditional rotary kiln, the present invention's research shows that the reduction temperature of kiln hood is controlled at 1150 ℃～1300 ℃; Guarantee that blast furnace contains the abundant fast restore of zinc gray; The tiny metal abrasive grit that also can let reduction process form is grown up, and the granularity of metallic iron can reach the 0.1mm level, reduces the magnetic separation separating difficulty of postorder and has improved the yield of iron.Because it is low that blast furnace contains in the zinc gray iron level, gangue content height and fusing point are higher, therefore moderately improve reduction temperature, and the kiln hood dross is less, guarantee continuously above level operation half a year.
In order to prevent that blast furnace from containing the airborne dust of zinc gray in rotary kiln, adopt the control blast furnace to contain the moisture content method of zinc gray.Our research shows, it is 10～30% more suitable that the moisture content that blast furnace contains zinc gray is controlled at.The moisture content that blast furnace contains in the zinc gray is very few, and dust emission is big; Cross wetly, blast furnace contains zinc gray and moves difficulty.
Blast furnace contains zinc gray needs enough quality in heating and reduction process carbon; This research shows; When the blast furnace that gets into kiln contains the zinc gray carbon content and reaches 20% above level, do not need extra fuel, when the blast furnace of entering kiln contains zinc gray carbon content less than 20%; Should replenish part of fuel, guarantee that carbon content reaches 20% above level.Carbonaceous fuels such as coal dust that replenishes or coke powder can contain zinc gray with blast furnace and mix back adding rotary kiln, also can spray in the rotary kiln from kiln hood separately.
At the kiln hood high-temperature area, except the reduction of red stone, the zinc that blast furnace contains in the zinc gray is also become zinc fume by carbon reduction, moves to the kiln tail with air-flow, and the reduction along with temperature becomes fine solid particle, in receiving ash system, reclaims zinc-containing dust at last and obtains rich zinc material.
In analyzing in the above; The present invention proposes novel smelting system (comprise and smelt atmosphere control, temperature control and contain the moisture content and the carbon content control of zinc gray) to going into the stove blast furnace; Guarantee that blast furnace contains iron and the zinc drastic reduction in the zinc gray; Also impel the trickle abrasive grit after the reduction to grow up and the technology direct motion simultaneously, obtain high degree of metalization and the metallic iron and the slag mixture of certain particle size size are arranged.
Hot metal iron and slag mixture need cooling; The existing shrend type of cooling; The indirect type of cooling is also arranged, and (water coolant does not directly contact with furnace charge; But utilize mode such as cylinder that the furnace charge heat is passed to water coolant through the contact wall), these two kinds of methods can effectively be cooled off hot metal iron and the slag mixture that present method obtains.
In the process of the test of magnetic separation, as long as the metallic iron that the present invention's reduction obtains and the mean particle size of slag mixture are crushed to 0.08mm-0.2mm, just can guarantee that metallic iron effectively separates with slag, the yield of iron surpasses 90%.Therefore adopt conventional fragmentation, ball milling and wet magnetic separator, just can obtain the metal iron powder of higher degree.Through conventional drying equipment, the water in the metal iron powder is removed again.Drying installation can adopt drum dried equipment, and dried metal iron powder obtains sponge iron blocks through the cold pressing block device again, and its full iron and degree of metalization surpass 85%.
Utilize blast furnace to contain method and we that zinc gray produces sponge iron and rich zinc material in above content statement to the inventive method according to the object of the invention proposed, a kind of blast furnace that utilizes contains the method that zinc gray is produced sponge iron and rich zinc material,
The present invention can effectively utilize blast furnace to contain iron, carbon, zinc resource in the zinc gray; They are all fully separated; Obtain sponge iron and rich zinc material; Improve value-added content of product, farthest reduce the extra fuel amount simultaneously, cut down finished cost, so the present invention has higher society and economic worth.
Characteristics such as contain the zinc gray treatment process with other blast furnace and compare, the present invention has resource and makes full use of, and added value of product is high, and the few and production cost of fixed investment is low are specially adapted to the processing that China contains blast-furnace dustes such as zinc, lead.
Description of drawings
Fig. 1 utilizes blast furnace to contain the schema that zinc gray is produced the method for sponge iron and rich zinc material.
Embodiment
Embodiment 1
The long 36m of rotary kiln * internal diameter 2.4m that practical implementation is used, 3 ° at pitch angle, rotating speed is according to output adjustable (3～50,000 tons/year), generally at 0.3～1rpm.
Blast furnace contains the zinc gray composition and sees table 1, and its carbonaceous amount content has surpassed 20%.Therefore not with addition of coal dust.
The implementing process flow process is seen Fig. 1.Through feeding system, blast furnace is contained zinc gray send into the kiln tail; The water cut that blast furnace contains zinc gray is controlled at 15%; Be blown into air at kiln hood, the kiln hood gas temperature reaches 1230 ℃; The CO volumetric concentration satisfies CO/ (CO in the kiln hood coal gas simultaneously
2+ CO)=75%, through induced draft fan zinc-containing dust is extracted into to receive the ash system from the kiln tail and obtains rich zinc material; Metal iron powder and slag mixture after the reduction are cooled off through shrend; Be crushed to below the 1mm through broken mean particle size again mixture; Mean particle size through the mixture of ball mill after with fragmentation is milled down to the 0.1mm level then, then through wet magnetic separator mixture separation is become metal iron powder and slag; At last that the metal iron powder after the magnetic separation is dry, water-content is 0.5%, becomes sponge iron blocks through briquetting again.
The zinc gray composition that obtains in the enforcement is seen table 2; The sponge iron composition is seen table 3.It is thus clear that the present invention can separate volatile materials such as the Zn in the blast-furnace dust, Pb well with iron, gangue three, and has obtained the high-quality sponge iron, the yield of iron is 93%.
Table 1 embodiment one blast-furnace dust staple/wt%
| TFe | CaO | SiO 2 | MgO | Al 2O 3 | C | Zn | Moisture content |
| 25.8 | 5.7 | 11.3 | 4.1 | 1.7 | 21.6 | 4.6 | 15.1 |
Table 2 zinc gray staple/wt%
| Zn | Fe | CaO | SiO 2 |
| 53.2 | 5.1 | 1.3 | 2.7 |
Table 3 sponge iron staple/wt%
| T.Fe | M.Fe | Degree of metalization |
| 90.6 | 81.5 | 90 |
Embodiment 2
Rotary kiln used in the enforcement is identical with embodiment one, distinguishes to some extent with embodiment one but the blast furnace that uses contains zinc gray composition (seeing table 4).Therefore its carbon content is merely 16.2%, contains in the zinc gray coke powder (fixed carbon 85%) with addition of 6% at blast furnace, keeps reduction and the needed carbonaceous amount of heating.
Through feeding system, the mixture that blast furnace is contained zinc gray and coke powder is sent into the kiln tail; The water cut that blast furnace contains zinc gray is controlled at 17% level; Be blown into air at kiln hood, the kiln hood gas temperature reaches 1250 ℃; The CO volumetric concentration satisfies CO/ (CO in the kiln hood coal gas simultaneously
2+ CO)=73%, through induced draft fan zinc-containing dust is extracted into to receive the ash system from the kiln tail and obtains rich zinc material; With metal iron powder and slag mixture after the reduction through water cooling; Be crushed to below the 1mm through broken mean particle size again mixture; Mean particle size through the mixture of ball mill after with fragmentation is milled down to the 0.1mm level then, then through wet magnetic separator mixture separation is become metal iron powder and slag; At last that the metal iron powder after the magnetic separation is dry, water-content is 0.5%, becomes sponge iron blocks through briquetting again.
The zinc gray composition that obtains in the enforcement is seen table 5; The sponge iron composition is seen table 6, and the yield of iron is 92%.
Table 4 embodiment two used blast-furnace dust staple/wt%
| TFe | CaO | SiO 2 | MgO | Al 2O 3 | C | Zn | Moisture content |
| 24.6 | 5.5 | 10.9 | 3.7 | 1.9 | 16.2 | 4.8 | 19.3 |
Table 5 zinc gray staple/wt%
| Zn | Fe | CaO | SiO 2 |
| 57.5 | 4.7 | 1.2 | 2.4 |
Table 6 sponge iron staple/wt%
| T.Fe | M.Fe | Degree of metalization |
| 89.1 | 79.2 | 88.9 |
Embodiment 3
Rotary kiln used in the enforcement is identical with embodiment one, distinguishes to some extent with embodiment one but the blast furnace that uses contains zinc gray composition (seeing table 4).Its carbon content is merely 16.2%, therefore replenishes 6% coke powder (fixed carbon 85%), sprays into the kiln internal combustion from kiln hood.
Through feeding system, blast furnace is contained zinc gray send into the kiln tail; The water cut that blast furnace contains zinc gray is controlled at 19% level; Be blown into air and coke powder at kiln hood, the kiln hood gas temperature reaches 1210 ℃; CO concentration satisfies CO/ (CO2+CO)=78% in the kiln hood coal gas simultaneously, through induced draft fan zinc-containing dust is extracted into to receive the ash system from the kiln tail to obtain rich zinc material; Metallic iron and slag mixture after the reduction are cooled off through revolving drum indirectly; Be crushed to below the 1mm through broken mean particle size again mixture; Mean particle size through the mixture of ball mill after with fragmentation is milled down to the 0.1mm level then, then through wet magnetic separator mixture separation is become metal iron powder and slag; At last that the metal iron powder after the magnetic separation is dry, water-content is 0.5%, becomes sponge iron blocks through briquetting again.
Zinc gray in zinc gray that obtains in the enforcement and sponge iron composition and the embodiment two is all more close with the yield of sponge iron composition and iron; Show that the present invention can separate volatile materials such as the Zn in the blast-furnace dust, Pb well with iron, gangue three, and obtained the high-quality sponge iron.
Claims (7)
1. one kind is utilized blast furnace to contain the method that zinc gray is produced sponge iron and rich zinc material, and technical process is that the reduction blast furnace contains zinc gray and obtains rich zinc material in rotary kiln, simultaneously cooled slag iron is carried out fragmentation, again through magnetic separation separation slag and rich iron substance; It is characterized in that: the technical parameter of in technology, controlling is:
The CO volumetric concentration satisfies CO/ (CO in the revolution kiln hood coal gas
2+ CO)>70% and the kiln hood gas temperature be 1150 ℃～1300 ℃; The water cut that blast furnace contains zinc gray when going into stove is at 10～30wt%; Carbonaceous amount content is not less than 20% in the charge composition of entering rotary kiln; In the slag iron mixture that the rotary kiln reduction obtains, the reduction ratio of iron is not less than 85wt% and the metallic iron particle size is not less than 0.1mm; Go into the mean particle size 0.08mm-0.2mm of the preceding slag iron mixture of magnetic separator; All iron content is not less than 85wt% in the metallic iron product after the separation, and degree of metalization is not less than 85wt%.
2. method according to claim 1; It is characterized in that: the carbon content that contains in the zinc gray when blast furnace is lower than 20 wt%; With addition of part coal dust or coke powder; Guarantee that carbonaceous amount content reaches more than 20 wt% in the feed stock for blast furnace, the carbonaceous fuel of adding contains zinc gray with blast furnace and mixes the back in kiln tail adding kiln, or sprays into the kiln internal combustion from kiln hood separately.
3. method according to claim 1 is characterized in that: the shrend type of cooling is adopted in hot metal iron that the rotary kiln reduction obtains and the cooling of slag mixture; Or the indirect type of cooling, promptly water coolant does not directly contact with furnace charge, but utilizes the cylinder mode that the furnace charge heat is passed to water coolant through the contact wall.
4. method according to claim 1; It is characterized in that: described slag iron mixture is milled down to 0.08mm-0.2mm through ball mill with the mean particle size of this slag iron mixture, or the mode that adds ball milling through fragmentation is milled down to 0.08mm-0.2mm with the mean particle size of slag iron mixture.
5. method according to claim 1 is characterized in that: adopt wet magnetic separator that the slag iron mixture is separated into metal iron powder and slag.
6. method according to claim 1 is characterized in that: it is dry that magnetic separation is separated the moisture metal iron powder that obtains, and water-content is less than 2 wt %.
7. method according to claim 6 is characterized in that: dried metal iron powder is directly used, or use through being cold-pressed into sponge iron blocks or ball.
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| CN106152145A (en) * | 2016-06-30 | 2016-11-23 | 湖南博环保科技有限公司 | A kind of method utilizing rotary kiln to dispose the fume afterheat containing zinc hazardous waste |
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