CN103589819A - Method for directly reducing nonferrous smelting slag through oxygenation - Google Patents
Method for directly reducing nonferrous smelting slag through oxygenation Download PDFInfo
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- CN103589819A CN103589819A CN201310475073.1A CN201310475073A CN103589819A CN 103589819 A CN103589819 A CN 103589819A CN 201310475073 A CN201310475073 A CN 201310475073A CN 103589819 A CN103589819 A CN 103589819A
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- smelting slag
- nonferrous smelting
- oxygenation
- reduction
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Abstract
The invention provides a method for directly reducing nonferrous smelting slag through oxygenation. The method comprises the following processing steps: step 1, adequately mixing nonferrous smelting slag, coal and oxygen producer according to the proportion of 1:(0.10-0.25):(0.15-0.30) until the materials are uniform mixed; step 2, sending the materials after uniformly mixing in the step 1 into a reducing device, roasting for 30-60min under the condition that the temperature is 1050-1200 DEG C to obtain a metallic mixture material; step 3: after cooling the material obtained in the step 2, crushing and grinding the material until 200 meshes of particles take up greater than 80%, and performing magnetic separation to obtain metallic iron powder. By adding oxygen producer in the nonferrous smelting slag, the reducing time of the nonferrous smelting slag is shortened to 30-60min from 60-120min, so that the productivity is improved, and meanwhile the reducing temperature is reduced to 1050-1200 DEG C from greater than 1300 DEG C, so that the fuel consumption is reduced.
Description
Technical field
The invention belongs to technical field of non-ferrous metallurgy, relate to a kind of method of nonferrous smelting slag oxygenation direct-reduction.
Background technology
Colored metallurgical industrial both domestic and external, in long-term production process, has produced a large amount of iron content nonferrous smelting slags, as the copper ashes producing in copper nickel production process, nickel slag etc., has caused the wasting of resources and environmental pollution.For utilizing cost-effectively nonferrous smelting slag resource, domestic many universities and colleges and scientific research institutions have carried out many research, main adopt acidleach, melting and reducing, pave the way, manufacture the methods such as material of construction and dispose, but all because of less economical, fail to realize commercial application.
Comparatively effectively treatment process has direct-reduction process at present, with coal-based, ferriferous oxide in nonferrous smelting slag is carried out to direct-reduction, specifically nonferrous smelting slag and coal dust are mixed after levigate by a certain percentage, pelletizing, dried green-ball is through the high-temperature roasting of certain hour in reduction apparatus, and making reduction of ferrous oxide in nonferrous smelting slag is metallic iron.Be generally the gasification rate that improves carbon, conventionally adopt 1300 ℃ of above reduction temperatures.In addition in nonferrous smelting slag, contain by FeO and SiO,
2combine and generate pyroxene (the FeO SiO of low melting point
2) and fayalite (2FeO SiO
2) etc. material, these materials adopt traditional direct-reduction technique to need higher temperature and longer recovery time to adopt higher reduction temperature.
Summary of the invention
The object of the invention is to the problem existing for prior art, a kind of method of nonferrous smelting slag oxygenation direct-reduction is provided, to reduce reduction temperature and to shorten the recovery time.
For this reason, the present invention adopts following technical scheme:
A method for nonferrous smelting slag oxygenation direct-reduction, comprises following processing step:
Step 1: nonferrous smelting slag, coal and oxygenation agent are fully mixed into evenly in 1:0.10～0.25:0.15～0.30 ratio;
Step 2: the material after step 1 is mixed is sent into reduction apparatus, is roasting 30～60min under 1050～1200 ℃ of conditions in temperature, obtains the mixture that metallizes;
Step 3: after step 2 gained material is cooling, crushing grinding to-200 orders account for more than 80%, obtain the iron powder that metallizes after magnetic separation.
Further, in step 1, described coal is preferably blue charcoal.
Further, in step 1, described oxygenation agent is Wingdale.
As a kind of comparatively concrete scheme, the method for described nonferrous smelting slag oxygenation direct-reduction comprises the following steps:
Step 1: account for more than 50% for-200 orders to granularity nonferrous smelting slag, coal dust, oxygenation agent are levigate respectively;
Step 2: above-mentioned nonferrous smelting slag, coal dust, oxygenation agent and binding agent are fully mixed in 1:0.10～0.20:0.15～0.20:0.01～0.04 ratio, and pelletizing post-drying, makes the carbonaceous pelletizing that granularity is 8～20mm;
Step 3: the carbonaceous pelletizing that step 2 is made is sent in reduction apparatus, is roasting 30～60min under 1050～1200 ℃ of conditions in temperature, obtains metallized pellet;
Step 4: by above-mentioned metallized pellet carry out cooling after, crushing grinding accounts for more than 80% to-200 orders, obtains the iron powder that metallizes after magnetic separation.
As another kind concrete scheme comparatively, the method for described nonferrous smelting slag oxygenation direct-reduction, comprises the following steps:
Step 1: nonferrous smelting slag, charcoal piece and oxygenation agent are fully mixed in 1:0.15～0.25:0.20～0.30 ratio, and wherein, nonferrous smelting slag size range is 1～8mm, and charcoal piece size range is 3～5mm, and limestone granularity scope is 10～25mm;
Step 2: the material after step 1 is mixed is sent in reduction apparatus and carried out, is roasting 30～60min under 1050～1200 ℃ of conditions in temperature, obtains the mixture that metallizes;
Step 3: after step 2 gained material is cooling, crushing grinding to-200 orders account for more than 80%, obtain the iron powder that metallizes after magnetic separation.
Improvement as a concrete scheme after pin, in step 3, by cooling rear material, first through magnetic pulley dry separation, by feed separation, be magnetic material and non-magnetic material, again the magneticmetal compound material obtaining is crushed to-200 orders and accounts for more than 80%, after magnetic separation, obtain the iron powder that metallizes.
Further, in step 3, non-magnetic material is after size classification, and the caustic lime block obtaining and charcoal piece, smelt sintering circuit batching for iron.
Principal reaction principle of the present invention is as follows:
Fe
2SiO
4(s)+?2C(s)→2Fe(s)+?SiO
2(s)?+2CO(g) （1）
2FeO(s)+2C(s)→2Fe(s)+2CO(g) （2）
2FeO(s)+C(s)→2Fe(s)+CO
2(g) （3）
FeO(s)+?CO(g)→Fe(s)+CO
2(g) （4）
CaCO
3(s)?→CaO(s)+CO
2(g) （5）
CO
2(g)+C(s)→2CO(g) （6）
From various above, can find out, the iron of nonferrous smelting slag is mainly with Fe
2siO
4or FeO form exists, the required Oxidant of carbon gasification in reduction process (referring to containing the high iron cpd of oxygen or containing the high carbonate material of oxygen etc.) content is lower, makes reduction process controlled by the gasification reaction of carbon.Reason is, selects all kinds of iron ores such as spathic iron ore, limonite and blast furnace gas plaster, converter OG sludge compared to difficulty, and in above-mentioned iron charge, the occurrence form of iron has the Fe of significant proportion
2o
3, Fe
3o
4or FeCO
3(neutral roasting can generate Fe
3o
4and emit CO and CO
2), these containing the high iron cpd of oxygen when by C (s) direct-reduction output more CO
2continue to react generation CO with CO(with ferriferous oxide
2), make CO
2+ C=2CO reaction is strengthened).And nonferrous smelting slag reduces required temperature drift, time and is partially longly rich in containing the low FeO(of oxygen with 2FeO. SiO just because of it
2with FeO. SiO
2form existence) characteristic determines.
While solid carbon and solid-state Fe
2siO
4although or the reaction of FeO has produced CO and CO
2, but due to the incomplete contact between solid particulate, the contact surface between two solid phases is less, Fe
2siO
4or CO and the CO of FeO and the release of C direct reaction
2be limited, be difficult at lesser temps and the reduction effect that reached in the short period.For this reason, the present invention has adopted Wingdale as oxygenation agent, and by the reaction descriptions of above-mentioned (5), (6) formula, decomposition of limestone produces CO
2reacting with C and produced a large amount of CO, is Fe
2siO
4or FeO direct-reduction provides sufficient CO, reduction reaction is carried out fast.Meanwhile, Wingdale is at 900～1200 ℃ of fast decoupleds, and this temperature range is also Fe
2siO
4or FeO changes Fe temperature spot, Fe into
2siO
4or FeO obtained a large amount of reducing gas CO at 900～1200 ℃, reducing medium concentration reaches more than 60%, makes Fe
2siO
4or the recovery time of FeO by 60～120min, shorten to 30～60min, reduction temperature is reduced to 1050～1200 ℃ above by 1300 ℃, makes the cost of nonferrous smelting slag direct-reduction, production capacity improves.
In addition, Wingdale (CaCO in the present invention
3) unslaked lime (CaO) that produces of decomposes can effectively play the effect of adjusting alkali desulfurization.Adjusting alkali to refer to and adjust material basicity, is mainly to adjust CaO/SiO
2ratio makes slag iron carry out effective separation in reduction process, and reason is CaO (s) and SiO
2(s) bonding force is greater than FeO (s) and SiO
2(s) bonding force, in nickel slag reducing roasting process, CaO and SiO
2in conjunction with and the FeO of the free state of dissociating, its reactive behavior is high, makes Fe
2siO
4(s) be easy to reduction, therefore, suitably adjust the reduction process that basicity is conducive to nonferrous smelting slag; Desulfurization mainly refers to that CaO generates CaS with free S in reduction process, then enters in slag, plays desulfidation.
Again, the present invention selects blue charcoal reason to be: (1) fixed carbon content is high, reaches more than 70%, and the gasified reverse by C should be able to produce a large amount of CO.(2) low price (approximately 380 yuan/ton), can be used as a kind of reductive agent of economy, and price is far below coke, even lower than most of super sea coal.
The composition of blue charcoal is as follows:
| Ash content | Fugitive constituent | Sulphur | Fixed carbon |
| 9-13% | 12-14% | 0.2-0.35% | 74-77% |
| ? | ? | ? | ? |
Beneficial effect of the present invention is:
1, by nonferrous smelting slag with addition of oxygenation agent, can make the recovery time shorten to 30～60min by 60～120min, improved production capacity; Meanwhile, can make reduction temperature by more than 1300 being reduced to 1050～1200 ℃, reduce fuel consumption;
2, the inventive method can utilize nonferrous smelting slag to produce iron grade more than 80% and more than 90% iron powder of degree of metalization;
3, the inventive method can effectively be disposed the nonferrous smelting slag of long-term accumulation, improves the recycle of waste resource, reduces environmental pollution.
Embodiment
Embodiment of the present invention nonferrous smelting slag used smelts from certain large-scale non-ferrous metallurgical enterprise nickel the nickel slag (top blast sedimentation electric furnace slag and top blast dilution slag) producing in production process, and its chemical analysis results is as follows:
| Composition | TFe | FeO | Ni | Cu | Co | S | CaO | MgO | SiO 2 |
| Content (%) | 30-45 | 40-56 | 0.1-0.37 | 0.2-0.39 | 0.04-0.24 | 0.5-1.9 | 0.7-3.3 | 1.4-10.5 | 20-45 |
Nonferrous smelting slag main component is FeO, MgO and SiO
2, submember is CaO, Fe
3o
4, Al
2o
3, Ni
3s
2, Cu
2s, FeS, CoS etc.The material phase analysis of nickel slag shows: in nickel slag, the occurrence form of iron is mainly the fayalite (2FeOSiO existing with silicate form
2) and pyroxene (FeOSiO
2).
embodiment 1:
A method for nonferrous smelting slag oxygenation direct-reduction, comprises following processing step:
Step 1: account for more than 50% for-200 orders to granularity nonferrous smelting slag, coal dust, Wingdale are levigate respectively.
Step 2: above-mentioned nonferrous smelting slag, coal dust, Wingdale and wilkinite are fully mixed in 1:0.10:0.17:0.01 ratio, and pelletizing post-drying, makes the carbonaceous pelletizing that granularity is 8～20mm;
Step 3: the carbonaceous pelletizing that step 2 is made is sent in stoving oven and carried out roasting reduction, is roasting 45min under 1150 ℃ of conditions in temperature, obtains metallized pellet;
Step 4: by above-mentioned metallized pellet carry out cooling after, crushing grinding accounts for more than 80% to-200 orders, obtains the iron powder that metallizes after magnetic separation.
The metallization iron powder index obtaining after magnetic separation is: TFe:85%, MFe:76.5%.
embodiment 2:
Embodiment 2 is with the difference of embodiment 1:
In step 2, nonferrous smelting slag, coal dust, Wingdale mix in 1:0.15:0.20:0.04 ratio with wilkinite;
In step 3, carbonaceous pelletizing is roasting 30min under 1200 ℃ of conditions in temperature.
The metallization iron powder index obtaining after step 4 magnetic separation is: TFe:82%, MFe:74%.
embodiment 3:
Embodiment 3 is with the difference of embodiment 1:
In step 2, nonferrous smelting slag, coal dust, Wingdale mix in 1:0.20:0.15:0.03 ratio with wilkinite;
In step 3, carbonaceous pelletizing is roasting 60min under 1050 ℃ of conditions in temperature.
The metallization iron powder index obtaining after step 4 magnetic separation is: TFe:80 %, MFe:72%.
embodiment 4:
A method for nonferrous smelting slag oxygenation direct-reduction, comprises following processing step:
Step 1: nonferrous smelting slag, blue charcoal and Wingdale are fully mixed in 1:0.15:0.25 ratio, and wherein nonferrous smelting slag size range is 1～8mm, and blue charcoal size range is 3～5mm, and limestone granularity scope is 10～25mm;
Step 2: the material after step 1 is mixed is sent in stoving oven and carried out roasting reduction, is roasting 60min under 1050 ℃ of conditions in temperature, obtains the mixture that metallizes;
Step 3: after step 2 gained material is cooling, carrying out dry separation through magnetic pulley, is magnetic material and non-magnetic material by feed separation; The magneticmetal compound material obtaining is crushed to-200 orders and accounts for more than 80%, obtains the iron powder that metallizes after magnetic separation; Non-magnetic material, after size classification, obtains caustic lime block and charcoal piece, and unslaked lime is for sintering circuit batching.
The metallization iron powder index obtaining after step 3 magnetic separation is: TFe:83%, MFe:75%.
embodiment 5:
Embodiment 5 is with the difference of embodiment 4:
In step 1, nonferrous smelting slag, coal dust, Wingdale mix in 1:0.20:0.20 ratio with wilkinite;
In step 2, carbonaceous pelletizing is roasting 45min under 1100 ℃ of conditions in temperature.
The metallization iron powder index obtaining after step 3 magnetic separation is: TFe:80%, MFe:72.4%.
embodiment 6:
Embodiment 6 is with the difference of embodiment 4:
In step 1, nonferrous smelting slag, coal dust, Wingdale mix in 1:0.25:0.30 ratio with wilkinite;
In step 2, carbonaceous pelletizing is roasting 30min under 1200 ℃ of conditions in temperature.
The metallization iron powder index obtaining after step 3 magnetic separation is: TFe:87%, MFe:78.3%.
Claims (7)
1. a method for nonferrous smelting slag oxygenation direct-reduction, is characterized in that, comprises following processing step:
Step 1: nonferrous smelting slag, coal and oxygenation agent are fully mixed into evenly in 1:0.10～0.25:0.15～0.30 ratio;
Step 2: the material after step 1 is mixed is sent in reduction apparatus, is roasting 30～60min under 1050～1200 ℃ of conditions in temperature, obtains the mixture that metallizes;
Step 3: after step 2 gained material is cooling, crushing grinding to-200 orders account for more than 80%, obtain the iron powder that metallizes after magnetic separation.
2. the method for a kind of nonferrous smelting slag oxygenation direct-reduction according to claim 1, is characterized in that, comprises the following steps:
Step 1: account for more than 50% for-200 orders to granularity nonferrous smelting slag, coal dust, oxygenation agent are levigate respectively;
Step 2: above-mentioned nonferrous smelting slag, coal dust, oxygenation agent and binding agent are fully mixed in 1:0.10～0.20:0.15～0.20:0.01～0.04 ratio, and pelletizing post-drying, makes the carbonaceous pelletizing that granularity is 8～20mm;
Step 3: the carbonaceous pelletizing that step 2 is made is sent in reduction apparatus, is roasting 30～60min under 1050～1200 ℃ of conditions in temperature, obtains metallized pellet;
Step 4: by above-mentioned metallized pellet carry out cooling after, crushing grinding accounts for more than 80% to-200 orders, obtains the iron powder that metallizes after magnetic separation.
3. the method for a kind of nonferrous smelting slag oxygenation direct-reduction according to claim 1, is characterized in that, comprises the following steps:
Step 1: nonferrous smelting slag, charcoal piece and oxygenation agent are fully mixed in 1:0.15～0.25:0.20～0.30 ratio, and wherein, nonferrous smelting slag size range is 1～8mm, and charcoal piece size range is 3～5mm, and limestone granularity scope is 10～25mm;
Step 2: the material after step 1 is mixed is sent in reduction apparatus and carried out, is roasting 30～60min under 1050～1200 ℃ of conditions in temperature, obtains the mixture that metallizes;
Step 3: after step 2 gained material is cooling, crushing grinding to-200 orders account for more than 80%, obtain the iron powder that metallizes after magnetic separation.
4. according to the method for any one nonferrous smelting slag oxygenation direct-reduction described in claim 1-3, it is characterized in that, in step 1, described coal is preferably blue charcoal.
5. according to the method for described a kind of nonferrous smelting slag oxygenation direct-reduction arbitrarily described in claim 1-3, it is characterized in that, in step 1, described oxygenation agent is Wingdale.
6. the method for a kind of nonferrous smelting slag oxygenation direct-reduction according to claim 3, it is characterized in that, in step 3, cooling rear material is first through magnetic pulley dry separation, by feed separation, be magnetic material and non-magnetic material, again the magneticmetal compound material obtaining is crushed to-200 orders and accounts for more than 80%, after magnetic separation, obtain the iron powder that metallizes.
7. the method for a kind of nonferrous smelting slag oxygenation direct-reduction according to claim 6, is characterized in that, in step 3, non-magnetic material is after size classification, and the caustic lime block obtaining and charcoal piece, smelt sintering circuit batching for iron.
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Cited By (4)
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| CN105838840A (en) * | 2016-05-24 | 2016-08-10 | 江苏省冶金设计院有限公司 | Method for preparing granular iron and system for preparing granular iron |
| CN107619940A (en) * | 2017-09-28 | 2018-01-23 | 深圳万佳互动科技有限公司 | A kind of method that copper is reclaimed from metallurgical slag |
| CN107674984A (en) * | 2017-09-28 | 2018-02-09 | 深圳万佳互动科技有限公司 | The recovery method of valuable metal in a kind of metallurgical slag |
| CN111748686A (en) * | 2020-07-06 | 2020-10-09 | 酒泉钢铁(集团)有限责任公司 | Process for producing metallized furnace charge by directly reducing nonferrous smelting slag |
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| CN111748686A (en) * | 2020-07-06 | 2020-10-09 | 酒泉钢铁(集团)有限责任公司 | Process for producing metallized furnace charge by directly reducing nonferrous smelting slag |
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Application publication date: 20140219 |