CN105063254B - Method for separating iron, zinc and carbon in blast furnace sludge - Google Patents
Method for separating iron, zinc and carbon in blast furnace sludge Download PDFInfo
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- CN105063254B CN105063254B CN201510420489.2A CN201510420489A CN105063254B CN 105063254 B CN105063254 B CN 105063254B CN 201510420489 A CN201510420489 A CN 201510420489A CN 105063254 B CN105063254 B CN 105063254B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
Abstract
The invention discloses a method for separating iron, zinc and carbon in blast furnace sludge. The method for separating the iron, the zinc and the carbon in the blast furnace sludge comprises the steps that the blast furnace sludge is oxidized after being directly magnetically roasted; wet magnetic separation is conducted after proper ore grinding, so that iron concentrate from magnetic separation and tailing zinc-rich materials are obtained; zinc in the zinc-rich materials is extracted by means of a leaching agent, so that a zinc-rich solution and carbon powder are obtained. All products obtained by treating the blast furnace sludge through the method can be effectively utilized, and zero discharge of solid waste of the blast furnace sludge is achieved. The method for separating the iron, the zinc and the carbon in the blast furnace sludge has the advantages that the technique is simple, investment is small, energy consumption is low, and the treatment effect is good. The method for separating the iron, the zinc and the carbon in the blast furnace sludge can provide important theoretical guidance and technical support for comprehensive utilization of blast furnace sludge resources in iron and steel plants.
Description
Technical field
The present invention relates to magnetizing roast, magnetic separation and Chemical Leaching, belong to technical field of beneficiation, and in particular to a kind of to separate blast furnace
The method of ferrum zinc carbon in gas mud.
Background technology
Gas mud is one of most important secondary resource of blast furnace ironmaking, mainly containing iron sesquioxide, simple substance charcoal, Zinc Oxide
Deng low zinc gas mud can be used directly as raw materials for sintering.But being continuously added for new raw material makes zinc in Concentrationin Blast Furnace, and production is made
Into adverse effect.The yield of the high zinc gas mud of China, can also if not only waste of resource is not used more than 10,000,000 tons/year
Bring environmental problem.Therefore the method for finding economical rationality is that current iron and steel enterprise is badly in need of solving to gas mud effective recycling
Problem.At present, gas mud recovery and utilization technology mainly has beneficiating method, Chemical Leaching method, direct-reduction process etc..
Chinese patent (application number 201110040852.X) " the technique side for extracting zinc using rotary kiln baking blast furnace gas mud
Method " propose thoroughly reduction gas mud in Zinc Oxide to extract zinc, by being placed in rotary kiln with addition of appropriate coke in gas mud
Roasting reduction, collects flue gas and obtains Zinc Oxide, metallization slag is left in kiln.When 1050 DEG C of reduction temperature, can obtain TFe >=
50%th, zinc-rich material of the metallization slag and secondary zinc oxide content of ZnO≤1%, degree of metalization >=70% more than 65%.The method
Ferrum zinc separating effect is preferable, but high energy consumption, need to additionally match somebody with somebody refuelling, and up to more than 1000 DEG C of reduction temperature is easily caused rotary kiln
Ring formation, and gained metallization slag Iron grade is low, granularity is little, it is difficult to be directly used in ironmaking in a large number or make steel.
Chinese patent (application number 201110354723.8) is " a kind of to reclaim iron ore concentrate and Jiao from blast furnace dust or gas mud
The technique of powdered carbon " proposes that Jing ore grindings, magnetic separation, flotation after gas mud magnetizing roast are reclaimed ferrum and carbon, and tailing is former as building
Material, realizes gas mud solid waste zero-emission.And the method does not consider the recovery problem of zinc, the gas high for Zn content
Its effect of mud is unknown.
The content of the invention
Instant invention overcomes the deficiencies in the prior art, there is provided a kind of method of ferrum zinc carbon in separation blast furnace gas mud, it is used for
Realize the recycling of valuable element in gas mud.
In view of the problems referred to above of prior art, according to one side disclosed by the invention, the present invention adopts following technology
Scheme：
A kind of method of ferrum zinc carbon in separation blast furnace gas mud, it comprises the following steps：
1) gas mud being carried out into autoreduction magnetizing roast, sintering temperature is 500 DEG C～900 DEG C, roasting time is 10～
120min；
2) ore deposit after above-mentioned roasting is placed in reducing atmosphere and is cooled to 380 DEG C～430 DEG C, be subsequently placed in oxygen in air
Change；
3) ore deposit after above-mentioned oxidation is carried out into wet ball-milling, Ball-milling Time is 3～20min；
4) ore deposit after above-mentioned wet ball-milling is made into into ore pulp with dispersant and tap water, the mass percentage concentration of ore pulp is
15%～35%；
5) above-mentioned ore pulp is obtained into magnetic separation of iron ore concentrate and zinc-rich mine tailing for wet magnetic separation, magnetic field intensity be 0.1T～
0.3T；
6) above-mentioned zinc-rich material is carried out leaching with addition of leaching agent, solid-liquid separation, obtain zinc-rich liquid and carbon powder.
In order to the present invention is better achieved, further technical scheme is：
An embodiment of the invention, the step 1) in control gained roasted ore in ferrum be changed into tool in a large number
Ferromagnetic martite.
Another embodiment of the invention, the dispersant addition are the step 1) mineral nitrogen amount after roasting
0.2%～3%.
Another embodiment of the invention, the dispersant are selected from ethanol, cellulose, waterglass, six inclined phosphorus
One kind in sour sodium, sodium pyrophosphate, sodium lauryl sulphate, paraffin, glycerol, polypropylene.
The present invention can also be：
Another embodiment of the invention, the step 6) in leaching agent be selected from ammonia, ammonium salt, sulphuric acid or
One kind in hydrochloric acid.
Compared with prior art, one of beneficial effects of the present invention are：
The method of ferrum zinc carbon in a kind of separation blast furnace gas mud of the present invention, will using the reducing agent carbon having by oneself in gas mud
Ferrum oxide is converted into magnetic iron ore, and using mineral after reaction, itself waste heat makes magnetic iron ore be oxidized to martite once again, makes institute
Obtain iron ore concentrate and the calcium ferrite for being beneficial to sintering process is more easily produced in sintering, can also retain ferromagnetism, in order to sort；Magnetic
Dispersant is added in ore pulp before choosing, is sufficiently separated mineral grain, magnetic separation effect is more preferable；Magnetic tailing zinc-rich material adopts solvent extraction method
Realize that zinc is separated with carbon, gained zinc-rich liquid and carbon powder are capable of achieving effectively utilizes；And the simple continuous, energy of present invention process
Consumption is low, and comprehensive resource utilization rate is high, has a extensive future, and can provide guidance for iron and steel enterprise's solid waste comprehensive utilization.
Description of the drawings
For clearer explanation present specification embodiment or technical scheme of the prior art, below will be to embodiment
Or accompanying drawing to be used is briefly described needed for the description of prior art, it should be apparent that, drawings in the following description are only
It is the reference to some embodiments in present specification, for those skilled in the art, is not paying creative work
In the case of, can be obtaining other accompanying drawings according to these accompanying drawings.
Fig. 1 shows that the method flow for separating ferrum zinc carbon in blast furnace gas mud according to an embodiment of the invention is illustrated
Figure.
Specific embodiment
The present invention is described in further detail with reference to embodiment, but embodiments of the present invention not limited to this.
To meet iron and steel enterprise's demand and realizing that the comprehensive conjunction of resource is utilized, the invention provides a kind of separate blast furnace gas mud
The method of middle ferrum zinc carbon, realizes the recycling of each valuable element in gas mud, i.e., by autoreduction magnetizing roast, makes gas mud
Middle ferrum is converted into ferromagnetic magnetic iron ore in a large number, and non-magnetic Zinc Oxide is not reduced substantially, carries out magnetic separation according to magnetic contrast
And separated, magnetic iron ore is aoxidized under preference temperature and obtains the more preferable martite of sintering character equally with magnetic, magnetic
Mine tailing zinc-rich material Jing Chemical Leachings, powdered carbon is selected to stay in solid phase and realize separating.Gained iron ore concentrate is used for sintering circuit, zinc-rich liquid
For carrying zinc, carbon powder can realize gas mud solid waste zero-emission as ironmaking each operation fuel.
Specifically, the technical scheme of the present embodiment is shown in Figure 1, a kind of side for separating ferrum zinc carbon in blast furnace gas mud
Method, comprises the steps：
1) gas mud is directly carried out autoreduction magnetizing roast, sintering temperature is 500 DEG C -900 DEG C, and roasting time is 10-
120min；
2) above-mentioned roasted ore is placed in reducing atmosphere and is cooled to 380 DEG C -430 DEG C, aoxidized in being subsequently placed in air；
3) above-mentioned slag is carried out into wet ball-milling, Ball-milling Time is 3-20min；
4) above-mentioned ball milling ore deposit is added into dispersant and tap water is made into ore pulp, pulp density 15%-35%；
5) above-mentioned ore pulp is obtained into magnetic separation of iron ore concentrate and zinc-rich mine tailing for wet magnetic separation, magnetic field intensity is 0.1T-0.3T；
6) above-mentioned zinc-rich material is carried out leaching with addition of leaching agent, solid-liquid separation, obtain zinc-rich liquid and carbon powder.
Wherein, gas mud directly carries out magnetizing roast, and without unclassified stores, without the need for any processing technique；Control institute
Obtain the ferrum in roasted ore and be changed into the ferromagnetic martite of tool in a large number.
The dispersant addition for roasted ore quality 0.2%-3%, the dispersant can be ethanol, cellulose,
One kind in waterglass, sodium hexameta phosphate, sodium pyrophosphate, sodium lauryl sulphate, paraffin, glycerol, polypropylene；For for soaking
The leaching agent for going out can be ammonia, ammonium salt, sulphuric acid or hydrochloric acid.
The method is mainly characterized in that：Ferrum oxide is converted into into magnetic iron ore using the reducing agent carbon having by oneself in gas mud, and
Using mineral after reaction, itself waste heat makes magnetic iron ore be oxidized to martite once again, gained iron ore concentrate is easier in sintering
Generation is beneficial to the calcium ferrite of sintering process, can also retain ferromagnetism and be easy to sorting；Dispersant is added before magnetic separation in ore pulp, ore deposit is made
Composition granule is sufficiently separated, and magnetic separation effect is more preferable；Using solvent extraction method, magnetic tailing zinc-rich material realizes that zinc is separated with carbon, gained zinc-rich
Liquid and carbon powder are capable of achieving effectively utilizes.
The dominant response being related to is as follows：
3Fe2O3+C=2Fe3O4+CO (g) (1)
3Fe2O3+CO (g)=2Fe3O4+CO2 (g) (2)
4Fe3O4+O2 (g)=6Fe2O3 (3)
ZnO+2H+=Zn2++H2O (4)
ZnO+2NH42+=Zn (NH3) 22++H2O (5)
Gas mud used by test takes from domestic certain steel plant, and its main chemical as shown in table 1, is known by table 1, the gas
In mud, iron content is 26.85%, ferrous less, is mainly existed with ferric form；Zn content is up to 20.23%, with very big
Recycling value；Carbon content is 12.40%, can provide sufficient reducing agent and fuel for its autoreduction magnetizing roast；
Other impurities content is less, is conducive to the separation of ferrum, zinc, carbon.
1 gas mud chemical analysis % of table
Embodiment 1：Laboratory is above-mentioned 600 DEG C to reduce 100min in being placed in Muffle furnace by gas mud, makes ferrum oxide
It is converted into magnetic iron ore；Gained calcining is placed in and is connected with the iron flask of nitrogen protection, and inserts thermocouple and be cooled to about 390 DEG C, is placed in
Room temperature is cooled in air, makes magnetic iron ore be converted into martite；Gained calcining granularity is thinner, and hardness is little, is placed in ball mill
Middle wet grinding 7min, granularity account for more than 85% less than 0.074mm's；Magnetic separation is carried out with addition of about 1% ethanol by mass fraction, magnetic field is strong
Spend for 0.1T, obtain iron ore concentrate and zinc-rich material；Gained zinc-rich material is with addition of 15% sulphuric acid with liquid-solid ratio 3:1 leaches 4h at 80 DEG C,
It is filtrated to get zinc-rich liquid and carbon powder.Gained iron ore concentrate iron content 43.6%, containing zinc 6.7%, carbon containing 0.8%, iron recovery
75.6%；Zinc-rich liquid Zn content 72.6g/L, zinc recovery 73.4%；Carbon powder carbon containing 37.1%, iron content 4.6%, containing zinc
1.9%, the carbon response rate 78.8%.
Embodiment 2：Gas mud described in table 1 is reduced into 80min at 700 DEG C in being placed in Muffle furnace, gained calcining is placed in
It is connected with the iron flask of nitrogen protection, and inserts thermocouple and be cooled to about 400 DEG C, is placed in air and is cooled to room temperature；Then with wet
Formula ball mill ore grinding 12min, carries out magnetic separation with addition of about 0.5% waterglass by mass fraction, and magnetic field intensity is 0.2T, obtains Haematite
Ore deposit and zinc-rich material；Gained zinc-rich material is with addition of 15% ammonium chloride with liquid-solid ratio 3:1 leaches 4h at room temperature, be filtrated to get zinc-rich liquid and
Carbon powder.Gained iron ore concentrate iron content 49.1%, containing zinc 5.0%, carbon containing 0.6%, iron recovery 80.1%；Zinc-rich liquid Zn content
71.3g/L, zinc recovery 72.2%；Carbon powder carbon containing 40.5%, iron content 5.9%, containing zinc 2.8%, the carbon response rate 79.4%.
Embodiment 3：Gas mud described in table 1 is reduced into 60min at 800 DEG C in being placed in Muffle furnace, gained calcining is placed in
It is connected with the iron flask of nitrogen protection, and inserts thermocouple and be cooled to about 420 DEG C, is placed in air and is cooled to room temperature；Then with wet
Formula ball mill ore grinding 15min, carries out magnetic separation with addition of about 1% glycerol by mass fraction, and magnetic field intensity is 0.3T, obtain iron ore concentrate and
Zinc-rich material；Gained zinc-rich material is with addition of 15% ammonia with liquid-solid ratio 3:1 leaches 4h at 50 DEG C, is filtrated to get zinc-rich liquid and carbon
Powder.Gained iron ore concentrate iron content 45.4%, containing zinc 5.6%, carbon containing 0.6%, iron recovery 78.9%；Zinc-rich liquid Zn content 81.3g/
L, zinc recovery 78.5%；Carbon powder carbon containing 35.9%, iron content 6.1%, containing zinc 1.4%, the carbon response rate 70.5%.
In this specification, each embodiment is described by the way of progressive, and what each embodiment was stressed is and other
The difference of embodiment, identical similar portion cross-reference between each embodiment.
" one embodiment ", " another embodiment ", " embodiment " for being spoken of in this manual, etc., refer to knot
Specific features, structure or the feature for closing the embodiment description is included at least one embodiment of the application generality description
In.It is not necessarily to refer to same embodiment that statement of the same race occur in multiple places in the description.Furthermore, it is understood that combine appointing
When one embodiment describes specific features, structure or a feature, to be advocated is this to realize with reference to other embodiment
Feature, structure or feature also fall within the scope of the present invention.
Although reference be made herein to invention has been described for multiple explanatory embodiments of the invention, however, it is to be understood that
Those skilled in the art can be designed that a lot of other modifications and embodiment, and these modifications and embodiment will fall in this Shen
Please be within disclosed spirit and spirit.More specifically, in the range of disclosure and claim, can be to master
The building block and/or layout of topic composite configuration carries out various modifications and improvement.Except what is carried out to building block and/or layout
Modification and improvement are outer, and to those skilled in the art, other purposes also will be apparent.
Claims (5)
1. a kind of method for separating ferrum zinc carbon in blast furnace gas mud, is characterized in that, it comprises the following steps：
1) gas mud is carried out into autoreduction magnetizing roast, sintering temperature is 600 DEG C～800 DEG C, and roasting time is 10～120min；
2) ore deposit after above-mentioned roasting is placed in reducing atmosphere and is cooled to 380 DEG C～430 DEG C, aoxidized in being subsequently placed in air；
3) ore deposit after above-mentioned oxidation is carried out into wet ball-milling process, the time that its wet ball-milling is processed is 3～20min；
4) ore deposit after above-mentioned wet ball-milling and dispersant and tap water being made into into ore pulp, the mass percentage concentration of ore pulp is 15%～
35%；
5) above-mentioned ore pulp is obtained into magnetic separation of iron ore concentrate and zinc-rich mine tailing for wet magnetic separation, magnetic field intensity is 0.1T～0.3T；
6) above-mentioned zinc-rich material is carried out leaching with addition of leaching agent, solid-liquid separation, obtain zinc-rich liquid and carbon powder.
2. a kind of method for separating ferrum zinc carbon in blast furnace gas mud according to claim 1, is characterized in that, the step 1)
Ferrum in roasted ore obtained by middle control is changed into the ferromagnetic martite of tool in a large number.
3. a kind of method for separating ferrum zinc carbon in blast furnace gas mud according to claim 1, is characterized in that, the dispersant
Addition is the step 1) mineral nitrogen amount after roasting 0.2%～3%.
4. it is according to claim 1 it is a kind of separate blast furnace gas mud in ferrum zinc carbon method, the dispersant is selected from wine
One kind in essence, cellulose, waterglass, sodium hexameta phosphate, sodium pyrophosphate, sodium lauryl sulphate, paraffin, glycerol, polypropylene.
5. a kind of method for separating ferrum zinc carbon in blast furnace gas mud according to claim 1, is characterized in that, the step 6)
In leaching agent be the one kind in ammonia, ammonium salt, sulphuric acid or hydrochloric acid.
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| KR101969106B1 (en) * | 2017-08-29 | 2019-04-15 | 주식회사 포스코 | Method for processing sludge |
| CN109530075B (en) * | 2017-09-22 | 2021-04-13 | 中南大学 | Method for separating and recovering carbon from raw material containing carbon with low cost and high efficiency |
| CN110039064B (en) * | 2019-05-31 | 2022-11-25 | 唐山鑫联环保科技有限公司 | Method for preparing reducing iron powder by using blast furnace gas ash smelting furnace slag |
| CN110433956B (en) * | 2019-08-15 | 2021-04-20 | 唐山鑫联环保科技有限公司 | Method for recovering zinc, iron and/or carbon from blast furnace gas ash |
| CN110564969B (en) * | 2019-10-14 | 2021-05-25 | 中钢集团马鞍山矿山研究总院股份有限公司 | Method for comprehensively recovering lead, zinc and iron in blast furnace gas ash |
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