CN110205430A - A method of strengthening reduction roasting and recycles red mud iron component - Google Patents
A method of strengthening reduction roasting and recycles red mud iron component Download PDFInfo
- Publication number
- CN110205430A CN110205430A CN201910615285.2A CN201910615285A CN110205430A CN 110205430 A CN110205430 A CN 110205430A CN 201910615285 A CN201910615285 A CN 201910615285A CN 110205430 A CN110205430 A CN 110205430A
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- China
- Prior art keywords
- red mud
- iron component
- reduction roasting
- separation
- iron
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Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21B—MANUFACTURE OF IRON OR STEEL
- C21B13/00—Making spongy iron or liquid steel, by direct processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
Abstract
The present invention relates to technical field of resource comprehensive utilization more particularly to a kind of methods for strengthening reduction roasting recycling red mud iron component.The present invention provides a kind of methods of reinforcing reduction roasting recycling red mud iron component, comprising the following steps: step 1: red mud progress pre-separation is obtained aluminosilicate saline solution and Fu Tie bottom ash；Step 2: the rich iron bottom ash being sufficiently mixed to obtain with cathode charcoal mix sample；Step 3: the mixing sample being roasted, obtains calcining after cold sudden, ball milling；By calcining through the isolated sponge iron of magnetic separation and non magnetic residue.The method provided by the invention for strengthening reduction roasting recycling red mud iron component solves the technical problem that existing separation and recovery iron multi-component approach reduction rate is lower, reduction and separation is difficult.
Description
Technical field
The present invention relates to technical field of resource comprehensive utilization more particularly to a kind of reinforcing reduction roasting to recycle red mud iron component
Method.
Background technique
Aluminum i ndustry is in critical role in non-ferrous metal industry, provides for national economy social development important basic
Raw material.China is used as world's alumina producing big country, and nearly 5 years average growth rates per annum are 8.6%.Due to the life of aluminium oxide per ton
Production process is generated along with 1.0-2.0 tons of red mud, it is estimated that the volume of cargo in storage to the year two thousand twenty China red mud is up to 800,000,000 tons.It is red
Mud is that a kind of chemical constituent is complicated, granular solids waste of strong basicity, and main chemical compositions have: Na2O、Fe2O3、SiO2、
Al2O3With CaO etc., it is difficult to comprehensively utilize, or even " cancer " of referred to as aluminum i ndustry.However, red mud is used as harmful solid waste, at present
China's red mud comprehensive utilization ratio is only 4%, is the key that restrict aluminium industry value chain there are serious security context hidden danger
One of bottleneck problem.
At the same time, in modern aluminum industry production, cryolite-alumina fused salt electrolysis process is mainly used.This method production
A large amount of waste and old cathode carbon can be generated during metallic aluminium.Waste and old cathode carbon is more than country because of its fluoride toxicity leaching concentration
Standard and be listed in hazardous waste.According to statistics, the waste and old cathode carbon that annual China's aluminium cell generates is more than 300,000 tons.Aluminum smelting technology
Production line high concentration and the innoxious ability of waste and old cathode carbon is low, even more exacerbate the environmentally friendly risk of aluminum electrolysis industry.Therefore, anxious
It need to design that waste and old cathode carbon is innoxious, technology path of recycling, open up the application field of the recycling of waste and old cathode carbon, realize
The Green Development of aluminium industry.
Iron component in reduction roasting-magnetic separation separation and recovery red mud is a kind of efficient cleaning procedure.Red mud Minerals exist
Series of phase transitions reaction, such as goethite, gibbsite, a diaspore, kaolinite ore knot can be occurred by being heated in reduction process
The removing of brilliant water becomes iron oxide, aluminium oxide and silica etc..Therefore, increase temperature be conducive to iron oxide in red mud also
Original improves the rate of recovery of iron component.However, excessively high temperature will lead to Ca (Fe, Al)2O4The generation of equal objects phase, causes " burning "
Phenomenon.Reduction process thermodynamics of reactions analysis shows, ferriferous oxide reduction generate FeO phase and Al2O3And SiO2Reaction generates
Fayalite and hercynite, the generation of such compound are unfavorable for FeO phase and are reduced into metal phase Fe.In going back original product, by
It is tiny in iron grain particles, be easy to be distributed the associations oxide such as aluminium oxide and silica of dispersion reaction generate fayalite and
The low-melting-point materials such as hercynite, part low-melting-point material are wrapped in iron grain particles, hinder the diffusion and migration of reducing gas, cause
Become difficult reduction and separation.Solid phase reaction is concurrently given birth in phase counterdiffusion between aluminium, Si oxide and ferriferous oxide, is largely being generated
Stage, which restores iron, influences maximum, is gradually reduced with the influence that carries out of reduction reaction, Al2O3Opposite SiO2For influence iron oxidation
Object reducing degree is more greatly.
Therefore, the method reduction rate of existing separation and recovery iron component is lower, reduction and separation is difficult becomes this field skill
Art personnel technical problem urgently to be resolved.
Summary of the invention
The present invention provides a kind of methods of reinforcing reduction roasting recycling red mud iron component, solve existing separation and recovery
The technical problem that the method reduction rate of iron component is lower, reduction and separation is difficult.
The present invention provides a kind of methods of reinforcing reduction roasting recycling red mud iron component, comprising the following steps:
Step 1: red mud progress pre-separation is obtained into aluminosilicate saline solution and Fu Tie bottom ash；
Step 2: the rich iron bottom ash being sufficiently mixed to obtain with cathode charcoal mix sample；
Step 3: the mixing sample being roasted, obtains calcining after cold sudden, ball milling；By calcining through the isolated sponge of magnetic separation
Iron and non magnetic residue.
It preferably, after step 1, further include by hydrothermal synthesis method before step 2 by obtained alumino-silicate to make
Standby artificial zeolite.
Preferably, the pre-separation is alkali fusion in step 1.
Preferably, the alkali fusion agent of the alkali fusion is sodium hydroxide.
Preferably, sodium hydroxide/red mud material ratio is 1:1-2:1.
Preferably, the temperature of the alkali fusion is 500-1000 DEG C.
Preferably, the time of the alkali fusion is 30-120min.
Preferably, cathode charcoal described in step 2 and the mass ratio of the rich iron bottom ash are 0.01-0.1.
Preferably, the temperature of roasting described in step 3 is 500-1200 DEG C.
Preferably, the time of roasting described in step 3 is 30-150min.
In the method provided by the invention for strengthening reduction roasting recycling red mud iron component, without to red mud and waste and old cathode carbon
It pre-processes, avoids the generation containing complicated ingredient waste water, reduce subsequent wastewater treatment pressure and input cost.The present invention
The method of offer is using cathode charcoal as carbon source and Fluorine source, reducing agent needed for providing not only calcination, and by with it is red
Mud substrate slag reacts under the roasting condition generates calcirm-fluoride (CaF2), avoid class catalyst CaF2Addition, make to strengthen reduction anti-
The generation answered, to improve the reduction efficiency and the rate of recovery of ferriferous oxide.Further it is proposed that technical solution in, no
The recycling of waste is only realized, and has reached the innoxious requirement for hazardous waste disposal.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention without any creative labor, may be used also for those of ordinary skill in the art
To obtain other attached drawings according to these attached drawings.
Fig. 1 is the process flow chart that red mud iron component is recycled in reinforcing reduction roasting provided by the invention；
Fig. 2 is red mud chemistry alkali soluble front and back comparison diagram in the embodiment of the present invention 3；
Fig. 3 is the XRD diagram of red mud base 4A zeolite in the embodiment of the present invention 3；
Fig. 4 is the FT-IR comparison diagram of red mud base 4A zeolite and commercialization 4A zeolite in the embodiment of the present invention 3；
Fig. 5 is the SEM figure of red mud base 4A zeolite in the embodiment of the present invention 3；
Fig. 6 is the chemical component figure in the embodiment of the present invention 3 in sponge iron；
Fig. 7 is the XRD diagram in the embodiment of the present invention 3 in sponge iron；
Fig. 8 is the SEM comparison diagram of red mud and sponge iron in the embodiment of the present invention 3.
Specific embodiment
The embodiment of the invention provides a kind of methods of reinforcing reduction roasting recycling red mud iron component, solve existing point
Method reduction rate from recycling iron component is lower, technical problem that reduction and separation is difficult.
In order to make the invention's purpose, features and advantages of the invention more obvious and easy to understand, below in conjunction with the present invention
Attached drawing in embodiment, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that disclosed below
Embodiment be only a part of the embodiment of the present invention, and not all embodiment.Based on the embodiments of the present invention, this field
Those of ordinary skill's all other embodiment obtained without making creative work, belongs to protection of the present invention
Range.
In order to which the present invention is described in more detail, below with reference to embodiment to a kind of reinforcing reduction roasting recycling provided by the invention
The method of red mud iron component is specifically described, and the process flow of the method is as shown in Figure 1.
Embodiment 1
A method of strengthening reduction roasting and recycle red mud iron component, includes the following steps:
(1) sample that mass ratio NaOH/ red mud is 1:1 is weighed, is suitably ground and is placed in Muffle furnace；
(2) mixing sample is placed at 600 DEG C after melting 30min and is taken out, mentioned by solid-to-liquid ratio 1:50 in 60 DEG C of water after cooling
30min is separated by solid-liquid separation while hot, is obtained rich in alumino-silicate filtrate and Fu Tie bottom ash；
(3) sial concentration of component in filtrate is measured, SiO is adjusted2/Al2O3:H2O/Na2The molar ratio of O is (1.5-3.2):
(30-120) reacts 120min at 100 DEG C, obtains powdered red mud base 4A zeolite after washed, filtering, drying；
(4) the rich iron bottom ash obtained after alkali fusion-water logging-separation of solid and liquid and 5wt.% waste and old cathode carbon is sufficiently mixed
It closes, under an inert atmosphere 700 DEG C of roasting 30min；Calcining is ground into 60min through cold sudden be placed in ball mill, is separated through magnetic separation
Recycle sponge iron.
Embodiment 2
(1) sample that mass ratio NaOH/ red mud is 1.5:1 is weighed, is suitably ground and is placed in Muffle furnace；
(2) mixing sample is placed at 700 DEG C after melting 60min and is taken out, mentioned by solid-to-liquid ratio 1:50 in 60 DEG C of water after cooling
30min is separated by solid-liquid separation while hot, is obtained rich in aluminosilicate solution and Fu Tie bottom ash；
(3) sial concentration of component in filtrate is measured, SiO is adjusted2/Al2O3:H2O/Na2The molar ratio of O meets (1.5-3.2):
(30-120) obtains powdered red mud base 4A zeolite after washed, filtering, drying in 100 DEG C of reaction 150min；
(4) the rich iron bottom ash obtained after alkali fusion-water logging-separation of solid and liquid and 7wt.% waste and old cathode carbon is sufficiently mixed
It closes, under an inert atmosphere 800 DEG C of roasting 90min；Calcining is ground into 60min through cold sudden be placed in ball milling ball mill, through magnetic separation
Separate and recover sponge iron.
Embodiment 3
(1) sample that mass ratio NaOH/ red mud is 2:1 is weighed, is suitably ground and is placed in Muffle furnace；
(2) mixing sample is placed at 800 DEG C after melting 90min and is taken out, mentioned by solid-to-liquid ratio 1:50 in 60 DEG C of water after cooling
30min is separated by solid-liquid separation while hot, is obtained rich in aluminosilicate solution and Fu Tie bottom ash；
(3) sial concentration of component in filtrate is measured, SiO is adjusted2/Al2O3:H2O/Na2The molar ratio of O is 1.5-3.2:30-
120, in 100 DEG C of reaction 200min, powdered red mud base 4A zeolite is obtained after washed, filtering, drying；
(4) the rich iron bottom ash obtained after alkali fusion-water logging-separation of solid and liquid and 10wt.% waste and old cathode carbon is sufficiently mixed
It closes, under an inert atmosphere 900 DEG C of roasting 120min；Calcining is ground into 60min through cold sudden be placed in ball milling ball mill, through magnetic separation
Separate and recover sponge iron.
Sponge iron made from the embodiment of the present invention is subjected to performance detection and analysis, carries out table through XRD, XRF, SEM, FT-IR
Sign, as a result as shown, as shown in Figure 2, soluble silicon can be converted by the sial component in red mud using alkali fusion-water logging mode
Aluminate.By 3 reaction condition of embodiment, the silicon components recovery rate in red mud is 52%, and silicon components recovery rate is 48%. iron components
38% is enriched to by original 23%.From the figure 3, it may be seen that can realize the preparation of red mud base 4A zeolite using hydrothermal synthesis method.By Fig. 4
It is found that red mud base 4A zeolite surface functional group is consistent with commercialization 4A zeolite, illustrate that red mud can be used as the silicon source and silicon source of 4A zeolite.
As shown in Figure 5, red mud base 4A zeolite has complete physique structure, shows that artificial zeolite has high-crystallinity.It will be appreciated from fig. 6 that
Through 3 conditioned response of embodiment, the rate of recovery of iron component is up to 88% in red mud.As shown in Figure 7, by 3 reaction condition of case study on implementation,
The recyclable sponge iron with high-crystallinity.As shown in Figure 8, it is based on reaction condition of the present invention, can effectively realize iron group in red mud
The high efficiente callback divided.
The above, the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although referring to before
Stating embodiment, invention is explained in detail, those skilled in the art should understand that: it still can be to preceding
Technical solution documented by each embodiment is stated to modify or equivalent replacement of some of the technical features；And these
It modifies or replaces, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of method for strengthening reduction roasting recycling red mud iron component, which comprises the following steps:
Step 1: red mud progress pre-separation is obtained into aluminosilicate saline solution and Fu Tie bottom ash；
Step 2: the rich iron bottom ash being sufficiently mixed to obtain with cathode charcoal mix sample；
Step 3: the mixing sample being roasted, obtains calcining after cold sudden, ball milling；By calcining through the isolated sponge iron of magnetic separation and
Non magnetic residue.
2. the method according to claim 1 for strengthening reduction roasting recycling red mud iron component, which is characterized in that in step 1
It later, further include by hydrothermal synthesis method before step 2 by obtained alumino-silicate to prepare artificial zeolite.
3. the method according to claim 1 for strengthening reduction roasting recycling red mud iron component, which is characterized in that in step 1
Described in pre-separation be alkali fusion.
4. the method according to claim 3 for strengthening reduction roasting recycling red mud iron component, which is characterized in that the alkali fusion
The alkali fusion agent of method is sodium hydroxide.
5. the method according to claim 3 for strengthening reduction roasting recycling red mud iron component, which is characterized in that hydroxide
Sodium/red mud material ratio is 1:1-2:1.
6. the method according to claim 3 for strengthening reduction roasting recycling red mud iron component, which is characterized in that the alkali fusion
The temperature of method is 500-1000 DEG C.
7. the method according to claim 3 for strengthening reduction roasting recycling red mud iron component, which is characterized in that the alkali fusion
The time of method is 30-120min.
8. the method according to claim 1 for strengthening reduction roasting recycling red mud iron component, which is characterized in that in step 2
The cathode charcoal and the mass ratio of the rich iron bottom ash are 0.01-0.1.
9. the method according to claim 1 for strengthening reduction roasting recycling red mud iron component, which is characterized in that in step 3
The temperature of the roasting is 500-1200 DEG C.
10. the method according to claim 1 for strengthening reduction roasting recycling red mud iron component, which is characterized in that in step 3
The time of the roasting is 30-150min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111217399A (en) * | 2019-10-17 | 2020-06-02 | 东北大学 | Direct reduction pre-magnetization method for hydrated calcium iron garnet |
| CN112877489A (en) * | 2021-01-12 | 2021-06-01 | 广东工业大学 | Method for recycling red mud iron by using cathode carbon |
| CN113716583A (en) * | 2021-09-22 | 2021-11-30 | 西安交通大学 | Method for preparing 4A zeolite by using MSWI fly ash and red mud hydrothermal method |
| CN114015865A (en) * | 2021-11-17 | 2022-02-08 | 昆明理工大学 | Method for reducing laterite-nickel ore by using waste cathode carbon |
| CN114672818A (en) * | 2022-03-25 | 2022-06-28 | 华北理工大学 | Method for preparing iron-aluminum-silicon carbide composite material by utilizing red mud |
| WO2022178037A1 (en) * | 2021-02-16 | 2022-08-25 | Gron Metallic Group, Inc. | Process for recovering metals and oxides from iron-containing tailings |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN112877489A (en) * | 2021-01-12 | 2021-06-01 | 广东工业大学 | Method for recycling red mud iron by using cathode carbon |
| WO2022178037A1 (en) * | 2021-02-16 | 2022-08-25 | Gron Metallic Group, Inc. | Process for recovering metals and oxides from iron-containing tailings |
| CN113716583A (en) * | 2021-09-22 | 2021-11-30 | 西安交通大学 | Method for preparing 4A zeolite by using MSWI fly ash and red mud hydrothermal method |
| CN114015865A (en) * | 2021-11-17 | 2022-02-08 | 昆明理工大学 | Method for reducing laterite-nickel ore by using waste cathode carbon |
| CN114672818A (en) * | 2022-03-25 | 2022-06-28 | 华北理工大学 | Method for preparing iron-aluminum-silicon carbide composite material by utilizing red mud |
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Application publication date: 20190906 |