CN109609775A - A kind of Resource comprehensive utilization method of steel slag - Google Patents
A kind of Resource comprehensive utilization method of steel slag Download PDFInfo
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- CN109609775A CN109609775A CN201811650115.XA CN201811650115A CN109609775A CN 109609775 A CN109609775 A CN 109609775A CN 201811650115 A CN201811650115 A CN 201811650115A CN 109609775 A CN109609775 A CN 109609775A
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- extractant
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/04—Working-up slag
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
- C22B26/22—Obtaining magnesium
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
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- 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
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
-
- 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
- C22B34/00—Obtaining refractory metals
- C22B34/20—Obtaining niobium, tantalum or vanadium
- C22B34/22—Obtaining vanadium
-
- 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
- C22B59/00—Obtaining rare earth metals
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- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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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- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of Resource comprehensive utilization method of steel slag, acid is added in steel slag and oxidant dissolves, by valuable element therein by the ionic state of Solid State Transformation Cheng Shuizhong, is separated by solid-liquid separation after heating stirring；Then extractant is added, mode is extracted using adverse current second level, extraction phase and solution phase is obtained, then separates two-phase, extraction phase is handled to obtain metallic element and filtrate；Its filtrate can be used as extractant reuse, and it is convenient that the present invention recycles, and craft science is low in cost, and environmental pollution is small.
Description
Technical field
The invention belongs to Technologies of Steel Slag Treatment field more particularly to a kind of Resource comprehensive utilization methods of steel slag.
Background technique
With the fast development of steel and iron industry, the waste residue amount being discharged in steel manufacture process is consequently increased.Steel slag is refining
The byproduct of steel production process, quantity are about the 10 ~ 15% of crude steel yield.According to statistics, China's crude steel yield in 2015 reaches
8.04 hundred million t, about 100,000,000 t of the yield of steel slag or so, and its comprehensive utilization ratio is only 22% or so.Most of steel slag only carries out
Simple heap abandoning processing, not only occupies the soil of large area, causes the waste of available resources, also give atmosphere, river, soil
Bring very serious pollution.Therefore, the comprehensive utilization of steel slag is imperative.The chemical component of steel slag mainly has: CaO, SiO2,
Al2O3, FeO, Fe2O3, MgO, MnO, P2O5 and f-CaO, f-MgO.Not due to different process for producing steel and iron and raw material
Together, there is also certain fluctuations for the ingredient of steel slag.
At this stage Technology of Steel Slag Processing mainly have roller crushing-waste heat have pressure heat it is bored, the direct pool heat of molten steel slag is bored,
Drum process, wind quenching method, hot application method etc..Steel slag product after processing sorting needs to extract slag steel, particle steel and magnetic from steel slag
It selects how remaining tailings after powder is utilized effectively, directly affects slag comprehensive utilization rate, also seriously restrict steel slag
Recyclingization.
The comprehensive utilization of steel slag can not only recycle a large amount of steel scrap, metallic iron, moreover it is possible to further increase iron and steel enterprise's mine
Resource utilization is produced, the production cost of enterprise is reduced, effectively alleviates steel slag stockpiling bring such as land occupation, pollution environment
Equal ecological environment problems, to the sustainable development for developing iron and steel enterprise's circular economy, realizing target for energy-saving and emission-reduction and iron and steel enterprise
Exhibition is all of great significance.
Summary of the invention
To solve the above problems, the invention discloses a kind of Resource comprehensive utilization methods of steel slag, steel slag is passed through into acid
With the dissolution of oxidant, by valuable element therein by the ionic state of Solid State Transformation Cheng Shuizhong, recycling is convenient, craft science, at
This is cheap, and environmental pollution is small.
In order to achieve the above objectives, technical scheme is as follows:
A kind of Resource comprehensive utilization method of steel slag, comprising the following steps:
(1) acid is added in steel slag and oxidant dissolves, heat 20 DEG C -80 DEG C, stir 1-10h, it is rear to be separated by solid-liquid separation；When dissolution, always
Solid-liquid mass ratio be 1:10, acid includes sulfuric acid, hydrochloric acid, nitric acid etc., concentration 4-10mol/L, and oxidant has oxidisability
Substance such as hydrogen peroxide, dual oxide sodium etc., additional amount are the 1%-15% of gross mass, are separated by solid-liquid separation and carry out solid-liquid point using centrifuge
From filter residue arrival cement kiln synergic processing solid waste technical specification enters heavy metal reference value (GB30760- in kiln raw material at this time
2014).
(2) sodium hydroxide is added in step (1) solution and adjusts pH value to 8-13, be separated by solid-liquid separation obtain filtrate and filter again
Slag, filter residue reach cement kiln synergic processing solid waste technical specification and enter heavy metal reference value (GB30760- in kiln raw material
2014), wherein naoh concentration is 0.5-4mol/L, is separated by solid-liquid separation using centrifuge separation.
(3) di (isooctyl) phosphate is added in filtrate obtained in step (2), tributyl phosphate, acetophenone, kerosene is as extraction
Agent is taken, mode, extraction time 5-20mim are extracted using adverse current second level.Extraction phase and solution phase are obtained, two-phase is then separated, is extracted
It takes and is mutually handled to obtain scandium oxide and a part of filtrate.Wherein the additional amount of di (isooctyl) phosphate is extractant gross mass
8%-15%；The additional amount of tributyl phosphate is extractant gross mass 1%-10%, and the additional amount of acetophenone is extractant gross mass
1%-10%, the additional amount of kerosene are the 10%-90% of extractant gross mass.
(4) solution in step (3) is mutually added to extractant again includes di (isooctyl) phosphate, tributyl phosphate and vulcanization
Kerosene and reducing agent are kept for 10-50 DEG C of temperature, and holding pH value to 2-5, extraction time 1-20min obtains extraction phase and solution
Phase, extraction phase obtain vanadic anhydride and filtrate by processing.Wherein the additional amount of di (isooctyl) phosphate is extractant gross mass
5%-30%；The additional amount of tributyl phosphate is extractant gross mass 1%-15%, and the additional amount for vulcanizing kerosene is the total matter of extractant
The 15%-80% of amount, for reducing agent not only to include sodium sulfite etc. with reducing substances, additional amount is extractant gross mass
1%-80%。
(5) solution in step (4) is mutually added to extractant again includes tributyl phosphate, positive certain herbaceous plants with big flowers alcohol, extraction time 2-
30min, obtains extraction phase and solution phase, and extraction phase obtains titanium oxide and filtrate by processing.Wherein tributyl phosphate is extraction
Agent gross mass 1%-45%, titanium oxide tributyl phosphate are extractant gross mass 1%-60%.
(6) filtrate generated in step (3) is returned into the extractant for configuration step (3)；The filter generated in step (4)
Liquid returns to the extractant for configuration step (4)；The filtrate generated in step (5) returns to the extractant for configuration step (5).
The beneficial effects of the present invention are:
(1) valuable metal is by solid state into liquid state.Steel slag is passed through the dissolution of acid and oxidant by the present invention, by valuable member therein
Element is by the ionic state of Solid State Transformation Cheng Shuizhong.
(2) the liquid reuse after treatment after being separated by solid-liquid separation.The solution of separation of solid and liquid after treatment can be used for matching
Solution required for extractant is set, the recycling of water is on the one hand realized, does not generate secondary wastewater, on the other hand reduces extraction
The amount of water for taking agent has been saved and has used water and cost, while can bring environmental benefit and economic benefit.
(3) a variety of existing metals can be isolated, this is not only equivalent to increase resource, but also reduces and break to environment
It is bad, there is highly important social effect.
Specific embodiment
With reference to embodiment, the present invention is furture elucidated, it should be understood that following specific embodiments are only used for
It is bright the present invention rather than limit the scope of the invention.
Embodiment 1
Steel slag in experiment comes from Jiangsu large steel-making plant, is a kind of typical converter slag, and long-term piles up to ring around
Cause very big harm in border.
Experimental procedure and effect such as table 1
1 experimental procedure of table and experimental result unit: mg/L
As it can be seen from table 1 addition of every step with different extractants, extracts required element.
Embodiment 2
Steel slag in experiment comes from Shandong large steel-making plant, is a kind of typical converter slag, existing to ecological environment around
Certain influence.
Experimental procedure and effect such as table 2
2 experimental procedure of table and experimental result unit: mg/L
From table 2 it can be seen that addition of every step with different extractants, extracts required element.
The technical means disclosed in the embodiments of the present invention is not limited only to technological means disclosed in above embodiment, further includes
Technical solution consisting of any combination of the above technical features.
Claims (2)
1. a kind of Resource comprehensive utilization method of steel slag, it is characterised in that: the following steps are included:
(1) acid is added in steel slag and oxidant dissolves, heat 20 DEG C -80 DEG C, stir 1-10h, it is rear to be separated by solid-liquid separation；When dissolution, always
Solid-liquid mass ratio be 1:10, acid include sulfuric acid, hydrochloric acid or nitric acid, concentration 4-10mol/L, oxidant be hydrogen peroxide or dioxygen
Change sodium, additional amount is the 1%-15% of gross mass；
(2) it by step (1) solution addition sodium hydroxide adjusting pH value to 8-13, is separated by solid-liquid separation obtains filtrate and filter residue again,
Middle naoh concentration is 0.5-4mol/L, is separated by solid-liquid separation using centrifuge separation；
(3) di (isooctyl) phosphate is added in filtrate obtained in step (2), tributyl phosphate, acetophenone, kerosene is as extraction
Agent extracts mode, extraction time 5-20mim using adverse current second level；
Extraction phase and solution phase are obtained, two-phase is then separated, extraction phase is handled to obtain scandium oxide and filtrate；Wherein di(2-ethylhexyl)phosphate
The additional amount of different monooctyl ester is the 8%-15% of extractant gross mass；The additional amount of tributyl phosphate is extractant gross mass 1%-10%,
The additional amount of acetophenone is the 1%-10% of extractant gross mass, and the additional amount of kerosene is the 10%-90% of extractant gross mass；
(4) it includes di (isooctyl) phosphate, tributyl phosphate and vulcanization kerosene that the solution in step (3) is mutually added to extractant again
And reducing agent, it is kept for 10-50 DEG C of temperature, keeps pH value to 2-5, extraction time 1-20min, obtain extraction phase and solution phase, extract
It takes and mutually obtains vanadic anhydride and filtrate by processing；Wherein the additional amount of di (isooctyl) phosphate is the 5%- of extractant gross mass
30%；The additional amount of tributyl phosphate is extractant gross mass 1%-15%, and the additional amount for vulcanizing kerosene is extractant gross mass
15%-80%, reducing agent are sodium sulfite, and additional amount is the 1%-80% of extractant gross mass；
(5) solution in step (4) is mutually added to extractant again includes tributyl phosphate, positive certain herbaceous plants with big flowers alcohol, extraction time 2-30min,
Extraction phase and solution phase are obtained, extraction phase obtains titanium oxide and filtrate by processing；Wherein tributyl phosphate is the total matter of extractant
1%-45% is measured, titanium oxide tributyl phosphate is extractant gross mass 1%-60%；
(6) filtrate generated in step (3) is returned into the extractant for configuration step (3)；The filtrate generated in step (4) is returned
To the extractant for being used for configuration step (4)；The filtrate generated in step (5) returns to the extractant for configuration step (5).
2. a kind of Resource comprehensive utilization method of steel slag according to claim 1, it is characterised in that: step (1) solid-liquid
Separation is separated by solid-liquid separation using centrifuge.
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| CN201811650115.XA CN109609775B (en) | 2018-12-31 | 2018-12-31 | Resource comprehensive utilization method of steel slag |
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| CN201811650115.XA CN109609775B (en) | 2018-12-31 | 2018-12-31 | Resource comprehensive utilization method of steel slag |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87101034A (en) * | 1987-05-08 | 1988-11-23 | 上海跃龙化工厂 | From ilmenite, reclaim scandium |
| CN1059762A (en) * | 1991-07-18 | 1992-03-25 | 丁中南 | The novel process of V 2 O 5 production by chloric acid chlorination method |
| CN101182600A (en) * | 2007-06-19 | 2008-05-21 | 昆明理工大学 | Combined technology for separating and extracting vanadium from high calcium and high ferro steel scoria |
| CN101397150A (en) * | 2007-09-25 | 2009-04-01 | 攀钢集团攀枝花钢铁研究院 | Method for extracting vanadium pentoxide from vanadium-containing rotary furnace steel slag |
| CN101914695A (en) * | 2010-08-11 | 2010-12-15 | 云南佰盾环保技术有限公司 | Method for recycling vanadium from vanadium ore containing high silicon and high carbon via wet process |
| CN103952568A (en) * | 2014-05-13 | 2014-07-30 | 李翔 | Method for treating titaniferous blast furnace slag |
| CN106191447A (en) * | 2016-07-11 | 2016-12-07 | 河南理工大学 | The substep purifying technique of scandium, titanium, vanadium in a kind of acid solution |
-
2018
- 2018-12-31 CN CN201811650115.XA patent/CN109609775B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87101034A (en) * | 1987-05-08 | 1988-11-23 | 上海跃龙化工厂 | From ilmenite, reclaim scandium |
| CN1059762A (en) * | 1991-07-18 | 1992-03-25 | 丁中南 | The novel process of V 2 O 5 production by chloric acid chlorination method |
| CN101182600A (en) * | 2007-06-19 | 2008-05-21 | 昆明理工大学 | Combined technology for separating and extracting vanadium from high calcium and high ferro steel scoria |
| CN101397150A (en) * | 2007-09-25 | 2009-04-01 | 攀钢集团攀枝花钢铁研究院 | Method for extracting vanadium pentoxide from vanadium-containing rotary furnace steel slag |
| CN101914695A (en) * | 2010-08-11 | 2010-12-15 | 云南佰盾环保技术有限公司 | Method for recycling vanadium from vanadium ore containing high silicon and high carbon via wet process |
| CN103952568A (en) * | 2014-05-13 | 2014-07-30 | 李翔 | Method for treating titaniferous blast furnace slag |
| CN106191447A (en) * | 2016-07-11 | 2016-12-07 | 河南理工大学 | The substep purifying technique of scandium, titanium, vanadium in a kind of acid solution |
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