CN110904329A - Pretreatment method for detoxification and comprehensive utilization of chromium slag - Google Patents
Pretreatment method for detoxification and comprehensive utilization of chromium slag Download PDFInfo
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- CN110904329A CN110904329A CN201911278409.9A CN201911278409A CN110904329A CN 110904329 A CN110904329 A CN 110904329A CN 201911278409 A CN201911278409 A CN 201911278409A CN 110904329 A CN110904329 A CN 110904329A
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- chromium
- chromium slag
- slag
- detoxification
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- 239000002893 slag Substances 0.000 title claims abstract description 85
- 239000011651 chromium Substances 0.000 title claims abstract description 79
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 78
- 238000001784 detoxification Methods 0.000 title claims description 25
- 238000002203 pretreatment Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 10
- 229910000805 Pig iron Inorganic materials 0.000 claims abstract description 9
- 150000001844 chromium Chemical class 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 4
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims 2
- 241001062472 Stokellia anisodon Species 0.000 claims 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims 1
- 229910001388 sodium aluminate Inorganic materials 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000729 antidote Substances 0.000 abstract 1
- 230000008569 process Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000004615 ingredient Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 235000019580 granularity Nutrition 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- C22B34/30—Obtaining chromium, molybdenum or tungsten
- C22B34/32—Obtaining chromium
-
- 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
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The method comprises the steps of drying, fine grinding and two-stage vortex separation of chromium slag, so that components with different characteristics in the chromium slag are separated, the separated components are a separator close to raw ore and a tail-stage separated sodium-containing slag, and the separated sodium-containing slag is calculated to return to a chromium salt roasting system, and the iron-containing slag is used for smelting chromium-containing pig iron; the resources are fully utilized, part of the chromium is reduced into pig iron, and the residual chromium is reduced into trivalent chromium to form a stable compound. The invention achieves the aim of recycling the antidote resources by the simplest method, achieves the effect of green production and simultaneously obtains better economic benefit.
Description
Technical Field
The invention belongs to the technical field of environmental protection and resource recycling, and relates to a method for chromium slag detoxification and resource recycling.
Background
The chromium slag is a byproduct generated in the production process of the dichromate, has high toxicity due to the hexavalent chromium contained in the chromium slag, is piled in the open air without treatment, causes certain pollution to air and water sources, endangers the health of human bodies and the growth of crops, and endangers the production of grasslands and animal husbandry.
The existing chromium slag method includes two methods of detoxification and utilization, wherein the detoxification method is to change hexavalent chromium with high toxicity into trivalent chromium, and a wet method and a fire method are adopted, wherein the wet method is to add a reducing agent to change Cr in the chromium slag into Cr6+The reduction detoxification method is difficult to be used for treating the chromium slag on a large scale and has high cost; the dry method is to reduce hexavalent chromium into trivalent chromium for detoxification by the reduction action of reducing gas at high temperature; the other pyrogenic process is to make the chromium slag into lump ore, reduce the iron and chromium in the lump ore into metal in an electric furnace or a blast furnace, or form stable compounds by the chromium oxide and other oxides, thereby achieving the aim of detoxification. On the other hand, the chromium slag is partially added into the building material for detoxification treatment; also can be used as a catalyst for comprehensive utilization and treatment. In the aspect of chromium slag treatment, a large number of patents are applied, and recently, there are many patents, namely, patent No. cn201810004238.x (a comprehensive treatment method of chromium slag), patent No. CN201410161228.9 (a wet detoxification method of chromium slag and chromium-containing pollutants), patent No. CN201810087145.8 (a method for treating chromium slag by combining chlorination roasting with hydrothermal mineralization), patent No. CN201910589590.9 (a wet detoxification process method of chromium slag for improving detoxification effect), patent No. CN201910762292.5 (a comprehensive utilization process of chromium-containing wastes), patent No. CN201610035266.9 (a synchronous technology for recycling plastics and making chromium slag harmless by using waste heat of blast furnace slag), and the like.
These patents can achieve better detoxification and resource utilization effects, and from the viewpoint of detoxification and resource reuse, the following resources are not fully utilized.
1. Because of the difference of the raw materials for producing the chromium salt and the difference of the crystallization state and the particle size of the chromite, a part of the chromite can not be completely reacted in the roasting process, a certain amount of raw chromite can be remained in the slag, the utilization rate of the raw materials is reduced, and the production cost is increased;
2. only the toxic materials are removed and added into the building materials to cause the waste of valuable metals of iron and sodium, and the oxide of magnesium can be used as an iron-making additive;
3. the chromium slag agglomeration is used as an iron-making raw material for reducing iron and chromium, and because the melting temperature of a compound containing sodium in the chromium slag agglomeration is low, chromium in a high-melting-point compound containing chromium cannot be reduced to enter slag, so that the waste of resources and energy is caused.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for separating and classifying different components in chromium slag.
The technical scheme of the method is as follows: because the chromite and alkali react, the particle size and the form of raw ore are different, the chromium slag comprises unreacted chromite, reaction products and a separated part rich in sodium oxide. Because of different mineral compositions, different gravities and different difficulty degrees of fine grinding, the granularity and the gravities of the fine-ground particles are different, the dried and fine-ground chromium slag is separated by a vortex separator to obtain fine powder with different main compositions, the fine powder is returned to a chromium salt roasting system and is subjected to reduction detoxification classification utilization, except detoxification, resources are fully utilized, and good economic benefit is generated.
The method specifically comprises the following steps:
(1) naturally drying the chromium slag in a stockpiling area or drying the chromium slag by a crisp-dry device, removing the water content of less than 2 percent, and drying the chromium slag;
(2) finely grinding the dried chromium slag for 1-3 hours;
(3) separating the finely ground chromium slag by a secondary vortex separator to obtain three different fine powders;
(4) and analyzing the fine powder obtained by the first-stage separation and the last fine powder, returning the fine powder and the last fine powder to a roasting system, and carrying out reduction iron making by independently agglomerating the fine powder separated by the second stage or agglomerating a part of the fine powder serving as a raw material to produce chromium-containing pig iron.
The method has the following advantages
1. The chromium slag with different granularities has different compositions by utilizing different reaction degrees of chromite in the roasting process and different levigating degrees in the fine grinding process;
2. effectively separating chromium slag with different compositions, and respectively utilizing the chromium slag according to the characteristics;
3. the primary separation mainly obtains the original chromite, and the secondary separation mainly obtains the residual iron oxide and other compounds after roasting and leaching; the last fine powder is mainly a sodium-containing compound;
4. the fine powder obtained by the first-stage separation and the last separation is used as a raw material and returns to a chromium salt roasting production system, and the fine powder obtained by the second-stage separation is directly ironed after agglomeration or is used as a part of ironmaking agglomeration raw materials;
5. reasonably realizes resource reutilization and detoxification, and has good social and economic benefits.
Drawings
FIG. 1 is a process flow diagram of chromium slag separation and detoxification.
The concrete implementation example is as follows
(1) Naturally drying the chromium slag in a stockpiling area or drying the chromium slag by drying equipment, and removing water by less than 2 percent to dry the chromium slag;
(2) finely grinding the dried chromium slag for 1-3 hours;
(3) separating the finely ground chromium slag by a secondary vortex separator to obtain three different fine powders, wherein the chromite of the chromium slag after classification accounts for 20-30%, the oxide mainly containing iron after reaction decomposition, aluminate, magnesium oxide and the like account for 40-50%, and the sodium oxide mainly accounts for 20-30%;
(4) the fine powder obtained by the first stage separation and the fine powder obtained at the end are analyzed and returned to a roasting system, and the fine powder obtained by the second stage separation is agglomerated and used for a blast furnace (electric furnace smelting) or used as a part of ironmaking raw materials to produce chromium-containing pig iron.
Example 1
(1) Drying the chromium slag, and removing the water content of less than 2 percent;
(2) finely grinding the dried chromium slag for 1 h;
(3) separating the finely ground slag by using a secondary separator to obtain 30% of primary slag, 45% of secondary slag and 25% of tailings;
(4) the obtained first-stage slag is used for replacing chromite, tailings are used for replacing alkali and return to a chromium salt roasting system, and the obtained second-stage slag is used for smelting pig iron or is used as a part of iron making ingredients.
Example 2
(1) Drying the chromium slag, and removing the water content of less than 2 percent;
(2) finely grinding the dried chromium slag for 2 hours;
(3) separating the finely ground slag by using a secondary separator to obtain 20% of primary slag, 50% of secondary slag and 30% of tailings;
(4) the obtained first-stage slag is used for replacing chromite, tailings are used for replacing alkali to return to a chromium salt roasting system, and the obtained second-stage slag is used for smelting pig iron or is used as a part of ironmaking ingredients.
Example 3:
(1) drying the chromium slag, and removing the water content of less than 2 percent;
(2) finely grinding the dried chromium slag for 3 hours;
(3) separating the finely ground slag by using a secondary separator to obtain 25% of primary slag, 55% of secondary slag and 20% of tailings;
(4) the obtained first-stage slag is used for replacing chromite, tailings are used for replacing alkali to return to a chromium salt roasting system, and the obtained second-stage slag is used for smelting pig iron or is used as a part of ironmaking ingredients.
The content of hexavalent chromium leached from the treated ironmaking slag is lower than the requirement of the national standard (HJ/T301-2007) chromium slag pollution treatment environmental protection technical specification, meets the requirement of GB 18599-.
Claims (7)
1. A pretreatment method for detoxification and comprehensive utilization of chromium slag is characterized by comprising the following steps:
(1) naturally drying or artificially drying the chromium slag to remove water;
(2) finely grinding the dried chromium slag;
(3) classifying the finely ground chromium slag by using a vortex separator;
(4) returning the graded chromium slag to a roasting system or smelting pig iron respectively.
2. The chromium slag detoxification comprehensive utilization pretreatment method according to claim 1, which is characterized in that: the chromium slag in the step (1) is chromium slag which is produced in the production process of chromium salt and mainly comprises chromite, iron oxide, sodium silicate, aluminate and magnesium oxide.
3. The chromium slag detoxification comprehensive utilization pretreatment method according to claim 1, which is characterized in that: naturally drying or artificially drying the chromium slag until the water content is less than 2 percent.
4. The chromium slag detoxification comprehensive utilization pretreatment method according to claim 1, which is characterized in that: and finely grinding the dried chromium slag for 1-3 h.
5. The chromium slag detoxification comprehensive utilization pretreatment method according to claim 1, which is characterized in that: and dividing the finely ground chromium slag into three stages by using a vortex separator.
6. The chromium slag detoxification comprehensive utilization pretreatment method according to claim 1, which is characterized in that: the chromium slag chromite after classification accounts for 20-30%, the oxide and aluminate containing iron and magnesium oxide after reaction decomposition accounts for 40-50%, and the sodium oxide is used as a main component and the sodium silicate accounts for 20-30%.
7. The comprehensive treatment method of chromium slag according to claim 1, characterized in that: calculating and returning chromite and powder mainly containing sodium oxide in the chromium slag obtained by grading to a chromium salt production system; the powder mainly containing iron oxide obtained by classification is agglomerated or is mixed with other iron ores to agglomerate to smelt chromium-containing pig iron for detoxification.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911278409.9A CN110904329A (en) | 2019-12-15 | 2019-12-15 | Pretreatment method for detoxification and comprehensive utilization of chromium slag |
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| CN201911278409.9A CN110904329A (en) | 2019-12-15 | 2019-12-15 | Pretreatment method for detoxification and comprehensive utilization of chromium slag |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064317A (en) * | 1991-02-12 | 1992-09-09 | 夏在舟 | Administer the absorption method of dissociating of chromium slag |
| CN101347663A (en) * | 2007-07-19 | 2009-01-21 | 东北大学 | Comprehensive utilization method of three kinds of waste slags containing chromium |
| CN201493302U (en) * | 2009-10-16 | 2010-06-02 | 殷大众 | Cyclone furnace fly ash remelting method chromium residue directly into furnace detoxification system |
| CN106733068A (en) * | 2016-10-19 | 2017-05-31 | 中信重工机械股份有限公司 | The recovery method of nickel chromium triangle metal in a kind of metallurgical tailings |
| CN107226703A (en) * | 2017-06-07 | 2017-10-03 | 西南科技大学 | A kind of preparation method of calcium-free roasting chromium slag compact refractory material |
| CN108213043A (en) * | 2018-01-03 | 2018-06-29 | 华南理工大学 | A kind of integrated conduct method of chromium slag |
| CN109780546A (en) * | 2018-12-29 | 2019-05-21 | 义马环保电力有限公司 | Improve the chromium residue detoxifying system and method that chromium slag mixes ratio |
-
2019
- 2019-12-15 CN CN201911278409.9A patent/CN110904329A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064317A (en) * | 1991-02-12 | 1992-09-09 | 夏在舟 | Administer the absorption method of dissociating of chromium slag |
| CN101347663A (en) * | 2007-07-19 | 2009-01-21 | 东北大学 | Comprehensive utilization method of three kinds of waste slags containing chromium |
| CN201493302U (en) * | 2009-10-16 | 2010-06-02 | 殷大众 | Cyclone furnace fly ash remelting method chromium residue directly into furnace detoxification system |
| CN106733068A (en) * | 2016-10-19 | 2017-05-31 | 中信重工机械股份有限公司 | The recovery method of nickel chromium triangle metal in a kind of metallurgical tailings |
| CN107226703A (en) * | 2017-06-07 | 2017-10-03 | 西南科技大学 | A kind of preparation method of calcium-free roasting chromium slag compact refractory material |
| CN108213043A (en) * | 2018-01-03 | 2018-06-29 | 华南理工大学 | A kind of integrated conduct method of chromium slag |
| CN109780546A (en) * | 2018-12-29 | 2019-05-21 | 义马环保电力有限公司 | Improve the chromium residue detoxifying system and method that chromium slag mixes ratio |
Non-Patent Citations (2)
| Title |
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Application publication date: 20200324 |