CN103122407A - Direct blast furnace innocent treatment method of chromic slag pressure block - Google Patents
Direct blast furnace innocent treatment method of chromic slag pressure block Download PDFInfo
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- CN103122407A CN103122407A CN2013100812955A CN201310081295A CN103122407A CN 103122407 A CN103122407 A CN 103122407A CN 2013100812955 A CN2013100812955 A CN 2013100812955A CN 201310081295 A CN201310081295 A CN 201310081295A CN 103122407 A CN103122407 A CN 103122407A
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Abstract
The invention discloses a direct blast furnace innocent treatment method of a chromic slag pressure block. The method comprises the steps of: adding water and evenly mixing chromic slag, an adhesive and rolling scale, or adding water and evenly mixing the chromic slag, the adhesive, the rolling scale and quick lime, adding water and evenly mixing the chromic slag, the adhesive and coal to prepare into blocks; baking or naturally drying and condensing, adding to a blast furnace with reducing atmosphere to smelt, and restoring hexavalent chromium into trivalent chromium and/or metal chromium. By adopting the treatment method disclosed by the invention, the chromic slag can be thoroughly detoxified and fully utilized; the treatment method has an obvious innocent treatment effect, and obvious social benefit, is free of any secondary pollution, and plays important roles in protection of soil texture, water quality and human health; the phenomenon that the chromium oxide value ascends due to the fact that the chromic slag is sintered at a high temperature firstly in the prior art is avoided; namely chromium is increased to sexavalence from trivalence; and the substance with larger toxicity is manufactured. Therefore, the direct blast furnace innocent treatment method has obvious social benefit and economic benefit.
Description
Technical field
The present invention relates to a kind of chromium slag innocent treatment method, the chromium slag briquetting of especially blast furnace of chromium slag input reducing atmosphere being processed is directly into the blast furnace method for innocent treatment.
Background technology
The solid waste of chromic salts industry---chromium slag, owing to containing water-soluble and the solubility in acid sexavalent chrome, entered environment can cause severe contamination and harm.The chromium metal nontoxicity, Cr3+ is the most stable valence state of chromium, toxicity is little.Large 100 times than Cr3+ of the toxicity of Cr6+, respiratory tract, digestive tube all there are stimulation, suck the dust or the smog that contain the Cr6+ compound, can cause that acute respiratory stimulates, can cause allergic asthma, the respiratory tract injury is also shown as nasoseptal ulcer, perforation and respiratory system cancer.Chromium cpd is caused stimulation and ulcer to the infringement main manifestations of eyes by eyelid and Corneal Contact chromium cpd, and symptom is that conjunctive bulbi is congested, and foreign body sensation is arranged, the shouting pain of shedding tears, and cause visual deterioration, when serious, corneal epithelium peels off.Cr6+ is corrosive, and can form the chromium skin ulcer to the human body skin injury, is commonly called as chrome ulcer, and its sickness rate is higher, easily betides hand, arm and foot.Cr6+ also has the general toxicity effect, can cause the blood dysfunction, the bone nonfunction, and human oral Cr6+ compound lethal dose is about 1.5～1.6g, can stimulate or corrode digestive tube when oral, has the symptoms such as frequent vomiting, bloody stool, dehydration to occur.
Cr6+ also has mutagenesis, by carbonate, vitriol or phosphoric acid salt carrier transport enter cell, enter intracellular Cr6+ near nucleus by the Triptide in cell paste, the material such as ascorbate salt and Citrate trianion is reduced into Cr3+, produce a large amount of active oxygen radicals in the process of reaction, destroy the biomass cells structure: be reduced to Cr3+ as Cr6+ in red corpuscle, glutathione reductase activity is suppressed, oxyphorase sex change and affect oxygen transportation, lip appears, nail is livid purple, expiratory dyspnea, blood pressure drops, the symptom of the renal failures such as anuria, and then be absorbed in shock, stupor.Simultaneously, the trivalent chromium compound that reaction produces and the combination of DNA chain cause the right mispairing of nucleic acid base, and organism is produced mutagenesis and carcinogenic effect.The mutagenesis testing of 9 kinds of Cr6+ shows, it is positive at cell levels more, and the abnormal digital display work of the micronucleus in workman's hemocyte of Occupational Exposure chromic salt is higher than the contrast crowd, and is proportionate with exposure level.
According to statistics, China's chromium salt production amount and consumption all rank first in the world, and 25 of chromium salt production enterprises are arranged, 32.9 ten thousand tons of yearly capacities.The whole nation totally produces more than 200 ten thousand tons of chromic salts, produces more than 600 ten thousand tons of chromium slags, wherein only has an appointment 2,000,000 tons and is disposed, and still has more than 400 ten thousand tons to store up the chromium slag and do not obtain harmlessness disposing.Long-term stacking contains the chromium refuse and can cause severe contamination to soil and groundwater, even can cause significant pollution accident.
Chromium residue detoxifying or method of comprehensive utilization are existing more than 10 kinds both at home and abroad.But there is certain limitation in the chromic wastes disposal technology, and some detoxifcations are thorough (as wet reducing, steamed brick processed and calcium iron powder) not, and has secondary pollution; Some chromium slag consumptions are few, and the disposal cycle is long, and too high being difficult to of expense accepted for chromium salt factory, and progress slow (as cast stone processed, slag wool, stoneware, artificial aggregate---haydite); Some fully utilizes product, as with chromium slag as cement mineralizer, the impact of environment be it be unclear that.In addition, process, cost of disposal is high, is also an important factor of restriction treatment of chromate slag.Therefore, how effectively cheap processing chromium slag is problem anxious to be resolved.
Summary of the invention
The chromic slag harmlessness that the present invention is directed to prior art process detoxifcation not thoroughly, long processing period, processing costs cross high deficiency, provides a kind of chromium slag briquetting of, decrease processing costs cost very thorough without detoxifcation directly into the blast furnace method for innocent treatment.
Technical scheme of the present invention: chromium slag briquetting the steps include: that directly into the blast furnace method for innocent treatment a kind of chromium slag briquetting directly into the blast furnace method for innocent treatment, is characterized in that comprising the steps:
(1) batching, prepare qualified steel rolling iron scale, chromium slag and caking agent, steel rolling iron scale weight proportion 45-70%, and chromium slag weight proportion 20-50%, caking agent weight proportion are 5-7%;
Described binding agent is calcium carbonate or salt of wormwood; Or both mixtures, the mixed weight ratio is calcium carbonate: salt of wormwood=(5-8): (3-6);
(2) be equipped with the water that weight accounts for compound gross weight 10-14%, after itself and caking agent are mixed, add in steel rolling iron scale, chromium slag, mix; Perhaps, first steel rolling iron scale, chromium slag and caking agent are mixed, then add entry and mix;
(3) mixture is pressed into bulk, cold solid after oven dry or seasoning, obtain containing the blocks of solid of chromium slag;
(4) blocks of solid is directly added in the blast furnace of reducing atmosphere and smelt, carry out the blast furnace harmless treatment, hexavalent chrome reduction is trivalent chromium and/or chromium metal.
Further feature is: described water temperature is between 90-100 ℃.
A kind of chromium slag briquetting is characterized in that comprising the steps: directly into the blast furnace method for innocent treatment
(1) batching, prepare qualified steel rolling iron scale, unslaked lime, chromium slag and caking agent,
Steel rolling iron scale weight proportion 35-55%, unslaked lime accounts for 3-9%, and chromium slag weight proportion 35-50%, caking agent weight proportion are 5-7%;
Described binding agent is calcium carbonate or salt of wormwood; Or both mixtures, the mixed weight ratio is (5-8): (3-6);
(2) be equipped with the water that weight accounts for compound gross weight 10-14%, after itself and caking agent are mixed, add in steel rolling iron scale, unslaked lime, chromium slag, mix; Perhaps, first steel rolling iron scale, unslaked lime, chromium slag and caking agent are mixed, then add entry and mix;
(3) mixture is pressed into bulk, cold solid after oven dry or seasoning, obtain containing the blocks of solid of chromium slag;
(4) blocks of solid is directly added in the blast furnace of reducing atmosphere and smelt, carry out the blast furnace harmless treatment, hexavalent chrome reduction is trivalent chromium and/or chromium metal.
A kind of chromium slag briquetting is characterized in that comprising the steps: directly into the blast furnace method for innocent treatment
(1) batching, prepare qualified coal, chromium slag and caking agent, coal weight proportion 10--25%, and chromium slag weight proportion 70--85%, the caking agent weight proportion is 5-7%; It is mixed;
Binding agent is calcium carbonate or salt of wormwood; Or both mixtures, the mixed weight ratio is (5-8): (3-6);
(2) be equipped with the water that weight accounts for compound gross weight 10-14%, after itself and caking agent are mixed, add in coal, chromium slag, mix; Perhaps, first coal, chromium slag and caking agent are mixed, then add entry and mix;
(3) mixture is pressed into bulk, cold solid after oven dry or seasoning, obtain containing the blocks of solid of chromium slag;
(4) blocks of solid is directly added in the blast furnace of reducing atmosphere and smelt, carry out the blast furnace harmless treatment, hexavalent chrome reduction is trivalent chromium and/or chromium metal.
Be further characterized in that: described water temperature is between 90-100 ℃.
Chromium slag briquetting of the present invention with respect to prior art, has following features directly into the blast furnace method for innocent treatment:
1, the present invention is a kind of chromic slag dry method detoxication treatment process, with chromium slag input high temperature with in the iron-smelting blast furnace of reducing atmosphere, furnace high-temperature and carbon monoxide strongly reducing atmosphere are even chromium metal of trivalent chromium with hexavalent chrome reduction in slag, chromium metal fuses into molten iron, other composition fuses into slag, can make the chromium slag thoroughly detoxify and can take full advantage of, the harmless treatment effect is apparent in view.
2, have obvious social benefit: and without any secondary pollution, protection soil property, water quality, HUMAN HEALTH are played an important role.
Still there are more than 400 ten thousand tons to store up the chromium slag and do not obtain harmlessness disposing and calculate if 3 produce 540 yuan of benefits, whole nations by one ton of chromium slag of the every processing of blast furnace, can produce 2.16 hundred million benefits.The expense of also not very paying for protection soil property, water quality, HUMAN HEALTH, these hold the loss of daring not accept especially.
4, avoid in prior art, the first at high temperature sintering of chromium slag being made the phenomenon of chromium oxidation value rising;
The chromium slag sintering of prior art is exactly a malicious process of system, and namely chromium is upgraded to 6 valencys from 3 valency oxidations, manufactures on the contrary the larger material of toxicity; And, the serious secondary pollution that the present invention can avoid sintering process to produce.
Embodiment
Chromium slag briquetting of the present invention is characterized in that comprising the steps: directly into the blast furnace method for innocent treatment
1, batching, prepare qualified steel rolling iron scale, chromium slag and caking agent, steel rolling iron scale weight proportion 45--70%, and chromium slag weight proportion 20--50%, the caking agent weight proportion is 5-7%;
Binding agent is inorganic adhesive, as calcium carbonate or salt of wormwood; Or both mixtures, the mixed weight ratio is (5-8): (3-6); Binding agent do the used time after being pressed into block, play cohesive action, the bondings such as steel rolling iron scale and chromium slag are got up, increase cohesive action power each other;
2, be equipped with the water that weight accounts for compound gross weight 10-14%, water temp can be normal temperature, or the hot water of heating, and water temperature be the best at 90-100 ℃, after itself and caking agent are mixed, adds in steel rolling iron scale, chromium slag, mixes; Perhaps, first steel rolling iron scale, chromium slag and caking agent are mixed, then add entry and mix; The water temperature that adds more can mix in the time of 90-100 ℃, and strengthens bond effect;
3, mixture is pressed into bulk, cold solid after oven dry or seasoning, obtain containing the blocks of solid of chromium slag; The invention provides concrete parameter: 70 ℃-120 ℃ of bake out temperatures, drying time 4 hours, 5 hours is until can satisfy needs of the present invention in 10 hours;
4, blocks of solid is directly added in the blast furnace of reducing atmosphere and smelt, carry out blast furnace harmless treatment (reduction is processed), hexavalent chrome reduction is trivalent chromium and/or chromium metal.
The briquetting of mixture carries out in existing pressure assembly; The briquetting that compacting obtains is common different shape, as shapes such as cylinder, rectangular parallelepiped, square or quadrangulars; As be cylinder, its concrete size can be: briquetting diameter 30mm, long 25-30mm; Briquetting pressure is generally 5000-8000 N.
The second chromium slag briquetting of the present invention is characterized in that comprising the steps: directly into the blast furnace method for innocent treatment
(1) batching, prepare qualified steel rolling iron scale, unslaked lime, chromium slag and caking agent, steel rolling iron scale weight proportion 35-55%, and unslaked lime accounts for 3-9%, and chromium slag weight proportion 35-50%, caking agent weight proportion are 5-7%; It is mixed;
Described binding agent is calcium carbonate or salt of wormwood; Or both mixtures, the mixed weight ratio is (5-8): (3-6);
(2) be equipped with the water that weight accounts for compound gross weight 10-14%, after itself and caking agent are mixed, add in steel rolling iron scale, unslaked lime, chromium slag, mix; Perhaps, first steel rolling iron scale, unslaked lime, chromium slag and caking agent are mixed, then add entry and mix;
(3) mixture is pressed into bulk, cold solid after oven dry or seasoning, obtain containing the blocks of solid of chromium slag;
(4) blocks of solid is directly added in the blast furnace of reducing atmosphere and smelt, carry out the blast furnace harmless treatment, hexavalent chrome reduction is trivalent chromium and/or chromium metal.
The third chromium slag briquetting of the present invention is characterized in that comprising the steps: directly into the blast furnace method for innocent treatment
1, batching, prepare qualified coal, chromium slag and caking agent, coal weight proportion 10--25%, and chromium slag weight proportion 70--85%, the caking agent weight proportion is 5-7%; It is mixed;
Binding agent is inorganic adhesive, as calcium carbonate or salt of wormwood; Or both mixtures, the mixed weight ratio is (5-8): (3-6); Binding agent do the used time after being pressed into block, play cohesive action, the bondings such as coal and chromium slag are got up, increase cohesive action power each other;
As the granularity of batching too greatly or larger, first fragmentation is to obtain suitable granularity;
2, be equipped with the water that weight accounts for compound gross weight (gross weight) 10-14%, water temp can be normal temperature, or the hot water of heating, and water temperature is best at 90-100 ℃; After itself and caking agent are mixed, add in coal, chromium slag, mix; Perhaps, first coal, chromium slag and caking agent are mixed, then add entry and mix;
3, mixture is pressed into bulk, cold solid after oven dry or seasoning, obtain containing the blocks of solid of chromium slag;
4, blocks of solid is directly added in the blast furnace of reducing atmosphere and smelt, carry out the blast furnace harmless treatment, hexavalent chrome reduction is trivalent chromium and/or chromium metal.
Coal in this component has two effects greatly: 1, can increase reductibility, reduce the usage quantity of coke; 2, after coal, can mix with the chromium slag increases its adhesiveproperties, can reduce the caking agent consumption, and improves the intensity of cold and hot, and experiment shows can increase by 30%.
Raw material of the present invention, steel rolling iron scale are a kind of material of the prior art, and in the formula of the first embodiment, its content can be 45%, 48%, 50%, 52%, 55%, 57%, 59%, 60%, 62%, 65%, 68%, 70% etc.; Chromium slag weight content can be 20%, 22%, 25%, 27%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 47%, 50% etc.; The caking agent weight content can be 5%, 5.5%, 5.8%, 6%, 6.2%, 6.5%, 6.7%, 7% etc., can satisfy needs of the present invention.
Raw material of the present invention, in the formula of the second embodiment, steel rolling iron scale 35%, 38%, 40%, 42%, 45%, 48%, 50%, 53%, 55% etc.; Unslaked lime content can be 3%, 4%, 5%, 6%, 7%, 8%, 9% etc.; Chromium slag weight content can be 35%, 38%, 40%, 42%, 46%, 46%, 48%, 50% etc., and the caking agent weight content can be 5%, 5.5%, 5.8%, 6%, 6.2%, 6.5%, 6.7%, 7% etc., can satisfy needs of the present invention.
Raw material of the present invention, in the formula of the third embodiment, coal content can be for 10%,
11%, 13%, 15%, 16%, 17%, 18%, 20%, 21%, 22%, 23%, 25% etc.; Chromium slag weight content can be 70%, 72%, 73%, 75%, 76%, 78%, 80%, 81%, 82%, 83%, 84%, 85% etc., the caking agent weight content can be 5%, 5.5%, 5.8%, 6%, 6.2%, 6.5%, 6.7%, 7% etc., can satisfy needs of the present invention.
Direct briquetting operation of the present invention, A, briquetting technique are simple, deposit to such an extent that intensity more of a specified duration is higher; B, produce without any flue dust dust; At C, high, medium and low temperature, all satisfy blast furnace metallurgical performance and requirement of strength; D, without the sintering circuit of usually seeing, directly briquetting is entered in blast furnace, can reduce sintering adapted charcoal and produce great amount of carbon dioxide and enter atmosphere and form the greenhouse gases effect; The caking agent of E, employing is brought into without any poisonous element in the iron and steel operation; F, meet 10.1 chromium slags dry detoxified of State Environmental Protection Administration's " standard " fully.
Chromium slag phase composition such as following table after the inventive method is processed:
| Title | Liquidus temperature ℃ | Gas phase temperature ℃ |
| Cr | 1578---2672 | 2672---2827 |
| FeO. Cr 2O 3 | Nothing | Nothing |
| MgO.. Cr 2O 3 | Nothing | Nothing |
| Na 2 O. Cr 2O 3 | Nothing | Nothing |
| K 2 CrO 4 | 971---1327 | Nothing |
Illustrate that chromium is rear without gas gas-phase objects in this technical matters process and all the compound reactions of each operation of iron and steel.Namely without any price chromium cpd in each operation of iron and steel with gas phase emission, avoid chromium cpd with gas phase emission such as atmosphere, form to pollute, toxic substance.
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although with reference to preferred embodiment, the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, can modify or be equal to replacement technical scheme of the present invention, and not breaking away from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of claim scope of the present invention.
Claims (6)
1. a chromium slag briquetting directly into the blast furnace method for innocent treatment, is characterized in that comprising the steps:
(1) batching, prepare qualified steel rolling iron scale, chromium slag and caking agent, steel rolling iron scale weight proportion 45-70%, and chromium slag weight proportion 20-50%, caking agent weight proportion are 5-7%;
Described binding agent is calcium carbonate or salt of wormwood; Or both mixtures, the mixed weight ratio is (5-8): (3-6);
(2) be equipped with the water that weight accounts for compound gross weight 10-14%, after itself and caking agent are mixed, add in steel rolling iron scale, chromium slag, mix; Perhaps, first steel rolling iron scale, chromium slag and caking agent are mixed, then add entry and mix;
(3) mixture is pressed into bulk, cold solid after oven dry or seasoning, obtain containing the blocks of solid of chromium slag;
(4) blocks of solid is directly added in the blast furnace of reducing atmosphere and smelt, carry out the blast furnace harmless treatment, hexavalent chrome reduction is trivalent chromium and/or chromium metal.
2. chromium slag briquetting directly into the blast furnace method for innocent treatment, is characterized in that according to claim 1: described water temperature is between 90-100 ℃.
3. a chromium slag briquetting directly into the blast furnace method for innocent treatment, is characterized in that comprising the steps:
(1) batching, prepare qualified steel rolling iron scale, unslaked lime, chromium slag and caking agent, steel rolling iron scale weight proportion 35-55%, and unslaked lime accounts for 3-9%, and chromium slag weight proportion 35-50%, caking agent weight proportion are 5-7%;
Described binding agent is calcium carbonate or salt of wormwood; Or both mixtures, the mixed weight ratio is (5-8): (3-6);
(2) be equipped with the water that weight accounts for compound gross weight 10-14%, after itself and caking agent are mixed, add in steel rolling iron scale, unslaked lime, chromium slag, mix; Perhaps, first steel rolling iron scale, unslaked lime, chromium slag and caking agent are mixed, then add entry and mix;
(3) mixture is pressed into bulk, cold solid after oven dry or seasoning, obtain containing the blocks of solid of chromium slag;
(4) blocks of solid is directly added in the blast furnace of reducing atmosphere and smelt, carry out the blast furnace harmless treatment, hexavalent chrome reduction is trivalent chromium and/or chromium metal.
4. chromium slag briquetting directly into the blast furnace method for innocent treatment, is characterized in that according to claim 3: described water temperature is between 90-100 ℃.
5. a chromium slag briquetting directly into the blast furnace method for innocent treatment, is characterized in that comprising the steps:
(1) batching, prepare qualified coal, chromium slag and caking agent, coal weight proportion 10-25%, and chromium slag weight proportion 70-85%, caking agent weight proportion are 5-7%;
Binding agent is calcium carbonate or salt of wormwood; Or both mixtures, the mixed weight ratio is (5-8): (3-6);
(2) be equipped with the water that weight accounts for compound gross weight 10-14%, after itself and caking agent are mixed, add in coal, chromium slag, mix; Perhaps, first coal, chromium slag and caking agent are mixed, then add entry and mix;
(3) mixture is pressed into bulk, cold solid after oven dry or seasoning, obtain containing the blocks of solid of chromium slag;
(4) blocks of solid is directly added in the blast furnace of reducing atmosphere and smelt, carry out the blast furnace harmless treatment, hexavalent chrome reduction is trivalent chromium and/or chromium metal.
6. chromium slag briquetting directly into the blast furnace method for innocent treatment, is characterized in that according to claim 5: described water temperature is between 90-100 ℃.
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| CN103691727A (en) * | 2013-12-06 | 2014-04-02 | 广东省生态环境与土壤研究所 | Detoxifying method for fixing detoxification through adopting chromium slag dry method |
| CN103952559A (en) * | 2014-04-10 | 2014-07-30 | 中国科学院过程工程研究所 | Method for high-temperature reduction detoxification and recovery utilization of potassium-containing toxic iron slag |
| CN104152206A (en) * | 2014-08-26 | 2014-11-19 | 张瑞瑜 | Recycling treatment method of fly ash, chromium slag and electroplating sludge dangerous waste |
| CN104907532A (en) * | 2015-05-05 | 2015-09-16 | 重庆大学 | Chromium slag harmlessness processing method by taking tailings and chromium slag as sintering fusing agents after steel slag magnetic separation |
| CN111455168A (en) * | 2020-04-22 | 2020-07-28 | 宝武集团环境资源科技有限公司 | Treatment method of chromium-containing wastewater |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103691727A (en) * | 2013-12-06 | 2014-04-02 | 广东省生态环境与土壤研究所 | Detoxifying method for fixing detoxification through adopting chromium slag dry method |
| CN103952559A (en) * | 2014-04-10 | 2014-07-30 | 中国科学院过程工程研究所 | Method for high-temperature reduction detoxification and recovery utilization of potassium-containing toxic iron slag |
| CN103952559B (en) * | 2014-04-10 | 2016-04-06 | 中国科学院过程工程研究所 | A kind of high temperature reduction and detoxication containing the poisonous scum of potassium and recoverying and utilizing method |
| CN104152206A (en) * | 2014-08-26 | 2014-11-19 | 张瑞瑜 | Recycling treatment method of fly ash, chromium slag and electroplating sludge dangerous waste |
| CN104152206B (en) * | 2014-08-26 | 2016-04-06 | 张瑞瑜 | Flying dust, chromium slag, electroplating sludge hazardous waste recycling processing method |
| CN104907532A (en) * | 2015-05-05 | 2015-09-16 | 重庆大学 | Chromium slag harmlessness processing method by taking tailings and chromium slag as sintering fusing agents after steel slag magnetic separation |
| CN104907532B (en) * | 2015-05-05 | 2017-04-26 | 重庆大学 | Chromium slag harmlessness processing method by taking tailings and chromium slag as sintering fusing agents after steel slag magnetic separation |
| CN111455168A (en) * | 2020-04-22 | 2020-07-28 | 宝武集团环境资源科技有限公司 | Treatment method of chromium-containing wastewater |
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| C06 | Publication | ||
| PB01 | Publication | ||
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