CN113247953B - Method for solidifying chromium slag by copper-containing electroplating sludge - Google Patents
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- 239000011651 chromium Substances 0.000 title claims abstract description 106
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 80
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000002893 slag Substances 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 54
- 239000010949 copper Substances 0.000 title claims abstract description 49
- 239000010802 sludge Substances 0.000 title claims abstract description 31
- 238000009713 electroplating Methods 0.000 title claims abstract description 30
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000001784 detoxification Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 238000009837 dry grinding Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 22
- 230000001988 toxicity Effects 0.000 claims description 15
- 231100000419 toxicity Toxicity 0.000 claims description 15
- 239000000654 additive Substances 0.000 abstract description 15
- 230000000996 additive effect Effects 0.000 abstract description 12
- 239000002910 solid waste Substances 0.000 abstract description 11
- 239000002920 hazardous waste Substances 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000010405 reoxidation reaction Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 8
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 8
- 238000000498 ball milling Methods 0.000 description 6
- 239000004568 cement Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 150000001844 chromium Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 229910016510 CuCrO2 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 108020004414 DNA Proteins 0.000 description 1
- 201000004624 Dermatitis Diseases 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 208000025865 Ulcer Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 241001232253 Xanthisma spinulosum Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- -1 chromite Substances 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
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- 229910000514 dolomite Inorganic materials 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 201000005202 lung cancer Diseases 0.000 description 1
- 208000020816 lung neoplasm Diseases 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/86—Chromium
- B01J23/868—Chromium copper and chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G37/00—Compounds of chromium
- C01G37/14—Chromates; Bichromates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Sludge (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the fields of chromium chemical industry and solid waste disposal, and particularly relates to a chromium slag detoxification method. The invention mixes the copper-containing electroplating sludge as an additive with the chromium slag, and the quantity ratio of Cu in the copper-containing electroplating sludge to Cr in the chromium slag is controlled to be n (Cu)/n (Cr) 1-1.2. After the copper-containing electroplating sludge and the chromium slag are mixed, a ball mill is used for dry grinding for 2-3h to mix uniformly, the mixed material is transferred into a high-temperature kiln to be heated for 1-2h, and the temperature is controlled at 1300 ℃ and 1350 ℃. The leaching concentration of hexavalent chromium in the treated sintering product is lower than the limit value of hazardous waste identification standard-toxicity identification (GB5085.3-2007), and the hexavalent chromium meets the regulation. The chromium slag detoxification method provided by the invention has the advantages of low cost, rapid reaction, difficult reoxidation of detoxified chromium slag, and good popularization and application prospects.
Description
Technical Field
The invention relates to the field of solid waste disposal, in particular to a method for solidifying chromium slag by copper-containing electroplating sludge.
Background
The chromium slag is the highly toxic solid waste slag discharged in the production process of chromium salt production plants and chromium iron plants. Because of the poor solubility of the trivalent chromium, in order to extract chromium, when producing chromium salt or metal chromium, the raw materials such as chromite, dolomite and soda ash are uniformly mixed, and then are roasted at the high temperature of 1100-1200 ℃, the trivalent chromium is oxidized into soluble hexavalent chromium in the process and then is leached by water, and the residual solid residue is the chromium slag. Generally, 7-10t of chromium slag is generated for each 1t of metallic chromium, and 3-5t of chromium slag is generated for each 1t of chromium salt. China is an industrial big country, the production demand of chromium salt and metal chromium is very large, so a large amount of chromium slag is brought, the discharged chromium slag reaches 20 ten thousand t every year, and the accumulated chromium slag accumulated at present exceeds 300 ten thousand t.
The toxicity and the solubility of the trivalent chromium after being oxidized into the hexavalent chromium are greatly enhanced, and the trivalent chromium is a main source of the toxicity of the chromium slag. Hexavalent chromium has strong oxidizing properties, is capable of oxidizing biological macromolecules (such as DNA, proteins, enzymes, etc.), and is irritating and corrosive to cells, causing dermatitis and ulceration. Meanwhile, research and research show that hexavalent chromium is a very strong carcinogen, is easy to cause lung cancer after long-term inhalation, and has great harm to organisms. If the chromium slag is randomly stacked without treatment, the chromium-containing dust will fly with the wind and pollute the surrounding environment and water. If the hexavalent chromium is washed by rainwater, the hexavalent chromium can be dissolved and transferred into soil and underground water, and then enters a food chain to cause serious harm to the environment and human health.
The current disposal method of chromium slag comprises solidification, cement kiln cooperative disposal for producing cement, dry detoxification and the like. The curing method is to seal the chromium slag in a cured body (such as cement) to prevent heavy metals such as chromium from transferring to the environment, but the curing method is remarkably compatibilized and the effect of suppressing leaching of heavy metals is not satisfactory. The cement kiln co-processing chromium slag to produce cement is more and more concerned domestically in recent years, and is a method for recycling the chromium slag, but the method has strict regulation on the kiln feeding amount of chromium, and related researches find that the doping of chromium can have adverse effects on the fired cement clinker, and can increase the potential safety hazard of heavy metal entering the environment. The chromium slag detoxification method mainly aims at hexavalent chromium, and reduces the hexavalent chromium into trivalent chromium by a chemical method, a biological method and the like so as to reduce the toxicity of the chromium. Currently, the most used methods are chemical detoxification methods, including: acid reduction, alkaline reduction, high temperature carbon reduction, and the like. The chemical method needs a large amount of chemical agents, so the cost is high, the reaction conditions are harsh, and the use of the additive also brings the risk of secondary pollution. Aiming at the problems of the chromium slag treatment process, the invention provides an economic and efficient chromium slag detoxification method, which has important practical significance for improving and perfecting the detoxification process of chromium slag.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for detoxifying chromium slag at high temperature, and particularly relates to a method for generating CuCrO by high-temperature reaction of copper-containing electroplating sludge and chromium slag2The method achieves the purpose of solidifying chromium ions, and has the advantages of simple process, quick reaction and obvious effect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for solidifying chromium slag by copper-containing electroplating sludge comprises the following steps:
step 1), adding copper-containing electroplating sludge into the chromium slag, wherein the mass ratio of Cu in the copper-containing electroplating sludge to Cr in the chromium slag is controlled to be n (Cu)/n (Cr) 1-1.2;
the component content of the sludge can be detected by XRF and other technical means, and then the two are weighed according to the mass ratio of the substances and mixed correspondingly; the calcium content (CaO) of the industrial electroplating sludge is generally about 10 percent, which can sufficiently meet the use requirement;
step 2), mixing the copper-containing electroplating sludge and the chromium slag, and then carrying out dry grinding by using a ball mill for 2-3 h;
step 3), transferring the ball-milled materials to a high-temperature kiln for calcination treatment, heating for 1-1.5h, controlling the temperature at 1300-2Thereby realizing the detoxification of the chromium slag.
The principle of the invention is as follows: the contents of calcium in the chromium slag and the electroplating sludge are higher, so that the hexavalent chromium is mainly CaCrO in the high-temperature treatment process4The product exists, in general, the chemical detoxification method of the chromium slag mostly adopts acidic substances as additives to stimulate the reduction of hexavalent chromium, but CuO used in the invention can also be combined with CaCrO4Reacting at 1300 ℃ to reduce the reaction product into CuCrO containing trivalent chromium2And compared to common reduction products such as CaCr2O4，CuCrO2Has better stability and acid resistance, and is not easy to be oxidized again. And the detoxification can be completed within 1.5 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) because the copper-containing electroplating sludge is used instead of a commercial chemical as an additive, the waste of the copper-containing electroplating sludge is utilized, the cost for purchasing the chemical additive is saved, and the method is economic and environment-friendly.
(2) CuCrO generated by high-temperature reaction2Wherein Cu and Cr are +1 and +3, respectively, which are chemically stable and not easily reoxidized, and have good acid resistance against HClO4And aqua regia also has good corrosion resistance and is not easy to migrate into the environment.
(3)CuCrO2Is a good hydrogen production photocatalyst, and CuCrO can be used subsequently2The separation and purification of the sintered product also has certain economic benefit.
Drawings
FIG. 1 is a process flow diagram for solidifying chromium slag using copper-containing electroplating sludge.
FIG. 2 is an XRD analysis pattern of the high temperature treated product.
Detailed Description
The invention is further described below with reference to examples, which are intended to illustrate the invention without further limiting it.
Example 1
Preparing simulated chromium slag in a laboratory by using Cr2O3Mixing with CaO, wherein the mass ratio of Cr to Ca is 1:1, ball-milling the materials for 1h by using a ball mill to ensure uniform mixing, and the reagents used in the experiment are all in analytical grade. Transferring the ball-milled materials into a muffle furnace, and calcining for 1h at 1000 ℃ to simulate chromium slag generated in the production of chromium salt by a calcification roasting method. After leaching tests, the concentration of hexavalent chromium in the leachate of the sintered product is 5000mg/L, which is far more than the limit value of 5mg/L specified in hazardous waste identification standard-toxicity identification (GB 5085.3-2007).
The CuO simulated copper-containing electroplating sludge is used as an additive, the CuO and the simulated chromium slag are mixed together and then ball-milled for 1.5h by a ball mill, wherein the mass ratio of the Cu to the Cr in the chromium slag is n (Cu)/n (Cr) is 1:1, the mixed material is transferred to a muffle furnace to be calcined for 1h at 1300 ℃, the temperature rise rate is 5 ℃/min, and the calcining atmosphere is air atmosphere. After the calcined product is cooled, the hexavalent chromium in the calcined product is detected by using a leaching method provided by a solid waste leaching toxicity leaching method, namely a sulfuric acid-nitric acid method (HJ/T299-2007), and the result shows that the concentration of the hexavalent chromium in the leachate is 3.8mg/L, which is lower than a limit value of 5mg/L specified in hazardous waste identification standard, namely toxicity identification (GB5085.3-2007), and meets the safety requirement.
Example 2
Mixing CuO simulated copper-containing electroplating sludge as an additive with simulated chromium slag, and then ball-milling for 1.5h by using a ball mill, wherein the mass ratio of Cu to Cr in the chromium slag is n (Cu)/n (Cr) is 1.1:1, transferring the mixed material to a muffle furnace, calcining for 1h at 1320 ℃, the heating rate is 5 ℃/min, and the calcining atmosphere is air atmosphere. After the calcined product is cooled, the hexavalent chromium in the calcined product is detected by using a leaching method provided by a solid waste leaching toxicity leaching method, namely a sulfuric acid-nitric acid method (HJ/T299-2007), and the result shows that the concentration of the hexavalent chromium in the leachate is 3.6mg/L, which is lower than a limit value of 5mg/L specified in hazardous waste identification standard, namely toxicity identification (GB5085.3-2007), and meets the safety requirement.
Example 3
Mixing CuO simulated copper-containing electroplating sludge as an additive with simulated chromium slag, and then ball-milling for 1.5h by using a ball mill, wherein the mass ratio of Cu to Cr in the chromium slag is n (Cu)/n (Cr) is 1.2:1, transferring the mixed material to a muffle furnace, calcining for 1h at 1350 ℃, and heating at a rate of 5 ℃/min, wherein the calcining atmosphere is an air atmosphere. After the calcined product is cooled, the hexavalent chromium in the calcined product is detected by using a leaching method provided by a solid waste leaching toxicity leaching method, namely a sulfuric acid-nitric acid method (HJ/T299-2007), and the result shows that the concentration of the hexavalent chromium in the leachate is 3.2mg/L, which is lower than a limit value of 5mg/L specified in hazardous waste identification standard, namely toxicity identification (GB5085.3-2007), and meets the safety requirement.
Comparative example 1
Comparative example 1 is different from example 1 in that: the calcination temperature was varied.
Mixing CuO simulated copper-containing electroplating sludge as an additive with simulated chromium slag, and then ball-milling for 1.5h by using a ball mill, wherein the mass ratio of Cu to Cr in the chromium slag is n (Cu)/n (Cr) is 1:1, transferring the mixed material to a muffle furnace, calcining for 1h at 900 ℃, the heating rate is 5 ℃/min, and the calcining atmosphere is air atmosphere. After the calcined product is cooled, the hexavalent chromium in the calcined product is detected by using a leaching method provided by a solid waste leaching toxicity leaching method, namely a sulfuric acid-nitric acid method (HJ/T299-2007), and the result shows that the concentration of the hexavalent chromium in the leachate is far higher than a limit value of 5mg/L specified in hazardous waste identification standard-toxicity identification (GB5085.3-2007), so that the safety requirement is not met.
Comparative example 2
Comparative example 2 differs from example 1 in that: the calcination temperature was varied.
Mixing CuO simulated copper-containing electroplating sludge as an additive with simulated chromium slag, and then ball-milling for 1.5h by using a ball mill, wherein the mass ratio of Cu to Cr in the chromium slag is n (Cu)/n (Cr) is 1:1, transferring the mixed material to a muffle furnace, calcining for 1h at 1200 ℃, the heating rate is 5 ℃/min, and the calcining atmosphere is air atmosphere. After the calcined product is cooled, the hexavalent chromium in the calcined product is detected by using a leaching method provided by a solid waste leaching toxicity leaching method, namely a sulfuric acid-nitric acid method (HJ/T299-2007), and the result shows that the concentration of the hexavalent chromium in the leachate is far higher than a limit value of 5mg/L specified in hazardous waste identification standard-toxicity identification (GB5085.3-2007), so that the safety requirement is not met.
Comparative example 3
Comparative example 3 differs from example 1 in that: the amount ratio of Cu to Cr in the chromium slag was different.
Mixing CuO simulated copper-containing electroplating sludge as an additive with simulated chromium slag, and then ball-milling for 1.5h by using a ball mill, wherein the mass ratio of Cu to Cr in the chromium slag is n (Cu)/n (Cr) is 0.5:1, transferring the mixed material to a muffle furnace, calcining for 1h at 1300 ℃, the heating rate is 5 ℃/min, and the calcining atmosphere is air atmosphere. After the calcined product is cooled, the hexavalent chromium in the calcined product is detected by using a leaching method provided by a solid waste leaching toxicity leaching method sulfuric acid-nitric acid method (HJ/T299-2007), and the result shows that the concentration of the hexavalent chromium in the leachate is higher than a limit value of 5mg/L specified in hazardous waste identification standard-toxicity identification (GB5085.3-2007), so that the safety requirement is not met.
Comparative example 4
Comparative example 4 differs from example 1 in that: the additives are different.
NiO simulation is used as an additive, NiO and simulated chromium slag are mixed together and then ball-milled for 1.5h by a ball mill, wherein the mass ratio of Ni to Cr in the chromium slag is n (Ni)/n (Cr) is 1:1, the mixed material is transferred to a muffle furnace to be calcined for 1h at 1300 ℃, the temperature rise rate is 5 ℃/min, and the calcining atmosphere is air atmosphere. After the calcined product is cooled, the hexavalent chromium in the calcined product is detected by using a leaching method provided by a solid waste leaching toxicity leaching method, namely a sulfuric acid-nitric acid method (HJ/T299-2007), and the result shows that the concentration of the hexavalent chromium in the leachate is higher than a limit value of 5mg/L specified in hazardous waste identification standard-toxicity identification (GB5085.3-2007), so that the safety requirement is not met.
Comparative example 5
Comparative example 5 differs from example 1 in that: the additives are different.
ZnO simulation is used as an additive, ZnO and simulated chromium slag are mixed together and then ball milled for 1.5h by a ball mill, wherein the mass ratio of Zn to Cr in the chromium slag is n (Zn)/n (Cr) is 1:1, the mixed material is transferred to a muffle furnace to be calcined for 1h at 1300 ℃, the temperature rise rate is 5 ℃/min, and the calcination atmosphere is air atmosphere. After the calcined product is cooled, the hexavalent chromium in the calcined product is detected by using a leaching method provided by a solid waste leaching toxicity leaching method, namely a sulfuric acid-nitric acid method (HJ/T299-2007), and the result shows that the concentration of the hexavalent chromium in the leachate is higher than a limit value of 5mg/L specified in hazardous waste identification standard-toxicity identification (GB5085.3-2007), so that the safety requirement is not met.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.
Claims (3)
1. The method for solidifying the chromium slag by using the copper-containing electroplating sludge is characterized by comprising the following steps of:
step (1): adding copper-containing electroplating sludge into the chromium slag, and controlling the mass ratio of Cu in the copper-containing electroplating sludge to Cr in the chromium slag; the amount ratio of Cu in the copper-containing electroplating sludge to Cr in the chromium slag is controlled to be n (Cu)/n (Cr) = 1-1.2: 1;
step (2): after the copper-containing electroplating sludge and the chromium slag are mixed, dry grinding is carried out by a ball mill, so that the two material components are uniformly mixed;
and (3): transferring the ball-milled material to a high-temperature kiln for calcination treatment, controlling the calcination temperature at 1300-1350 ℃, the calcination time at 1-2h, and the calcination atmosphere at air atmosphere to obtain CuCrO after the calcination reaction2Thereby realizing the detoxification of the chromium slag.
2. The method for solidifying the chromium slag by using the copper-containing electroplating sludge as claimed in claim 1, wherein the copper-containing electroplating sludge and the chromium slag are mixed in the step (2) and then are subjected to dry grinding by using a ball mill for 2-3 h.
3. The method for solidifying chromium slag from copper-containing electroplating sludge according to claim 1, wherein the leaching toxicity value of hexavalent chromium in the calcined product is lower than 5 mg/L.
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