WO2023004925A1 - 含铬污泥与含铬废渣协同利用富集、回收铬资源的方法 - Google Patents
含铬污泥与含铬废渣协同利用富集、回收铬资源的方法 Download PDFInfo
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- 239000011651 chromium Substances 0.000 title claims abstract description 248
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 213
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 211
- 238000000034 method Methods 0.000 title claims abstract description 67
- 239000002699 waste material Substances 0.000 title claims abstract description 61
- 239000010802 sludge Substances 0.000 title claims abstract description 57
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000011084 recovery Methods 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 12
- 239000011029 spinel Substances 0.000 claims abstract description 12
- 239000012141 concentrate Substances 0.000 claims abstract description 11
- 238000007885 magnetic separation Methods 0.000 claims abstract description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 18
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000008188 pellet Substances 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 239000006148 magnetic separator Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000010349 pulsation Effects 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 8
- 239000002920 hazardous waste Substances 0.000 abstract description 8
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910015189 FeOx Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 10
- 238000010586 diagram Methods 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- 239000002910 solid waste Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229910000604 Ferrochrome Inorganic materials 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 231100001261 hazardous Toxicity 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
- 239000011707 mineral Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910015372 FeAl Inorganic materials 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910001392 phosphorus oxide Inorganic materials 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052815 sulfur oxide Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
-
- 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
- C22B7/04—Working-up slag
-
- 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
Definitions
- the invention belongs to the field of resource utilization of chromium in hazardous/solid waste, and more specifically, mainly relates to a method for synergistic utilization of chromium-containing sludge and chromium-containing waste residue in iron and steel plants and enrichment of chromium resources therein.
- Hazardous/solid waste containing chromium usually contains high content of Fe, Cr, V and other elements, which is not only a toxic hazardous waste and environmental pollutant, but also an important strategic resource. Therefore, it will have significant environmental, economic and social benefits to "reduce, harmless, and resourceful" it.
- the main methods used are hydrometallurgy (acid leaching, alkali leaching, water leaching and salt leaching), pyrometallurgy (high temperature smelting and roasting-leaching) method) and bio-extraction technology.
- the Chinese patent "A Method for Detoxification and Chromium Recovery of Chromium-containing Waste Residue" (CN108220604B) proposes a method for resource utilization of chromium in chromium-containing waste residue: the waste residue is oxidized and roasted, followed by ultrasonic treatment and water Thermal reaction and other means are used to separate the solid residue from the chromium-containing solution.
- the Chinese patent "a method for recovering hexavalent chromium resources from chromium slag" (CN102191390A) adopts hydrochloric acid and sulfuric acid to leach hexavalent chromium from chromium slag at normal temperature, but the chromium recovery rate is only about 60-80%, which can neither Efficiently recovering chromium resources, the large amount of acid produced also brings serious hidden dangers to the environment.
- Most of the methods for recovering chromium from traditional chromium-containing resources have problems such as high cost, complicated process flow, cumbersome operation and easy generation of secondary pollutants, and there is a large room for improvement in the process.
- the methods for recovering chromium in chromium-containing sludge and chromium-containing waste residue mainly include: reduction precipitation method, ion exchange method, extraction separation method, etc., but these methods all have the following disadvantages: reduction precipitation The method consumes a lot of acid and the product purity is low, so it is not a suitable method from the perspective of environment and cost; the ion exchange method has a long process cycle and is not suitable for large-scale production; the extraction and separation method is only suitable for some specific The ion separation effect is better, but the effect is greatly affected by impurity ions. These factors limit the industrial application of these methods to a certain extent.
- the invention provides a method for jointly enriching chromium by using chromium-containing sludge and chromium-containing waste residue.
- the chromium-containing sludge and chromium-containing waste residue are used in combination.
- the present invention provides a high-temperature chemical method to realize the pre-enrichment of chromium in chromium-containing sludge and chromium-containing waste residue, The dispersion degree of chromium is reduced, and a chromium-rich phase with high chromium content and suitable for subsequent separation is obtained.
- the purpose of the present invention is to solve the existing problems of resource utilization of chromium-containing sludge and chromium-containing waste residue, such as complex process flow, large consumption of chemicals, high treatment cost, easy to produce secondary pollution, and incapable of large-scale production, etc., to provide a A method for synergistically utilizing chromium-containing sludge and chromium-containing waste residue to enrich and recover chromium resources can efficiently, environmentally friendly and low-cost co-process chromium-containing sludge and chromium-containing waste residue to enrich and recover chromium resources.
- the technical idea of the method for synergistic utilization of chromium-containing sludge and chromium-containing waste residue to enrich and recycle chromium resources in the present invention is: to utilize the compositional characteristics and advantages of chromium-containing sludge and chromium-containing waste residue, and through chromium-containing sludge and chromium-containing waste residue.
- the combined use of chromium supplemented by adjusting the roasting atmosphere and roasting system, realizes the high-efficiency enrichment of chromium in chromium-containing sludge and chromium-containing waste residue, and the obtained chromium-containing enriched phase-chromium iron spinel Fe 3-x Cr x O 4
- the chromium enrichment degree is high, and the physical and chemical properties of the chromium-rich phase and other mineral phases in the material are quite different.
- the separation and recovery of the chromium-rich phase can be realized in the later stage through a simple beneficiation method, which
- the method for enriching and reclaiming chromium resources by synergistic utilization of chromium-containing sludge and chromium-containing waste residue of the present invention adopts the following processes and steps:
- Raw material treatment prepare the chromium-containing sludge containing CaO, MgO, SiO 2 , Al 2 O 3 , FeO x and the chromium-containing waste residue containing CaO, MgO, SiO 2 , Al 2 O 3 , FeO x into alkalinity ((CaO%+MgO%)/(SiO 2 %+Al 2 O 3 %)) in the range of 0.6 to 1.5, the FeO x content ⁇ 15.0% of the mixture is added to the ball mill for fine grinding and mixing to prepare the mixture , the Cr 2 O 3 content in the chromium-containing sludge is ⁇ 8.0%, and the Cr 2 O 3 content in the chromium-containing waste residue is ⁇ 3.0%.
- the mass percentages of the main components in the chromium-containing sludge are: SiO 2 4.0-8.0%, Al 2 O 3 2.0-8.0%, FeO x 3.0-8.0%, CaO 10.0-20.0%, Cr 2 O 3 10.0-15.0%, the rest are P 2 O 5 , MnO, MgO and other components; the mass percentages of the main components in the chromium-containing waste residue are: SiO 2 15.0-20.0%, Al 2 O 3 3.0 ⁇ 8.0%, FeO x 20.0 ⁇ 45.0%, CaO2.0 ⁇ 5.0%, Cr 2 O 3 3.0 ⁇ 10.0%, MgO1.0 ⁇ 5.0%, and the rest are MnO, TiO 2 , V 2 O 3 and other components.
- Reduction roasting Under a reducing reaction atmosphere, carry out reduction roasting on the mixture in step 1) at a temperature range of 1100-1500°C, so that the chromium in the chromium-containing sludge and chromium-containing waste residue can be enriched by chemical reaction. Chromium-containing enriched phase - chromium-iron spinel Fe 3-x Cr x O 4 phase; reduction roasting is optimal at 1350-1500°C.
- step 3 Magnetic separation and recovery: the roasted product in step 2) is crushed and ground, and the grinding particle size is controlled at -0.074mm particle size content ⁇ 80.0%. The spar is separated to obtain chrome concentrate with Cr 2 O 3 content ⁇ 20.0% and Cr 2 O 3 recovery rate ⁇ 85.0%.
- pellets with a diameter of 4.0-10.0 mm are prepared from the mixture prepared in step 1), and the pellets are fed into step 2) for reduction roasting.
- the diameter of the pellets is preferably between 4 and 8mm.
- carbon powder as the reducing agent; of course, hydrogen reduction can also be used to reduce the emission of carbon dioxide.
- the magnetic separation process in step 3) adopts a vertical ring electromagnetic pulsation high-gradient magnetic separator for separation, and the magnetic induction intensity is 0.4-1.0 Tesla.
- the specific values of grinding fineness and magnetic induction intensity can be determined through experiments. It is necessary to ensure that the Cr 2 O 3 grade in the chrome concentrate is ⁇ 20.0%, and the recovery rate of Cr 2 O 3 is ⁇ 85.0%.
- the method of the present invention for synergistic utilization of chromium-containing sludge and chromium-containing waste residue to enrich and recover chromium resources has the following advantages:
- the method for synergistic utilization of chromium-containing sludge and chromium-containing waste slag to enrich and recover chromium resources is to combine these two different chromium-containing hazardous wastes, and to analyze the composition and roasting of the mixed raw materials
- the system is effectively controlled, and then the chromium enrichment of chromium-containing waste residue and chromium-containing sludge is realized at the same time.
- the enrichment degree of chromium is as high as more than 90%, and the physical properties of the obtained chromium-enriched phase are quite different from those of other mineral phases, which greatly reduces the difficulty of its separation and recovery in the later stage.
- the Cr 2 O 3 grade in the chromium concentrate is ⁇ 20.0%, and the Cr 2 O 3 recovery rate is ⁇ 85.0%.
- the enrichment efficiency of chromium in the present invention is higher, and the whole process does not produce harmful substances to the environment, creating conditions for efficient and green recovery of chromium, which is in line with the actual industry Production needs, has a good prospect for application and promotion.
- the chromium-containing enriched phase obtained by the method of the present invention is not easy to form a solid solution with sulfur oxides and phosphorus oxides in the slag, which also creates conditions for the subsequent acquisition of high-purity and high-performance chromium products.
- the chromium in the chromium-containing waste residue and chromium-containing sludge can be enriched into the iron-chromium spinel phase.
- the tailings obtained by separating the chromium-rich phase can be used as raw materials for glass-ceramics and cementitious materials, which not only reduces the secondary pollution of waste residues, but also realizes its resource utilization.
- Fig. 1 is the principle process flow diagram of the method for enriching and reclaiming chromium resources by synergistic utilization of chromium-containing sludge and chromium-containing waste residue of the present invention
- Figure 2 is the ⁇ r G ⁇ -T relationship diagram of the reaction between FeO(s) and SiO 2 (s), Al 2 O 3 , Cr 2 O 3 in the temperature range of 700-1600K;
- Fig. 3 is the comparative figure of XRD result when calcination temperature is respectively 1373K and 1473K;
- Fig. 4 is a scanning electron microscope analysis result diagram of the sample after firing in a reducing firing atmosphere at 1473K.
- the main components of the mixture include SiO 2 , Al 2 O 3 , Cr 2 O 3 , and also contain a small amount of MgO.
- Table 1 shows the numerical value of the standard Gibbs free energy of FeO reacting with SiO 2 , Al 2 O 3 and Cr 2 O 3 to form FeSiO 3 , FeAl 2 O 4 and FeCr 2 O 4 at different temperatures.
- Figure 1 shows the comparative relationship diagram of ⁇ r G ⁇ -T for reactions (1) to (3) within the temperature range of 700-1600K.
- the main components of the chromium-containing waste residue selected in this embodiment are shown in Table 2. It can be known from Table 2 that the content of Cr 2 O 3 in the waste residue can reach 9.12%. In addition, the waste residue also contains a certain amount of metal oxides such as Mn and Ti. Table 3 shows the main components of chromium-containing sludge obtained from an electroplating factory. It can be seen from Table 2 that the content of Cr 2 O 3 in the chromium-containing sludge is relatively high, which can reach 14.18%, and the content of Fe 2 O 3 is Significantly low.
- Chromium resource method is implemented using the following steps:
- Raw material treatment After crushing chromium-containing sludge and chromium-containing waste slag by ball milling, they are mixed according to a certain proportion to make the alkalinity ((CaO%+MgO%)/(SiO 2 %+Al 2 O 3 %)) between 0.6 and 1.5 range, the mixture with FeO x content ⁇ 15.0%. It should be noted that in order to provide a reducing roasting atmosphere, it is necessary to add an appropriate amount of carbon powder to the mixture as a reducing agent.
- Reduction roasting the obtained mixture is made into pellets, and the diameter of the pellet sample is controlled at 4-8 mm. After the sample is dried, it is placed under reducing roasting conditions for reduction roasting, so that the chromium-containing sludge 1.
- the chromium in the chromium-containing waste residue is enriched into the chromium-containing enrichment phase—chromium-iron spinel Fe 3-x Cr x O 4 phase through chemical reaction; the roasting temperature is selected as 1373K and 1473K, and the roasting time is selected as 3h, and at the same time Blow in an appropriate amount of argon to exhaust the air in the furnace, so that the reduction reaction can be fully carried out.
- the temperature of the sample is lowered at a rate of 5-10K/min.
- the chromium in the chromium-containing sludge and chromium-containing waste residue can enter the pre-designed chromium-containing enrichment phase.
- the chromium-rich phase obtained by roasting does not contain impurity elements such as P, Na and S, which is beneficial to the leaching and extraction of chromium in the subsequent process or the separation and separation of other processes.
- the roasted product in step 2) is crushed and ground, and the grinding particle size is controlled at -0.074mm particle size content ⁇ 80.0%.
- the spar is separated to obtain chrome concentrate with Cr 2 O 3 content ⁇ 20.0% and Cr 2 O 3 recovery rate ⁇ 85.0%.
- the magnetic separation process uses a vertical ring electromagnetic pulsation high-gradient magnetic separator for separation, and the magnetic induction intensity is between 0.4 and 1.0 Tesla.
- the present invention also adopts spiral chute to carry out gravity separation to the product after ore grinding, has obtained the chrome concentrate of Cr2O3 content 21.5%, Cr2O3 recovery rate 86.0%, adopts Nielsen ( knelson ) to the product after ore grinding
- the ore concentrator carried out re-election to obtain chrome concentrate with a Cr 2 O 3 content of 22.3% and a Cr 2 O 3 recovery rate of 86.5%.
- the product after grinding was re-selected by a spiral chute-Nelson concentrator, A chrome concentrate with a Cr 2 O 3 content of 24.8% and a Cr 2 O 3 recovery rate of 86.2% was obtained, and unexpected technical effects were achieved.
- fly ash and other ingredients can be added to prepare building materials such as curing bricks, and other building materials, such as ceramsite, can also be prepared to achieve no solid waste discharge.
Abstract
一种含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，将含铬污泥和含铬废渣进行细磨、混合制备出混合料，混合料碱度((CaO%+MgO%)/(SiO 2%+Al2O3%))在0.6～1.5范围、FeOx含量≥15.0%。对混合料进行还原焙烧，焙烧温度控制在1100～1500℃范围。对焙烧产物碎磨处理后，采用强磁选工艺将铁铬尖晶石分离出来，获得Cr2O3含量≥20.0%、Cr2O3回收率≥85.0％的铬精矿。将含铬污泥与含铬废渣这两种含铬危废资源进行联用，同时富集这两种资源中的铬，所获得的含铬富集相中铬的品位高，且利用后续分离，具有效率高、污染小且适用范围广等特点，适于应用在含铬资源中铬富集与分离的技术领域。
Description
本发明属于危/固废中铬的资源化利用领域，更具体地说，主要涉及一种将钢铁厂含铬污泥与含铬废渣协同利用，并富集其中铬资源的方法。
我国含铬危/固废的排放量巨大。据测算，年排放量可以达到150万吨左右，累积堆存量更是达到了千万吨。含铬危/固废中通常含有较高含量的Fe、Cr、V等元素，不仅是具有毒性的危险废弃物与环境污染物，更是重要的战略资源。因此，对其进行“减量化、无害化、资源化”处理，将具有重大的环境、经济和社会效益。
目前对于含铬危/固废中重金属元素铬的分离回收，主要采用的方法主要有湿法冶金(酸浸、碱浸、水浸及盐浸)、火法冶金(高温熔炼法及焙烧-浸出法)以及生物提取技术等。中国专利“一种含铬废渣的脱毒及铬回收的方法”(CN108220604B)提出了一种对含铬废渣中的铬进行资源化利用的方法：对废渣进行氧化焙烧，随后通过超声处理及水热反应等手段，将固体残渣与含铬溶液进行分离，在进行铬的分离回收时，还需要添加HCl、NaHCO
3及Na
2CO
3等作为表界面调控剂以促进反应的进行。该方法工艺流程较为繁琐，且药剂消耗量较大，并对环境造成新的二次污染，因此没有在工业上得到广泛地应用。中国专利“一种从铬渣中回收六价铬资源的方法”(CN102191390A)在常温下采用盐酸及硫酸浸出铬渣的六价铬，但铬回收率仅有60～80％左右，这既不能高效地回收铬资源，产生的大量酸液也给环境带来了严重的隐患。传统含铬资源中铬回收的方法大多存在着成本高、工艺流程复杂、操作繁琐及易产生二次污染物等问题，在工艺上存在着较大的改进空间。鉴于上述缺点，近年 来提出的含铬污泥与含铬废渣中铬回收的方法主要有：还原沉淀法、离子交换法、萃取分离法等，但这些方法都存在着以下几种弊端：还原沉淀法耗酸量较大，且得到的产品纯度低，从环境及成本的角度，都不是较为适宜的方法；离子交换法工艺周期较长，不适合大规模生产；萃取分离法只对某些特定的离子分离效果较好，但效果受杂质离子影响较大。这些因素都在一定程度上限制了这些方法在工业上的推广应用。
综上所述，对于含铬危/固废中铬的富集、分离及回收，从经济、环保及工艺流程简化的角度，目前并没有较为切实可行的方法，含铬危/固废的高效、绿色循环利用仍是一个亟待解决的问题。本发明提供了一种含铬污泥与含铬废渣联合富集铬的方法，将含铬污泥与含铬废渣进行联用。由于含铬污泥与含铬废渣中的铬难以通过常规的物理选矿方法进行富集，本发明提供了一种高温化学的方法，实现含铬污泥与含铬废渣中铬的预富集，减小了铬的分散程度，获得了铬含量高，且适宜后续分离的铬富集相。
发明内容
本发明的目的就是针对现有含铬污泥、含铬废渣资源化利用存在的工艺流程复杂、药剂消耗量大、处理成本高、易产生二次污染、无法大规模生产等问题，而提供一种含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，能够高效、环保且低成本低地对含铬污泥与含铬废渣进行协同处置并富集、回收铬资源。
本发明含铬污泥与含铬废渣协同利用富集、回收铬资源的方法的技术构思是：利用含铬污泥与含铬废渣自身的成分特点与优势，通过含铬污泥与含铬废渣的联用，辅以调整焙烧气氛及焙烧制度，实现对含铬污泥及含铬废渣中铬的高效富，得到的含铬富集相—铬铁尖晶石Fe
3-xCr
xO
4相中，铬富集程度高，且富铬相与物料中的其他 矿相物理化学性质差别较大，后期通过简单的选矿方式即可实现对其的分离回收，降低了选冶成本的同时，也减轻了对环境的污染。
为实现本发明的上述目的，本发明含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，采用以下工艺、步骤：
1)原料处理：将含有CaO、MgO、SiO
2、Al
2O
3、FeO
x的含铬污泥和含有CaO、MgO、SiO
2、Al
2O
3、FeO
x的含铬废渣配制成碱度((CaO％+MgO％)/(SiO
2％+Al
2O
3％))在0.6～1.5范围、FeO
x含量≥15.0％的混合料并加入到球磨机中细磨、混合，制备出混合料，所述的含铬污泥中Cr
2O
3含量≥8.0％，所述的含铬废渣中Cr
2O
3含量≥3.0％。
所述的含铬污泥中主要组份的质量百分含量为：SiO
24.0～8.0％、Al
2O
32.0～8.0％、FeO
x 3.0～8.0％、CaO 10.0～20.0％、Cr
2O
310.0～15.0％，其余为P
2O
5、MnO、MgO及其它组份；所述的含铬废渣中主要组份的质量百分含量为：SiO
215.0～20.0％、Al
2O
33.0～8.0％、FeO
x20.0～45.0％、CaO2.0～5.0％、Cr
2O
33.0～10.0％、MgO1.0～5.0％，其余为MnO、TiO
2、V
2O
3及其它组份。
在此步骤，如果混合料中的FeO
x含量低于15％时，可以向混合料中添加适量的Fe
2O
3粉，以充当铬的富集载体。
2)还原焙烧：在还原性的反应气氛下，对步骤1)之混合料在1100～1500℃温度范围内进行还原焙烧，使含铬污泥、含铬废渣中的铬通过化学反应富集到含铬富集相—铬铁尖晶石Fe
3-xCr
xO
4相中；还原焙烧在1350～1500℃范围为优。
3)磁选分离、回收：对步骤2)之焙烧产物进行碎磨处理，磨矿粒度控制在－0.074mm粒级含量≥80.0％，对磨矿后的产物采用强磁选工艺将铁铬尖晶石离出来，获得Cr
2O
3含量≥20.0％、Cr
2O
3回收率≥85.0％的铬精矿。
进一步地，将步骤1)中制备出的混合料，再制备出直径在4.0～10.0mm的球团，球团给入步骤2)进行还原焙烧。球团直径在4～8mm之间为佳。
进一步地，采用碳粉为还原剂为宜；当然也可以采用氢还原，以减少二氧化碳的排放。
更进一步地，步骤3)中的磁选工艺采用立环电磁脉动高梯度磁选机进行分选，磁感应强度为0.4～1.0特斯拉。磨矿细度、磁感应强度的具体值可以通过试验确定，既要保证铬精矿中Cr
2O
3品位≥20.0％，又要保证Cr
2O
3回收率≥85.0％。
与现有技术相比，本发明含铬污泥与含铬废渣协同利用富集、回收铬资源的方法具有如下优点：
(1)本发明所提供的含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，通过将这两种不同的含铬危废进行联用，并对混合原料的成分及焙烧制度进行有效地控制，进而实现对含铬废渣及含铬污泥同时进行铬富集。该工艺流程中，铬的富集程度高达90％以上，且得到的铬富集相与其他矿相的物理性质差异较大，这大大降低了后期对其进行分离回收的难度，磁选分离出的铬精矿中Cr
2O
3品位≥20.0％、Cr
2O
3回收率≥85.0％。
(2)与传统的铬富集工艺流程相比，本发明中铬的富集效率更高，且整个过程并不产生对环境有害的物质，为高效、绿色回收铬创造了条件，符合实际工业生产的需要，具有较好的应用推广前景。
(3)通过本发明方法获得的含铬富集相，不易与渣中的硫氧化物与磷氧化物形成固溶体，这也为后续高纯度、高性能铬产品的获得创造了条件。
(4)通过本发明提供的方法，可以将含铬废渣与含铬污泥中的铬富集到铁铬尖晶石相中。将富铬相分离后得到的尾渣，可以作为 微晶玻璃、胶凝材料的原料，这不仅降低了废渣的二次污染，也实现了其资源化的利用。
图1为本发明含铬污泥与含铬废渣协同利用富集、回收铬资源的方法的原则工艺流程图；
图2为温度在700～1600K的范围内FeO(s)与SiO
2(s)、Al
2O
3、Cr
2O
3反应的Δ
rG
θ-T关系图；
图3为焙烧温度分别为1373K及1473K时XRD结果的对比图；
图4为还原性的焙烧气氛、1473K时，焙烧后样品的扫描电镜分析结果图。
为描述本发明，下面结合附图和实施例对本发明含铬污泥与含铬废渣协同利用富集、回收铬资源的方法做进一步详细说明。
为了验证本发明方法的可行性，本发明将含铬污泥与含铬废渣按照一定的比例混合后，混合物的主要成分包括SiO
2、Al
2O
3、Cr
2O
3，此外还含有少量的MgO。采用碳粉作为还原剂、在还原性的焙烧条件下进行反应时，由于过量的FeO
x的存在，会发生如下所示的反应：
FeO(s)+SiO
2(s)＝FeSiO
3(s) (1)
FeO(s)+Al
2O
3＝FeAl
2O
4(s) (2)
FeO(s)+Cr
2O
3＝FeCr
2O
4(s) (3)
通过从Factsage中查阅的相关热力学数据，可以得到上述各个反应的标准吉布斯自由能的大小，结果如表1及图1所示。
表1反应(1)～(3)在不同温度下的标准生成吉布斯自由能变化
表1表示的是不同温度下FeO与SiO
2、Al
2O
3及Cr
2O
3反应生成FeSiO
3、FeAl
2O
4及FeCr
2O
4的标准吉布斯自由能的数值大小。图1表示的是700～1600K温度范围内反应(1)～(3)的Δ
rG
θ-T对比关系图。
由表1及图1中的数据可以看出：FeO与Cr
2O
3反应生成FeCr
2O
4的Δ
rG
θ最小。这表明：在700～1600K的温度范围内，在含铬污泥与含铬废渣构成的体系中，FeCr
2O
4是最易形成的化合物，即在热力学上，将含铬污泥与含铬废渣中的铬富集至铬铁尖晶石相中是完全可行的。
本实施例中选择的含铬废渣主要成分如表2所示。由表2可知，该废渣中，Cr
2O
3的含量可以达到9.12％。此外，该废渣中还含有一定量的Mn、Ti等金属氧化物。表3为从某电镀厂获得的含铬污泥的主要成分表，由表2可知，该含铬污泥中Cr
2O
3的含量较高，可以达到14.18％，Fe
2O
3的含量则明显偏低。
表2含铬提钒尾渣的主要化学成分表
表3含铬污泥的主要化学成分表
由图1所示的本发明含铬污泥与含铬废渣协同利用富集、回收铬资源的方法的原则工艺流程图看出，本发明含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，采用以下步骤实施：
1)原料处理：将含铬污泥和含铬废渣球磨破碎后，按一定比例混合配制成碱度((CaO％+MgO％)/(SiO
2％+Al
2O
3％))在0.6～1.5范围、FeO
x含量≥15.0％的混合料。需要注意的是，为了提供还原性的焙烧气氛，需要向混合料中加入适量的碳粉充当还原剂。此外，为了将含铬污泥与含铬废渣中的Cr充分富集回收，仍需要向混合料中补充稍过量的Fe
2O
3粉作为铬的富集载体。需要进行说明的是，Fe
2O
3粉和碳粉的加入量需要根据含铬污泥与含铬废渣中的铬含量进行确定。
2)还原焙烧：将得到的混合料制成球团，球团样品的直径控制在4～8mm，待样品干燥后，将其置于还原性的焙烧条件下进行还原焙烧，使含铬污泥、含铬废渣中的铬通过化学反应富集到含铬富集相—铬铁尖晶石Fe
3-xCr
xO
4相中；焙烧温度选择为1373K及1473K，焙烧时间选择为3h，同时吹入适量的氩气以排净炉内的空气，使还原反应得到充分地进行。焙烧反应结束后，将样品以5～10K/min的速度降温。在此过程中，含铬污泥及含铬废渣中的铬能够进入预先设计好的含铬富集相中。
焙烧得到的含铬富集相中，并不含P、Na及S等杂质元素，这有利于后续工艺中铬的浸出提取或采用其它工艺分离、分选。
3)磁选分离、回收：对步骤2)之焙烧产物进行碎磨处理，磨矿粒度控制在－0.074mm粒级含量≥80.0％，对磨矿后的产物采用强磁选工艺将铁铬尖晶石离出来，获得Cr
2O
3含量≥20.0％、Cr
2O
3回收率≥85.0％的铬精矿。磁选工艺采用立环电磁脉动高梯度磁选机进行分选，磁感应强度在0.4～1.0特斯拉之间。
本发明还对磨矿后的产物采用螺旋溜槽进行重选，获得了Cr
2O
3含量21.5％、Cr
2O
3回收率86.0％的铬精矿，对磨矿后的产物采用尼尔森(knelson)选矿机进行重选，获得了Cr
2O
3含量22.3％、Cr
2O
3回收率86.5％的铬精矿；采用对磨矿后的产物采用螺旋溜槽－尼尔森(knelson)选矿机联合重选，获得了Cr
2O
3含量24.8％、Cr
2O
3回收率86.2％的铬精矿，取得了意想不到的技术效果。
为了验证本发明方法中提供方案的可行性，需要鉴定焙烧后的矿物中是否有铁铬尖晶石相的生成，对焙烧温度分别为1373K及1473K时得到的样品进行XRD分析，对比结果如图3所示。通过对比不同焙烧温度时样品的XRD结果可以发现：焙烧后的矿物中，确实生成了铁铬尖晶石相；并且，对比焙烧温度分别为1373K及1473K时的样品可以发现，随着焙烧温度的升高，焙烧后矿物中生成的铁铬尖晶石相含量也逐渐升高。图4为还原性的焙烧气氛、1473K时，焙烧后样品的扫描电镜分析结果图，由图4结果可知：焙烧后样品中，Fe及Cr的富集行为较为一致，且不含P、S等杂质元素。综合上述结果可以发现：在还原性的焙烧气氛下，利用FeO
x作为富集载体，通过含铬污泥与含铬废渣联用，能够将其中丰富的Cr资源富集至铁铬尖晶石相中。该富集相富集效率高，且不含P、S有害杂质元素。这表明，通过本专利中提供的方法，确实对含铬污泥及含铬钢渣中的铬起到了较好的联合富集的效果。
此外，对磁选工艺排出的低铬尾矿，可以添加粉煤灰等配料制备成养护砖等建材产品，也可以制备其它建筑材料，如陶粒等，做到无固废排放。
Claims (8)
- 一种含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，其特征在于采用以下步骤实施：1)原料处理：将含有CaO、MgO、SiO 2、Al 2O 3、FeO x的含铬污泥和含有CaO、MgO、SiO 2、Al 2O 3、FeO x的含铬废渣配制成碱度((CaO％+MgO％)/(SiO 2％+Al 2O 3％))在0.6～1.5范围、FeO x含量≥15.0％的混合料并加入到球磨机中细磨、混合，制备出混合料，所述的含铬污泥中Cr 2O 3含量≥8.0％，所述的含铬废渣中Cr 2O 3含量≥3.0％；2)还原焙烧：在还原性的反应气氛下，对步骤1)之混合料在1100～1500℃温度范围内进行还原焙烧，使含铬污泥、含铬废渣中的铬通过化学反应富集到含铬富集相—铬铁尖晶石Fe 3-xCr xO 4相中；3)磁选分离、回收：对步骤2)之焙烧产物进行碎磨处理，磨矿粒度控制在－0.074mm粒级含量≥80.0％，对磨矿后的产物采用强磁选工艺将铁铬尖晶石离出来，获得Cr 2O 3含量≥20.0％、Cr 2O 3回收率≥85.0％的铬精矿。
- 一种含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，其特征在于采用以下步骤实施：1)原料处理：将含有CaO、MgO、SiO 2、Al 2O 3、FeO x的含铬污泥和含有CaO、MgO、SiO 2、Al 2O 3、FeO x的含铬废渣配制成碱度((CaO％+MgO％)/(SiO 2％+Al 2O 3％))在0.6～1.5范围、FeO x含量≥15.0％的混合料并加入到球磨机中细磨、混合，制备出混合料，所述的含铬污泥中Cr 2O 3含量≥8.0％，所述的含铬废渣中Cr 2O 3含量≥3.0％；2)还原焙烧：在还原性的反应气氛下，对步骤1)之混合料在1100～1500℃温度范围内进行还原焙烧，使含铬污泥、含铬废渣中的铬通过化学反应富集到含铬富集相—铬铁尖晶石Fe 3-xCr xO 4相中；3)重选分离、回收：对步骤2)之焙烧产物进行碎磨处理，磨矿粒度控制在－0.074mm粒级含量≥80.0％，对磨矿后的产物分别采 用螺旋溜槽、尼尔森(knelson)选矿机或者二者的联合分选，获得Cr 2O 3含量≥21.0％、Cr 2O 3回收率≥85.5％的铬精矿。
- 如权利要求2所述的一种含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，其特征在于：对磨矿后的产物采用螺旋溜槽－尼尔森(knelson)选矿机进行联合重选，获得了Cr 2O 3含量≥22.0％、Cr 2O 3回收率≥86.0％的铬精矿。
- 如权利要求1、2或3所述的含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，其特征在于：所述的含铬污泥中主要组份的质量百分含量为：SiO 24.0～8.0％、Al 2O 32.0～8.0％、FeO x3.0～8.0％、CaO 10.0～20.0％、Cr 2O 310.0～15.0％，其余为P 2O 5、MnO、MgO及其它组份；所述的含铬废渣中主要组份的质量百分含量为：SiO 215.0～20.0％、Al 2O 33.0～8.0％、FeO x20.0～45.0％、CaO 2.0～5.0％、Cr 2O 33.0～10.0％、MgO 1.0～5.0％，其余为MnO、TiO 2、V 2O 3及其它组份。
- 如权利要求4所述的含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，其特征在于它还包括以下步骤：将步骤1)中制备出的混合料，再制备出直径在4.0～10.0mm的球团，球团给入步骤2)进行还原焙烧。
- 如权利要求5所述的含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，其特征在于：在步骤1)中，还向混合料中加入碳粉作为还原剂以保证步骤2)的还原气氛。
- 如权利要求6所述的含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，其特征在于：步骤2)中还原焙烧温度为1350～1500℃。
- 如权利要求7所述的含铬污泥与含铬废渣协同利用富集、回收铬资源的方法，其特征在于：步骤3)中的磁选工艺采用立环电磁脉动高梯度磁选机进行分选，磁感应强度为0.4～1.0特斯拉。
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