CN113564363B - Method for enriching and recovering chromium resource by synergistic utilization of chromium-containing sludge and chromium-containing waste residue - Google Patents
Method for enriching and recovering chromium resource by synergistic utilization of chromium-containing sludge and chromium-containing waste residue Download PDFInfo
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
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- C22B34/32—Obtaining chromium
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Abstract
The invention discloses a method for enriching and recovering chromium resources by utilizing chromium-containing sludge and chromium-containing waste residues cooperatively, which is characterized in that the chromium-containing sludge and the chromium-containing waste residues are finely ground and mixed to prepare a mixture, and the outdoor alkalinity of the mixture ((CaO% + MgO%)/(SiO) 2 ％+Al 2 O 3 %) in the range of 0.6 to 1.5, FeO x The content is more than or equal to 15.0 percent. And carrying out reduction roasting on the mixture, wherein the roasting temperature is controlled within the range of 1100-1500 ℃. After the roasted product is crushed and ground, the ferrochrome spinel is separated out by adopting a strong magnetic separation process to obtain Cr 2 O 3 The content is more than or equal to 20.0 percent, and the Cr content 2 O 3 The recovery rate is more than or equal to 85.0 percent. The method combines the chromium-containing sludge and the chromium-containing waste residue, and simultaneously enriches chromium in the two resources, so that the obtained chromium-containing enrichment phase has high grade of chromium, utilizes subsequent separation, has the characteristics of high efficiency, small pollution, wide application range and the like, and is suitable for being applied to the technical field of chromium enrichment and separation in the chromium-containing resources.
Description
Technical Field
The invention belongs to the field of resource utilization of chromium in dangerous/solid waste, and particularly relates to a method for synergistically utilizing chromium-containing sludge and chromium-containing waste residues in a steel plant and enriching chromium resources in the sludge and the waste residues.
Background
The discharge amount of chromium-containing hazardous/solid waste in China is huge. According to measurement and calculation, the annual emission can reach about 150 ten thousand tons, and the accumulated stock reaches more than ten million tons. Chromium-containing hazardous/solid waste generally contains high contents of elements such as Fe, Cr, V and the like, and is not only toxic hazardous waste and environmental pollutants, but also an important strategic resource. Therefore, the treatment of 'reduction, harmlessness and reclamation' on the waste water has great environmental, economic and social benefits.
At present, the method mainly adopted for separating and recovering the heavy metal element chromium in the chromium-containing dangerous/solid waste mainly comprises wet metallurgy (acid leaching, alkali leaching, water leaching and salt leaching), fire metallurgy (high-temperature smelting method and roasting-leaching method), biological extraction technology and the like. Chinese patent 'a method for detoxifying and recovering chromium from chromium-containing waste residue' (CN108220604B) proposes a method for resource utilization of chromium in chromium-containing waste residue: oxidizing and roasting the waste residue, separating the solid residue from the chromium-containing solution by means of ultrasonic treatment, hydrothermal reaction and the like, and adding HCl and NaHCO when separating and recovering chromium 3 And Na 2 CO 3 Etc. as surface interface controlling agents to promote the reaction. The method has the disadvantages of complicated process flow, high medicament consumption and new secondary pollution to the environment, and is not widely applied to the industry. Chinese patent 'a method for recovering hexavalent chromium resources from chromium slag' (CN102191390A) leaching with hydrochloric acid and sulfuric acid at normal temperatureHexavalent chromium in the chromium slag, but the chromium recovery rate is only about 60-80%, which can not efficiently recover chromium resources, and the generated large amount of acid liquor also brings serious hidden troubles to the environment. Most of the traditional methods for recovering chromium from chromium-containing resources have the problems of high cost, complex process flow, complex operation, easy generation of secondary pollutants and the like, and have larger improvement space in the process. In view of the above disadvantages, methods for recovering chromium from chromium-containing sludge and chromium-containing slag have been proposed in recent years mainly as follows: reduction precipitation, ion exchange, extraction separation, etc., but these methods all have the following disadvantages: the reduction precipitation method has large acid consumption, and the obtained product has low purity, so the method is not a more suitable method from the aspects of environment and cost; the ion exchange method has longer process period and is not suitable for large-scale production; the extraction separation method has good separation effect only on certain specific ions, but the effect is greatly influenced by impurity ions. These factors limit the industrial application of these methods to some extent.
In conclusion, for the enrichment, separation and recovery of chromium in the chromium-containing hazardous/solid waste, no feasible method exists at present from the viewpoints of economy, environmental protection and process flow simplification, and the efficient and green recycling of the chromium-containing hazardous/solid waste is still a problem to be solved urgently. The invention provides a method for enriching chromium by combining chromium-containing sludge and chromium-containing waste residue. Because chromium in the chromium-containing sludge and the chromium-containing waste residue is difficult to enrich through a conventional physical beneficiation method, the invention provides a high-temperature chemical method, which realizes the pre-enrichment of chromium in the chromium-containing sludge and the chromium-containing waste residue, reduces the dispersion degree of chromium, and obtains a chromium-enriched phase which has high chromium content and is suitable for subsequent separation.
Disclosure of Invention
The invention aims to solve the problems of complex process flow, large medicament consumption, high treatment cost, easy generation of secondary pollution, incapability of large-scale production and the like of the conventional resource utilization of chromium-containing sludge and chromium-containing waste residue, and provides a method for enriching and recovering chromium resources by utilizing the chromium-containing sludge and the chromium-containing waste residue in a synergistic manner, so that the chromium-containing sludge and the chromium-containing waste residue can be efficiently, environmentally-friendly, low in cost and subjected to synergistic treatment, enrichment and recovery of the chromium resources.
The technical concept of the method for enriching and recovering chromium resources by utilizing the chromium-containing sludge and the chromium-containing waste residue in a synergistic manner is as follows: by utilizing the self component characteristics and advantages of the chromium-containing sludge and the chromium-containing waste residue, the high-efficiency enrichment of chromium in the chromium-containing sludge and the chromium-containing waste residue is realized by combining the chromium-containing sludge and the chromium-containing waste residue and adjusting the roasting atmosphere and the roasting system, and the obtained chromium-containing enriched phase-ferrochrome spinel Fe 3-x Cr x O 4 In the phase, the chromium enrichment degree is high, the chromium-rich phase has a large difference with other mineral phases in the material in physical and chemical properties, and the chromium-rich phase can be separated and recovered in a later stage through a simple ore dressing mode, so that the cost of dressing and metallurgy is reduced, and the pollution to the environment is also reduced.
In order to realize the purpose, the method for enriching and recovering chromium resources by utilizing the chromium-containing sludge and the chromium-containing waste residue synergistically adopts the following processes and steps:
1) raw material treatment: containing CaO, MgO and SiO 2 、Al 2 O 3 、FeO x The chromium-containing sludge contains CaO, MgO and SiO 2 、Al 2 O 3 、FeO x The chromium-containing waste residue is prepared into alkalinity ((CaO% + MgO%)/(SiO) 2 ％+Al 2 O 3 %) in the range of 0.6 to 1.5, FeO x Adding the mixture with the content of more than or equal to 15.0% into a ball mill, finely grinding and mixing to prepare a mixture, wherein Cr in the chromium-containing sludge 2 O 3 The content is more than or equal to 8.0 percent, and the Cr in the chromium-containing waste residue 2 O 3 The content is more than or equal to 3.0 percent.
The chromium-containing sludge comprises the following main components in percentage by mass: SiO 2 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 to 15.0 percent of the total weight of the composition, and the balance of P 2 O 5 MnO, MgO and other components; the chromium-containing waste residue comprises the following main components in percentage by mass: SiO 2 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 balance of MnO and TiO 2 、V 2 O 3 And other components.
In this step, if FeO is present in the mix x When the content is less than 15 percent, a proper amount of Fe can be added into the mixture 2 O 3 Powder to act as an enrichment carrier for chromium.
2) Reduction roasting: in a reductive reaction atmosphere, carrying out reductive roasting on the mixture obtained in the step 1) at the temperature of 1100-1500 ℃, so that chromium in the chromium-containing sludge and chromium-containing waste residue is enriched to chromium-containing enriched phase-ferrochrome Fe through a chemical reaction 3-x Cr x O 4 Phase (c); the reduction roasting is preferably carried out at 1350-1500 ℃.
3) Magnetic separation and recovery: crushing and grinding the roasted product obtained in the step 2), controlling the grinding granularity to be-0.074 mm and the grain fraction content to be more than or equal to 80.0%, and separating the iron-chromium spinel from the ground product by adopting a strong magnetic separation process to obtain Cr 2 O 3 The content is more than or equal to 20.0 percent and the Cr content 2 O 3 The recovery rate of the chromium concentrate is more than or equal to 85.0 percent.
Further, preparing pellets with the diameter of 4.0-10.0 mm from the mixture prepared in the step 1), and feeding the pellets into the step 2) for reduction roasting. The diameter of the pellet is preferably 4-8 mm.
Further, carbon powder is preferably used as a reducing agent; of course, hydrogen reduction may also be employed to reduce carbon dioxide emissions.
Furthermore, the magnetic separation process in the step 3) adopts a vertical ring electromagnetic pulse high gradient magnetic separator for separation, and the magnetic induction intensity is 0.4-1.0 Tesla. The specific values of the grinding fineness and the magnetic induction intensity can be determined through tests, and the Cr in the chromium concentrate is ensured 2 O 3 The grade is more than or equal to 20.0 percent, and the Cr is ensured 2 O 3 The recovery rate is more than or equal to 85.0 percent.
Compared with the prior art, the method for enriching and recovering chromium resources by synergistically utilizing the chromium-containing sludge and the chromium-containing waste residues has the following advantages:
(1) the invention provides the synergy of the chromium-containing sludge and the chromium-containing waste residueBy utilizing the method for enriching and recovering chromium resources, the two different chromium-containing hazardous wastes are combined, and the components and the roasting system of the mixed raw materials are effectively controlled, so that the chromium enrichment of the chromium-containing waste residue and the chromium-containing sludge is realized simultaneously. In the process flow, the enrichment degree of chromium is as high as more than 90%, and the obtained chromium enrichment phase has larger difference with the physical properties of other mineral phases, so that the difficulty of separating and recovering the chromium enrichment phase at the later stage is greatly reduced, and the Cr in the chromium concentrate separated by magnetic separation 2 O 3 Grade is not less than 20.0 percent and Cr 2 O 3 The recovery rate is more than or equal to 85.0 percent.
(2) Compared with the traditional chromium enrichment process flow, the method has higher chromium enrichment efficiency, does not generate substances harmful to the environment in the whole process, creates conditions for efficiently and environmentally recovering chromium, meets the requirements of actual industrial production, and has better application and popularization prospects.
(3) The chromium-containing enriched phase obtained by the method is not easy to form a solid solution with oxysulfide and phosphorus oxide in the slag, and conditions are created for obtaining subsequent high-purity and high-performance chromium products.
(4) By the method, chromium in the chromium-containing waste residue and the chromium-containing sludge can be enriched into the hercynite phase. The tailings obtained after the chromium-rich phase separation can be used as raw materials of microcrystalline glass and cementing materials, so that the secondary pollution of the waste residues is reduced, and the resource utilization of the waste residues is realized.
Drawings
FIG. 1 is a schematic process flow diagram of the method for enriching and recovering chromium resources by utilizing chromium-containing sludge and chromium-containing waste residues in a synergistic manner according to the invention;
FIG. 2 shows FeO(s) and SiO at a temperature of 700-1600K 2 (s)、Al 2 O 3 、 Cr 2 O 3 Reacted Δ rG θ -a T-relationship graph;
FIG. 3 is a graph comparing XRD results at 1373K and 1473K firing temperatures, respectively;
FIG. 4 is a scanning electron microscope analysis result of a sample after baking in a reducing baking atmosphere at 1473K.
Detailed Description
In order to describe the invention, the method for the enrichment and recovery of chromium resources by the synergistic utilization of chromium-containing sludge and chromium-containing waste residue according to the invention is further described in detail with reference to the accompanying drawings and examples.
In order to verify the feasibility of the method, the chromium-containing sludge and the chromium-containing waste residue are mixed according to a certain proportion, and the main component of the mixture comprises SiO 2 、Al 2 O 3 、Cr 2 O 3 And in addition, the magnesium oxide also contains a small amount of MgO. When carbon powder is used as a reducing agent and the reaction is carried out under the reducing roasting condition, because of excessive FeO x In the presence of (b), the following reactions occur:
FeO(s)+SiO 2 (s)＝FeSiO 3 (s) (1)
FeO(s)+Al 2 O 3 ＝FeAl 2 O 4 (s) (2)
FeO(s)+Cr 2 O 3 ＝FeCr 2 O 4 (s) (3)
the magnitude of the standard gibbs free energy for each reaction described above can be obtained from the relevant thermodynamic data reviewed in Factsage, and the results are shown in table 1 and fig. 1.
TABLE 1 Standard formation Gibbs free energy changes at different temperatures for reactions (1) - (3)
Table 1 shows FeO and SiO at different temperatures 2 、Al 2 O 3 And Cr 2 O 3 Reaction to form FeSiO 3 、FeAl 2 O 4 And FeCr 2 O 4 The magnitude of the standard gibbs free energy. FIG. 1 shows the Δ of reactions (1) to (3) in the temperature range of 700 to 1600K r G θ -T contrast plot.
As can be seen from the data in table 1 and fig. 1: FeO and Cr 2 O 3 Reaction to form FeCr 2 O 4 Delta of r G θ And minimum. This indicates that: in a temperature range of 700-1600K, in a system formed by the chromium-containing sludge and the chromium-containing waste residue, FeCr 2 O 4 Is the most easily formed compound, namely, it is completely feasible to enrich chromium in the chromium-containing spinel phase from chromium-containing sludge and chromium-containing waste residue thermodynamically.
The main components of the chromium-containing slag selected in this example are shown in Table 2. As can be seen from Table 2, Cr is contained in the slag 2 O 3 The content of (A) can reach 9.12%. In addition, the slag also contains a certain amount of metal oxides such as Mn, Ti and the like. Table 3 shows the main components of chromium-containing sludge obtained from a certain plating plant, and Table 2 shows that Cr in the chromium-containing sludge 2 O 3 The content of (C) is higher and can reach 14.18 percent, and Fe 2 O 3 The content of (A) is significantly lower.
TABLE 2 Main chemical composition table of chromium-containing vanadium extraction tailings
TABLE 3 Main chemical composition Table of chromium-containing sludge
As shown in a principle process flow chart of the method for enriching and recovering chromium resources by utilizing the chromium-containing sludge and the chromium-containing waste residues synergistically, the method for enriching and recovering chromium resources by utilizing the chromium-containing sludge and the chromium-containing waste residues synergistically is implemented by the following steps:
1) raw material treatment: after the chromium-containing sludge and the chromium-containing waste residue are ball-milled and crushed, the chromium-containing sludge and the chromium-containing waste residue are mixed according to a certain proportion to prepare alkalinity ((CaO% + MgO%)/(SiO) 2 ％+Al 2 O 3 %) in the range of 0.6 to 1.5, FeO x The content is more than or equal to 15.0 percent. It is noted that in order to provide a reducing firing atmosphere, an appropriate amount of carbon powder is added to the mix to act as a reducing agent. In addition, in order to charge the chromium-containing sludge and Cr in the chromium-containing slagSeparate enrichment and recovery are still needed to supplement a little excessive Fe into the mixture 2 O 3 The powder acts as an enrichment carrier for chromium. In addition, Fe 2 O 3 The adding amount of the powder and the carbon powder is determined according to the chromium content in the chromium-containing sludge and the chromium-containing waste residue.
2) Reduction roasting: preparing the obtained mixture into pellets, controlling the diameter of a pellet sample to be 4-8 mm, drying the sample, and then placing the sample under a reductive roasting condition for reductive roasting, so that chromium in the chromium-containing sludge and chromium-containing waste residues is enriched to a chromium-containing enriched phase, namely ferrochrome spinel Fe through a chemical reaction 3-x Cr x O 4 Phase (c); the calcination temperature was selected to be 1373K and 1473K, the calcination time was selected to be 3 hours, and an appropriate amount of argon gas was blown in to exhaust the air in the furnace, so that the reduction reaction was sufficiently performed. And after the roasting reaction is finished, cooling the sample at the speed of 5-10K/min. In the process, the chromium in the chromium-containing sludge and the chromium-containing waste residue can enter a pre-designed chromium-containing enrichment phase.
The chromium-containing enriched phase obtained by roasting does not contain impurity elements such as P, Na, S and the like, so that the chromium is beneficial to leaching and extracting in subsequent processes or separating and sorting by adopting other processes.
3) Magnetic separation and recovery: crushing and grinding the roasted product obtained in the step 2), controlling the grinding granularity to be-0.074 mm and the grain fraction content to be more than or equal to 80.0%, and separating the iron-chromium spinel from the ground product by adopting a strong magnetic separation process to obtain Cr 2 O 3 The content is more than or equal to 20.0 percent and the Cr content 2 O 3 The recovery rate is more than or equal to 85.0 percent. The magnetic separation process adopts a vertical ring electromagnetic pulse high-gradient magnetic separator for separation, and the magnetic induction intensity is between 0.4 and 1.0 Tesla.
The invention also adopts a spiral chute to reselect the product after ore grinding, thereby obtaining Cr 2 O 3 21.5% of Cr 2 O 3 The recovery rate of the chromium concentrate is 86.0 percent, and the product after ore grinding is reselected by a Nielson (Knelson) concentrator to obtain Cr 2 O 3 22.3% of Cr 2 O 3 The recovery rate of chromium concentrate is 86.5 percent; the product after ore grinding is processed by adopting a spiral chute-NiThe combined reselection of the Knelson concentrator obtains Cr 2 O 3 Content of 24.8% Cr 2 O 3 The recovery rate of the chromium concentrate is 86.2 percent, and unexpected technical effects are achieved.
In order to verify the feasibility of the scheme provided in the method of the present invention, it is necessary to identify whether the calcined ore has a hercynite phase, XRD analysis is performed on the samples obtained at the calcination temperatures of 1373K and 1473K, respectively, and the comparison result is shown in fig. 3. By comparing XRD results of samples at different roasting temperatures, it can be found that: the ferro-chromium spinel phase is generated in the roasted minerals; furthermore, comparing the samples at 1373K and 1473K roasting temperatures, it can be seen that the content of hercynite phase generated in the roasted minerals gradually increases with the increase of the roasting temperature. FIG. 4 is a scanning electron microscope analysis result chart of a sample after baking under reducing baking atmosphere of 1473K, and the results in FIG. 4 show that: in the roasted sample, the enrichment behaviors of Fe and Cr are consistent, and the impurity elements such as P, S and the like are not contained. The combination of the above results can find that: under the reducing roasting atmosphere, FeO is utilized x As an enrichment carrier, the chromium-containing sludge and the chromium-containing waste residue are combined, so that abundant Cr resources in the chromium-containing sludge can be enriched into a ferrochrome spinel phase. The enriched phase has high enrichment efficiency and does not contain P, S harmful impurity elements. This shows that the method provided by the patent can indeed achieve better combined enrichment effect on chromium in the chromium-containing sludge and the chromium-containing steel slag.
In addition, the low-chromium tailings discharged by the magnetic separation process can be added with ingredients such as fly ash and the like to prepare building material products such as maintenance bricks and the like, and can also be used for preparing other building materials such as ceramsite and the like, so that no solid waste is discharged.
Claims (6)
1. A method for enriching and recovering chromium resources by synergistically utilizing chromium-containing sludge and chromium-containing waste residues is characterized by comprising the following steps:
1) raw material treatment: containing CaO, MgO and SiO 2 、Al 2 O 3 、FeO x The chromium-containing sludge contains CaO, MgO and SiO 2 、Al 2 O 3 、FeO x The chromium-containing waste residue is prepared into alkalinity ((CaO% + MgO%)/(SiO) 2 ％+Al 2 O 3 %) in the range of 0.6 to 1.5, FeO x Adding the mixture with the content of more than or equal to 15.0% into a ball mill for fine grinding and mixing to prepare the mixture, wherein Cr in the chromium-containing sludge 2 O 3 The content is more than or equal to 8.0 percent, and the Cr in the chromium-containing waste residue 2 O 3 The content is more than or equal to 3.0 percent, and FeO x The content is 20.0-45.0%;
2) reduction roasting: in a reductive reaction atmosphere, the mixture obtained in the step 1) is subjected to reductive roasting at the temperature of 1100-1500 ℃, so that chromium in the chromium-containing sludge and chromium-containing waste residue is enriched to chromium-containing enriched phase-ferrochrome Fe through chemical reaction 3-x Cr x O 4 Phase (c);
3) magnetic separation and recovery: crushing and grinding the roasted product obtained in the step 2), controlling the grinding granularity to be-0.074 mm and the grain fraction content to be more than or equal to 80.0%, and separating the iron-chromium spinel from the ground product by adopting a strong magnetic separation process to obtain Cr 2 O 3 The content is more than or equal to 20.0 percent and the Cr content 2 O 3 The recovery rate of the chromium concentrate is more than or equal to 85.0 percent; the magnetic separation process adopts a vertical ring electromagnetic pulse high-gradient magnetic separator for separation, and the magnetic induction intensity is 0.4-1.0 Tesla.
2. A method for enriching and recovering chromium resources by synergistically utilizing chromium-containing sludge and chromium-containing waste residues is characterized by comprising the following steps:
1) raw material treatment: containing CaO, MgO and SiO 2 、Al 2 O 3 、FeO x The chromium-containing sludge contains CaO, MgO and SiO 2 、Al 2 O 3 、FeO x The chromium-containing waste residue is prepared into alkalinity ((CaO% + MgO%)/(SiO) 2 ％+Al 2 O 3 %) in the range of 0.6 to 1.5, FeO x Adding the mixture with the content of more than or equal to 15.0% into a ball mill for fine grinding and mixing to prepare the mixture, wherein Cr in the chromium-containing sludge 2 O 3 The content is more than or equal to 8.0 percent, and the Cr in the chromium-containing waste residue 2 O 3 The content is more than or equal to 3.0 percent, and FeO x The content is 20.0-45.0%;
2) reduction roasting: in a reductive reaction atmosphere, carrying out reductive roasting on the mixture obtained in the step 1) at the temperature of 1100-1500 ℃, so that chromium in the chromium-containing sludge and chromium-containing waste residue is enriched to chromium-containing enriched phase-ferrochrome Fe through a chemical reaction 3-x Cr x O 4 Phase (c);
3) and (3) reselection separation and recovery: crushing and grinding the roasted product obtained in the step 2), controlling the grinding granularity to be-0.074 mm, and controlling the grain fraction content to be more than or equal to 80.0%, and performing combined reselection on the ground product by adopting a spiral chute-Nielsen concentrator to obtain Cr 2 O 3 The content is more than or equal to 22.0 percent and the Cr content 2 O 3 The recovery rate is more than or equal to 86.0 percent.
3. The method for enriching and recovering chromium resources by synergistically utilizing chromium-containing sludge and chromium-containing waste residue according to claim 1 or 2, which comprises the following steps: the chromium-containing sludge comprises the following main components in percentage by mass: SiO 2 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% and the balance of P 2 O 5 MnO, MgO and other components; the chromium-containing waste residue comprises the following main components in percentage by mass: SiO 2 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 balance of MnO and TiO 2 、V 2 O 3 And other components.
4. The method for enriching and recovering chromium resources by utilizing the chromium-containing sludge and the chromium-containing waste residue in a synergistic manner according to claim 3, characterized by further comprising the following steps: and (3) preparing pellets with the diameter of 4.0-10.0 mm from the mixture prepared in the step 1), and feeding the pellets into the step 2) for reduction roasting.
5. The method for enriching and recovering chromium resources by utilizing the chromium-containing sludge and the chromium-containing waste residue in a synergistic manner according to claim 4, wherein the method comprises the following steps: in the step 1), carbon powder is also added into the mixture as a reducing agent to ensure the reducing atmosphere in the step 2).
6. The method for enriching and recovering chromium resources by utilizing the chromium-containing sludge and the chromium-containing waste residue in a synergistic manner as claimed in claim 5, wherein the method comprises the following steps: the reduction roasting temperature in the step 2) is 1350-1500 ℃.
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|---|---|---|---|---|
| JPS5556897A (en) * | 1978-10-20 | 1980-04-26 | Hokkaido | Treatment method of chromium-containing waste with sewage sludge |
| CN1021058C (en) * | 1990-07-05 | 1993-06-02 | 锦州市环境保护科学研究所 | Technology of processing chromium slag by vacuum reducing for obtaining variable kinds of products |
| CN101138670A (en) * | 2006-09-08 | 2008-03-12 | 隋智通 | Novel process of the high temperature reduction and detoxication of industrial chromic slag |
| CN100507013C (en) * | 2006-09-13 | 2009-07-01 | 宝山钢铁股份有限公司 | Method for directly producing ferrochromium from chrome ore powder and coal |
| CN103361484A (en) * | 2012-03-26 | 2013-10-23 | 云南曲靖越钢集团有限公司 | Harmless treatment method of chromium slag generated by preparation of chromium salt employing little calcium roasting method, and application of method |
| CN102796879B (en) * | 2012-09-10 | 2014-04-16 | 湖北振华化学股份有限公司 | Method for preparing chromium-containing iron powder by direct reduction of calcium-free chromium slag |
| US9534275B2 (en) * | 2013-03-06 | 2017-01-03 | Midrex Technologies, Inc. | Methods and systems for reducing chromium containing raw material |
| WO2015081775A1 (en) * | 2013-12-05 | 2015-06-11 | 中国科学院过程工程研究所 | Method for comprehensively using high-chromium-content vanadium-titanium magnetite concentrate |
| CN103937961A (en) * | 2014-04-15 | 2014-07-23 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Magnetization roasting treatment process for chromite rotary kiln |
| CN109207736B (en) * | 2018-11-12 | 2020-06-02 | 中国安全生产科学研究院 | Method for producing ferrochromium alloy and aluminum oxide by using chromium-containing aluminum mud and red mud |
| CN111455170B (en) * | 2020-03-11 | 2021-10-29 | 武汉理工大学 | Method for separating and enriching chromium in chromium-containing sludge |
-
2021
- 2021-07-26 CN CN202110843690.7A patent/CN113564363B/en active Active
- 2021-09-01 WO PCT/CN2021/116007 patent/WO2023004925A1/en unknown
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2022
- 2022-04-28 ZA ZA2022/04726A patent/ZA202204726B/en unknown
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| Publication number | Publication date |
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| WO2023004925A1 (en) | 2023-02-02 |
| ZA202204726B (en) | 2022-06-29 |
| CN113564363A (en) | 2021-10-29 |
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