CN111996366B - Method for producing porous silicate supported micro-nano iron sulfide copper alloy by using copper slag - Google Patents
Method for producing porous silicate supported micro-nano iron sulfide copper alloy by using copper slag Download PDFInfo
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- CN111996366B CN111996366B CN202010790967.XA CN202010790967A CN111996366B CN 111996366 B CN111996366 B CN 111996366B CN 202010790967 A CN202010790967 A CN 202010790967A CN 111996366 B CN111996366 B CN 111996366B
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/16—Sintering; Agglomerating
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
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Abstract
The invention provides a method for producing porous silicate supported micro-nano iron sulfide copper alloy by using copper slag, belonging to the technical field of resource utilization. The method comprises the steps of crushing and grinding copper slag, uniformly mixing the copper slag with a carbonaceous reducing agent, a binder, an additive and water to prepare carbon-containing pellets, drying the carbon-containing pellets, and then carrying out reduction roasting at 950-1200 ℃ in a reducing atmosphere to obtain the porous silicate supported micro-nano iron sulfide copper alloy. The method realizes the high-efficiency utilization of the environmental pollutant copper slag, and has the advantages of wide raw material source, short flow, low cost and high product added value. The porous silicate supported micro-nano iron sulfide copper alloy provided by the invention is applied to industrial wastewater treatment, heavy metals and organic pollutants in wastewater can be effectively removed, COD and chroma of the wastewater are reduced, biodegradability is improved, and the operation and use effects are stable.
Description
Technical Field
The invention relates to the technical field of resource utilization, in particular to a method for producing porous silicate supported micro-nano iron sulfide copper alloy by using copper slag.
Background
Copper slag is waste slag generated in the pyrometallurgical process of copper concentrate, and 2.2 tons of copper slag are generated in average per ton of copper produced. The yield of the copper slag in China per year is up to 1500 ten thousand tons, and the accumulated accumulation amount is one ton of copper slag. Although the components of copper slag produced by different smelting methods are different, the contents of iron and copper are generally higher (the contents of Fe and Cu are usually 30-50% and 0.5-2.1%), which are far higher than the recoverable grade of iron ore (TFe > 27%) and the mined grade of copper ore (Cu > 0.3%) in China, and in addition, the slag also contains a large amount of noble metals such as cobalt, antimony and the like. The existence of a large amount of waste copper slag not only occupies a large amount of land, but also causes environmental pollution. Under the conditions that copper ore and iron ore resources are gradually reduced and the environmental protection requirement is gradually improved, how to realize the comprehensive utilization and green development of the resources becomes urgent need for the development of society and enterprises. At present, a large number of researchers research on the recovery of valuable metals from copper slag, including electric furnace depletion method, flotation method, magnetic separation method and the like, can realize the recovery of copper, but have the problems of low copper recovery rate, high copper grade of tailings and unavailable utilization of iron components.
The zero-valent iron method is a process for treating wastewater by a metal corrosion chemical principle, particularly aiming at the treatment of wastewater with high concentration, high toxicity, high chroma and difficult biochemical treatment of organic matters, the chroma and COD of the wastewater can be greatly reduced, and the biodegradability of the wastewater is improved; in addition, the zero-valent iron can also adsorb and reduce various heavy metal ions, so that the zero-valent iron technology is widely applied to treatment of various industrial wastewater such as printing and dyeing, papermaking, chemical industry, electroplating, printed circuit boards, pharmacy and the like. On the basis of zero-valent iron, various micro-electrolysis processes such as Fe-C, Fe-Cu, Fe-Ni, Fe-Co and the like are developed. The potential difference between C, Cu, Ni, Co and Fe is utilized to accelerate the corrosion of the metallic iron, thereby improving the removal efficiency of pollutants. In the process of treating wastewater, Cu, Ni and Co play the role of catalysts, and are protected by metallic iron and are rarely dissolved out. In addition, the zero-valent iron sulfide is also concerned, the effective utilization rate of electrons is high when the zero-valent iron sulfide degrades pollutants, and the removal of the pollutants can be accelerated. The main methods for vulcanization modification include a sulfide method, a dithionite method, a thiosulfate method, an elemental sulfur ball milling method and the like.
The particle size is one of the key factors influencing the activity of the zero-valent iron, the particle size is reduced, the specific surface area is increased, and the removal efficiency of pollutants can be improved. Therefore, a plurality of scholars research the application of the nano zero-valent iron (1-100nm) in wastewater treatment, and the results show that the nano zero-valent iron can rapidly degrade pollutants in the wastewater. However, the specific surface area of the nano zero-valent iron is large, magnetite is generated after reaction, and the magnetite is easy to gather in a water body under the action of Van der Waals force and magnetic force, so that the migration capacity is reduced, and the reaction activity is reduced. In order to overcome the defect, a plurality of researchers load the nano zero-valent iron on the surfaces of porous materials such as clay minerals, activated carbon, chitosan, polymer polymers and the like, so that the aggregation of the nano iron is avoided, the stability of the nano iron is improved, and meanwhile, the porous carrier also participates in the reaction directly or indirectly, so that the removal efficiency of pollutants is improved. The preparation method of the load type nano iron mainly comprises the following steps: 1) mixing porous carrier and ferric salt water solution, and subjecting to NaHB in liquid phase4Or KBH4Reducing or drying and reducing with reducing gas at high temperature; 2) the porous carbon material and the aqueous solution of ferric salt are mixed and then subjected to reduction roasting at a high temperature. However, the cost of the preparation methods is high, so that the application of the supported nano iron in water treatment is limited. Therefore, the research and development of low-cost and high-performance fine-grained iron materials are the key research direction of the zero-valent molten iron treatment technology.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for producing porous silicate supported micro-nano iron sulfide copper alloy by using copper slag.
The method specifically comprises the following steps:
(1) preparing carbon-containing pellets of copper slag: crushing the copper slag to-0.1 mm, mixing the crushed copper slag with a carbonaceous reducing agent, an additive and a binder according to a certain proportion, adding water to pelletize or press the pellets, and preparing carbon-containing pellets;
(2) reduction roasting: drying the carbon-containing pellets obtained in the step (1), and reducing the carbon-containing pellets under the reducing atmosphere condition of roasting temperature of 950-1250 DEG CAnd (4) roasting. The gangue components form a high viscosity liquid phase at high temperatures and form a porous structure under the action of the coal, binder and reactive gas. Reducing iron mineral and copper mineral to form iron-copper alloy, controlling roasting condition to induce iron-copper alloy to form preferentially on the surface of silicate hole and inhibit the combined growth of iron-copper alloy, and oxidizing sulfide ore additive to form SO2，SO2And vulcanizing the iron-copper alloy, wherein iron-copper components in the sulfide ore enter the iron-copper alloy to generate the micro-nano iron-copper sulfide alloy.
(3) After the reaction is finished, rapidly cooling the reaction product under the condition of isolating oxygen, forming silicate glass in a liquid phase, and finally obtaining the porous silicate supported micro-nano iron sulfide copper alloy material.
Wherein the iron content of the copper slag used in the step (1) is more than 30%, and the copper slag with lower iron content can be used for producing the porous silicate supported micro-nano iron sulfide copper alloy after the iron content is increased to more than 30% by means of ore dressing or smelting.
The carbonaceous reducing agent in the step (1) is one or a combination of more of anthracite, bituminous coal, active carbon, coke, semicoke and petroleum coke;
the additive in the step (1) is one or a combination of a plurality of pyrite, pyrrhotite and chalcopyrite;
the binder in the step (1) is one or more of waste syrup, sodium carboxymethyl cellulose, starch and water glass;
in the step (1), the mass ratio of the copper slag, the carbonaceous reducing agent, the additive and the binder is as follows: 100 (10-40), (4-10) and (0.5-10).
The roasting time in the step (2) is 30-300 min.
And (3) carrying out reduction roasting in the step (2) under the condition of oxygen isolation, and cooling the roasted product under the condition of oxygen isolation.
The porosity of the porous silicate supported micro-nano iron sulfide copper alloy material obtained in the step (2) is more than 50%, more than 70% of iron sulfide copper alloy is distributed on the surface of silicate pores, the sulfur content of the iron sulfide copper alloy is more than 3%, the copper content is more than 0.5%, the granularity is between 100nm and 10 mu m, and the mass ratio of the nano-scale iron sulfide copper alloy is not less than 50%.
The technical scheme of the invention has the following beneficial effects:
in the above scheme, the porous silicate supported micro-nano iron sulfide copper alloy is directly produced from the copper slag, and has the characteristics of wide raw material source, short flow and environmental friendliness.
Drawings
FIG. 1 is a flow chart of a method for producing porous silicate supported micro-nano iron sulfide copper alloy by using copper slag.
Detailed Description
In order to make the technical problems, technical solutions and advantages of the present invention more apparent, the following detailed description is given with reference to the accompanying drawings and specific embodiments.
The invention provides a method for producing porous silicate supported micro-nano iron sulfide copper alloy by copper slag, which comprises the steps of proportioning, pelletizing, drying, reduction roasting, cooling and the like, and is described by combining specific embodiments below, wherein the process flow is shown in figure 1.
Example 1
The multi-element analysis of a certain copper slag is shown in Table 1, and the copper slag is crushed to-0.1 mm before use. The carbonaceous reducing agent used was anthracite, the coal quality analysis is shown in table 2, and the carbonaceous reducing agent was crushed to-0.1 mm before use, and the additive was pyrite, crushed to-0.1 mm before use.
TABLE 1 multielement analysis of copper slags
TABLE 2 Industrial analysis results of coal
Copper slag: anthracite coal: sodium carboxymethylcellulose: the pyrite is prepared from 100:25: 0.5: 5 weighing and mixing, then adding 12% of water and mixing evenly. Preparing the mixed material into carbon-containing pellets on a double-roller ball press, and drying the carbon-containing pellets at 105 ℃. And (3) putting the carbon-containing pellets into an atmosphere furnace, charging nitrogen to protect the carbon-containing pellets, heating to 1250 ℃, then preserving the heat for 20min, and cooling the carbon-containing pellets along with the furnace under the protection of the nitrogen after roasting is finished to obtain the porous silicate supported micro-nano iron sulfide copper alloy. The porosity is 73%, the sulfur content is 3.5%, the copper content is 0.6%, 80% of iron-copper alloy is distributed on the surface of silicate pores, the granularity is mainly between 100nm and 10 microns, wherein the nano level accounts for 54%.
The porous silicate supported micro-nano iron sulfide copper alloy prepared by the embodiment is applied to treat certain dyeing and printing wastewater (the chroma is about 1000 times, the COD is about 1500mg/L, and the pH is 5.3-5.5), the pH is adjusted to about 4, under the condition that the hydraulic retention time is 40min, the wastewater chroma removal rate is 95%, and the COD removal efficiency is 65%; the reactor is continuously operated for 1 month, no obvious hardening phenomenon is found, and the operation is stable.
Example 2
The multi-element analysis of a certain copper slag is shown in Table 3, and the copper slag is crushed to-0.1 mm before use.
TABLE 3 multielement analysis of copper slags
Copper slag: carbonaceous reducing agent: adhesive: the additive is prepared from the following components in percentage by mass of 100:35: 5:8, weighing and mixing, and then adding 12% of water to mix evenly. The carbonaceous reducing agent comprises anthracite: bituminous coal: activated carbon: coke: semi-coke: the mass ratio of the petroleum coke is 40: 20: 10: 10: 10: 10; the binder comprises the following components: sodium carboxymethylcellulose: starch: the mass ratio of the waste syrup is 40: 10: 10: 40; the additive comprises the following components: pyrrhotite: the mass ratio of the chalcopyrite is 30:30: 40.
Preparing the mixed material into carbon-containing pellets on a double-roller ball press, and drying the carbon-containing pellets at 105 ℃. And (3) putting the carbon-containing pellets into an atmosphere furnace, charging nitrogen to protect the carbon-containing pellets, heating the carbon-containing pellets to 950 ℃, then preserving the heat for 240min, and cooling the carbon-containing pellets along with the furnace under the protection of the nitrogen after roasting is finished to obtain the porous silicate supported micro-nano iron sulfide copper alloy. The porosity is 55%, the S content is 5.5%, the copper content is 2.3%, 99% of the iron-copper alloy is distributed between 100nm and 10 microns, wherein the nano-level accounts for 67%, and 83% of the iron-copper alloy is distributed on the surface of the silicate hole.
The porous silicate supported micro-nano iron sulfide copper alloy prepared by the embodiment is applied to treat chromium-containing wastewater in certain industry, wherein Cr is Cr6+The concentration was 560 mg/L. Adjusting the pH value of the wastewater to about 3, and under the condition that the hydraulic retention time is 1h, Cr6+The removal rate was 95%. Continuously running for 5 weeks, Cr6+The removal effect is stable, and no obvious hardening phenomenon is found.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (3)
1. A method for producing porous silicate supported micro-nano iron sulfide copper alloy by using copper slag is characterized by comprising the following steps: the method comprises the following steps:
(1) preparing carbon-containing pellets of copper slag: mixing copper slag, a carbonaceous reducing agent, an additive and a binder according to a certain proportion, adding water to make pellets or press pellets, and preparing carbon-containing pellets; the carbonaceous reducing agent is one or more of anthracite, bituminous coal, active carbon, coke, semicoke and petroleum coke; the additive is one or more of pyrite, pyrrhotite and chalcopyrite; the mass ratio of the copper slag to the carbonaceous reducing agent to the additive to the binder is 100:25: 5: 0.5 or 100:35: 8: 5;
(2) reduction roasting: drying the carbon-containing pellets obtained in the step (1), and then carrying out reduction roasting at the roasting temperature of 950-1250 ℃ in a reducing atmosphere; the roasting time is 20 min-300 min;
(3) after the reaction is finished, rapidly cooling under the condition of isolating oxygen, forming silicate glass in a liquid phase, and finally obtaining the porous silicate supported micro-nano iron sulfide copper alloy material; wherein:
the porosity of the porous silicate supported micro-nano iron sulfide copper alloy material obtained in the step (3) is more than 50%, more than 70% of iron sulfide copper alloy is distributed on the surface of silicate pores, the sulfur content of the iron sulfide copper alloy is more than 3%, the copper content is more than 0.5%, the granularity is 100nm to 10 mu m, and the mass ratio of the nano-scale iron sulfide copper alloy is not less than 50%.
2. The method for producing the porous silicate supported micro-nano iron sulfide copper alloy by using the copper slag according to claim 1, which is characterized by comprising the following steps of: the iron content of the copper slag is more than 30%, and the copper slag is crushed to be less than 0.1 mm.
3. The method for producing the porous silicate supported micro-nano iron sulfide copper alloy by using the copper slag according to claim 1, which is characterized by comprising the following steps of: the binder is one or more of waste syrup, sodium carboxymethyl cellulose, starch and water glass.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107200392A (en) * | 2017-07-31 | 2017-09-26 | 山东大学 | A kind of sulfide modifier Fe Cu bimetallic materials, preparation method and the method for removing chromate waste water |
| WO2019071788A1 (en) * | 2017-10-10 | 2019-04-18 | 东北大学 | Manufacturing method using copper and iron containing mixing slag |
| CN111266572A (en) * | 2020-03-20 | 2020-06-12 | 中国科学院过程工程研究所 | Iron-copper bimetal load ferrous sulfide composite material, preparation method and application thereof |
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| CA3050758A1 (en) * | 2018-07-26 | 2020-01-26 | The Royal Institution For The Advancement Of Learning/Mcgill Universit | Sulfidated nanoscale zerovalent iron and method of use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107200392A (en) * | 2017-07-31 | 2017-09-26 | 山东大学 | A kind of sulfide modifier Fe Cu bimetallic materials, preparation method and the method for removing chromate waste water |
| WO2019071788A1 (en) * | 2017-10-10 | 2019-04-18 | 东北大学 | Manufacturing method using copper and iron containing mixing slag |
| CN111266572A (en) * | 2020-03-20 | 2020-06-12 | 中国科学院过程工程研究所 | Iron-copper bimetal load ferrous sulfide composite material, preparation method and application thereof |
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| Title |
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| "铜渣改性制备多孔硅酸盐负载微纳米零价铁及其去除废水中的Cr( VI)";胡美世等;《矿产保护与利用》;20200630(第3期);第40-45页 * |
| "铜渣火法强化贫化工艺研究";陈海清等;《湖南有色金属》;20060630;第22卷(第3期);第16-18页 * |
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