CN111020201B - Method for purifying and removing impurities from smelting flue gas desulfurization gypsum - Google Patents
Method for purifying and removing impurities from smelting flue gas desulfurization gypsum Download PDFInfo
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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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/468—Purification of calcium sulfates
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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
- C22B13/00—Obtaining lead
- C22B13/04—Obtaining lead by wet processes
- C22B13/045—Recovery from waste materials
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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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
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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
- C22B17/00—Obtaining cadmium
- C22B17/04—Obtaining cadmium by wet processes
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
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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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/30—Obtaining zinc or zinc oxide from metallic residues or scraps
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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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin scrap
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/20—Obtaining alkaline earth metals or magnesium
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/04—Obtaining arsenic
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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
- C22B7/006—Wet processes
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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
Abstract
The invention belongs to the field of nonferrous metal hydrometallurgy, comprehensive utilization of resources and environmental protection, and provides a method for purifying and removing impurities from smelted flue gas desulfurization gypsum, which takes the smelted flue gas desulfurization gypsum of materials containing tin and lead as raw materials and comprises the processes of acid leaching treatment of the raw materials, suction filtration, neutralization, filtering separation and the like, the method can realize effective impurity removal treatment on the flue gas desulfurization gypsum, has high recovery rate of tin metal, and does not belong to dangerous waste after purifying and removing impurities from the smelted flue gas desulfurization gypsum of the materials containing tin and copper; the tin is recovered in the form of tin slag, and the recovery rate of the tin is over 70 percent; the process is simple to operate and environment-friendly. The economic efficiency is better, the cost is saved, the influence on the environment is less, and the economic and social effects are good.
Description
The technical field is as follows:
the invention relates to the field of non-ferrous metal hydrometallurgy, comprehensive resource utilization and environmental protection, in particular to a method for purifying gypsum by removing impurities from smelting flue gas desulfurization gypsum of materials containing tin and lead, and particularly relates to a method for purifying and removing impurities from smelting flue gas desulfurization gypsum.
Background art:
limestone-gypsum method flue gas desulfurization is a process which is most widely applied to sulfur dioxide flue gas desulfurization in the industries of steel smelting and coal-fired power generation. In the process of flue gas desulfurization by limestone-gypsum method, a large amount of desulfurization gypsum is generated, and how to effectively treat and recycle the desulfurization gypsum is a major problem concerned and faced by relevant departments and industries of China. Currently, there are two main application approaches of desulfurized gypsum: one is used as retarder of silicate cement, and the other is used for producing building gypsum or gypsum products taking building gypsum as main raw material. Because the domestic natural gypsum resources are abundant, and the corresponding policies, regulations, standards and technical guarantees for comprehensive utilization of the desulfurized gypsum are relatively lacked, a considerable part of desulfurized gypsum is still disposed by adopting a stacking mode, not only occupies a large amount of land, but also can cause secondary pollution to the surrounding environment, so that the resource utilization of the desulfurized gypsum is urgently needed to be solved.
Based on the superiority of limestone-gypsum method in technology and economy, the process is increasingly applied to the flue gas desulfurization of low-concentration sulfur dioxide produced by non-ferrous metal pyrometallurgy, but the effective treatment and resource utilization of the produced desulfurized gypsum or flue gas desulfurized gypsum face higher pressure.
In particular, in the process of pyrometallurgical comprehensive recovery of copper and lead materials containing tin, zinc, cadmium, arsenic and other metals, the desulfurized gypsum produced by flue gas desulfurization by limestone-gypsum method is very likely to be classified as a hazardous waste because it contains a certain amount of heavy metals. Namely, the desulfurized gypsum is likely to belong to hazardous waste according to the "hazardous waste discrimination Standard Leaching toxicity discrimination" (GB 5085.3-2007) Leaching toxicity discrimination Standard, and the corresponding "solid waste Leaching toxicity Leaching method Sulfuric acid-nitric method" (HJ/T299-2007).
How to effectively treat and utilize the desulfurized gypsum or flue gas desulfurized gypsum has more technical researches at home. However, in the pyrometallurgical comprehensive recovery process of copper and lead materials containing various metals such as tin, zinc, cadmium, arsenic and the like, the dilemma of how to go out desulfurized gypsum produced by flue gas desulfurization by a limestone-gypsum method, which may belong to dangerous wastes, and further reduce resource utilization ways, and comprehensively recover valuable metals is not seen at present.
For example, Chinese patent publication No. CN 109574060A, "a method for removing impurities and decolorizing desulfurized gypsum". The technical scheme disclosed by the method is that firstly, the desulfurized gypsum is subjected to drying, grinding, screening, ultrasonic treatment and the like, so that the dispersion of gypsum crystals can be promoted, the removal of impurities on the surfaces of the crystals and among the crystals is facilitated, the washing efficiency is improved, the consumption of water, the discharge of washing waste liquid and the washing times are reduced, the operation is simplified, and the environmental pollution is reduced. Then, on the basis of ultrasonic water washing, heating and acid washing are carried out by using sulfuric acid, so that the release of colored impurities wrapped in the crystal can be promoted. After the acid washing reaction is finished, the acid washing reaction is immediately filtered, so that impurities can be prevented from being wrapped in the crystals again in the recrystallization process, and the impurity removal and decoloration effects are improved. Meanwhile, the sulfuric acid is used for replacing hydrochloric acid, and new impurities cannot be introduced. After impurity removal operation, the impurity content of the desulfurized gypsum is reduced from 2.75 percent to below 1.27 percent, and the whiteness is improved from 30.26 percent to over 90 percent, but the method can not well remove and recover heavy metals. Also disclosed in Chinese patent publication No. CN 103910371A is a method for preparing calcium carbonate and co-producing ammonium sulfate by using flue gas desulfurization gypsum or desulfurization ash slag, which comprises the following steps: 1) adding water into the desulfurized gypsum or desulfurized ash slag according to the solid-liquid mass ratio of 10-30%, and uniformly stirring and dispersing into a suspension; 2) according to the formula NH 4 HCO 3: NH 3. H2O: the amount ratio of CaSO 4 in the desulfurized gypsum or desulfurized ash residue is 1-1.6: 1 to 1.6: 1, adding NH 4 HCO 3 solid and NH 3. H2O with the mass percent concentration of 1-30% into the suspension, stirring the mixture consisting of the suspension, the NH 4 HCO 3 solid and the NH 3. H2O, and reacting for 0.5-2H; 3) carrying out solid-liquid separation on the reaction product obtained in the step 2) to obtain calcium carbonate solid and ammonium sulfate solution. The invention utilizes NH 4 HCO 3 and NH 3. H2O as transforming agents to respectively transform calcium and sulfur elements in desulfurized gypsum or desulfurized ash into calcium carbonate and ammonium sulfate at room temperature, the transformation efficiency of the calcium and the sulfur reaches more than 95 percent, the resource recycling of the calcium and the sulfur elements is realized, the energy is greatly saved, the purpose of energy saving and environmental protection is achieved while the comprehensive utilization of resource and energy is realized, but the invention also only discloses the application of the desulfurized gypsum, and does not disclose how to remove harmful metals in flue gas desulfurized gypsum, so that the flue gas desulfurized gypsum becomes the leaching toxicity identification standard according to the hazardous waste identification standard leaching toxicity identification (GB 5085.3-2007), and is not classified as a hazardous waste product.
But the technical approach described above. The impurity removal treatment of the flue gas desulfurization gypsum produced by smelting the tin-containing copper and lead materials is not specific, so that the flue gas desulfurization gypsum becomes the desulfurization gypsum which does not belong to dangerous waste according to the leaching toxicity identification standard of the hazardous waste identification standard (GB 5085.3-2007) and the corresponding sulfuric acid-nitric method of the solid waste leaching toxicity leaching method (HJ/T299-2007).
Therefore, how to provide the desulfurization gypsum for effective treatment and resource utilization, namely how to remove the desulfurization gypsum produced by flue gas desulfurization by a limestone-gypsum method in the pyrometallurgical comprehensive recovery process of copper and lead materials containing tin, zinc, cadmium, arsenic and other metals belongs to a dangerous waste and resource utilization way, and meanwhile, valuable metal tin can be effectively and maximally recovered, and the comprehensive utilization of the flue gas desulfurization gypsum is realized, and the research or detailed report of related technical methods is not seen at present.
The invention content is as follows:
the invention aims to provide a method for purifying and removing impurities from smelted flue gas desulfurization gypsum, which takes the smelted flue gas desulfurization gypsum of materials containing tin and lead as raw materials and comprises the processes of raw material acid leaching treatment, suction filtration, neutralization, filtering separation and the like; the tin is recovered in the form of tin slag, and the recovery rate of the tin is over 70 percent; the process is simple to operate and environment-friendly. The economic efficiency is better, the cost is saved, the influence on the environment is less, and the economic and social effects are good.
The invention discloses a method for purifying and decontaminating smelting flue gas desulfurization gypsum, which takes the smelting flue gas desulfurization gypsum of tin-containing copper and lead materials as raw materials and comprises the following process steps:
1) the acid leaching treatment of the raw material is carried out,
adding an acid solution into a flue gas desulfurization gypsum raw material smelted by a material containing tin and lead, and continuously stirring and mixing to obtain desulfurization gypsum leaching slurry;
2) filtering the mixture by suction filtration,
placing the desulfurized gypsum leaching slurry prepared in the step 1) in a preparation suction filtration device for suction filtration treatment, adding water for washing and suction filtration at the final stage of suction filtration, and repeating the suction filtration treatment for a plurality of times to obtain purified gypsum and a suction filtration liquid;
3) the neutralization is carried out on the mixture of the raw materials,
treating the suction filtration liquid obtained by the suction filtration in the step 2) into tin-rich filtrate, and then adding calcium salt into the tin-rich filtrate for neutralization reaction to obtain neutralization reaction slurry;
4) the mixture is filtered and separated, and then,
and (3) filtering the neutralization reaction slurry obtained by neutralization in the step 3) to obtain tin slag and waste water liquid.
Preferably, the acid solution added in the acid leaching treatment of the raw material in the step 1) is sulfuric acid or a mixed solution of sulfuric acid and hydrochloric acid; the mass of the copper and lead materials containing tin added into each 1.5-2.5L of the acid solution for smelting the flue gas desulfurization gypsum is controlled to be 150-250g, and the concentration of the acid solution is controlled to be 45-55 g/L.
Preferably, the neutralization control in the step 3) is that the tin content in the tin-rich filtrate is more than or equal to 3 g/L; and controlling the calcium salt added into the tin-rich filtrate to be calcium sulfate or calcium sulfate and calcium chloride or calcium sulfate and calcium oxide, and controlling the pH of the neutralization reaction slurry to be = 4.8-5.8.
Further, the recovery rate of tin in the raw material of the flue gas desulfurization gypsum obtained by smelting copper and lead materials containing tin is controlled to be more than or equal to 70 Wt%; step 4), controlling the content of copper and arsenic in the tin slag to be less than or equal to 0.1 Wt%; the content of tin is more than or equal to 3Wt percent.
The tin-containing copper and lead material smelting flue gas desulfurization gypsum comprises the following components in percentage by mass: 85-90% of calcium sulfate dihydrate dry basis, 13-17% of attached water wet basis, 0.007-0.011% of lead, 0.008-0.012% of arsenic, 0.0014-0.0018% of cadmium, 0.001-0.005% of zinc, 0.15-0.19% of tin, 0.006-0.009% of copper and 0.1-0.3% of chlorine.
The invention relates to a method for purifying and removing impurities from smelting flue gas desulfurization gypsum, which comprises the following steps of 1) performing acid leaching treatment on raw materials, wherein the acid leaching treatment time is controlled to be 2.5-3.5 h, and the acid solution is prepared by mixing concentrated sulfuric acid and concentrated hydrochloric acid according to the mass ratio of 60-40: 40-60 parts; and leaching under the condition of continuous stirring.
The invention discloses a method for purifying and removing impurities from smelting flue gas desulfurization gypsum, which is mainly used for purifying and removing impurities from smelting flue gas containing tin and copper materials by a limestone-gypsum method by adopting a wet metallurgy method to produce purified gypsum and tin slag, wherein the produced purified gypsum does not belong to dangerous waste, the tin slag is used as a tin recovery raw material, and waste water is additionally treated. The method has the following main characteristics:
1. after the tin-containing copper and lead materials are subjected to purification and impurity removal treatment by the method, the smelting flue gas desulfurization gypsum does not belong to dangerous waste;
2. the method of the invention recovers tin in the form of tin slag, and the recovery rate of tin is more than or equal to 70 percent;
3. the method has simple process operation and is environment-friendly. Under the same conditions, compared with the traditional process, the method saves the use of raw materials and better protects the environment, does not belong to hazardous waste and changes waste into valuable after the desulfurization gypsum produced by a limestone-gypsum method is used for treating the smelting flue gas of the copper and lead materials containing tin, and can recycle the non-ferrous metal tin to lead, thereby reducing the recycling cost of recycling valuable metal tin and achieving good effect.
The preparation process comprises the following steps: smelting a flue gas desulfurization gypsum raw material by using a tin-containing copper and lead material, and reducing the raw material by using an acid solution → mixing → leaching → filtering → purifying the desulfurization gypsum → filtering liquid; filtrate → calcium salt → neutralization → filtration → tin dross and waste water liquid.
The invention discloses a method for purifying and removing impurities from smelting flue gas desulfurization gypsum, which mainly utilizes the characteristics that lead sulfate is slightly soluble in water, calcium arsenate is easily soluble in dilute sulfuric acid, cadmium sulfate and zinc sulfate as solution entrainment and the like, and adopts sulfuric acid solution to leach lead, arsenic, cadmium and zinc in the desulfurization gypsum, namely leach raw materials of the smelting flue gas desulfurization gypsum containing tin and lead materials, wherein the desulfurization gypsum purified by the method is the purified gypsum according to the leaching toxicity identification standard of hazardous waste identification standard (GB 5085.3-2007) and the corresponding sulfuric acid-nitric acid method (HJ/T299-2007) of the solid waste leaching toxicity leaching method, and does not belong to hazardous waste any more;
on the other hand, because the tin and the copper in the desulfurized gypsum exist in hydroxide forms, the aim of the invention can be achieved by leaching and filtering the desulfurized gypsum by adopting a sulfuric acid solution and adding calcium carbonate to neutralize the filtrate.
The specific implementation mode is as follows:
the present invention will be described in further detail with reference to specific embodiments; each component referred to as used in the following embodiments refers to mass or mass percentage.
Aiming at low-grade complex multi-metal dangerous waste containing various valuable metals such as copper, lead, zinc, tin, indium, silver, gold and the like but only 1-5% of the total quantity of the valuable metals, the method provides a method which adopts shaft furnace reduction smelting to produce matte and water quenching slag, and discharges the flue gas after dust collection by a cloth bag and pneumatic emulsification desulfurization treatment to reach the standard, thereby realizing the comprehensive recovery of the multi-metal and obtaining higher metal recovery rate.
The method takes low-grade multi-metal hazardous waste as a raw material, adopts a shaft furnace for reduction smelting to produce matte and water quenching slag, and discharges the flue gas after reaching the standard after bag dust collection and pneumatic emulsification desulfurization treatment.
The invention discloses a method for purifying and decontaminating smelting flue gas desulfurization gypsum, which takes hazardous wastes of low-grade various metals as raw materials and smelting flue gas desulfurization gypsum from tin-containing copper and lead materials as raw materials and comprises the following process steps:
2) the acid leaching treatment of the raw material is carried out,
adding an acid solution into a raw material of flue gas desulfurization gypsum smelted from a material containing tin and copper, and lead, and continuously stirring and mixing, wherein the added acid solution is sulfuric acid or a mixed solution of sulfuric acid and hydrochloric acid; if the sulfuric acid and the hydrochloric acid are added and mixed, the mass ratio of the sulfuric acid to the hydrochloric acid is controlled to be 50-80: 50-20, or controlling the addition of sulfuric acid and hydrochloric acid to completely and fully dissolve and leach metals such as lead, arsenic, cadmium, zinc, copper and the like in the gypsum, and ensuring that the purified desulfurized gypsum obtained by filtering is no longer hazardous waste. Namely: according to the contents of metals such as lead, arsenic, cadmium, zinc, copper and the like and the content of residual limestone in the tin-containing copper and lead material smelting flue gas desulfurization gypsum, the mass of the tin-containing copper and lead material smelting flue gas desulfurization gypsum is controlled to be 250g per 1.5-2.5L of acid solution according to the leaching toxicity identification standard value of hazardous waste identification standard leaching toxicity identification (GB 5085.3-2007), and the concentration of the acid solution is controlled to be 45-55 g/L. Is desulfurized gypsum leaching slurry;
2) carrying out suction filtration,
carrying out suction filtration treatment on the desulfurized gypsum leaching slurry prepared in the step 1) in a preparation suction filtration device, adding water to wash and carry out suction filtration at the final stage of suction filtration, and repeating the suction filtration treatment for a plurality of times to obtain purified gypsum and a filtrate, wherein the tin content in the filtrate is controlled to be more than or equal to 2 g/L;
3) the neutralization is carried out on the mixture of the raw materials,
performing tin-rich treatment on the filtrate obtained in the step 2) to obtain tin-rich filtrate, controlling the calcium salt added into the tin-rich filtrate to be calcium sulfate or calcium sulfate and calcium chloride or calcium sulfate and calcium oxide, and controlling the pH of the neutralization reaction slurry to be = 4.8-5.8; obtaining a neutralization reaction slurry; neutralizing to control the tin content in the tin-rich filtrate to be more than or equal to 5 g/L;
4) the mixture is filtered and separated, and then,
and (3) filtering the neutralization reaction slurry obtained by neutralization in the step 3) to obtain tin slag and waste water liquid.
Example 1:
mass or mass ratio
The invention discloses a method for purifying and removing impurities from smelting flue gas desulfurization gypsum, which takes the smelting flue gas desulfurization gypsum of materials containing tin and lead as a raw material, called the desulfurization gypsum raw material, and adopts a hydrometallurgical process to prepare purified gypsum and tin slag, wherein the specific process technical method of waste water comprises the following steps:
1. acid leaching treatment of raw materials, namely leaching: 6000g of a raw material 6000g of flue gas desulfurization gypsum smelted by a material containing tin and lead is taken, and the raw material is detected to comprise the following main components in percentage by mass: 87% of calcium sulfate dihydrate (dry basis), 15% of attached water (wet basis), 0.009% of lead, 0.01% of arsenic, 0.0016% of cadmium, 0.003% of zinc, 0.17% of tin, 0.008% of copper and 0.2% of chlorine; the acid solution of the acid leaching treatment is sulfuric acid solution, namely 2L of sulfuric acid-containing solution with the sulfuric acid concentration of 50g/L is prepared, 200g of raw material of the flue gas desulfurization gypsum smelted by the copper and lead materials containing tin is added into the prepared 2L of sulfuric acid solution, stirring leaching is carried out at normal temperature and normal pressure, and the leaching time is controlled for 3 hours to obtain desulfurization gypsum leaching slurry;
2. and (3) suction filtration: placing the desulfurized gypsum leaching slurry into a suction filtration device for suction filtration treatment, namely suction filtration is carried out on the desulfurized gypsum leaching slurry obtained in the previous step, and 30ml of water is added to wash and suction filtration at the final stage of the suction filtration to obtain purified gypsum and filtrate, wherein the filtrate is suction filtration liquid;
the acid solution can be prepared by adding a certain amount of sulfuric acid and water to the filtrate to adjust the sulfuric acid concentration to 2L of a sulfuric acid-containing solution of 50 g/L. Repeating the leaching and filtering, namely, the leaching operation is repeated for a plurality of times until the leaching and the filtering of 6000g of the raw material of the flue gas desulfurization gypsum generated by smelting the tin-containing copper and lead materials are completed, so as to obtain purified gypsum and a leaching solution; the step of processing the suction filtration liquid into a tin-rich solution is to repeat the suction filtration and filtration process until the tin content in the suction filtration liquid reaches more than 3g/L, namely the tin-rich solution;
3. neutralizing: treating the suction filtration liquid obtained in the step 2) into a solution with tin content reaching 3g/L to obtain tin-rich filtrate, and adding calcium carbonate into the tin-rich solution to perform neutralization reaction until the pH of the neutralization reaction solution is =5 to obtain neutralization reaction slurry;
4. and (3) filtering: and 3) carrying out suction filtration on the neutralization reaction slurry obtained in the step 3) to obtain tin slag and filtrate.
The main components of the purified gypsum obtained by the treatment of the method of the embodiment are detected by relevant departments to be composed of the following components: 96% of calcium sulfate dihydrate (dry basis), 10% of attached water (wet basis), 0.003% of lead, 0.002% of arsenic, 0.0006% of cadmium, 0.0004% of zinc, 0.04% of tin, 0.003% of copper and 0.03% of chlorine; the obtained tin slag contains 3.1% of tin, 0.1% of copper and 0.1% of arsenic, and the recovery rate of tin is 72%; the filtrate mainly contains lead, arsenic, cadmium, zinc, calcium, magnesium, chlorine and the like, and is separately treated and recycled.
Example 2
The following examples are the same as those of example 1 except for the following descriptions;
the method for purifying and removing impurities from smelting flue gas desulfurization gypsum disclosed by the method takes the smelting flue gas desulfurization gypsum from materials containing tin and lead as raw materials, and adopts a hydrometallurgical process to prepare purified gypsum and tin slag, wherein the specific process technical method of the waste water comprises the following steps:
1. acid leaching treatment of raw materials, namely leaching: 6000g of a raw material of tin-containing copper and lead smelting flue gas desulfurization gypsum is taken, and the main components of the raw material comprise the following components in percentage by mass: 84 percent of calcium sulfate dihydrate (dry basis), 14 percent of attached water (wet basis), 0.0085 percent of lead, 0.016 percent of arsenic, 0.0018 percent of cadmium, 0.0028 percent of zinc, 0.18 percent of tin, 0.009 percent of copper and 0.15 percent of chlorine. The acid solution of the acid leaching treatment is a mixed solution of sulfuric acid and hydrochloric acid, the mass ratio of the sulfuric acid to the hydrochloric acid is 60% of sulfuric acid and 40% of hydrochloric acid, the sulfuric acid and the hydrochloric acid are concentrated sulfuric acid and concentrated hydrochloric acid, namely 2L of a sulfuric acid and hydrochloric acid containing solution with the concentration of 50g/L of sulfuric acid and hydrochloric acid is prepared, 200g of the desulfurized gypsum raw material is added into the prepared 2L of the mixed solution of sulfuric acid and hydrochloric acid, stirring leaching is carried out at normal temperature and normal pressure, and the leaching time is controlled for 2.6h, so that desulfurized gypsum leaching slurry is obtained;
2. and (3) suction filtration: placing the desulfurized gypsum leaching slurry into a suction filtration device for suction filtration treatment, namely suction filtration is carried out on the desulfurized gypsum leaching slurry obtained in the previous step, and 30ml of water is added to wash and suction filtration at the final stage of the suction filtration to obtain purified gypsum and filtrate, wherein the filtrate is suction filtration liquid;
the acid solution can be prepared by adding a certain amount of sulfuric acid, hydrochloric acid and water to the filtrate, and adjusting the mass ratio of the sulfuric acid to the hydrochloric acid to be 60% of the mixed solution of sulfuric acid and hydrochloric acid with the concentration of 50g/L of 40% of hydrochloric acid to be 2L. Repeating the leaching and filtering, namely, the leaching operation is repeated for a plurality of times until the leaching and the filtering of 6000g of the raw material of the flue gas desulfurization gypsum generated by smelting the tin-containing copper and lead materials are completed, so as to obtain purified gypsum and a leaching solution;
3. neutralizing: treating the suction filtration liquid obtained in the step 2) into a solution with tin content reaching 3g/L, and then adding calcium sulfate into the solution for neutralization reaction until the pH value in the neutralization reaction solution is =5, so as to obtain a neutralization reaction slurry;
4. and (3) filtering: and carrying out suction filtration on the neutralization reaction slurry to obtain the tin dross and filtrate.
The main components of the purified gypsum obtained by the treatment by the method of the embodiment comprise 96 percent (dry basis) of calcium sulfate dihydrate, 10 percent (wet basis) of attached water, 0.0028 percent of lead, 0.0018 percent of arsenic, 0.0007 percent of cadmium, 0.00039 percent of zinc, 0.046 percent of tin, 0.0036 percent of copper and 0.038 percent of chlorine; the tin slag contains 3.1% of tin, 0.1% of copper and 0.1% of arsenic; the detection proves that the recovery rate of tin in the raw material of the flue gas desulfurization gypsum generated by smelting the copper and lead materials containing tin is 71.3 percent; the main components in the filtrate contain lead, arsenic, cadmium, zinc, calcium, magnesium, chlorine, etc., and are separately treated and recovered.
It should be noted that: the above technical solutions disclosed in the present invention are not limited thereto; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; such modifications and substitutions do not depart from the spirit and scope of the present invention, and they should be construed as being included in the following claims and description.
Claims (2)
1. A method for purifying and decontaminating smelting flue gas desulfurization gypsum, which takes the smelting flue gas desulfurization gypsum of tin-containing copper and lead materials as raw materials, and is characterized by comprising the following process steps:
the acid leaching treatment of the raw material is carried out,
adding an acid solution into a flue gas desulfurization gypsum raw material smelted by a material containing tin and lead, and continuously stirring and mixing to obtain desulfurization gypsum leaching slurry;
2) filtering the mixture by suction filtration,
placing the desulfurized gypsum leaching slurry prepared in the step 1) in a preparation suction filtration device for suction filtration treatment, adding water for washing and suction filtration at the final stage of suction filtration, and repeating the suction filtration treatment for a plurality of times to obtain purified gypsum and a suction filtration liquid;
3) the neutralization is carried out on the mixture of the raw materials,
treating the suction filtration liquid obtained by the suction filtration in the step 2) into tin-rich filtrate, and then adding calcium salt into the tin-rich filtrate for neutralization reaction to obtain neutralization reaction slurry;
4) the mixture is filtered and separated, and then,
filtering the neutralization reaction slurry obtained by neutralization in the step 3) to obtain tin slag and waste water liquid;
step 1) the acid solution added in the acid leaching treatment of the raw material is sulfuric acid or a mixed solution of sulfuric acid and hydrochloric acid; the mass of the flue gas desulfurization gypsum produced by smelting copper and lead materials containing tin is controlled to be 150-250g per 1.5-2.5L of the acid solution, and the concentration of the acid solution is controlled to be 45-55 g/L;
step 3) neutralizing and controlling the tin content in the tin-rich filtrate to be more than or equal to 3 g/L; controlling the calcium salt added into the tin-rich filtrate to be calcium sulfate or calcium sulfate and calcium chloride or calcium sulfate and calcium oxide, and controlling the pH of the neutralization reaction slurry to be = 4.8-5.8;
controlling the recovery rate of tin in the raw material of the flue gas desulfurization gypsum smelted from the copper and lead materials containing tin to be more than or equal to 70 percent; step 4), controlling the content of copper and arsenic in the tin slag to be less than or equal to 0.1 Wt%; the content of tin is more than or equal to 3Wt percent.
2. The method for purifying and removing impurities in flue gas desulfurization gypsum smelting according to claim 1, wherein in the step 1), the acid leaching treatment of the raw material is performed for 2.5 to 3.5 hours, and the acid solution is prepared by mixing concentrated sulfuric acid and concentrated hydrochloric acid according to a mass ratio of 60 to 40: 40-60 parts; and leaching under the condition of continuous stirring.
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