CN107032571B - Resource treatment system and process for heavy metal sulfide sludge - Google Patents
Resource treatment system and process for heavy metal sulfide sludge Download PDFInfo
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- CN107032571B CN107032571B CN201710446060.XA CN201710446060A CN107032571B CN 107032571 B CN107032571 B CN 107032571B CN 201710446060 A CN201710446060 A CN 201710446060A CN 107032571 B CN107032571 B CN 107032571B
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a resource treatment system and process for heavy metal sulfide sludge, and belongs to the field of water treatment and the field of resource of dangerous solid wastes. The resource treatment system for the heavy metal sulfide sludge comprises an acid sludge stirring and dissolving device, a flocculant preparation device, a hydrogen sulfide absorption device and a solid waste separation device, wherein the acid sludge stirring and dissolving device is respectively connected with the flocculant preparation device, the hydrogen sulfide absorption device and the solid waste separation device. The resource treatment process of the heavy metal sulfide sludge comprises the following steps: stirring and dissolving the acid sludge, preparing a ferric trichloride flocculating agent, purifying hydrogen sulfide tail gas and separating solid waste. The invention can realize the resource treatment of the heavy metal sulfide sludge, thereby preparing industrial products with higher added value.
Description
Technical Field
The invention belongs to the field of water treatment and the field of recycling of dangerous solid wastes, and particularly relates to a recycling treatment system and a recycling treatment process for heavy metal sulfide sludge.
Background
At present, the heavy metal pollution in wastewater in China is serious, and the heavy metal pollution is mainly from the industries of nonferrous metal mining and selection, smelting and the like. The content, the type and the existence form of the heavy metals in the wastewater discharged by different production enterprises are different. At present, a great amount of acid wastewater rich in lead, zinc and iron is mainly generated in the metallurgical manufacturing industry, if the acid wastewater is directly discharged into a water body, the pH value of the water body is changed, the growth of microorganisms is inhibited or influenced, the self-purification effect of the water body is influenced, and meanwhile, heavy metals have toxicity and can cause harm to the health of human bodies and other organisms. So that it can cause regional environmental pollution to a great extent if it cannot be properly disposed of.
At present, the method for treating heavy metal acidic wastewater mainly comprises two methods: the first method is that alkaline substances are added into the wastewater to precipitate lead, zinc and iron, and then the lead, zinc and iron are directly discharged, but the method has the problems of large sludge yield, complex operation conditions and the like; the other method is a sodium sulfide precipitation method, which has higher removal efficiency on lead ions and is easy for sludge concentration and dehydration treatment, but has the problem that the generated heavy metal sulfide sludge is difficult to dispose.
Generally, sludge disposal methods mainly include landfill, land utilization, incineration and the like, and heavy metal sulfide sludge has high metal content and belongs to dangerous waste, and the landfill and the land utilization cause heavy metal pollution to soil; direct incineration also has a low calorific value due to low solid content, and a large amount of auxiliary fuel is consumed due to failure to maintain effective spontaneous combustion, so that disposal cost is obviously increased. Therefore, the development of a resource disposal mode becomes the key point which needs to be solved urgently in the industry at present.
Through retrieval, the research on the resource treatment of heavy metal sulfide sludge is published at present, and for example, in the document "treating lead-containing wastewater by a sulfide precipitation method", the influence of the operation conditions such as the addition amount of sodium sulfide, the initial pH value of the reaction and the like on the lead ion removal effect is explored, so that a theoretical basis is provided for the engineering application of treating the lead-containing wastewater by the sodium sulfide precipitation method. The research treats the waste water containing single heavy metal, the obtained lead sulfide precipitate can be directly recycled, but the problem of precipitation caused by the treatment of the waste water containing multiple heavy metals is not considered.
Also for example, chinese patent application No. CN2015105453892 discloses a method for removing mercury from hydrometallurgical acidic wastewater, which comprises settling metallurgical acidic wastewater, adding calcium hydroxide solution to the supernatant of the settled acidic wastewater to neutralize the acidic wastewater to pH 5-6; and (3) carrying out filter pressing on the neutralized acidic wastewater, sequentially adding sodium sulfide and a flocculating agent into the neutralized clear liquid to remove mercury, and carrying out solid-liquid separation on the neutralized clear liquid. The treatment process of the application can generate mercury sulfide precipitate, still belongs to dangerous waste and needs further advanced treatment.
For another example, chinese patent application No. CN2015106732915 discloses a method for preparing a polyferric chloride flocculant from steel wire rope sludge and waste salt. The application dissolves steel wire rope acid-washing sludge by waste hydrochloric acid, and removes lead ions in a dissolving solution by a sulfide precipitation method to obtain a polyferric chloride flocculant; the generated hydrogen sulfide gas meets the national emission standard of malodorous pollutants after falling film absorption, packed tower absorption and active carbon adsorption treatment, and meanwhile, the sulfur element is recycled in the whole process; the solidification and stabilization of the heavy metals are realized by adding cement into the sludge residues for solidification. The application does not consider the removal of zinc element, the zinc contained in the sulfide sludge is leached into the flocculant in a very small amount, and the zinc still exists in the sludge in a very large amount and is treated as dangerous waste, and simultaneously does not consider the treatment of sulfide precipitation products, so that further optimization is needed.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention aims to overcome the defect that heavy metal sulfide sludge generated by treating heavy metal acidic wastewater in the current metallurgical industry is difficult to treat, and provides a resource treatment system and process for heavy metal sulfide sludge. By adopting the technical scheme of the invention, the treatment of the heavy metal sulfide sludge can be realized, the reduction of the hazardous waste can be realized, the defects of the traditional process can be overcome, the ferric chloride flocculating agent which is an industrial product with higher added value can be prepared, and the recycling of the hazardous waste can be realized, so that certain profits are brought to enterprises.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention discloses a resource treatment system for heavy metal sulfide sludge, which comprises an acid sludge stirring and dissolving device, a flocculating agent preparing device, a hydrogen sulfide absorbing device and a solid waste separating device, wherein the acid sludge stirring and dissolving device is respectively connected with the flocculating agent preparing device, the hydrogen sulfide absorbing device and the solid waste separating device.
Furthermore, the hydrogen sulfide absorption device comprises a first hydrogen sulfide absorption tower and a second hydrogen sulfide absorption tower which are sequentially connected, and the first hydrogen sulfide absorption tower is connected with an exhaust port of the acid sludge stirring and dissolving device through a pipeline.
Furthermore, a pipeline for communicating the first hydrogen sulfide absorption tower with the second hydrogen sulfide absorption tower is provided with a hydrogen sulfide leakage alarm.
Furthermore, the solid waste separation device is connected with a sludge discharge port of the acid sludge stirring and dissolving device through a pipeline, and a valve is arranged on the pipeline connecting the solid waste separation device and the acid sludge stirring and dissolving device.
The invention relates to a resource treatment process of heavy metal sulfide sludge, which comprises the following steps:
A. stirring and dissolving acid sludge: adding heavy metal sulfide sludge to be treated into an acid sludge stirring and dissolving device, adding acid liquor into the acid sludge stirring and dissolving device, stirring and standing the mixture, and pumping supernatant into a flocculant preparation device;
B. preparing a ferric chloride flocculating agent: detecting Fe in solution introduced into flocculant preparation device2+And Fe3+And an oxidizing agent is prepared according to the content of the Fe-B-Fe-B alloy2+In the molar ratio of n (oxidizing agent): n (Fe)2+) 1: (3-6), adding the oxidant into a flocculant preparation device for stirring reaction, and after the reaction is finished, carrying out formation treatment to prepare a ferric trichloride flocculant;
C. hydrogen sulfide tail gas purification: absorbing the hydrogen sulfide gas introduced into the hydrogen sulfide absorption device by using saturated alkali liquor;
D. solid-waste separation: and (4) leading the mixed precipitate generated in the step A to enter a solid-waste separation device.
Furthermore, the adding amount of the sludge in the step A is 1/5-1/2 volume of the acid sludge stirring and dissolving device, the acid liquor is one or a mixture of at least two of hydrochloric acid, nitric acid and sulfuric acid, and the pH value of the acid liquor is 3-4.
Further, the mass ratio of the sludge added in the step A to the acid liquor is m (sludge): m (acid solution) ═ 1: (1-10). Furthermore, the rotation speed of stirring and dissolving in the acid sludge stirring and dissolving device in the step A is 200-500r/min, the stirring time is 0.5-2h, and the standing time is 1-8 h.
Furthermore, the oxidant in the step B is one or a mixture of sodium chlorate and potassium chlorate, the rotation speed of stirring and dissolving is 200-500r/min, the stirring time is 0.5-2h, the time of formation treatment is 15-30h, and 10-50% of water is evaporated after the formation treatment to prepare the ferric trichloride flocculant.
Furthermore, the hydrogen sulfide gas in the step C is firstly introduced into a first hydrogen sulfide absorption tower for absorption treatment, the treated hydrogen sulfide gas passes through a hydrogen sulfide leakage alarm, and if the hydrogen sulfide gas does not alarm, the hydrogen sulfide gas is directly discharged through a second hydrogen sulfide absorption tower; and if the alarm is given, the hydrogen sulfide gas is returned to the first hydrogen sulfide absorption tower from the second hydrogen sulfide absorption tower, then the hydrogen sulfide leakage alarm does not give an alarm and is directly discharged through the second hydrogen sulfide absorption tower, and the alkali liquor in the first hydrogen sulfide absorption tower and the alkali liquor in the second hydrogen sulfide absorption tower are one or a mixture of sodium hydroxide, calcium hydroxide and potassium hydroxide solutions.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) the invention relates to a resource treatment system of heavy metal sulfide sludge, which comprises an acid sludge stirring and dissolving device, a flocculating agent preparation device, a hydrogen sulfide absorption device and a solid waste separation device. Supernatant produced in the acid sludge stirring and dissolving device enters a flocculating agent preparation device to prepare the ferric trichloride flocculating agent, and insoluble substances precipitated at the bottom are discharged into a solid-waste separation device, so that the treatment of heavy metal sulfide sludge is realized, the reduction and resource utilization of hazardous wastes are realized, and certain profits are brought to enterprises.
(2) According to the resource treatment system for the heavy metal sulfide sludge, hydrogen sulfide generated by the acid sludge stirring and dissolving device is discharged into the hydrogen sulfide absorption device, and absorption treatment is performed through alkali liquor, so that direct discharge and environmental pollution are prevented.
(3) According to the resource treatment system for the heavy metal sulfide sludge, the hydrogen sulfide absorption device comprises a first hydrogen sulfide absorption tower and a second hydrogen sulfide absorption tower which are sequentially connected. The two-stage absorption tower can ensure the sufficient absorption of the hydrogen sulfide and reduce the environmental pollution.
(4) According to the resource treatment system for the heavy metal sulfide sludge, the hydrogen sulfide leakage alarm is arranged on the pipeline between the first hydrogen sulfide absorption tower and the second hydrogen sulfide absorption tower, so that hydrogen sulfide contained in the discharged gas can be monitored, the hydrogen sulfide is completely absorbed, the hydrogen sulfide is prevented from leaking, the hydrogen sulfide is further fully absorbed, and the environmental pollution is reduced.
(5) According to the resource treatment system for the heavy metal sulfide sludge, the solid-waste separation device is provided with the valve, so that the insoluble substances can be effectively separated, and then cement is prepared, and thus the heavy metal can be immobilized and stabilized.
(6) According to the resource treatment process of the heavy metal sulfide sludge, the mass ratio of the sludge and the acid liquor added in the stirring and dissolving process of the acid sludge is m (sludge): m (acid solution) ═ 1: (1-10), the maximization of the amount of the dissolved heavy metal sulfide sludge can be effectively ensured.
Drawings
FIG. 1 is a schematic structural diagram of a resource disposal system for heavy metal sulfide sludge according to the present invention;
FIG. 2 is a flow chart of a resource disposal process of heavy metal sulfide sludge according to the present invention.
The reference numerals in the schematic drawings illustrate: 1. an acid sludge stirring and dissolving device; 2. a flocculant preparation device; 3. a first hydrogen sulfide absorption tower; 4. a second hydrogen disulfide absorption tower; 5. a hydrogen sulfide leak alarm; 6. a solid waste separation device; 7. and (4) a valve.
Detailed Description
For a further understanding of the invention, reference should be made to the following detailed description taken in conjunction with the accompanying drawings.
The present invention will be further described with reference to the following examples.
As shown in fig. 1, the resource treatment system for heavy metal sulfide sludge of the present invention comprises an acid sludge stirring and dissolving device 1, a flocculant preparation device 2, a hydrogen sulfide absorption device and a solid waste separation device 6, wherein the acid sludge stirring and dissolving device 1 is respectively connected with the flocculant preparation device 2, the hydrogen sulfide absorption device and the solid waste separation device 6. All be equipped with the agitator in the device 2 is prepared to acid sludge stirring dissolving device 1, flocculating agent, and be equipped with the elevator pump on the pipeline that device 2 links to each other is prepared to acid sludge stirring dissolving device 1 and flocculating agent, and this elevator pump adopts acid-fast corrosion elevator pump.
According to the invention, the sludge to be treated and the dilute acid solution are mixed, stirred and dissolved by the acid sludge stirring and dissolving device 1, the generated supernatant is pumped into the flocculant preparation device 2 by the lift pump to prepare the flocculant, the hydrogen sulfide gas generated in the acid sludge stirring and dissolving device 1 is absorbed by the hydrogen sulfide absorption device to prevent direct emission and environmental pollution, and insoluble substances at the bottom of the acid sludge stirring and dissolving device 1 are separated by the solid-waste separation device 6. The system can effectively realize the resource treatment of the heavy metal sulfide sludge, reduce the environmental pollution, has simple operation process and can realize automation.
The hydrogen sulfide absorption device comprises a first hydrogen sulfide absorption tower 3 and a second hydrogen sulfide absorption tower 4 which are connected in sequence, wherein the first hydrogen sulfide absorption tower 3 is connected with an exhaust port of an acid mud stirring and dissolving device 1 through a pipeline, spraying devices are arranged at the tops of the first hydrogen sulfide absorption tower 3 and the second hydrogen sulfide absorption tower 4, and absorption liquid sprayed by the spraying devices absorbs hydrogen sulfide gas. Because the hydrogen sulfide that produces is less, and the two-stage absorption tower can guarantee the abundant absorption to hydrogen sulfide, is equipped with hydrogen sulfide leakage alarm 5 on the pipeline of first hydrogen sulfide absorption tower 3 and second hydrogen sulfide absorption tower 4 simultaneously to can monitor the hydrogen sulfide that contains in the exhaust gas. If the hydrogen sulfide leakage alarm 5 does not alarm, the hydrogen sulfide is directly discharged through the second hydrogen sulfide absorption tower 4; if the hydrogen sulfide leakage alarm 5 gives an alarm, the hydrogen sulfide gas is led back to the first hydrogen sulfide absorption tower 3 from the second hydrogen sulfide absorption tower 4, and then the hydrogen sulfide leakage alarm 5 does not give an alarm and is directly discharged from the second hydrogen sulfide absorption tower 4.
According to the invention, the solid waste separation device 6 is connected with the sludge discharge port of the acid sludge stirring and dissolving device 1 through a pipeline, the valve 7 is arranged on the pipeline connecting the solid waste separation device 6 with the acid sludge stirring and dissolving device 1, the effective separation of insoluble substances can be ensured through the solid waste separation device 6, and then the separated insoluble substances are made into cement, so that the immobilization and stabilization treatment of heavy metals is realized.
The process of the resource treatment process of the heavy metal sulfide sludge is shown in fig. 2, the resource treatment of the heavy metal sulfide sludge is realized through acid sludge stirring and dissolving, flocculant preparation, hydrogen sulfide tail gas purification and solid-waste separation, and the process procedures and process parameters of the above steps are optimally designed, so that the resource treatment effect of the heavy metal sulfide sludge is ensured, and the pollution to the environment is effectively reduced. The process comprises the following specific steps:
A. stirring and dissolving acid sludge: the method comprises the steps of feeding heavy metal sulfide sludge to be treated into an acid sludge stirring and dissolving device 1, and then adding an acid liquor into the acid sludge stirring and dissolving device, wherein the feeding amount of the sludge is 1/5-1/2 volume parts of the acid sludge stirring and dissolving device 1, the fed acid liquor is one or a mixture of at least two of hydrochloric acid, nitric acid and sulfuric acid, the pH value of the acid liquor is 3-4, and the mass ratio of the fed sludge to the acid liquor is m (sludge): m (acid solution) ═ 1: (1-10), the rotation speed of stirring and dissolving in the acid sludge stirring and dissolving device 1 is 200-500r/min, the stirring time is 0.5-2h, the standing time is 1-8h, and then the supernatant is pumped to the flocculant preparation device 2. The adding proportion of the sludge and the acid liquor, the stirring time, the standing time and the like are effectively controlled, so that the sufficient dissolution of the acid sludge is ensured.
B. Preparing a ferric chloride flocculating agent: detecting Fe in the solution introduced into the flocculant preparation device 22+And Fe3+And an oxidizing agent is prepared according to the content of the Fe-B-Fe-B alloy2+In the molar ratio of n (oxidizing agent): n (Fe)2+) 1: (3-6), adding the oxidant into the flocculant preparation device 2 for stirring reaction, wherein the oxidant is one or the mixture of sodium chlorate and potassium chlorate, the rotating speed of stirring and dissolving is 200-500r/min, the stirring time is 0.5-2h, the formation treatment time is 15-30h, and after the formation treatment, 10-50% of water is evaporated to prepare the ferric trichloride flocculationAnd (3) preparing.
C. Hydrogen sulfide tail gas purification: and (3) introducing the hydrogen sulfide gas generated by the acid sludge stirring and dissolving device 1 into a hydrogen sulfide absorption device, and absorbing by using saturated alkali liquor. Introducing hydrogen sulfide gas into a first hydrogen sulfide absorption tower 3 for absorption treatment, wherein the treated hydrogen sulfide gas passes through a hydrogen sulfide leakage alarm 5, and if the treated hydrogen sulfide gas does not give an alarm, the treated hydrogen sulfide gas is directly discharged through a second hydrogen sulfide absorption tower 4; if the alarm is given, the hydrogen sulfide gas is led back to the first hydrogen sulfide absorption tower 3 from the second hydrogen sulfide absorption tower 4, then the hydrogen sulfide leakage alarm 5 does not give an alarm and is directly discharged through the second hydrogen sulfide absorption tower 4, and the alkali liquor in the first hydrogen sulfide absorption tower 3 and the second hydrogen sulfide absorption tower 4 is one or the mixture of more than one of the sodium hydroxide solution, the calcium hydroxide solution and the potassium hydroxide solution.
D. Solid-waste separation: lead and zinc mixed precipitates precipitated at the bottom of the acid sludge stirring and dissolving device 1 are discharged into a solid-waste separation device 6, the effective separation of insoluble substances is controlled through a valve 7, and then cement is prepared, so that the immobilization and stabilization treatment of heavy metals is realized.
For a further understanding of the invention, reference will now be made in detail to the present invention with reference to the accompanying drawings and examples.
Example 1
Referring to fig. 1 and 2, 100kg of heavy metal sulfide sludge (with a water content of 40% -70%) is added into an acid sludge stirring and dissolving device 1, wherein the adding amount of the sludge is added to 1/2 volume of the acid sludge stirring and dissolving device 1, so that sufficient space is reserved for subsequent acid liquor addition, and effective reaction is guaranteed; and adding a hydrochloric acid solution (pH is 4) into the acid sludge stirring and dissolving device 1, wherein the mass ratio of the added sludge to the acid solution is m (sludge): m (acid solution) ═ 1: 10. stirring rotation speed of a stirrer in the acid sludge stirring and dissolving device 1 is 500r/min, stirring and reacting for 1h, standing for 4h, and pumping supernatant into the flocculating agent preparation device 2 by using an acid corrosion resistant lifting pump. The detection shows that the Pb content in the supernatant (namely the acid sludge mixed solution) is 7mg/L, the Zn content is 469mg/L, and the Fe content is2+Content 105g/L, Fe3+The content was 28 g/L. According to Fe2+Content (wt.)Preparing an oxidant, namely sodium chlorate with the mass of 66.5kg as the oxidant adopted in the embodiment, adding water to dissolve the sodium chlorate, adding the sodium chlorate into a flocculant preparation device 2, stirring and reacting for 1 hour at the rotating speed of 200r/min, naturally carrying out formation treatment for 24 hours, and evaporating 50% of water to obtain the ferric trichloride flocculant. Introducing hydrogen sulfide gas generated by the acid sludge stirring and dissolving device 1 into a hydrogen sulfide absorption device for absorption treatment, pumping alkali liquor in the hydrogen sulfide absorption device into spraying devices at the tops of the first hydrogen sulfide absorption tower 3 and the second hydrogen sulfide absorption tower 4 through pipelines and a lifting pump by adopting saturated sodium hydroxide solution, and spraying the hydrogen sulfide gas by the spraying devices. And opening a valve 7 to discharge the lead-zinc precipitation mixture generated by the acid sludge stirring and dissolving device 1 to a solid waste separation device 6 so as to prepare cement for immobilization treatment later.
The flocculant prepared in this example was tested, and the results were as follows:
TABLE 1 Mass content of the flocculants prepared in this example
| Index (I) | Numerical value |
| FeCl3 | 39.2％ |
| FeCl2 | 0.3％ |
| Density of | 1.16g/cm3 |
| Insoluble substance | 0.4％ |
| Free acid | 0.3％ |
| Pb | 0.0008％ |
The result shows that the prepared flocculant meets the GB4482-2006 industrial standard. When the flocculant is used for treating printing and dyeing wastewater (turbidity is 100NTU, COD is 912mg/L), experiments show that the removal of the turbidity can reach about 85 percent, and the removal rate of the COD can reach about 75 percent.
Example 2
The process for recycling heavy metal sulfide sludge in this embodiment is basically the same as in embodiment 1, except that in this embodiment, 100kg of heavy metal sulfide sludge (with a water content of 40% to 70%) is added to the acid sludge stirring and dissolving device 1, the amount of the added sludge is added to 1/5 volumes of the acid sludge stirring and dissolving device 1, and then a hydrochloric acid and nitric acid mixed solution (pH 3) is added to the acid sludge stirring and dissolving device 1, where the amount of the added sludge is m (sludge): m (acid solution) ═ 1: 5. stirring rotation speed of a stirrer in the acid sludge stirring and dissolving device 1 is 200r/min, stirring and reacting for 0.5h, standing for 1h, and pumping supernatant into the flocculating agent preparation device 2 by using an acid corrosion resistant lifting pump. Through detection, the Pb content of the acid mud mixed solution is 10mg/L, the Zn content is 645mg/L, and Fe2+93g/L of Fe3+The content was 37 g/L. According to Fe2+The oxidant is configured according to the content, the oxidant adopted in the embodiment is potassium chlorate, the mass of the potassium chlorate is 21kg, the potassium chlorate is dissolved by adding water and then is added into the flocculant preparation device 2, the mixture is stirred and reacts for 0.5h at the rotating speed of 500r/min, the mixture is naturally decomposed for 15h, and 10% of water is evaporated after the formation treatment to obtain the ferric trichloride flocculant. In this example, the alkali solution in the hydrogen sulfide absorption apparatus was saturated calcium hydroxide solution.
The flocculant prepared in this example was tested, and the results were as follows:
TABLE 2 quality index of the flocculant prepared in this example
| Index (I) | Numerical value |
| FeCl3 | 40.3％ |
| FeCl2 | 0.4％ |
| Density of | 1.22g/cm3 |
| Insoluble substance | 0.3％ |
| Free acid | 0.2％ |
| Pb | 0.0009％ |
The result shows that the prepared flocculant meets the GB4482-2006 industrial standard. When the flocculant is used for treating printing and dyeing wastewater (the turbidity is 200NTU, and the COD is 1000mg/L), experiments show that the removal of the turbidity can reach about 80 percent, and the removal rate of the COD can reach about 71 percent.
Example 3
The recycling treatment process of heavy metal sulfide sludge in this embodiment is basically the same as that in embodiment 1, except that in this embodiment, 100kg of heavy metal sulfide sludge (with a water content of 40% -70%) is added to the acid sludge stirring and dissolving device 1, and the adding amount of the sludge is 1/3 bodies added to the acid sludge stirring and dissolving device 1And adding a mixed solution of hydrochloric acid, nitric acid and sulfuric acid (pH is 3.5) into the acid sludge stirring and dissolving device 1, wherein the adding amount is m (sludge): m (acid solution) ═ 1: 1. stirring speed of a stirrer in the acid sludge stirring and dissolving device 1 is 350r/min, and after stirring reaction for 2 hours and standing for 8 hours, a lifting pump resistant to acid corrosion is used for pumping supernatant into the flocculant preparation device 2. Through detection, the Pb content of the acid mud mixed solution is 9mg/L, the Zn content is 732mg/L, and Fe2+The content of Fe is 110g/L3+The content was 32 g/L. According to Fe2+The content configuration oxidant, the oxidant that this embodiment adopted is potassium chlorate, and the potassium chlorate quality is 8kg, and the flocculant preparation device 2 is added to after potassium chlorate adds the water and dissolves to throw into to react 2h with the rotational speed stirring of 300r/min, becomes 30h under the natural circumstances, evaporates 40% moisture after the formation processing and obtains the ferric trichloride flocculant. In this example, the alkali solution in the hydrogen sulfide absorption apparatus was saturated potassium hydroxide solution.
The flocculant prepared in this example was tested, and the results were as follows:
TABLE 3 quality index of the flocculant prepared in example 3
| Index (I) | Numerical value |
| FeCl3 | 38.7％ |
| FeCl2 | 0.3％ |
| Density of | 1.35g/cm3 |
| Insoluble substance | 0.5％ |
| Free acid | 0.4％ |
| Pb | 0.001％ |
The result shows that the prepared flocculant meets the GB4482-2006 industrial standard. When the flocculant is used for treating printing and dyeing wastewater (the turbidity is 300NTU, and the COD is 800mg/L), experiments show that the removal of the turbidity can reach about 77 percent, and the removal rate of the COD can reach about 68 percent.
Example 4
The process for recycling heavy metal sulfide sludge in this embodiment is basically the same as in embodiment 1, except that in this embodiment, 100kg of heavy metal sulfide sludge (with a water content of 40% to 70%) is added to the acid sludge stirring and dissolving device 1, the amount of the added sludge is added to 1/3 volumes of the acid sludge stirring and dissolving device 1, and then a mixed solution of hydrochloric acid and sulfuric acid (pH 4) is added to the acid sludge stirring and dissolving device 1, where the amount of the added sludge is m (sludge): m (acid solution) ═ 1: 3. stirring and reacting for 1.5h at the rotating speed of 300r/min, standing for 6h, and pumping the supernatant into the flocculant preparation device 2 by using an acid corrosion resistant lifting pump. Through detection, the Pb content of the acid mud mixed solution is 10mg/L, the Zn content is 867mg/L, and Fe2+The content of Fe is 101g/L3+The content was 35 g/L. According to Fe2+Preparing an oxidant by content, mixing potassium chlorate and sodium chlorate by the oxidant, adding 15kg of the oxidant by mass, adding water for dissolving, adding the mixture into a flocculant preparation device 2, stirring and reacting at a rotating speed of 400r/min for 1.5h, naturally forming for 20h, and evaporating 30% of water to obtain the ferric trichloride flocculant. In this embodiment, the alkali solution in the hydrogen sulfide absorption device is a mixed solution of sodium hydroxide and calcium hydroxide.
The flocculant prepared in this example was tested, and the results were as follows:
TABLE 4 quality index of the flocculant obtained in example 4
| Index (I) | Numerical value |
| FeCl3 | 42.0％ |
| FeCl2 | 0.4％ |
| Density of | 1.14g/cm3 |
| Insoluble substance | 0.2％ |
| Free acid | 0.1％ |
| Pb | 0.0006％ |
The result shows that the prepared flocculant meets the GB4482-2006 industrial standard. When the flocculant is used for treating printing and dyeing wastewater (the turbidity is 500NTU, and the COD is 900mg/L), experiments show that the removal of the turbidity can reach about 78 percent, and the removal rate of the COD can reach about 75 percent.
Example 5
The recycling treatment process of heavy metal sulfide sludge in this embodiment is basically the same as that in embodiment 1, except that in this embodiment, 100kg of heavy metal sulfide sludge (with a water content of 40% -70%) is added into the acid sludge stirring and dissolving device 1, and the adding amount of the sludge is added into the acid sludge stirring and dissolving deviceAt 1/4 volume of the decomposition device 1, adding a hydrochloric acid and sulfuric acid mixed solution (pH 3) into the acid sludge stirring and dissolving device 1, wherein the adding amount is m (sludge): m (acid solution) ═ 1: 8. after stirring and reacting for 1 hour at 350r/min and standing for 5 hours, the supernatant was pumped to a flocculant preparing apparatus 2 using an acid corrosion resistant lift pump. Through detection, the Pb content of the acid sludge mixed solution is 8mg/L, the Zn content is 623mg/L, and Fe2+The content of Fe is 125g/L3+The content was 17 g/L. According to Fe2+The content is provided with an oxidant, the oxidant adopted in the embodiment is potassium chlorate, the mass of the potassium chlorate is 37kg, the potassium chlorate is dissolved by adding water and then is added into the flocculant preparation device 2, the mixture is stirred and reacts for 2 hours at the rotating speed of 300r/min, the mixture is naturally decomposed for 15 hours, and 20% of water is evaporated after the decomposition treatment to obtain the ferric trichloride flocculant. In this embodiment, the alkali solution in the hydrogen sulfide absorption device is a mixed solution of sodium hydroxide and potassium hydroxide.
The flocculant prepared in this example was tested, and the results were as follows:
TABLE 5 quality index of the flocculant prepared in example 5
| Index (I) | Numerical value |
| FeCl3 | 40.8％ |
| FeCl2 | 0.3％ |
| Density of | 1.26g/cm3 |
| Insoluble substance | 0.3％ |
| Free acid | 0.2％ |
| Pb | 0.0008％ |
The result shows that the prepared flocculant meets the GB4482-2006 industrial standard. When the flocculant is used for treating printing and dyeing wastewater (the turbidity is 400NTU, and the COD is 1100mg/L), experiments show that the removal of the turbidity can reach about 81 percent, and the removal rate of the COD can reach about 73 percent.
Example 6
The process for recycling heavy metal sulfide sludge in this embodiment is basically the same as in embodiment 1, except that in this embodiment, the acid solution added to the acid sludge stirring and dissolving device 1 is a sulfuric acid solution (pH 3), and the alkali solution in the hydrogen sulfide absorption device is a mixed solution of calcium hydroxide and potassium hydroxide.
Example 7
The process for recycling heavy metal sulfide sludge in this embodiment is basically the same as in embodiment 1, except that in this embodiment, the acid solution added to the acid sludge stirring and dissolving device 1 is a nitric acid solution (pH 4), and the alkali solution in the hydrogen sulfide absorption device is a mixed solution of sodium hydroxide, calcium hydroxide and potassium hydroxide.
Example 8
The process for recycling heavy metal sulfide sludge in this embodiment is basically the same as in embodiment 1, except that the acid solution added to the acid sludge stirring and dissolving device 1 in this embodiment is a mixed solution of nitric acid and sulfuric acid (pH 4).
The present invention and its embodiments have been described above schematically, without limitation, and what is shown in the drawings is only one of the embodiments of the present invention, and the actual structure is not limited thereto. Therefore, if the person skilled in the art receives the teaching, without departing from the spirit of the invention, the person skilled in the art shall not inventively design the similar structural modes and embodiments to the technical solution, but shall fall within the scope of the invention.
Claims (1)
1. The resource treatment process of the heavy metal sulfide sludge is characterized in that a sludge resource treatment system is utilized and is carried out according to the following steps, wherein the sludge resource treatment system comprises an acid sludge stirring and dissolving device (1), a flocculant preparation device (2), a hydrogen sulfide absorption device and a solid waste separation device (6), and the acid sludge stirring and dissolving device (1) is respectively connected with the flocculant preparation device (2), the hydrogen sulfide absorption device and the solid waste separation device (6); the hydrogen sulfide absorption device comprises a first hydrogen sulfide absorption tower (3) and a second hydrogen sulfide absorption tower (4) which are sequentially connected, wherein the first hydrogen sulfide absorption tower (3) is connected with an exhaust port of the acid sludge stirring and dissolving device (1) through a pipeline; the solid waste separation device (6) is connected with a sludge discharge port of the acid sludge stirring and dissolving device (1) through a pipeline, and a valve (7) is arranged on the pipeline connecting the solid waste separation device (6) and the acid sludge stirring and dissolving device (1); a pipeline for communicating the first hydrogen sulfide absorption tower (3) with the second hydrogen sulfide absorption tower (4) is provided with a hydrogen sulfide leakage alarm (5);
the method comprises the following steps:
A. stirring and dissolving acid sludge: adding heavy metal sulfide sludge to be treated into an acid sludge stirring and dissolving device (1), adding acid liquor into the acid sludge stirring and dissolving device, stirring and standing the mixture, and pumping supernatant into a flocculant preparation device (2); the adding amount of the sludge is that the sludge is added to the 1/5-1/2 volume part of the acid sludge stirring and dissolving device (1), the acid liquor is one or the mixture of at least two of hydrochloric acid, nitric acid and sulfuric acid, and the pH value of the acid liquor ranges from 3 to 4; the mass ratio of the added sludge to the acid liquor is m (sludge): m (acid solution) ═ 1: (1-10); in the step A, the rotation speed of stirring and dissolving in the acid sludge stirring and dissolving device (1) is 200-500r/min, the stirring time is 0.5-2h, and the standing time is 1-8 h;
B. preparing a ferric chloride flocculating agent: detecting Fe in the solution introduced into the flocculant preparation device (2)2+And Fe3+And an oxidizing agent is prepared according to the content of the Fe-B-Fe-B alloy2+In the molar ratio of n (oxidizing agent): n (Fe)2+) 1: (3-6) addingAdding the oxidant into a flocculant preparation device (2) for stirring reaction, and preparing the ferric trichloride flocculant through formation treatment after the reaction is finished; the oxidant in the step B is one or a mixture of sodium chlorate and potassium chlorate, the rotation speed of stirring and dissolving is 200-500r/min, the stirring time is 0.5-2h, the time of formation treatment is 15-30h, and 10-50% of water is evaporated after the formation treatment to prepare the ferric trichloride flocculant;
C. hydrogen sulfide tail gas purification: absorbing the hydrogen sulfide gas introduced into the hydrogen sulfide absorption device by using saturated alkali liquor; c, introducing the hydrogen sulfide gas into a first hydrogen sulfide absorption tower (3) for absorption treatment, and directly discharging the treated hydrogen sulfide gas through a second hydrogen sulfide absorption tower (4) if the treated hydrogen sulfide gas passes through a hydrogen sulfide leakage alarm (5); if the alarm is given, the hydrogen sulfide gas is returned to the first hydrogen sulfide absorption tower (3) from the second hydrogen sulfide absorption tower (4), then the hydrogen sulfide leakage alarm (5) does not give an alarm and is directly discharged through the second hydrogen sulfide absorption tower (4), and the alkali liquor in the first hydrogen sulfide absorption tower (3) and the second hydrogen sulfide absorption tower (4) is one or the mixture of more than one of sodium hydroxide, calcium hydroxide and potassium hydroxide solution;
D. solid-waste separation: and (4) leading the mixed precipitate generated in the step A to enter a solid waste separation device (6).
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