CN111056610A - Device and method for reinforcing contaminated acid heavy metal vulcanization by utilizing hydrogen sulfide micro-nano bubbles - Google Patents
Device and method for reinforcing contaminated acid heavy metal vulcanization by utilizing hydrogen sulfide micro-nano bubbles Download PDFInfo
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Abstract
The invention relates to a device and a method for strengthening contaminated acid heavy metal vulcanization by utilizing hydrogen sulfide micro-nano bubbles, wherein the device comprises a high-speed dissolved air pump (1) and a gas-liquid injection pipe (2) with a high-efficiency gas-liquid dispersion element, the inlet end of the high-speed dissolved air pump (1) is connected with a contaminated acid vulcanization reactor (3) and a hydrogen sulfide air supply pipeline (4), the outlet end of the high-speed dissolved air pump is connected with the gas-liquid injection pipe (2) through a circulating pipeline, and an injection port of the gas-liquid injection pipe (2) is arranged in the contaminated acid vulcanization reactor (3). Before the hydrogen sulfide is introduced into the waste acid, the hydrogen sulfide is bubbled through the micro-nano bubble generating device, and in the introduction of the waste acid, the hydrogen sulfide entering the waste acid in the form of micro-nano bubbles is removed through the high-efficiency gas-liquid mass transfer contact for strengthening the vulcanization of heavy metals in the waste acid. Compared with the prior art, the method can realize high-efficiency vulcanization of the waste acid and high vulcanizing agent utilization rate, has better economic and environmental benefits and has better application and popularization prospects.
Description
Technical Field
The invention belongs to the field of non-ferrous smelting environment protection, relates to a method and a device for strengthening heavy metal vulcanization of contaminated acid by utilizing hydrogen sulfide micro-nano bubbles, and particularly relates to a method and a device for removing heavy metal by strengthening vulcanization of contaminated acid by utilizing hydrogen sulfide in a non-ferrous smelting process.
Background
The nonferrous metal is an important environmental resource for industrial development in China, the nonferrous metal mineral reserves in China are rich, the nonferrous metal industry develops rapidly in nearly 30 years, the yield is at the head of the world in successive years, the yields of various nonferrous metals in China are obviously increased in the first half of 2019, and the yields of refined copper, raw aluminum, refined lead, zinc, electrolytic nickel, tin, antimony, magnesium, sponge titanium and mercury are 452 ten thousand tons, 1741 ten thousand tons, 286 ten thousand tons, 281 ten thousand tons, 9.27 thousand tons, 8.98 thousand tons, 11.1 thousand tons, 38.5 thousand tons, 4.1 thousand tons and 0.11 thousand tons respectively. The high-concentration sulfur dioxide flue gas generated in the non-ferrous smelting process is one of the main raw materials for producing industrial sulfuric acid, and the high-concentration heavy metal elements such as arsenic contained in the flue gas can poison a catalyst in the acid making process and have adverse effect on the acid making process, so that before the acid making process, the flue gas must be washed and purified by a purification process, a large amount of acidic wastewater can be generated in the process, and the heavy metal pollutants such as arsenic, zinc, cadmium, lead and the like in the flue gas enter waste acid, which is called 'waste acid'. Along with the circulation of the washing process, the pollutants are gradually enriched, and in order to prevent the accumulation of impurities and influence the purification and the subsequent acid making processes, certain waste acid must be periodically discharged to a waste acid treatment process. Because the waste acid has high acidity, the toxic substances such as arsenic and heavy metal have high content, and the waste acid is easy to discharge, the harm to the environment is obvious, and simultaneously, the waste of arsenic resources, dilute acid resources and heavy metal resources is caused, and the sustainable development of non-ferrous metal smelting enterprises is even restricted. It is necessary to effectively treat the contaminated acid.
The sulfide precipitation method is one of the main methods of the waste acid treatment process of nonferrous metal companies in China. The method is characterized in that sulfides such as sodium sulfide, hydrogen sulfide, sodium hydrosulfide and the like are added into the polluted acid and react with heavy metals to generate insoluble matters, so that toxic heavy metal ions are effectively treated. However, there are some disadvantages in the using process, for the contaminated acid with high heavy metal content and large content fluctuation, the sulfuration removal is incomplete, the treatment effect is not ideal, moreover, the amount of the vulcanizing agent used in the sulfuration reaction stage is too large, the cost is high, and the generated hydrogen sulfide is more and easy to leak, the danger is large, the sulfuration precipitation method is not suitable for removing the trace heavy metal in the sewage, and only suitable for the primary sulfuration removal of the sewage with high heavy metal content in the industrial production, and other methods are used for assisting in the standard discharge of the industrial sewage.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the device and the method for strengthening the sulfuration of the heavy metal in the contaminated acid by utilizing the hydrogen sulfide micro-nano bubbles, which can obviously improve the sulfuration effect of the hydrogen sulfide on the heavy metal in the contaminated acid and improve the utilization rate of a vulcanizing agent.
The micro-nano bubbles generally refer to micro-bubbles with a diameter of less than 50 μm, wherein the micro-bubbles with a diameter of more than 1 μm are called micro-bubbles, the ultra-micro-bubbles with a diameter of less than 1 μm and more than 1nm are further called nano-bubbles, and the micro-nano bubbles not only have a much smaller volume than that of ordinary bubbles, but also have some special properties different from ordinary bubbles. The micro-bubbles show the characteristics of long existence time, high mass transfer efficiency and the like due to small size. The invention applies the micro-nano bubble technology to environmental pollution treatment and water environmental pollution remediation, and has the advantages of high mass transfer efficiency, good treatment effect and low operation cost.
The purpose of the invention can be realized by the following technical scheme: the utility model provides an utilize micro-nano bubble of hydrogen sulfide to strengthen dirty sour heavy metal vulcanizer, its characterized in that, the device include high-speed solution pump (1), have gas-liquid injection pipe (2) of high-efficient gas-liquid dispersion component, high-speed solution pump (1) entrance point connect dirty sour vulcanization reactor (3) and hydrogen sulfide air supply line (4), the exit end passes through circulating line and connects gas-liquid injection pipe (2), the jet orifice of this gas-liquid injection pipe (2) is arranged in dirty sour vulcanization reactor (3).
The gas-liquid injection pipe (2) with the high-efficiency gas-liquid dispersion element consists of a spiral sheet (21) with fine holes and a short diffusion pipe type Venturi ejector (22).
The short-diffuser-type Venturi ejector (22) comprises a throat and a diffuser which are communicated with each other and integrally arranged, the diameter of the throat is 2-20 mm, and the length of the throat is 1-3 times of the diameter of the throat; the diffusion angle of the diffusion tube is 5-8 degrees, the length of the diffusion tube is 2-3 times of the length of the throat, and the liquid flow velocity at the throat of the throat is 25-40 m/s.
The spiral sheet (21) with the fine holes is arranged in the diffusion tube, and the hole diameter of the open hole on the spiral sheet is as follows: 0.1 to 0.2mm, and 10 to 30% of open area.
The spiral sheet (21) with the fine holes is a metal sheet, the width of the metal sheet is 0.8-0.9 d, the length of the metal sheet is 2-3 d, and d is the inner diameter of the diffusion tube, one end of the spiral sheet is fixed during processing, and the other end of the spiral sheet is uniformly twisted by 180 degrees.
The top of the waste acid vulcanization reactor (3) is provided with an air chamber (31), the air chamber (31) is connected to a hydrogen sulfide air supply pipeline (4) through an exhaust pipe, and the high-speed dissolved air pump (1) is introduced after the air chamber is connected in parallel.
The method for reinforcing the sulfuration of the contaminated acid heavy metal by using the hydrogen sulfide micro-nano bubbles by adopting the device is characterized by comprising the following steps:
firstly, respectively sucking circulating waste acid and hydrogen sulfide gas into a pump body by using a high-speed dissolved air pump (1), and forming micro-nano bubbles of hydrogen sulfide by the dispersion action of high-speed rotating blades;
secondly, micro-nano bubble-containing waste acid from the high-speed dissolved air pump (1) is further dispersed by a gas-liquid injection pipe (2) with a high-efficiency gas-liquid dispersion element, and finally is directly injected into a waste acid vulcanization reactor (3);
and thirdly, the hydrogen sulfide in contact with the waste acid in the form of micro-nano bubbles can effectively strengthen the sulfuration reaction of the hydrogen sulfide and heavy metals in the waste acid due to the characteristics of high bubble dispersion degree, long retention time, high mass transfer efficiency and the like, so that the heavy metal pollution is efficiently removed.
The waste acid refers to acidic wastewater containing heavy metal pollutants generated in the nonferrous smelting industry, and the heavy metal pollutants comprise arsenic, mercury, cadmium, lead or copper.
In the first step, the hydrogen sulfide introduced into the high-speed gas dissolving pump (1) is high-concentration gas with the concentration of the hydrogen sulfide being more than 20 percent.
In the second step, micro-nano bubbles containing hydrogen sulfide micro-bubbles with the diameter less than 50 mu m are injected into the contaminated acid vulcanization reactor (3);
in the second step, the flow of the high-speed air dissolving pump (1) is as follows: 2 to 20m3H, the bubble diameters produced are: 100 nm-10 μm.
Compared with the prior art, the invention has the following advantages:
1. according to the invention, the hydrogen sulfide gas is contacted with the waste acid in the form of micro-nano bubbles by using the hydrogen sulfide micro-nano bubble generating device, so that the diffusion efficiency of the hydrogen sulfide can be improved, and the vulcanization efficiency of heavy metals in the waste acid can be improved;
2. the residual hydrogen sulfide can be recycled by using the circulating device, so that the utilization rate of the vulcanizing agent is improved, and the cost is saved;
3. according to the invention, the hydrogen sulfide gas is contacted with the waste acid in the form of micro-nano bubbles by using the hydrogen sulfide micro-nano bubble generating device, so that the retention time of the hydrogen sulfide in the waste acid is prolonged, and the vulcanization and removal of heavy metals can be enhanced.
Drawings
Fig. 1 is a schematic diagram of a hydrogen sulfide micro-nano bubble generating device.
FIG. 2 is a schematic view showing the structure of a gas-liquid injection tube having a high-efficiency gas-liquid dispersion element.
Fig. 3 is a schematic view of a structure of a spiral sheet with fine holes.
Detailed Description
The present invention is further illustrated by the following specific examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
Example 1
As shown in figure 1, the device for strengthening the contaminated acid heavy metal vulcanization by utilizing the hydrogen sulfide micro-nano bubbles comprises a high-speed dissolved air pump 1 and a gas-liquid injection pipe 2 with a high-efficiency gas-liquid dispersion element, wherein the inlet end of the high-speed dissolved air pump 1 is connected with a contaminated acid vulcanization reactor 3 and a hydrogen sulfide gas supply pipeline 4, the outlet end of the high-speed dissolved air pump is connected with the gas-liquid injection pipe 2 through a circulating pipeline, and an injection port of the gas-liquid injection pipe 2 is arranged in the contaminated acid vulcanization reactor 3. The top of the waste acid vulcanization reactor 3 is provided with an air chamber 31, the air chamber 31 is connected to a hydrogen sulfide gas supply pipeline 4 through an exhaust pipe, and the high-speed gas dissolving pump 1 is introduced after the air chamber 31 is connected in parallel.
The gas-liquid injection pipe 2 with the high-efficiency gas-liquid dispersion element consists of a spiral sheet 21 with fine holes and a short diffusion pipe type Venturi ejector 22. The short diffuser type Venturi ejector 22 comprises a throat and a diffuser which are communicated with each other and integrally arranged, the diameter of the throat is 10mm, and the length of the throat is 2 times of the diameter of the throat; the diffusion angle of the diffusion tube is 6 degrees, the length of the diffusion tube is 2 times of the length of the throat tube, the spiral sheet 21 with the fine holes is arranged in the diffusion tube, and the hole diameter of the open hole on the spiral sheet is as follows: 0.1mm, 25% open pore. The spiral sheet 21 with the fine holes is a metal sheet, the width of the metal sheet is 0.8, the length of the metal sheet is 2, d is the inner diameter of the diffusion pipe, one end of the spiral sheet is fixed during processing, and the other end of the spiral sheet is uniformly twisted by 180 degrees.
In the embodiment, a stainless steel tank with a cylindrical upper part and a conical bottom is used as the contaminated acid vulcanizing reactor 3, and the treatment capacity of contaminated acid is 2m3The waste acid contains heavy metals such as arsenic and copper, wherein the concentration of arsenic is 5000mg/L, the concentration of copper is 500mg/L, and the concentration of hydrogen sulfide used is 40%. The top of the contaminated acid vulcanization reactor 3 is provided with a hydrogen sulfide gas discharged from a gas chamber 31, the hydrogen sulfide gas is mixed with the hydrogen sulfide gas input from a hydrogen sulfide gas supply pipeline 4 and then enters a high-speed gas dissolving pump 1, the high-speed gas dissolving pump 1 rotates at the rotating speed of 800-1200 rmp, and the hydrogen sulfide is mechanically shearedThe gas is mixed in the contaminated acid to stably generate hydrogen sulfide micro-nano bubbles, the contaminated acid carrying the hydrogen sulfide micro-nano bubbles enters a contaminated acid vulcanization reactor 3 through a gas-liquid injection pipe 2 with a high-efficiency gas-liquid dispersion element, and the result shows that the arsenic and the copper can be removed at a rate of over 99% after the vulcanization is continuously conducted for 3 hours, wherein the concentration of the arsenic can be reduced to 1 mg/L.
Example 2
In the embodiment, a stainless steel tank with a cylindrical upper part and a conical bottom is used as a contaminated acid vulcanization reactor 3, and the structure of the related reaction device is the same as that of the embodiment 1, wherein the throat diameter of a short diffusion tube type Venturi ejector 22 is 2mm, and the length of the throat is 1 time of the diameter of the venturi ejector; the diffusion angle of the diffusion tube is 5 degrees, the length of the diffusion tube is 2 times of the length of the throat, and the liquid flow velocity at the throat of the throat is 25 m/s. The pore diameter of the opening on the spiral sheet is as follows: 0.1mm, 10% open pore, 0.8d width of the spiral piece 21, 2d length, d is the inner diameter of the diffuser.
The treatment capacity of the waste acid is 2m3The waste acid contains heavy metals such as arsenic and copper, wherein the concentration of arsenic is 5000mg/L, the concentration of copper is 500mg/L, and the concentration of hydrogen sulfide used is 60%. The top of the contaminated acid vulcanization reactor 3 is provided with a hydrogen sulfide gas discharged from a gas chamber 31, the hydrogen sulfide gas is mixed with a hydrogen sulfide gas input by a hydrogen sulfide gas supply pipeline 4 and then enters a high-speed gas dissolving pump 1, the high-speed gas dissolving pump 1 rotates at the rotating speed of 800-1200 rmp, the hydrogen sulfide gas is mixed in contaminated acid in a mechanical shearing mode to stably generate hydrogen sulfide micro-nano bubbles, the contaminated acid carrying the hydrogen sulfide micro-nano bubbles enters a vulcanization device through a gas-liquid injection pipe with a high-efficiency gas-liquid dispersion element, and the result shows that the hydrogen sulfide is continuously introduced for 2 hours, the removal rate of arsenic and copper can reach more than 99%, and the concentration of arsenic can be reduced to 1 mg/L.
Example 3
In the embodiment, a stainless steel tank with a cylindrical upper part and a conical bottom is used as a contaminated acid vulcanization reactor 3, and the structure of the related reaction device is the same as that of the embodiment 1, wherein the throat diameter of a short diffusion tube type Venturi ejector 22 is 20mm, and the length of the throat is 3 times of the diameter of the venturi ejector; the diffusion angle of the diffusion tube is 8 degrees, the length of the diffusion tube is 3 times of the length of the throat, and the liquid flow velocity at the throat of the throat is 40 m/s. The pore diameter of the opening on the spiral sheet is as follows: 0.2mm, and the aperture ratio is 30%. The width of the spiral piece 21 is 0.9d, the length is 3d, and d is the inner diameter of the diffusion tube.
The treatment capacity of the waste acid is 2m3The waste acid contains heavy metals such as arsenic and copper, wherein the concentration of arsenic is 5000mg/L, the concentration of copper is 500mg/L, and the concentration of hydrogen sulfide used is 60%. The top of the contaminated acid vulcanization reactor 3 is provided with a hydrogen sulfide gas discharged from a gas chamber 31, the hydrogen sulfide gas is mixed with a hydrogen sulfide gas input by a hydrogen sulfide gas supply pipeline 4 and then enters a high-speed gas dissolving pump 1, the high-speed gas dissolving pump 1 rotates at the rotating speed of 800-1200 rmp, the hydrogen sulfide gas is mixed in contaminated acid in a mechanical shearing mode to stably generate hydrogen sulfide micro-nano bubbles, the contaminated acid carrying the hydrogen sulfide micro-nano bubbles enters a vulcanization device through a gas-liquid injection pipe with a high-efficiency gas-liquid dispersion element, and the result shows that the arsenic and copper removal rate can reach more than 99% when the hydrogen sulfide is continuously introduced for 1.5 hours, wherein the concentration of the arsenic is less than 1 mg/.
Claims (10)
1. The utility model provides an utilize micro-nano bubble of hydrogen sulfide to strengthen dirty sour heavy metal vulcanizer, its characterized in that, the device include high-speed solution pump (1), have gas-liquid injection pipe (2) of high-efficient gas-liquid dispersion component, high-speed solution pump (1) entrance point connect dirty sour vulcanization reactor (3) and hydrogen sulfide air supply line (4), the exit end passes through circulating line and connects gas-liquid injection pipe (2), the jet orifice of this gas-liquid injection pipe (2) is arranged in dirty sour vulcanization reactor (3).
2. The device for strengthening the sulfuration of the contaminated acid and the heavy metal by utilizing the hydrogen sulfide micro-nano bubbles according to claim 1, wherein the gas-liquid injection pipe (2) with the high-efficiency gas-liquid dispersion element consists of a spiral plate (21) with fine holes and a short-diffuser-pipe-type Venturi ejector (22).
3. The device for strengthening the sulfuration of the contaminated acid heavy metal by utilizing the hydrogen sulfide micro-nano bubbles according to claim 2, wherein the short-diffuser-type venturi ejector (22) comprises a throat and a diffuser which are communicated with each other and integrally arranged, the diameter of the throat is 2-20 mm, and the length of the throat is 1-3 times of the diameter of the throat; the diffusion angle of the diffusion tube is 5-8 degrees, the length of the diffusion tube is 2-3 times of the length of the throat, and the liquid flow velocity at the throat of the throat is 25-40 m/s.
4. The device for strengthening the sulfuration of the contaminated acid and the heavy metal by utilizing the hydrogen sulfide micro-nano bubbles according to claim 3, wherein the spiral plate (21) with the fine holes is arranged in the diffusion tube, and the hole diameter of the open hole on the spiral plate is as follows: 0.1 to 0.2mm, and 10 to 30% of open area.
5. The device for strengthening the sulfuration of the waste acid heavy metal by utilizing the hydrogen sulfide micro-nano bubbles as claimed in claim 4, wherein the spiral plate (21) with the fine holes is a metal plate, the width of the metal plate is 0.8-0.9 d, the length of the metal plate is 2-3 d, d is the inner diameter of the diffusion tube, one end of the spiral plate is fixed, and the other end of the spiral plate is uniformly twisted by 180 degrees during processing.
6. The device for strengthening the sulfuration of the contaminated acid heavy metal by utilizing the hydrogen sulfide micro-nano bubbles according to claim 1, wherein the top of the contaminated acid sulfuration reactor (3) is provided with an air chamber (31), the air chamber (31) is connected to a hydrogen sulfide gas supply pipeline (4) through a gas discharge pipe, and the gas is connected in parallel and then introduced into the high-speed gas dissolving pump (1).
7. The method for strengthening the sulfuration of the contaminated acid heavy metal by using the hydrogen sulfide micro-nano bubbles by using the device of claim 1 is characterized by comprising the following steps:
firstly, respectively sucking circulating waste acid and hydrogen sulfide gas into a pump body by using a high-speed dissolved air pump (1), and forming micro-nano bubbles of hydrogen sulfide by the dispersion action of high-speed rotating blades;
secondly, micro-nano bubble-containing waste acid from the high-speed dissolved air pump (1) is further dispersed by a gas-liquid injection pipe (2) with a high-efficiency gas-liquid dispersion element, and finally is directly injected into a waste acid vulcanization reactor (3);
and thirdly, the hydrogen sulfide in contact with the waste acid in the form of micro-nano bubbles can effectively strengthen the sulfuration reaction of the hydrogen sulfide and heavy metals in the waste acid, so that the heavy metal pollution is efficiently removed.
8. The method for strengthening the sulfuration of the heavy metal in the contaminated acid by utilizing the hydrogen sulfide micro-nano bubbles according to claim 7, wherein the contaminated acid refers to acidic wastewater containing heavy metal pollutants generated in the nonferrous smelting industry, and the heavy metal pollutants comprise arsenic, mercury, cadmium, lead or copper.
9. The method for strengthening the sulfuration of the contaminated acid heavy metal by utilizing the hydrogen sulfide micro-nano bubbles according to claim 7, wherein the hydrogen sulfide introduced into the high-speed gas dissolving pump (1) in the first step is a high-concentration gas with the concentration of the hydrogen sulfide being more than 20%.
10. The method for strengthening the sulfuration of the contaminated acid heavy metal by utilizing the hydrogen sulfide micro-nano bubbles according to the claim 7, characterized in that the micro-nano bubbles injected into the contaminated acid sulfuration reactor (3) in the second step are hydrogen sulfide micro-bubbles with the diameter less than 50 μm;
in the second step, the flow of the high-speed air dissolving pump (1) is as follows: 2 to 20m3H, the bubble diameters produced are: 100 nm-10 μm.
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