CN213569541U - Selenium mercury recovery plant - Google Patents
Selenium mercury recovery plant Download PDFInfo
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- CN213569541U CN213569541U CN202022741115.XU CN202022741115U CN213569541U CN 213569541 U CN213569541 U CN 213569541U CN 202022741115 U CN202022741115 U CN 202022741115U CN 213569541 U CN213569541 U CN 213569541U
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Abstract
Selenium mercury recovery plant belongs to metallurgical technology field, including pretreatment equipment, mercury recovery plant, selenium recovery plant and exhaust-gas treatment equipment the utility model discloses in, pretreatment equipment includes pretreatment tank and rotary kiln, and pretreatment tank connects the acid mud greatly to add lime, pretreatment tank pass through screw conveyer and connect the rotary kiln, the condenser is connected to the end of giving vent to anger of rotary kiln, and exhaust-gas treatment equipment is connected to the gas outlet of condenser, and mercury recovery plant is connected to the liquid outlet of condenser, and selenium recovery plant is connected to the solid discharge end of rotary kiln. The utility model discloses novel structure, think about ingenious, the rate of recovery is high, and it is high to retrieve product purity, and the investment is little, with low costs, profit is high, economy is reasonable, and the environmental protection is practiced thrift effectually, and tail gas treatment is efficient, to environmental protection.
Description
Technical Field
The utility model belongs to the field of metallurgical technology, in particular to a method for recovering and treating acid sludge in a zinc smelting flue gas acid making process, in particular to equipment for recovering selenium and mercury from acid sludge.
Background
Sulfuric acid is a common chemical product, is an important chemical raw material, is widely applied to various industrial fields, and has great market demand on sulfuric acid. The zinc smelting flue gas contains high-concentration SO 2Generally, acid is prepared by two-time conversion and two-time absorption contact methods, a large amount of acid mud is generated in the acid preparation process, the acid mud contains a large amount of recoverable elements such as selenium and mercury, the selenium content can reach 20%, the mercury content is 6%, the direct discharge of the acid mud can cause great permanent pollution to the environment, and meanwhile, serious resource waste is caused, and the selenium and the mercury are important industrial raw materials. Wherein the dangerous mark of selenium is 15, which belongs to harmful products, is used for manufacturing rectifiers, photocells, photometers, glass, ceramics, catalysts, paints and the like, and is industrially recovered from anode mud of electrolytic copper and waste materials of flue dust and acid mud of sulfuric acid plants; mercury, commonly known as mercury, hazard label 20, is a corrosive substance widely used as a thermometerBarometers, diffusion pumps and other instruments; also used for manufacturing fluorescent lamps, mercury switches and other electrical equipment, as well as pesticides, catalysts, antifouling paints, batteries and the like; also used as mercury electrode of mercury electrolytic tank in chlor-alkali industry; under the participation of microorganisms, inorganic mercury deposited in a water body can be converted into highly toxic methyl mercury, the methyl mercury biosynthesized in the deposit can be continuously released into water, the methyl mercury has strong lipophilic ability, so that low-quantity methyl mercury in the water can be absorbed by aquatic organisms, the health and safety of human beings are threatened by gradual enrichment and transfer through a food chain, more than 95 percent of mercury can be rapidly absorbed or fixed by soil after entering the soil, and the mercury is easy to accumulate in the soil.
In the prior art, the recovery process of selenium and mercury in acid mud is not few, but the recovery efficiency is low, the pollution to the environment exists in the process, and the problems always bring troubles to technical personnel in the field.
SUMMERY OF THE UTILITY MODEL
In order to solve the defects of the prior art, the utility model provides a selenium and mercury recovery device, which is used for recovering selenium and mercury from acid sludge generated in an acid making process.
The to-be-solved technical problem of the utility model is realized through following technical scheme:
selenium mercury recovery plant, including pretreatment equipment, mercury recovery plant, selenium recovery plant and exhaust-gas treatment equipment, in the utility model discloses a, pretreatment equipment includes pretreatment tank and rotary kiln, and pretreatment tank connects the acid mud to add lime, and pretreatment tank passes through screw conveyer and connects the rotary kiln, and the gas outlet end of rotary kiln connects the condenser, and the gas outlet of condenser connects exhaust-gas treatment equipment, and the liquid outlet of condenser connects mercury recovery plant, and the solid discharge end of rotary kiln connects selenium recovery plant; the selenium recovery equipment comprises crude selenium recovery equipment and refined selenium preparation equipment which are connected in sequence.
The utility model discloses in, coarse selenium recovery plant is including ball mill, one-level leaching tank and the heavy coarse selenium groove that connects gradually, and the solid discharge end of rotary kiln is connected to the ball mill, and the one-level leaching tank is connected vacuum filter with sinking between the coarse selenium groove. And (3) discharging calcium selenite which is roasted in the rotary kiln, reducing selenite through the reaction of a primary leaching tank, carrying out solid-liquid separation through a vacuum filter, and further reducing the filtrate in a crude selenium precipitation tank to obtain crude selenium.
Further, the grinding granularity of the ball mill reaches 180-200 meshes, sulfuric acid is added into a primary leaching tank, the leaching time is 4-5h, and the leaching temperature is 90 ℃; sulfur dioxide is introduced into the crude selenium precipitation tank, and the reaction temperature is not lower than 70 ℃.
The utility model discloses in, smart selenium preparation equipment is including the second grade leaching tank, the smart selenium that connect gradually appearing groove and smart selenium water scrubber, and heavy coarse selenium groove is connected to the second grade leaching tank, and the result of smart selenium water scrubber is sent into in the oven. And (3) heating the recovered crude selenium product to react with sodium sulfite to generate a sodium selenosulfate solution, cooling the solution in a refined selenium precipitation tank to precipitate, adding sodium sulfide to remove impurities during precipitation, feeding the precipitated refined selenium crystals to a refined selenium washing tank for washing, and keeping the precipitated mother liquor for later use.
Further, the equipment for preparing the refined selenium also comprises an acidification tank, wherein the acidification tank is arranged between the refined selenium precipitation tank and the refined selenium water washing tank, is respectively connected with the refined selenium precipitation tank and the refined selenium water washing tank, is used for containing the mother liquor precipitated by the refined selenium precipitation tank, and is used for delivering the refined selenium obtained by acidification to the refined selenium water washing tank, and the acidification tank is a closed reaction tank.
Further, sodium sulfite is added into the secondary leaching tank, the leaching time is 4 hours, the leaching temperature is 100-fold, the acidification is carried out for 7 days once, each acidification is 8 hours, the oven is an electric heating oven, and the drying temperature is 100 ℃.
The utility model discloses in, mercury recovery plant is including the water sealed mercury collecting tank and the hydraulic cyclone that connect gradually, the liquid outlet of condenser is connected to water sealed mercury collecting tank. The mercury vapor calcined by the rotary kiln is condensed into liquid by a condenser, is sent into a water-sealed mercury collecting tank to be collected and deposited at the bottom, and is separated into crude mercury products by a hydrocyclone after slurrying with water.
The utility model discloses in, exhaust-gas treatment equipment is including absorbing adsorption tower, venturi knockout tower and terminal absorption tower, and wherein the absorption adsorption tower adsorbs the absorption including the one-level absorption adsorption tower, second grade absorption adsorption tower and the tertiary absorption that connect graduallyThe tower, the gas outlet of condenser is connected to the one-level absorption adsorption tower, fills hydrogen peroxide solution and active carbon, and inferior sodium chloride and active carbon are filled to the second grade absorption adsorption tower, and tertiary absorption adsorption tower fills sodium sulfide and active carbon, and the venturi knockout tower is connected between tertiary absorption adsorption tower and terminal absorption tower, and the filler of terminal absorption tower is potassium permanganate, sodium sulfide and active carbon in proper order. As the flue gas of the rotary kiln contains nitrogen, water vapor, metal oxidation volatile matters and SO besides mercury vapor2、CO2And substances such as fine dust and the like brought in by the airflow are cooled by the condenser, mercury vapor remaining in the tail gas reacts with hydrogen peroxide and is converted into mercury oxide precipitate, mercury is further recovered, other gases are sequentially absorbed and adsorbed by the towers, and finally the emptied tail gas meets the emission standard after desulfurization and dust removal. In the whole treatment process, the method of condensation, hydrogen peroxide absorption activated carbon adsorption, sodium hypochlorite absorption activated carbon adsorption, sodium sulfide absorption activated carbon adsorption, venturi wet dust removal and desulfurization, potassium permanganate absorption, sodium sulfide absorption and 2-level activated carbon adsorption and absorption treatment is adopted, the purification treatment requirements of demercuration, desulfurization and dust removal in waste gas are met, and the tail gas emission is pollution-free and environment-friendly.
The utility model discloses in, selenium mercury recovery plant sets up in sealed unmanned workshop, avoids the acid mist of effusion to endanger staff's healthy, also prevents its contaminated air.
Compared with the prior art, the utility model has the advantages of it is following:
(1) the crude selenium recovery process has various processing means in each link, can recover most of selenium in materials, has high recovery rate and fine and smooth fine selenium preparation process, separates out selenium crystals by respectively heating and cooling, and recovers the selenium crystals in the mother liquor by acidification, so that the obtained fine selenium product has high purity;
(2) the crude mercury recovery process respectively utilizes the water-sealed mercury collecting tank and the hydrocyclone, can remove impurities in the mercury while recovering the mercury, and has high purity of the recovered mercury;
(3) byproducts in each stage of the whole recovery process are recycled, so that the environment-friendly and saving effect is good;
(4) in the tail gas treatment process, multi-stage equipment is used for mercury removal, desulfurization and dust removal, the tail gas purification effect is good, and mercury products in the tail gas can be further recovered;
(5) advanced equipment performance, advanced technical level and equipment level, low material consumption and energy consumption of unit products, higher processing degree and processing capacity, stable equipment operation, higher production capacity and labor productivity, higher continuous, mechanical and automatic degrees, higher safety and sanitary requirements;
(6) The applicability is strong, the method is adaptive to market conditions, the production regulation can be performed, and the development of domestic and foreign markets is facilitated; the method is suitable for the processing requirements of raw materials and other auxiliary materials; the method is suitable for the technical requirements of the process, is matched with the production capacity of the project, and is matched with main equipment and auxiliary equipment; the method is suitable for construction scale and product scheme, and meets the use requirement and maintenance requirement under the prior art condition; is suitable for safety and environmental protection, ensures safe production and reduces the discharge of three wastes as much as possible;
(7) the reliability is high, the maturity of the equipment is high, and the equipment which is fully verified and used is adopted; the production stability is high, and no danger is caused to personnel; the service life is long;
(8) the technology is economic and reasonable, the equipment selection is based on the domestic condition, the equipment configuration is balanced and reasonable, the comprehensive economy of the whole production line configuration is considered, and the economic and reasonable equipment selection scheme with low investment, low cost, high profit is selected.
To sum up, the utility model discloses novel structure thinks about ingeniously, and the rate of recovery is high, and it is high to retrieve product purity, and the investment is little, with low costs, profit is high, economy is reasonable, and the environmental protection is practiced thrift effectually, and tail gas treatment is efficient, to environment friendly.
Drawings
Fig. 1 is a schematic view of the equipment distribution process of the present invention.
In the figure: the device comprises a pretreatment tank 1, a screw conveyor 2, a rotary kiln 3, a ball mill 4, a primary leaching tank 5, a vacuum filter 6, a coarse selenium precipitation tank 7, a secondary leaching tank 8, a fine selenium precipitation tank 9, an acidification tank 10, a fine selenium water washing tank 11, an oven 12, a condenser 13, a water-sealed mercury collecting tank 14, a hydrocyclone 15, a primary absorption adsorption tower 16, a secondary absorption adsorption tower 17, a tertiary absorption adsorption tower 18, a venturi separation tower 19 and a terminal absorption tower 20.
Detailed Description
The invention will be further described with reference to the drawings and specific preferred embodiments without limiting the scope of the invention.
The utility model provides a selenium mercury recovery plant, including pretreatment facilities, mercury recovery plant, selenium recovery plant and exhaust-gas treatment equipment, wherein, pretreatment facilities includes pretreatment tank 1, screw conveyer 2 and rotary kiln 3, pretreatment tank 1 connects the acid mud greatly, and add lime, pretreatment tank 1 passes through screw conveyer 2 and connects rotary kiln 3, the discharge end of screw conveyer 2 is connected to 3 feed ends of rotary kiln, condenser 13 is connected to the end of giving vent to anger of rotary kiln 3, the end of giving vent to anger of rotary kiln 3 is connected to the air inlet of condenser 13, exhaust-gas treatment equipment is connected to the gas outlet of condenser 13, the liquid outlet of condenser 13 is connected to mercury recovery plant, selenium recovery plant is connected to the solid discharge end of rotary kiln 3.
Tail gas recovery plant includes the absorption adsorption tower, venturi knockout tower 19 and terminal absorption tower 20, wherein the absorption adsorption tower is including the one-level absorption adsorption tower 16 that connects gradually, second grade absorption adsorption tower 17 and tertiary absorption adsorption tower 18, the gas outlet of condenser 13 is connected to one-level absorption adsorption tower 16, fill hydrogen peroxide solution and active carbon, sodium hypochlorite and active carbon are filled to second grade absorption adsorption tower 17, tertiary absorption adsorption tower 18 is filled sodium sulfide and active carbon, venturi knockout tower 19 is connected between tertiary absorption adsorption tower 18 and terminal absorption tower 20, the filler of terminal absorption tower 20 is potassium permanganate in proper order, sodium sulfide and active carbon.
The mercury recovery equipment comprises a water-sealed mercury collecting tank 14 and a hydrocyclone 15 which are connected in sequence, wherein the water-sealed mercury collecting tank 14 is connected with a liquid outlet of the condenser 13.
The selenium recovery equipment comprises crude selenium recovery equipment and fine selenium preparation equipment which are sequentially connected, the crude selenium recovery equipment comprises a ball mill 4, a primary leaching tank 5, a vacuum filter 6 and a coarse selenium precipitating tank 7 which are sequentially connected, the ball mill 4 is connected with the solid discharge end of a rotary kiln 3, the fine selenium preparation equipment comprises a secondary leaching tank 8, a fine selenium precipitating tank 9, an acidification tank 10, a fine selenium water scrubbing tank 11 and an oven 12, the feed port of the secondary leaching tank 8 is connected with the discharge port of the coarse selenium precipitating tank 7 to receive the roughly processed selenium crystals, the liquid outlet of the secondary leaching tank 8 is connected with the liquid inlet of the fine selenium precipitating tank 9, the discharge port of the fine selenium precipitating tank 9 is connected with the feed port of the fine selenium water scrubbing tank 11, the precipitated selenium crystals are sent to the fine selenium water scrubbing tank 11 to be washed and purified, the liquid outlet of the fine selenium precipitating tank 9 is connected with the acidification tank 10, the discharge port of the acidification tank 10 is connected with the feed, the separated mother liquor is subjected to acidification reaction in the acidification tank 10, further separated selenium crystals are sent to a refined selenium washing tank 11 for washing and purification, a discharge port of the refined selenium washing tank 11 is connected with an oven 12, and the pure selenium crystals are dried by the oven 12.
When the utility model is applied to the sulfuric acid-making process, the acid sludge produced by the acid-making process is sent into the pretreatment tank 1, lime and water are added to remove acid substances in the acid sludge, and the lime reacts with the water to obtain calcium hydroxide, thereby not only playing a role in neutralization and decomposition, but also having a role in solidifying metal; the pretreated acid sludge is placed in a rotary kiln 3 for aerobic roasting, selenide and calcium oxide react in the roasting process to generate calcium selenite, mercury escapes in a steam form, and the calcium selenite is separated from selenium after being condensed by a condenser 13; the condensation temperature is set to be 20-30 ℃, the condensation mode is indirect cooling, liquid metal mercury and mercury soot obtained by condensation enter the lower water-sealed mercury collecting tank 14, the mercury is deposited at the bottom of the water-sealed mercury collecting tank 14 due to the higher density of the mercury, the mercury volatilization entering the atmosphere can be effectively reduced, elemental mercury is converted into mercury oxide precipitate after mercury-containing flue gas is sprayed by hydrogen peroxide, and the mercury is further recovered; then the flue gas is desulfurized and dedusted respectively to remove the pollution components in the flue gas, and the flue gas is discharged into the atmosphere as pollution-free tail gas; the mercury soot is mainly composed of fine mercury beads, mine dust, oxides of arsenic and antimony, mercury sulfide, mercury sulfate, hydrocarbon, water and the like, is a multiphase system substance, is treated by a hydrocyclone 15, and utilizes the characteristic that the density of mercury is greatly different from that of other impurities, under the action of friction extrusion of centrifugal force, the small mercury beads collide with each other to be combined into mercury particles which fall along the wall of the vessel to achieve the purpose of separation, and the separated crude mercury contains 99.9% of mercury.
Through roasting in a rotary kiln 3, the mercury-removed slag with better oxidation mainly exists in a form of calcium selenite, water is added, wet grinding is carried out through a ball mill 4, sulfuric acid is adopted for leaching, the calcium selenite can be better dissolved in sulfuric acid solution, selenite is obtained through reduction, solid-liquid separation is carried out through a vacuum filter 6, filtrate is pumped into a crude selenium precipitation tank 7, and sulfur dioxide is introduced into the filtrate for reduction to obtain crude selenium; leaching the crude selenium by using sodium sulfite, heating and stirring during leaching to generate a selenosulfate solution, removing insoluble impurities by filtering part of impurities which are insoluble in the sodium sulfite solution, and adding a sodium sulfide solution during leaching to remove impurities such as Cu, Hg and the like in a sulfide form, thereby achieving the purposes of separation and refining; pumping the supernatant into a fine selenium precipitation tank 9 for cooling after temperature rise reaction, cooling to normal temperature, precipitating fine selenium, sending the precipitated mother liquor into an acidification tank 10, adding sulfuric acid for acidification and reduction to obtain fine selenium, sending the precipitated selenium to a fine selenium washing tank 11 for washing, drying the washed semi-finished product by an oven 12, and packaging as a final product, wherein the purity of the fine selenium is more than 99%.
By using the process, the recovery rate of selenium is 87.4 percent, and the recovery rate of mercury is 96.9 percent.
Consequently, combine above-mentioned structure and recovery process to discover, selenium mercury recovery plant novel structure, think about ingenious, the rate of recovery is high, it is high to retrieve product purity, the investment is little, with low costs, profit is high, economy is reasonable, the environmental protection is practiced thrift effectually, tail gas treatment efficiency is high, friendly to the environment.
Claims (5)
1. Selenium mercury recovery plant, including pretreatment equipment, mercury recovery plant, selenium recovery plant and exhaust-gas treatment equipment, its characterized in that: the pretreatment device comprises a pretreatment tank and a rotary kiln, the pretreatment tank is used for containing acid sludge and adding lime, the pretreatment tank is connected with the rotary kiln through a screw conveyor, the gas outlet end of the rotary kiln is connected with a condenser, the gas outlet of the condenser is connected with a waste gas treatment device, the liquid outlet of the condenser is connected with a mercury recovery device, and the solid discharge end of the rotary kiln is connected with a selenium recovery device; the selenium recovery equipment comprises crude selenium recovery equipment and refined selenium preparation equipment which are connected in sequence.
2. The selenium-mercury recovery plant of claim 1, wherein: the crude selenium recovery equipment comprises a ball mill, a primary leaching tank and a crude selenium precipitating tank which are sequentially connected, wherein the ball mill is connected with the solid discharge end of the rotary kiln, and a vacuum filter is connected between the primary leaching tank and the crude selenium precipitating tank.
3. The selenium-mercury recovery plant of claim 1, wherein: the fine selenium preparation equipment comprises a secondary leaching tank, a fine selenium precipitation tank and a fine selenium washing tank which are sequentially connected, wherein the secondary leaching tank is connected with a coarse selenium precipitation tank, and the product of the fine selenium washing tank is sent into an oven.
4. The selenium-mercury recovery plant of claim 3, wherein: the equipment for preparing the refined selenium also comprises an acidification tank, wherein the acidification tank is arranged between the refined selenium precipitation tank and the refined selenium washing tank and is respectively connected with the refined selenium precipitation tank and the refined selenium washing tank, and the acidification tank is a closed reaction tank.
5. The selenium-mercury recovery plant of claim 1, wherein: the mercury recovery equipment comprises a water-sealed mercury collecting tank and a hydrocyclone which are connected in sequence, wherein the water-sealed mercury collecting tank is connected with a liquid outlet of the condenser.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202022741115.XU CN213569541U (en) | 2020-11-24 | 2020-11-24 | Selenium mercury recovery plant |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202022741115.XU CN213569541U (en) | 2020-11-24 | 2020-11-24 | Selenium mercury recovery plant |
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| CN213569541U true CN213569541U (en) | 2021-06-29 |
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| CN202022741115.XU Active CN213569541U (en) | 2020-11-24 | 2020-11-24 | Selenium mercury recovery plant |
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| GR01 | Patent grant | ||
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| CB03 | Change of inventor or designer information |
Inventor after: Chang Dezheng Inventor after: Zhang Jiguang Inventor after: Lu Di Inventor after: Shi Qi Inventor after: Hua Wei Inventor after: Han Shuangcheng Inventor after: Lu Ranying Inventor after: Zhao Yan Inventor after: Li Shuai Inventor before: Chang Dezheng Inventor before: Zhang Jiguang Inventor before: Lu Di Inventor before: Shi Qi Inventor before: Hua Wei Inventor before: Han Shuangcheng Inventor before: Lu Ranying Inventor before: Zhao Yan Inventor before: Li Shuai |
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| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211012 Address after: 435412 Meichuan Zhen Quan Kou Cun Quan Kou Huan, Wuxue City, Huanggang City, Hubei Province Patentee after: Wuxue Tianma Nonferrous Metals Co.,Ltd. Address before: 450002 No. 4-1, Huanghe North Street, Jinshui District, Zhengzhou City, Henan Province Patentee before: HENAN INSTITUTE OF METALLURGY Co.,Ltd. Patentee before: HENAN ACADEMY OF SCIENCES |
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| TR01 | Transfer of patent right |
Effective date of registration: 20230628 Address after: 459011 100 meters north of Liandong village, Wulongkou Town, Jiyuan City, Henan Province Patentee after: Jiyuan Xiaoyuan Industrial Co.,Ltd. Address before: 435412 Meichuan Zhen Quan Kou Cun Quan Kou Huan, Wuxue City, Huanggang City, Hubei Province Patentee before: Wuxue Tianma Nonferrous Metals Co.,Ltd. |