CN109761514B - Beryllium slag detoxification and cement kiln cooperative recycling treatment system and process - Google Patents
Beryllium slag detoxification and cement kiln cooperative recycling treatment system and process Download PDFInfo
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- CN109761514B CN109761514B CN201910113576.1A CN201910113576A CN109761514B CN 109761514 B CN109761514 B CN 109761514B CN 201910113576 A CN201910113576 A CN 201910113576A CN 109761514 B CN109761514 B CN 109761514B
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Abstract
The invention discloses a beryllium slag detoxification and cement kiln cooperative recycling treatment system and process, wherein beryllium slag is washed by water under an acidic condition to form a beryllium sulfate solution and solid slag, wherein the beryllium sulfate solution reacts with ammonia water to generate a beryllium hydroxide precipitate, and the precipitate is separated and then used for recovering beryllium hydroxide; and the solid slag is treated and then sent into a system cement kiln for high-temperature calcination, beryllium contained in the solid slag is melted in cement clinker lattices to form minerals such as calcium ferrite beryllium, calcium aluminum beryllium, calcium beryllium and the like, the beryllium content in the cement reaches a trace amount, the leaching solubility is less than 0.1 mu g/l, the requirement of cement raw materials is met, ammonia nitrogen compounds generated in the reaction process are converted into ammonia water or ammonium salt, the ammonia nitrogen compounds can be used as a cement kiln denitration agent or returned to a beryllium smelting plant as an auxiliary agent, the residue can be completely eliminated, the toxic property is completely eliminated, and the beryllium slag is recycled and harmlessly treated.
Description
Technical Field
The invention belongs to a treatment method for detoxifying waste residues in a beryllium metal refining process, and particularly relates to a system and a method for treating beryllium residues by utilizing a cement kiln to cooperate with resource utilization.
Background
Beryllium is an off-white alkaline earth metal, can be dissolved in acid and alkali, is an amphoteric metal, is extremely toxic to beryllium and compounds thereof, and is listed as a carcinogen in a carcinogen list published by international cancer research institution of international world health organization in 2017.
Beryllium is a rare light metal with unique and excellent physical, chemical, mechanical and nuclear properties, and since the discovery of beryllium element by human beings, the properties of beryllium have attracted great attention of scientists. With the development of science and technology, three main forms of beryllium, namely metal, alloy and oxide, are widely applied to industries such as atomic energy, rockets, missiles, satellites, aviation, aerospace, electronics, instruments, petrifaction and ceramics. It was noted since 1926 that small amounts of beryllium added to different metals could improve their properties. Beryllium has subsequently gained a variety of applications, and particularly in recent years, due to the development and demand of electronics and aerospace technology, research work on beryllium alloys has become more active and more common. Beryllium copper alloy products have penetrated almost all industrial fields, and the application in civil fields is continuously expanded in recent years. Beryllium oxide is mainly used for producing beryllium copper alloy, a small part of beryllium oxide is applied in the form of metal beryllium, and a small part of beryllium oxide is used as beryllium oxide ceramic and the like, so that beryllium oxide is a high value-added base material. With the rapid development of the high-tech field in recent years, the beryllium oxide and the beryllium copper alloy are in short supply and demand, the market potential is huge, and the vigorous research and development of the beryllium smelting industrial technology has huge social and economic benefits and has important strategic significance.
More than 30 beryllium-containing minerals exist in nature, only the andalusite has process value, and the andalusite is a beryllium silicate ore with the BeO content of 9-13%. Although the technology for extracting and separating beryllium from andalusite is advanced to a certain extent, the prior methods include a sulfuric acid method, a sulfuric acid extraction method, a fluorination method and the like, but the large-scale industrial application method is few, the beryllium extracting production process adopted by the six factories in the water gap mountain in China is a flux melting method, and the process flow is as follows: beryllium ore + calcite → smelting → acid leaching → evaporative crystallization → neutralization and iron removal → precipitation → beryllium hydroxide → calcination. The total recovery rate of metal is 73-75%, and the quality of BeO is 95-99%.
The beryllium slag is waste slag generated in the beryllium extraction process, and comprises acid dissolving slag (also called beryllium slag) and alum settling slag (also called aluminumholtum slag), wherein more than 100 tons of acid dissolving slag and 14-18 tons of aluminumholtum slag are generated when 1 ton of beryllium is produced in the production, and because the waste slag contains 0.1-0.3 percent of beryllium, the beryllium in the beryllium slag is represented by BeO and Be (OH)2、BeSO4The compounds exist in the form of similar compounds, the toxicity of the compounds is far higher than the test standard of the toxicity of the leaching (less than 0.1mg/l), and a large amount of ammonia nitrogen compounds exist, and the compounds are listed in national hazardous waste list HW 20-beryllium-containing waste. Under the current technical conditions, beryllium residues are not effectively and scientifically treated, most of the beryllium residues are directly poured into a residue dam, and when rainwater occurs, water-soluble beryllium in the beryllium residues is dissolved in water and enters the ground surface, farmlands, rivers and the like, so that serious damage to lives and properties of people is caused, and serious environmental pollution is caused.
In order to reduce the harm of harmful solid wastes to the environment, the beryllium slag is recycled and harmlessly by utilizing the cement kiln co-processing technologyThe treatment is to recover beryllium resources and simultaneously convert ammonia water and ammonium sulfate into ammonia nitrogen compounds which can be used in the beryllium extraction industry and can also be used as cement kiln denitrifier for treatment, and other impurities such as SiO2And compounds such as calcium, aluminum, iron and the like can be completely used as cement raw materials, so that the beryllium slag detoxification and resource treatment are realized.
The existing beryllium slag treatment process mainly has the problems of high treatment cost, high energy consumption, incapability of realizing harmless treatment and secondary pollution:
(1) trace beryllium still exists in the washed solid residue, and the direct discharge still causes serious threat to the environment and human health.
(2) The nitrogen oxides generated in the washing and detoxification process of the beryllium slag and the ammonia gas generated in the reaction process can cause pollution to the environment after being directly discharged.
(3) A large amount of waste liquid is generated in the treatment process, and a certain amount of metal beryllium and other heavy metal ions exist in the waste liquid, so that the resources are wasted and the environment is polluted after the waste liquid is directly discharged.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a beryllium slag detoxification and cement kiln cooperative recycling treatment system and process, wherein the beryllium slag is repeatedly washed by water under an acidic condition for multiple times to realize solid-liquid separation, the beryllium enters a liquid phase, and then is subjected to deslagging and beryllium precipitation to obtain Be (OH)2And simultaneously, the solid waste and the liquid waste are cooperatively treated by using a cement kiln, so that harmless treatment with the beryllium slag is realized.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the idea and principle for solving the technical problems of the invention are as follows:
firstly, circulating grinding, soaking and washing the beryllium residues by using a wet ball mill to ensure that the beryllium residues form BeSO under the acidic condition4Entering into solution, and performing stirring washing process at least twice to obtain liquid (BeSO)4Solution and (NH)4)2SO4Solution) and solid slag, wherein the content of beryllium in the solid slag is reduced to trace (less than 0.1mg/kg), which meets the requirementThe requirements of cement raw materials.
Secondly, BeSO produced during the beryllium slag reaction4Solution and (NH)4)2SO4Adding ammonia water into the solution to generate Be (OH)2Solids and (NH)4)2SO4Aqueous ammonia solution Be (OH)2And returning the solid to a beryllium smeltery to be used as a beryllium refining raw material to prepare the beryllium oxide.
Thirdly, when washing the acid-soluble slag (beryllium slag), the mud after washing is SiO2、CaSO4、MgSO4Can be used as cement raw material after being treated, and when alum slag (aluminum ammonium alum slag) is washed and precipitated, the washed slurry is NH4Al(SO4)2Adding Ca (OH)2) After the reaction, liquid and solid are generated, wherein the liquid is (NH)4)2SO4And ammonia water, the solid is CaSO4And Al (OH)3The liquid can be used as beryllium slag washing liquid for storage and standby, and the solid can be used as a cement raw material.
Finally, the cement kiln is used for co-processing, and SiO generated in the processing process2、CaSO4、MgSO4And Al (OH)3Can be sent into a cement kiln for high-temperature calcination to melt trace beryllium into the crystal lattice of cement clinker to form minerals such as calcium ferrite beryllium, calcium aluminum beryllium, calcium beryllium and the like; generated during the reaction (NH)4)2SO4The solution can be used as a cement kiln denitration agent, gas generated in the reaction process is collected in a centralized manner, and the gas is introduced into a high-temperature zone of the cement kiln for treatment.
The concrete solution of the invention is as follows:
a beryllium slag detoxification and cement kiln cooperative recycling treatment process comprises the following steps:
s1: directly discharging acid-dissolving slag and alum settling slag transported by a special transportation vehicle for hazardous wastes into a storage warehouse for storage, wherein the acid-dissolving slag and the alum settling slag are respectively stacked in the storage warehouse;
s2: hoisting acid dissolving slag or alum settling slag to a steady flow bin in a storage warehouse by a grab bucket, conveying the acid dissolving slag or the alum settling slag to a metering belt scale by a plate type feeding machine, metering, conveying the acid dissolving slag or the alum settling slag to a wet ball mill by a belt conveyor, grinding and washing the acid dissolving slag or the alum settling slag, adjusting the acid dissolving slag or the alum settling slag by an ammonium sulfate solution, adjusting the pH value to 3-5, adjusting the pH value to be proper using concentration by water, separating the slurry which is uniformly stirred and mixed, wherein the coarse material is ground for the second time, and the fine material enters a washing warehouse for washing;
s3, separating the washed fine materials in the S2 to obtain a solution A and slurry B, wherein the solution A is used for separating and recovering beryllium, and the slurry B is treated and then sent to a cement kiln batching system, and is prepared into cement clinker after being calcined at high temperature in a cement kiln;
s4, adding ammonia water into the solution A obtained in the step S3 to adjust the pH value to 9-11, reacting the solution A with the ammonia water to obtain a solid C and a liquid D, wherein the solid C is treated and then returned to a beryllium smelter for later use, the liquid D is added with a sulfuric acid solution to react to obtain a liquid E, and the liquid E is used as a cement kiln denitration agent, a beryllium refining agent or is evaporated and crystallized to form a high-concentration solution for later use.
Further, when the material is acid-soluble slag, performing solid-liquid separation on the slurry B in the S3 through a filtering device to obtain liquid F and solid G, standing and settling the separated liquid F, and sending the separated solid G into a cement kiln batching system.
Further, when the material is alum precipitation slag, adding a calcium hydroxide solution into the slurry B in the S3, carrying out solid-liquid separation on the slurry after reaction through a filtering device to obtain a liquid H and a solid I, standing and settling the separated liquid H, and sending the separated solid I into a cement kiln batching system.
Further, the S2 comprises a first washing and a second washing, the solution A obtained after the first washing is used for separating and recovering beryllium, and the clear liquid recovered after the second washing is used for water for wet ball mill grinding.
Further, the primary washing water is clear liquid recovered after secondary washing, and the secondary washing water is externally introduced clean water.
Further, the clear liquid recovered after the secondary washing is stored in the first clear liquid tank.
And further, after the liquid F and the liquid H are subjected to standing and sedimentation, supernatant liquid is obtained and collected in the first clear liquid pool, and settled solids are returned to the secondary washing pool.
Further, the solid C in the S4 is filtered, the filtered solid is dried by a low-temperature belt type evaporator and then returns to a beryllium smeltery, and the filtered liquid is collected in a second clear liquid pool.
Furthermore, in the washing process, repeated washing and separation are carried out for not less than two times according to the beryllium content in the solid slag, so as to meet the washing requirements.
A system for the beryllium slag detoxification and cement kiln cooperative recycling treatment process is characterized by comprising a storage warehouse, a pretreatment system, a washing system and a beryllium separation system which are sequentially connected;
the storage warehouse is a sealed type transferring garage with an intelligent grab crane, the storage warehouse is designed according to the requirement of a dangerous goods temporary storage warehouse, a steady flow bin is arranged at the bottom of the storage warehouse, the storage warehouse adopts a centralized ventilation mode, and gas pumped in the storage warehouse is sent to a cement kiln system to be used as air for a high-temperature section of the grate cooler;
the pretreatment system comprises a wet ball mill, a stirring tank and a cyclone separator, wherein a discharge port of the wet ball mill is connected with a feed port of the stirring tank, a discharge port of the stirring tank is connected with a feed port of the cyclone separator, a coarse material outlet at the bottom of the cyclone separator is connected with a feed port of the wet ball mill, a fine material outlet at the upper part of the cyclone separator is connected with a feed port at the upper part of a primary washing warehouse, and a feed port of the wet ball mill is connected with a water solution pipeline separated after secondary washing;
the washing system comprises a primary washing warehouse, a secondary washing warehouse, a plurality of washing warehouses and a recovery device which are connected in sequence, wherein each washing warehouse is provided with a feeding hole, a middle overflow hole, a discharging hole, a top exhaust port and a compressed air inlet pipe;
the beryllium separation system comprises a beryllium separation bank, a filter, a second clear liquid tank and a low-temperature belt evaporator, wherein the beryllium separation bank is provided with a feed inlet, a middle overflow port and a discharge port, the discharge port of the beryllium separation bank is connected with the feed inlet of the filter device, the liquid discharge port of the filter device is connected with the second clear liquid tank, and the solid discharge port of the filter device is connected with the low-temperature belt evaporator.
Further, the discharge hole of the primary washing warehouse is connected with the feed hole of the secondary washing warehouse, the middle overflow port of the primary washing warehouse is connected with the feed hole of the beryllium separation warehouse, the middle overflow port of the secondary washing warehouse is connected with the first clear liquid tank, the first clear liquid tank is connected with the feed hole of the primary washing warehouse, and the discharge hole of the secondary washing warehouse is connected with the filtering equipment.
Further, recovery unit includes solid recovery unit and liquid recovery unit, the solid recovery unit includes belt conveyor and solid sediment homogenization storage canopy, the belt conveyor feed end links to each other with filtration equipment solid discharge gate, the belt conveyor discharge end links to each other with solid sediment homogenization storage canopy, liquid recovery unit includes the collecting pit, the collecting pit includes feed inlet, middle part overflow mouth, discharge gate, the feed inlet links to each other with filtration equipment liquid discharge gate, the middle part overflow mouth links to each other with first clear liquid pond, the discharge gate links to each other with the secondary washing storehouse feed inlet.
Further, the washing warehouse and the beryllium separation warehouse are provided with pneumatic stirring devices and are connected with an air compressor station through pipelines or are washed in a mechanical stirring mode.
Furthermore, suction machines are arranged at exhaust ports at the tops of the washing warehouse and the beryllium separation warehouse, and the gas is uniformly output through the suction machines and is introduced into a high-temperature zone of the cement kiln for treatment.
Further, the filter is one of a centrifuge, a plate and frame filter press, a belt filter and a disc spiral filter.
Furthermore, the wet ball mill is one or a combination of a plurality of open flow ball mills, vertical sand mills and horizontal sand mills, adopts acid-resistant media and is generally made of high-alumina ceramic materials.
The beryllium content of the washed solid slag is less than one ten thousandth, if 70 tons of beryllium slag are processed every day in a production line of 3500 tons of cement clinker produced every day, the doping amount is 2 percent, the beryllium content in the clinker can reach the requirement of 5 mu g/kg grade, and toxicity can not be generated. And meanwhile, beryllium slag is calcined at high temperature by a cement kiln to form cement clinker, and the cement clinker enters a cement clinker vitreous body, so that the beryllium content in the leachate is less than 1 mu g/l, and the risk of leaching toxicity is further eliminated.
The invention has the following beneficial effects:
(1) the toxic beryllium slag treated by the method basically meets the requirements of cement raw materials by washing and detoxifying, only trace beryllium and compounds thereof enter cement clinker, the beryllium and the compounds thereof are solidified and melted in the cement clinker by high-temperature calcination, the leaching toxicity can completely meet the environmental protection requirement, thereby realizing the harmless treatment of the beryllium slag, strategic material beryllium oxide can be recovered in the beryllium slag treatment process, generally, Be (OH) can be recovered every 1 ton of beryllium slag is treated210-30kg, and really realizes the recycling of resources.
(2) Ammonia nitrogen compounds generated in the treatment process are converted into ammonia water or ammonium salts, can be used as a cement kiln denitration agent or returned to a beryllium smeltery to be used as a medicament, can completely eliminate residues, and thoroughly eliminates the toxic property;
(3) in the treatment process, the solution can generate water vapor through crystallization and concentration, and the water vapor is condensed and then returned for washing the beryllium slag and is not discharged outside. The required heat is evaporated at low temperature, and the low-temperature waste heat of a cement plant is used as a heat source for disposing evaporative crystallization, so that the disposal energy consumption is saved.
(4) All closed containers are arranged in the treatment process, and the gas is collected in a centralized manner and is introduced into a high-temperature zone of the cement kiln for treatment, so that low-cost treatment and zero emission can be realized.
(5) In the high-temperature calcination process, the heavy metals are solid-dissolved in the silicate minerals to form water-insoluble minerals, so that the leaching hazard of the minerals is eliminated. A small amount of ammonia nitrogen waste gas is collected and enters a cement system in the treatment process, the waste water is recycled, no external emission is generated, no dust emission is generated by adopting a wet process, the disposal process is environment-friendly, and no secondary pollution is generated.
(6) Mature equipment and facilities adopted by the process have the advantages of simple structure, convenient operation, adoption of negative pressure operation, energy conservation, environmental protection, small occupied area and low equipment cost.
Drawings
FIG. 1 is a schematic diagram of a beryllium slag detoxification process;
FIG. 2 is a schematic view of a beryllium slag detoxification treatment system;
11. a steady flow bin; 12. a plate feeder; 13. a metering belt scale;
21. a wet ball mill; 22. a stirring tank; 23. a slurry pump; 24. a cyclone separator;
311. a feed inlet; 312. a middle overflow port; 313. a discharge port; 314. a top exhaust port; 315. a compressed air inlet pipe; 316. a suction machine;
321. a first clear liquid tank; 322. a sewage pump; 323. a slurry pump; 324. a filtration device; 325. a belt conveyor; 326. collecting pool
41. A feed inlet; 42. a middle overflow port; 43. a discharge port; 44. a sludge pump; 45. a filter; 46. a second clear liquid tank; 47. a low temperature belt evaporator; 48. a suction machine.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and specific embodiments.
As shown in fig. 2, the invention provides a beryllium slag detoxification and cement kiln cooperative recycling treatment system, which comprises a storage warehouse, a pretreatment system, a washing system and a beryllium separation system which are connected in sequence;
the beryllium slag is directly unloaded into the storage warehouse after being transported into a factory by adopting a special transport vehicle for hazardous wastes, the storage warehouse is a sealed transferring garage with an intelligent grab crane, the storage warehouse is designed according to the temporary storage requirement of hazardous articles, a centralized ventilation mode is adopted, gas pumped in the storage warehouse is sent into a cement kiln system to be used as air for a high-temperature section of a grate cooler, and a steady flow bin 11 is arranged in the storage warehouse.
The beryllium slag is hoisted into a steady flow bin 11 in a beryllium slag storage warehouse by using a grab bucket, the bottom of the steady flow bin 11 is connected with a plate type feeding machine 12, the beryllium slag is conveyed onto a metering belt scale 13 by the plate type feeding machine 12, and the beryllium slag is conveyed into a wet ball mill 21 by using a belt conveyer after being metered.
The pretreatment system comprises a wet ball mill 21, a stirring tank 22, a slurry pump 23 and a cyclone separator 24 which are connected in sequence, wherein the wet ball mill 21 is an open-flow ball mill, an acid-resistant medium is adopted, generally a high-aluminum ceramic material is adopted, beryllium slag enters the stirring tank 22 from a discharge hole of the wet ball mill 21, a discharge hole at the bottom of the stirring tank 22 is connected with a feed hole of the slurry pump 23, an outlet of the slurry pump 23 is connected with a feed hole of the cyclone separator 24, a coarse material outlet at the bottom of the cyclone separator 24 is connected with a feed hole of the wet ball mill 21, a fine material outlet at the upper part of the cyclone separator 24 is connected with a feed hole at the upper part of a primary washing tank, and.
The washing system comprises a primary washing warehouse, a secondary washing warehouse, a plurality of washing warehouses and a recovery device which are sequentially connected, wherein each group of washing warehouse is provided with 3 washing tanks for realizing the alternate operation of washing, precipitation and discharging, each washing warehouse is provided with a feeding hole 311, a middle overflow hole 312, a bottom discharging hole 313, a top exhaust hole 314 and a compressed air inlet pipe 315, the washing warehouse adopts a pneumatic stirring mode, air for stirring is supplied by arranging an air compressor station, the top exhaust hole of the washing warehouse is provided with a suction machine 316, and the air is uniformly output and introduced into a high-temperature zone of the cement kiln for treatment through the suction machine 316.
The middle overflow port 312 of the primary washing warehouse is connected with the beryllium separation warehouse inlet 41 through a pipeline, the bottom outlet 313 is connected with the secondary washing warehouse inlet 311, the middle overflow port 312 of the secondary washing warehouse is connected with the first clear liquid tank 321, the first clear liquid tank 321 is connected with the primary washing warehouse inlet 311 through a sewage pump 322 and a pipeline, the secondary washing warehouse outlet 313 is connected with the filter press 324 through a slurry pump 323, and solid-liquid separation of slurry is realized through filter pressing.
Recovery unit includes solid recovery unit and liquid recovery unit, solid recovery unit includes belt conveyor 325 and solid sediment homogenization storage shed, belt conveyor 325 feed end links to each other with filtration equipment 324 solid discharge gate, belt conveyor 325 discharge end links to each other with solid sediment homogenization storage shed, exports solid sediment through belt conveyor 325, liquid recovery unit includes collecting pit 326, collecting pit 326 includes feed inlet, middle part overflow mouth, discharge gate, the feed inlet links to each other with filtration equipment 324 liquid discharge gate, the middle part overflow mouth links to each other with first clear liquid pond 321, the discharge gate links to each other with secondary washing storehouse feed inlet 311.
The beryllium separation system comprises a beryllium separation warehouse, a filter, a second clear liquid tank and a low-temperature belt evaporator, wherein the beryllium separation warehouse is provided with a feed inlet 41, a middle overflow port 42 and a discharge port 43, the discharge port 43 of the beryllium separation warehouse is connected with the feed inlet of the filter 45 through a sludge pump 44, the liquid discharge port of the filter 45 is connected with the second clear liquid tank 46, the solid discharge port of the filter 45 is connected with the low-temperature belt evaporator 47, and the filtered solid is output through the low-temperature belt evaporator 47. The beryllium separation warehouse is designed to be consistent with a washing warehouse and comprises 3 washing tanks for realizing the alternate operation of washing, precipitation and discharging, the beryllium separation warehouse adopts a pneumatic stirring mode, an air compressor station is arranged to supply air for stirring or a mechanical stirring mode is adopted for washing, a suction machine 48 is arranged at an exhaust port at the top of the beryllium separation warehouse, the gas is uniformly output together with the gas sucked out from the washing warehouse through the suction machine 48 and is led into a cement kiln high-temperature zone for treatment, and the filter 45 is one of a centrifuge, a plate and frame filter press, a belt filter and a disc spiral filter.
The beryllium slag detoxification and cement kiln cooperative recycling treatment system adopted by the invention is characterized in that connecting pipelines and containers among all systems are made of corrosion-resistant stainless steel, all liquid pipelines and all washing separation storehouses adopt intelligent detection instruments and control instruments, and the whole production line realizes automatic control and unmanned operation.
The beryllium slag comprises acid dissolving slag and alum settling slag, as shown in figure 1, the acid dissolving slag or the alum settling slag is separated by a cyclone separator after being ground by a wet method, the separated fine materials are washed and filtered, and a solution A and slurry B are obtained after filtering and separating, wherein the solution A is added with ammonia water to react to obtain a solid C and a liquid D, the solid C is treated and then returned to a beryllium smelting plant for later use, and the liquid D is added with a sulfuric acid solution to react to obtain a liquid E.
When the material is acid-soluble slag, slurry B is subjected to solid-liquid separation to obtain liquid F and solid G, when the material is alum precipitation slag, a calcium hydroxide solution is added into the slurry B, and after reaction, the slurry is subjected to solid-liquid separation to obtain liquid H and solid I, wherein the solid G and the solid I are used as cement raw materials, and the liquid E and the liquid H are used as cement kiln denitration agents.
The beryllium slag treatment is carried out by applying a beryllium slag detoxification and cement kiln cooperative recycling treatment system, which comprises the following steps:
example one
Treatment of acid-soluble slag (beryllium slag)
The method comprises the following steps: transportation and storage of acid-soluble slag
Acid-soluble slag transported by a special transportation vehicle for hazardous wastes is directly unloaded into a storage warehouse for storage after being transported into a factory, wherein the storage warehouse is a sealed type transferring garage with an intelligent grab crane, the storage warehouse is designed according to the temporary storage requirement of hazardous articles, and the gas pumped in the storage warehouse is sent into a cement kiln system to be used as air for a high-temperature section of a grate cooler in a centralized ventilation mode.
Step two: washing and detoxifying acid dissolving slag
And (2) hoisting the acid-soluble slag into a steady flow bin in a storage warehouse by using a grab bucket, connecting the bottom of the steady flow bin with a plate-type feeder, connecting the plate-type feeder with a metering belt scale, connecting the metering belt scale with the feed inlet of the wet ball mill by using a belt conveyor, and conveying the beryllium slag into the wet nodular graphite mill for grinding and washing by using the belt conveyor after metering the beryllium slag by using the plate-type feeder.
Discharging the ground slurry from the tail of the wet-process nodular graphite machine, feeding the slurry into a stirring tank, adjusting the concentration and the pH value to 3-5 by using an ammonium sulfate solution, then adjusting the concentration of the slurry to an appropriate value by using water, feeding the slurry which is uniformly stirred and mixed in the stirring tank into a cyclone flow divider from a discharge port at the bottom of the stirring tank through a slurry pump, separating the slurry by using the cyclone flow divider, feeding the coarse material at the bottom of the coarse material cyclone separator into a wet-process grinding machine for secondary grinding, and feeding the fine material from a fine material outlet at the upper part of the cyclone separator into a primary washing warehouse for washing.
The ground acid-soluble residue slurry is washed by adopting a two-stage washing mode to ensure the washing effect, the acid-soluble residue slurry is washed by a primary washing warehouse, a secondary washing warehouse or multiple times of washing, each group of washing warehouse is provided with 3 washing tanks for realizing the alternate operation of washing, precipitation and discharging, the washing process of the beryllium residue slurry is realized, wherein the primary washing warehouse is washed by clear liquid collected by a first clear liquid tank, the secondary washing warehouse is washed by clean water accessed from the outside, after the slurry enters the primary washing warehouse, beryllium-containing liquid enters a beryllium separation warehouse from an overflow port in the middle of the primary washing warehouse through a pipeline, the residual slurry enters the secondary washing warehouse from a discharge port of the primary washing warehouse, after the washing in the secondary washing warehouse is finished, the supernatant overflows from the middle of the secondary washing warehouse and enters the first clear liquid tank, and the residual slurry enters a filtering device through a discharge port at the bottom of the secondary washing, make mud solid-liquid separation through filtration equipment, wherein the solid sediment is sent to the former canopy of cement through the belt and is stored, and liquid is through the collecting pit sedimentation of stewing, and the supernatant after the rest gets into in the first clear solution pond through collecting pit middle part overflow mouth, and the sediment after the rest returns in the secondary washing storehouse.
And the clear liquid collected in the first clear liquid pool enters the wet ball mill and the primary washing warehouse through a sewage pump and a pipeline for grinding water and primary washing warehouse water, and the washing times are determined according to the beryllium content in the solid slag in the washing process so as to meet the washing requirements.
Step three: beryllium separation and recovery
Adding NH into the beryllium-containing solution after the first washing and sedimentation separation in the washing warehouse4Adjusting the pH value of the OH solution to ensure that BeSO in the library4Conversion of the solution to Be (OH)2Precipitating to obtain Be (OH)2Solid slag and (NH)4)2SO4Solution, after beryllium separation reservoir function, in which the liquid ((NH)4)2SO4Solution and ammonia) enters a second clear liquid tank through an overflow port in the middle of the beryllium separating tank, and Be (OH)2And (3) the precipitate enters a filtering device from a discharge hole of the beryllium separation reservoir through a sludge pump, the filtered solid is returned to a beryllium smeltery by a special vehicle to be used as a beryllium refining raw material to prepare BeO after being evaporated by a low-temperature belt type evaporator, and the filtered liquid is collected in a second clear liquid tank.
Step four: cement kiln system resource treatment
Produced in the washing process of acid-soluble slagThe raw solid slag is mainly SiO2、CaSO4And MgSO4The raw materials can be sent into a cement kiln for high-temperature calcination to enable trace beryllium to be solid-melted in the crystal lattice of cement clinker and (NH) generated in the reaction process4)2SO4The solution can be used as a cement kiln denitrifier or concentrated into high-concentration (NH)4)2SO4The solution is applied, and gas generated in the reaction process is collected in a centralized way and is introduced into a high-temperature zone of a cement kiln for treatment.
Example two
Treatment of precipitated alum slag
The method comprises the following steps: transport and storage of alum precipitation slag
After the alum sludge transported by the special transportation vehicle for hazardous wastes is transported into a factory, the alum sludge is directly unloaded into a storage warehouse for storage, wherein the storage warehouse is a sealed type transferring garage with an intelligent grab crane, the storage warehouse is designed according to the temporary storage requirement of hazardous articles, a centralized ventilation mode is adopted, and the gas pumped in the storage warehouse is sent into a cement kiln system to be used as air for a high-temperature section of a grate cooler.
Step two: washing and detoxifying acid dissolving slag
The main component of ammonium alum slag is ammonium aluminum sulfate, and the ammonium alum slag is generally packaged by adopting a fiber bag, so that a bale breaker is added before grinding, a glass fiber bag is separated, and a glass fiber belt is directly sent to a cement kiln for incineration treatment. And measuring ammonium alum slag, connecting the measured ammonium alum slag with a feed inlet of a wet ball mill through a belt conveyor, measuring beryllium slag by using a plate-type feeding machine, and conveying the measured beryllium slag into a wet nodular graphite machine through the belt conveyor for grinding and washing.
Discharging the ground slurry from the mill tail of the wet ball mill, then feeding the slurry into a stirring tank, adjusting the concentration and the pH value to 3-5 by using an ammonium sulfate solution, then adjusting the concentration of the slurry to a proper concentration by using water, feeding the slurry which is uniformly stirred and mixed in the stirring tank into a cyclone flow divider from a discharge port at the bottom of the stirring tank through a slurry pump, separating the slurry by using the cyclone flow divider, feeding the coarse material at the bottom of the coarse material cyclone separator into a wet mill for secondary grinding, and feeding the fine material from the fine material outlet at the upper part of the cyclone separator into a primary washing tank for washing.
The ground ammonium alum residue slurry is washed by a primary washing warehouse and a secondary washing warehouse respectively by adopting a two-stage washing mode, each group of washing warehouse is provided with 3 washing tanks for realizing the alternate operation of washing, sedimentation and discharging, the washing process of the beryllium residue slurry is realized, wherein the primary washing warehouse is washed by clear liquid collected by a first clear liquid tank, the secondary washing warehouse is washed by clean water accessed from the outside, after the slurry enters the primary washing warehouse, beryllium-containing liquid enters a beryllium separation warehouse from an overflow port in the middle of the primary washing warehouse through a pipeline, the residual slurry enters the secondary washing warehouse from a discharge port of the primary washing warehouse, after the washing in the secondary washing warehouse is finished, supernatant overflows from the middle of the secondary washing warehouse and enters the first clear liquid tank, and the residual slurry enters a filter device through a discharge port at the bottom of the secondary washing warehouse under the action of a slurry pump, make mud solid-liquid separation through filtration equipment, wherein the solid sediment is sent to the former canopy of cement through the belt and is stored, and liquid is through the collecting pit sedimentation of stewing, and the supernatant after the rest gets into in the first clear solution pond through collecting pit middle part overflow mouth, and the sediment after the rest returns in the secondary washing storehouse.
And the clear liquid collected in the first clear liquid tank enters the wet ball mill and the primary washing warehouse through a sewage pump and a pipeline for grinding water and primary washing warehouse water, and the washing times are determined according to the beryllium content in the solid slag in the washing process so as to meet the washing requirements.
Step three: beryllium separation and recovery
Adding NH into the beryllium-containing solution after the first washing and sedimentation separation in the washing warehouse4Adjusting the pH value of the OH solution to ensure that BeSO in the library4Conversion of the solution to Be (OH)2Precipitating to obtain Be (OH)2Solid slag and (NH)4)2SO4Solution, after beryllium separation reservoir function, in which the liquid ((NH)4)2SO4Solution and ammonia) enters a second clear liquid tank through an overflow port in the middle of the beryllium separating tank, and Be (OH)2The sediment enters a filter from a discharge hole of the beryllium separation warehouse through a sludge pump, the filtered solid is evaporated through a low-temperature belt evaporator, then the solid is returned to a beryllium smeltery by a special vehicle to be used as a beryllium refining raw material to prepare BeO, and the BeO is filteredAnd collecting the liquid in a second clear liquid pool.
Step four: cement kiln system resource treatment
The solid slag generated in the ammonium alum slag washing process is mainly CaSO4And Al (OH)3The raw materials can be sent into a cement kiln for high-temperature calcination to enable trace beryllium to be solid-melted in the crystal lattice of cement clinker and (NH) generated in the reaction process4)2SO4The solution can be used as a cement kiln denitrifier or concentrated into high-concentration (NH)4)2SO4The solution is applied, and gas generated in the reaction process is collected in a centralized way and is introduced into a high-temperature zone of a cement kiln for treatment.
The beryllium content of the washed solid slag is less than 0.1 mg/kg. The raw materials can be sent into a cement kiln for high-temperature calcination to be solid-melted in trace beryllium in cement clinker lattices to form minerals such as calcium ferrite beryllium, calcium aluminum beryllium, calcium beryllium and the like; if 70 tons of beryllium slag are treated every day in a production line of 3500 tons of cement clinker produced per day, the doping amount is 2 percent, the beryllium content in the clinker can reach the requirement of less than 1 mu g/kg, and the toxicity hazard is eliminated. And meanwhile, beryllium slag is calcined at high temperature by a cement kiln to form cement clinker, and the cement clinker enters a cement clinker vitreous body, so that the beryllium content in the leachate is less than 1 mu g/l, and the risk of leaching toxicity is further eliminated.
According to the beryllium slag detoxification and cement kiln cooperative recycling treatment system and process disclosed by the invention, after washing and detoxification, the beryllium slag basically meets the requirements of cement raw materials, only trace amount of highly toxic beryllium and compounds thereof enter cement clinker, and the beryllium and the compounds thereof are solid-melted in the cement clinker through high-temperature calcination to form water-insoluble minerals, so that the leaching hazard of the minerals is eliminated. The low-temperature waste heat of the cement plant is used as a heat source for disposing evaporative crystallization, so that energy is saved. In the treatment process, a small amount of ammonia nitrogen waste gas is collected and enters a cement system, the waste water is recycled without being discharged externally, no dust is discharged by adopting a wet process, no secondary pollution is caused, and one ton of beryllium slag can be recovered by 10-30kg of Be (OH)2Meanwhile, about 200kg of ammonium salt can be recycled, other raw materials can be used as cement raw materials, the cement raw materials are saved, the recycling and energy-saving treatment is really realized, and the energy-saving and energy-saving effects are realizedAnd (4) resource and development of circular economy.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and is not intended to limit the practice of the invention to these embodiments. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (15)
1. A beryllium slag detoxification and cement kiln cooperative recycling treatment process is characterized by comprising the following steps:
s1, storing the acid dissolving slag and the alum settling slag by a special storage warehouse after transportation and stacking respectively;
s2, washing and grinding the acid dissolution slag or the alum precipitation slag through a wet ball mill after metering, adjusting the pH value to 3-5 with an ammonium sulfate solution, adjusting the concentration with water, separating the slurry which is uniformly stirred, wherein the coarse material returns to the wet ball mill for circular grinding, and the fine material enters a washing warehouse for washing;
s3, separating the washed fine materials in the S2 to obtain a solution A and slurry B, wherein the solution A is used for separating and recovering beryllium, and the slurry B is treated and then sent to a cement kiln batching system, and is prepared into cement clinker after being calcined at high temperature in a cement kiln;
s4, adding ammonia water into the solution A obtained in the step S3 to adjust the pH value to 9-11, reacting with the ammonia water to obtain a solid C and a liquid D, wherein the solid C is treated and then returned to a beryllium smelter for later use, the liquid D is added with a sulfuric acid solution and then reacts to obtain a liquid E, and the liquid E is used as a cement kiln denitration agent, a beryllium refining agent or is evaporated and crystallized into a high-concentration solution for later use;
the system adopting the treatment process comprises the following steps: the storage warehouse, the pretreatment system, the washing system and the beryllium separation system are connected in sequence;
the storage warehouse is a sealed type transferring garage with an intelligent grab crane, the bottom of the storage warehouse is provided with a steady flow cabin, and the storage warehouse is provided with a centralized ventilation device;
the pretreatment system comprises a wet ball mill, a stirring tank and a cyclone separator, wherein a discharge port of the wet ball mill is connected with a feed port of the stirring tank, a discharge port of the stirring tank is connected with a feed port of the cyclone separator, a coarse material outlet at the bottom of the cyclone separator is connected with a feed port of the wet ball mill, a fine material outlet at the upper part of the cyclone separator is connected with a feed port at the upper part of a primary washing warehouse, and a feed port of the wet ball mill is connected with a water solution pipeline separated after secondary washing;
the washing system comprises a primary washing warehouse, a secondary washing warehouse, a plurality of washing warehouses and a recovery device which are connected in sequence, wherein each washing warehouse is provided with a feeding hole, a middle overflow hole, a discharging hole, a top exhaust port and a compressed air inlet pipe;
the beryllium separation system comprises a beryllium separation bank, a filter, a second clear liquid tank and a low-temperature belt evaporator, wherein the beryllium separation bank is provided with a feed inlet, a middle overflow port and a discharge port, the discharge port of the beryllium separation bank is connected with the feed inlet of the filter, the liquid discharge port of the filter is connected with the second clear liquid tank, and the solid discharge port of the filter is connected with the low-temperature belt evaporator.
2. The beryllium slag detoxification and cement kiln cooperative resource treatment process as claimed in claim 1, wherein when the material is acid-soluble slag, the slurry B in S3 is subjected to solid-liquid separation through a filter device to obtain liquid F and solid G, the separated liquid F is subjected to standing sedimentation, and the separated solid G is sent to a cement kiln batching system.
3. The beryllium slag detoxification and cement kiln cooperative resource treatment process as claimed in claim 1, wherein when the material is alum precipitation slag, the slurry B in S3 is added with calcium hydroxide solution, the slurry is subjected to solid-liquid separation by a filter device after reaction to obtain liquid H and solid I, the separated liquid H is subjected to standing sedimentation, and the separated solid I is sent to a cement kiln batching system.
4. The beryllium slag detoxification and cement kiln cooperative resource treatment process as claimed in claim 1, wherein the S2 comprises a first washing and a second washing, the solution A obtained after the first washing is used for separating and recovering beryllium, the clear liquid recovered after the second washing is used for water for wet ball mill grinding, and the washing times are determined according to the beryllium content in the solid slag after each washing.
5. The beryllium slag detoxification and cement kiln cooperative recycling treatment process as claimed in claim 4, wherein the primary washing water is a clear liquid recovered after the secondary washing, and the secondary washing water or the last washing water is clean water introduced from outside.
6. The beryllium slag detoxification and cement kiln cooperative recycling process as claimed in claim 5, wherein the clear solution recovered after the second washing is stored in a first clear solution tank.
7. The beryllium slag detoxification and cement kiln cooperative recycling treatment process as claimed in claim 2 or 3, wherein after the liquid F and the liquid H are subjected to standing and sedimentation, the obtained supernatant is collected in a first clear liquid tank, and the settled solids are returned to a secondary washing warehouse.
8. The beryllium slag detoxification and cement kiln cooperative recycling treatment process as claimed in claim 1, wherein the solid C in S4 is filtered, the filtered solid is dried by a low-temperature belt evaporator and then returned to a beryllium smeltery, and the filtered liquid is collected in a second clear liquid tank.
9. A system for the beryllium slag detoxification and cement kiln cooperative recycling treatment process according to any one of claims 1 to 8, which comprises a storage warehouse, a pretreatment system, a washing system and a beryllium separation system which are connected in sequence;
the storage warehouse is a sealed type transferring garage with an intelligent grab crane, the bottom of the storage warehouse is provided with a steady flow cabin, and the storage warehouse is provided with a centralized ventilation device;
the pretreatment system comprises a wet ball mill, a stirring tank and a cyclone separator, wherein a discharge port of the wet ball mill is connected with a feed port of the stirring tank, a discharge port of the stirring tank is connected with a feed port of the cyclone separator, a coarse material outlet at the bottom of the cyclone separator is connected with a feed port of the wet ball mill, a fine material outlet at the upper part of the cyclone separator is connected with a feed port at the upper part of a primary washing warehouse, and a feed port of the wet ball mill is connected with a water solution pipeline separated after secondary washing;
the washing system comprises a primary washing warehouse, a secondary washing warehouse, a plurality of washing warehouses and a recovery device which are connected in sequence, wherein each washing warehouse is provided with a feeding hole, a middle overflow hole, a discharging hole, a top exhaust port and a compressed air inlet pipe;
the beryllium separation system comprises a beryllium separation bank, a filter, a second clear liquid tank and a low-temperature belt evaporator, wherein the beryllium separation bank is provided with a feed inlet, a middle overflow port and a discharge port, the discharge port of the beryllium separation bank is connected with the feed inlet of the filter, the liquid discharge port of the filter is connected with the second clear liquid tank, and the solid discharge port of the filter is connected with the low-temperature belt evaporator.
10. The beryllium slag detoxification and cement kiln cooperative resource treatment system as claimed in claim 9, wherein the discharge port of the primary washing warehouse is connected with the feed port of the secondary washing warehouse, the middle overflow port of the primary washing warehouse is connected with the feed port of the beryllium separation warehouse, the middle overflow port of the secondary washing warehouse is connected with the first clear liquid tank, the first clear liquid tank is connected with the feed port of the primary washing warehouse, and the discharge port of the secondary washing warehouse is connected with the filtering device.
11. The beryllium slag detoxification and cement kiln cooperative resource treatment system according to claim 9, wherein the recovery device comprises a solid recovery device and a liquid recovery device, the solid recovery device comprises a belt conveyor and a solid slag homogenization storage shed, the feed end of the belt conveyor is connected with a solid discharge port of a filter device, the discharge end of the belt conveyor is connected with the solid slag homogenization storage shed, the liquid recovery device comprises a collecting tank, the collecting tank comprises a feed inlet, a middle overflow port and a discharge port, the feed inlet is connected with a liquid discharge port of the filter device, the middle overflow port is connected with a first clear liquid tank, and the discharge port is connected with a feed inlet of a secondary washing tank.
12. The beryllium slag detoxification and cement kiln cooperative recycling treatment system as claimed in claim 9, wherein the washing reservoir and the beryllium separation reservoir are provided with pneumatic stirring devices, and are connected with an air compressor station through a pipeline, or are washed by adopting a mechanical stirring mode.
13. The beryllium slag detoxification and cement kiln cooperative resource treatment system as claimed in claim 9, wherein the top exhaust ports of the washing and beryllium separation banks are provided with suction machines.
14. The beryllium slag detoxification and cement kiln cooperative resource treatment system according to claim 9, wherein the filter is one of a centrifuge, a plate and frame filter press, a belt filter and a stacked spiral filter.
15. The beryllium slag detoxification and cement kiln cooperative resource treatment system as claimed in claim 9, wherein the wet ball mill is one or a combination of open flow ball mill, vertical sand mill and horizontal sand mill, and is made of acid-proof medium and high-alumina ceramic material.
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