Double-decomposition detoxification regeneration device for harmless treatment of barium slag

Abstract

The utility model provides a double decomposition detoxification regeneration device for harmless treatment of barium slag, which comprises a sand mill and a reaction kettle, the sand mill comprises a feed port for feeding barium slag mixture, a grinding cavity and a discharge pipe, and a grinding module is arranged in the grinding cavity; the reaction kettle comprises a reaction cavity, a discharge pipe of the sand mill is communicated with the reaction cavity, a stirrer driven by a stirring motor to rotate is arranged in the reaction cavity, at least one dosing port is formed in the top or the upper end of the reaction cavity, a discharge port is formed in the lower end or the bottom of the reaction cavity, and a discharge port is formed in the outer side wall of the reaction cavity. And a heating coil is wound. The device integrates the functions of crushing, grinding, dosing, stirring, pulping and heating, can remove the toxicity of metal barium in the barium slag to form non-toxic regenerated barium slag, and is low in cost and high in automation degree.

Description

TECHNICAL FIELD

[0001] The utility model belongs to solid waste treatment technical field, especially relate to a complex decomposition detoxification regeneration device for barium residue harmless treatment. BACKGROUND

[0002] Barium residue is solid residue produced in the process of producing barium carbonate and thiourea by barium salt enterprises using carbonization reduction method, contains a large amount of soluble barium, has toxicity and strong alkali corrosivity, and its leaching rate is as high as 92.8%, which constitutes potential toxicity risk to plants and animals.

[0003] Harmless treatment is also called safe treatment, that is, using advanced technology and process to reduce the influence of waste toxicity and its derivatives on the environment and reduce waste discharge by reducing biological or chemical harmful substances in toxic and harmful waste.

[0004] At present, the main way of barium residue harmless treatment is incineration and chemical precipitation to increase the removal rate of toxic and harmful barium ions.

[0005] Since the just produced barium residue is viscous and contains a lot of solid impurities, its flow performance is poor, and it is inconvenient to carry out harmless treatment, so the viscous residue needs to be incinerated into solid waste first. However, this treatment method cannot effectively remove toxic and harmful substances in barium residue, and due to the lack of perfect tail gas treatment facilities and heat recovery system, the incineration method has the problems of high energy consumption, low utilization rate, high treatment cost and secondary pollution.

[0006] Chemical precipitation method can treat waste with toxic components, change toxic components into insoluble form, weaken toxicity and hinder migration. However, barium residue is a dangerous waste, which needs to be converted into ordinary industrial solid waste to facilitate efficient reuse. The toxic free barium in barium residue is precipitated in the form of barium sulfate, which is a kind of insoluble substance with stable chemical properties, and it is difficult to have reversible reaction and incomplete precipitation in chemical reaction, which is harmful to human health. The soluble barium ions in barium residue can also be precipitated with other waste residues to form insoluble substances, thereby reinforcing barium ions and reducing the leaching rate of soluble harmful barium ions to some extent.

[0007] Therefore, it is necessary to solve the defects of the prior art. SUMMARY

[0008] The utility model discloses a kind of complex decomposition detoxification regeneration devices for barium residue harmless treatment, the toxicity of metal barium in barium residue can be removed, form non-toxic regenerated barium residue, and cost is low, degree of automation is high.

[0009] The utility model provides a complex decomposition detoxification regeneration device for barium dregs harmlessness treatment, including sand mill and reaction kettle, the sand mill includes the feed inlet for putting barium dregs mixture, grinding chamber and discharge pipe, be equipped with grinding module in the grinding chamber, the reaction kettle includes reaction cavity, the discharge pipe of sand mill with reaction cavity intercommunication, be equipped with the stirrer that rotates by stirring motor in the reaction cavity, the top or upper end of reaction cavity is equipped with at least one dosing port, the lower end or bottom of reaction cavity is equipped with the discharge gate, on the lateral wall of reaction cavity, surround with heating coil.

[0010] Optionally, the dosing port is provided with four, placed on the top of the reaction cavity.

[0011] Optionally, the heating coil includes the pipeline that makes hot steam flow and is spirally surrounded on the lateral wall of the reaction cavity, the pipeline is equipped with steam inlet and steam outlet respectively at both ends, and the steam inlet is connected with a heat source.

[0012] Optionally, the stirrer includes a stirring shaft and stirring blades, the stirring shaft is driven to rotate by the stirring motor, is vertically arranged at the central position in the reaction cavity, the stirring blades are provided with at least three layers, are arranged along the radial direction of the stirring shaft, and the distance between the stirring blades and the inner lateral wall of the reaction cavity is 300-500mm.

[0013] Optionally, the sand mill is a vertical sand mill and is placed on the top of the reaction cavity.

[0014] The utility model has the following technical effects:

[0015] (1) the complex decomposition detoxification regeneration device for barium dregs harmlessness treatment provided by the utility model is a device integrating crushing, grinding, dosing, stirring, beating and heating functions, the barium dregs and desulfurization waste gypsum after crushing and grinding are mixed with acid solution and dissolved solution in the reaction cavity of the reaction kettle through the dosing port, and are fully dispersed by the stirrer, the solubility barium is complex decomposed to generate barium sulfate precipitate insoluble in water by using mixing, acidification and coupling barium ion-complex decomposition reaction, so as to remove the toxicity of metal barium and form non-toxic regenerated barium dregs.

[0016] (2) the complex decomposition detoxification regeneration device for barium dregs harmlessness treatment provided by the utility model is provided with heating coil around the outer wall of the reaction cavity of the reaction kettle, can fully utilize the hot steam generated by the rotary kiln of barium salt enterprises as a heat source, accelerates the complex decomposition reaction, reduces the operation cost of barium dregs harmlessness treatment, improves the stability of barium dregs harmlessness treatment, and provides favorable conditions for subsequent barium dregs resource utilization.

[0017] (3) The utility model is suitable for harmless treatment of barium slag in barium salt industrial production process, has low required energy consumption, high automation degree and better popularization value. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 It is the structure schematic diagram of the utility model embodiment. DETAILED DESCRIPTION

[0019] In order to make the utility model purposes, technical schemes and advantages more clearly, the following is further detailed with examples.The specific embodiments described here are only used to explain the utility model and not to limit the utility model.

[0020] It should be noted that when an element is referred to as being "connected", "disposed" or "arranged" to another element, it can be directly on the other element or can have an intermediate element.

[0021] It should also be noted that the terms "inner", "outer", "top", "bottom", "side wall", "upper end", "lower end" and the like in the utility model embodiments are only relative concepts or are referenced based on the normal use state of the product or the position displayed based on the drawings, and are only for the convenience of describing the utility model and simplifying the description, and therefore should not be considered as indicating or implying that the device or element must have a specific orientation, structure and operation, and therefore should not be considered as limiting.

[0022] Referring to Figure 1 The utility model embodiment provides a complex decomposition detoxification regeneration device for barium slag harmless treatment, including sand mill 1 and reaction kettle 2, wherein sand mill 1 includes feed inlet 11, grinding cavity 12 and discharge pipe 15, feed inlet 11 is used for putting barium slag mixture, and the mixture is mixed by barium slag and desulfurization waste gypsum, wherein the barium slag is solid waste after barium carbonate production of barium salt enterprise, and the desulfurization waste gypsum is solid by-product obtained after desulfurization and purification treatment of flue gas generated after combustion of sulfur-containing fuel (coal, oil etc.) in barium salt enterprise production process limestone-gypsum method, and the mass ratio of barium slag and desulfurization waste gypsum is 2-15:1.In grinding cavity 12, grinding module 13 is arranged, and the barium slag and desulfurization waste gypsum mixture put into feed inlet 11 can be crushed and ground, and complete grinding effect can be achieved.Reaction kettle 2 includes reaction cavity 21, and the discharge pipe 15 of sand mill 1 is communicated with reaction cavity 21, and the mixture after grinding of sand mill 1 is directly put into reaction cavity 21 through discharge pipe 15.In reaction cavity 21, stirrer 21 is arranged, and stirrer 21 is driven to rotate by stirring motor 22.At least one medicine inlet 23 is arranged at the top or upper end of reaction cavity 21, and the medicine inlet 23 is communicated with the outside, and the medicine inlet 23 is used for putting the medicine for reaction, and the medicine is the desulfurization waste gypsum and barium slag mixture, and the mass ratio of the desulfurization waste gypsum and barium slag mixture is 2-15:1. Figure 1The embodiment shown is arranged at the top of the reaction cavity 21, and is used for adding chemical reagents required for the reaction. Figure 1 The embodiment shown is arranged at the lower end of the reaction cavity 21, and the mixture put into the reaction cavity 21 of the sand mill 1 and the chemical reagent solution added through the adding port 23 can be fully stirred and mixed uniformly to form slurry by the stirrer 21, and the reaction process can be completed in the mixing and beating process. The outer wall of the reaction cavity 21 is also surrounded by a heating coil 24, and hot air or hot water can flow in the heating coil 24, so that the reaction cavity 21 can be heated as required, so that the product of the reaction cavity 21 can be carried out under the set reaction condition and reaction temperature, and the reaction requirement can be met.

[0023] The utility model discloses based on the chemical precipitation method foundation, starting from the " waste control waste " concept, introduce the synergic precipitation mechanism, mix barium residue and desulfurization waste gypsum, utilize the effective component in desulfurization gypsum waste material to fix the soluble barium ion in barium residue, solve the corresponding industrial solid waste problem, add chemical reagent simultaneously, and make barium ion in barium residue into non-toxic barium sulfate through double decomposition reaction, to solve the problem of the toxicity of acid-soluble barium ion in barium residue. In this way, by reasonably utilizing the existing desulfurization gypsum waste material resources of barium salt enterprises, the cost of harmless treatment of barium residue is reduced, the stability of the harmless treatment of barium residue is improved, and favorable conditions are provided for the subsequent reuse of barium residue.

[0024] Referring to Figure 1 In the specific embodiment, the adding port 23 is provided with four adding ports, which are arranged at the top of the reaction cavity 21, wherein the first adding port 231 is used for adding acid liquid, which is used for acidifying the mixture of barium residue and desulfurization waste gypsum in the reaction cavity 21, reducing the pH value of the product, and making most of the barium ions (Ba 2+ ) in the barium residue after acidification react with the sulfate ions (SO4 2- ) in the desulfurization waste gypsum to form non-toxic BaSO4 which is insoluble in water; the second adding port 232 is used for adding coupling agent sodium dimethyl dithiocarbamate (SDMC) or sodium diethyl dithiocarbamate (DDTC), so that the coupling agent reacts with the free barium ions, BaCO3, BaSO3 and BaO in the mixture to perform coupling and competitive coordination reaction, and create better conditions for the double decomposition reaction; the third adding port 233 is used for adding sulfate solution, and the sulfate can be any one of sodium bisulfate (NaHSO4), Na2SO4, K2SO4, KHSO4 and (NH4)2SO4, so as to perform double decomposition reaction on the chelate barium chelated and enriched in the mixture, and make the barium ions (Ba 2+ ) in the remaining barium carbonate, barium sulfite or barium oxide in the product form non-toxic barium sulfate precipitate; and the fourth adding port 234 is used for adding ferrous sulfate solution, so as to make the remaining sulfur ions (S 2-) and ferrous ions (Fe 2+ ) to form stable iron sulfide (FeS) precipitates to remove sulfur ions (S 2- ).

[0025] Referring to Figure 1 , the heating coil 24 in the specific embodiment of the utility model includes a pipeline 241 spirally surrounding the outer sidewall of the reaction cavity 21, the pipeline 241 is used for hot steam flow, steam inlets 242 and steam outlets 243 are respectively arranged at two ends of the pipeline 241, the steam inlets 242 are connected with heat sources, and the heat sources can come from the rotary kiln flue gas waste heat in the production process of a barium salt enterprise, so that the effective resources of the barium salt enterprise are fully utilized, and the harmless treatment cost of the barium residue is further reduced.

[0026] Referring to Figure 1 , in the specific embodiment of the utility model, the stirrer 26 includes a stirring shaft 261 and stirring blades 262, the stirring shaft 261 is vertically arranged at the central position in the reaction cavity 21, the stirring motor 22 is arranged at the center of the top of the reaction cavity 21, the output shaft of the stirring motor 22 penetrates the top of the reaction cavity 21 and is fixedly connected with the stirring shaft 261, so that the stirring shaft 261 is driven to rotate by the stirring motor 22. The stirring blades 262 are provided with at least three layers and are arranged along the radial direction of the stirring shaft 261. The multi-layer arrangement of the stirring blades 262 enables the mixed material in the reaction cavity 21 to be completely stirred, so that the mixed material and the chemical reagent are uniformly mixed. The spacing L between the stirring blades 262 and the inner sidewall of the reaction cavity 21 is 300-500 mm, so that there is a certain channel between the stirring blades 262 and the inner sidewall of the reaction cavity 21, and the stirring blades 262 are prevented from being stuck during rotation.

[0027] Referring to Figure 1 , in the specific embodiment of the utility model, the sand mill 1 is preferably a vertical sand mill, and the vertical sand mill is arranged at the top of the reaction cavity 21, and the medicine feeding port 23 arranged opposite the top is arranged in another area. The barium residue and the desulfurization waste gypsum mixture are fed into the reaction cavity 21 from the feeding port 11, and the mixture is crushed by the high-speed rotation, extrusion and centrifugal force of the grinding module 13 in the grinding cavity 11 and is then sent upward after being crushed, is sieved through the screen 14 and is then sent into the reaction cavity 21 from the upper discharge pipe 15. The vertical grinding machine is adopted, the mixed material can achieve complete grinding effect, the mixed material is ground in the fully-closed grinding cavity 11, no pollution is caused, the working environment is ensured, the vertical sand mill does not occupy space, is convenient to operate, is suitable for sand grinding and dispersion of materials with various viscosities, has high production efficiency and good dispersibility.

[0028] The working process of the embodiment of the utility model is as follows:

[0029] The barium slag and desulfurization waste gypsum are mixed and fed into the grinding cavity 12 of the vertical sand mill 1 through the feeding port 11. Under the action of the grinding module 13, the barium slag particles are ground from large particles to small particles. With continuous grinding, the mixture reaches the aperture of the screen 14, and is fed into the reaction cavity 21 of the reaction kettle 2 through the discharge pipe 15. The discharge port 25 is closed, the stirring motor 22 is started, and the stirrer 26 starts to rotate. At the same time, the first dosing port 231 is opened, and the acid solution is added to acidify the continuously stirred mixture in the reaction cavity 21. Meanwhile, the steam inlet 242 is opened, and hot steam flows from top to bottom along the heating coil 24 to keep the temperature in the reaction cavity 21 within the range of 40-85℃. The acid-soluble barium ions and water-soluble barium ions (Ba 2+ ) in the solution gradually dissolve in the solution under the action of the acid and heat, react with the sulfate ions (SO4 2- ) in the desulfurization waste gypsum, and are converted into barium sulfate precipitate. After 15-30 minutes of stirring and acidification, the first dosing port 231 and the steam inlet 242 are closed, the second dosing port 232 is opened, and the dissolved dimethyl dithiocarbamic acid sodium (DTDMAC) or diethyl dithiocarbamic acid sodium (DDTC) is added. Based on the strong complexing ability of DTDMAC and DDTC to heavy metal ions, the free barium ions in the mixture and BaCO3, BaSO3, BaO and other barium salts are coupled and compete for coordination reaction. The toxic ingredients of heavy metal ions in the mixture form stable complex precipitate, reducing the concentration of toxic ingredients in the mixture. After 5-30 minutes of stirring, the second dosing port 232 is closed, the third dosing port 233 is opened, and the sulfate salt solution is added to perform metathesis reaction with the chelate barium in the mixture. At this time, the steam inlet 242 is opened again to keep the temperature in the reaction cavity 21 within the range of 40-85℃, providing heat source for the metathesis reaction to promote the reaction process and increase the reaction speed, thereby shortening the reaction time. The sulfate salt is completely ionized in the aqueous solution to generate Na + , H + and SO4 2- . The hydrogen ions (H + ) react with the hydroxyl ions (OH - ) to further reduce the pH value of the mixture, and the sulfate ions (SO4 2- ) combine with the barium ions (Ba 2+ ) to form non-toxic barium sulfate precipitate which is insoluble in water. After 60-180 minutes of stirring, the third dosing port 233 is closed, the fourth dosing port 234 is opened, and the ferrous sulfate solution is added to make the sulfur ions (S 2- ) in the mixture combine with the ferrous ions (Fe 2+ ) in the ferrous sulfate to form iron sulfide (FeS) precipitate, and the sulfate ions (SO4 2- ) combine with the residual barium ions (Ba 2+) combined to form a barium sulfate precipitate, ensuring that the barium ion concentration is reduced to a very low level. After stirring for 10-30 minutes, close the fourth dosing port 234, and close the steam inlet 242 and the steam outlet 243, open the discharge port 25, and discharge the regenerated barium residue slurry with a water content of 30-45%. After the reaction is completed, the regenerated barium residue slurry is subjected to drying treatment to obtain regenerated barium residue with a water content of 10-20%. The regenerated barium residue is detected according to the Hazardous Waste Identification Standard Leaching Toxicity Identification (GB5085.3-2007) and the General Industrial Solid Waste Storage and Landfill Pollution Control Standard (GB 18599-2020), and after meeting the general solid waste Class 1 residue standard, it is subjected to resource utilization.

[0030] The above embodiments of the utility model shown in the embodiment of the utility model only part of the preferred embodiment of the utility model, and it cannot be limited to the utility model, under the condition of not departing from the essence of the utility model, any modification, equivalent replacement and improvement made by the person skilled in the art, etc. all belong to the protection scope of the utility model.

Claims

1. A double decomposition detoxification and regeneration device for barium slag harmless treatment, characterized in that, The sand mill comprises a feeding port for feeding barium residue mixture, a grinding cavity provided with a grinding module, and a discharge pipe; the reaction kettle comprises a reaction cavity, the discharge pipe of the sand mill is communicated with the reaction cavity, the reaction cavity is provided with a stirrer driven by a stirring motor, the top or upper end of the reaction cavity is provided with at least one feeding port, the lower end or bottom of the reaction cavity is provided with a discharge port, and a heating coil is arranged around the outer wall of the reaction cavity.

2. The double decomposition detoxification and regeneration apparatus for barium slag harmless treatment according to claim 1, characterized by, The four feeding ports are arranged on the top of the reaction cavity.

3. The double decomposition detoxification and regeneration apparatus for barium slag harmless treatment according to claim 1, characterized by, The heating coil comprises a pipe for flowing hot steam, which is spirally arranged around the outer wall of the reaction cavity, and the two ends of the pipe are respectively provided with a steam inlet and a steam outlet, and the steam inlet is connected with a heat source.

4. The double decomposition detoxification and regeneration apparatus for barium slag harmless treatment according to claim 1, characterized by, The stirrer comprises a stirring shaft and stirring blades, the stirring shaft is driven by the stirring motor to rotate vertically at the center of the reaction cavity, the stirring blades are arranged in at least three layers along the radial direction of the stirring shaft, and the distance between the stirring blades and the inner wall of the reaction cavity is 300-500 mm.

5. The double decomposition detoxification and regeneration apparatus for barium slag harmless treatment according to any one of claims 1 to 4, characterized by, The sand mill is a vertical sand mill arranged on the top of the reaction cavity.

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