CN114380316A - Method for harmlessly recycling barium carbonate from barium slag - Google Patents
Method for harmlessly recycling barium carbonate from barium slag Download PDFInfo
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- CN114380316A CN114380316A CN202210194771.3A CN202210194771A CN114380316A CN 114380316 A CN114380316 A CN 114380316A CN 202210194771 A CN202210194771 A CN 202210194771A CN 114380316 A CN114380316 A CN 114380316A
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- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/186—Strontium or barium carbonate
- C01F11/188—Barium carbonate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C13/00—Disintegrating by mills having rotary beater elements ; Hammer mills
- B02C13/02—Disintegrating by mills having rotary beater elements ; Hammer mills with horizontal rotor shaft
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
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- B02C13/00—Disintegrating by mills having rotary beater elements ; Hammer mills
- B02C13/14—Disintegrating by mills having rotary beater elements ; Hammer mills with vertical rotor shaft, e.g. combined with sifting devices
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C13/00—Disintegrating by mills having rotary beater elements ; Hammer mills
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C21/00—Disintegrating plant with or without drying of the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The invention provides a method for harmlessly recycling barium carbonate from barium slag synchronously, belonging to the technical field of solid waste treatment. The barium slag is barium-containing waste slag generated after dephosphorization is carried out on high-phosphorus molten iron by using a barium-based slag system, and the main component of the barium slag is Ba3(PO4)2The invention carries out harmless treatment on the barium-containing waste slag generated after dephosphorization is carried out on the high-phosphorus molten iron, and then carries out recycling on the barium carbonate precipitate, thereby greatly reducing the barium contentThe toxicity of the waste residue reduces the environmental pollution, and in the treatment process, the process is optimized according to different adding modes of liquid-liquid reaction and solid-liquid reaction, the pertinence is strong, the mixing uniformity of different reactants can be improved to the maximum extent, the maximum recovery of barium carbonate is facilitated, and the method has the advantages of energy conservation and emission reduction.
Description
Technical Field
The invention belongs to the technical field of solid waste treatment, and particularly relates to a method for harmlessly recycling barium carbonate from barium slag.
Background
The industrial solid waste refers to solid waste generated in industrial production activities, and is various waste residues, dust and other waste discharged into the environment in the industrial production process, and barium residue is a common industrial solid waste.
A certain amount of barium-containing waste residues are generated when stainless steel and other new steel grades are smelted in the metallurgical industry, and belong to one of dangerous solid wastes generated in industrial production, after barium-containing furnace slag is oxidized and dephosphorized, a large amount of barium-containing waste residues are generated and accumulated in the open air, so that soluble barium salt with high toxicity is leached by rainwater and permeates into underground water, the content of barium ions in the underground water is seriously exceeded, serious problems such as biological teratogenesis, carcinogenesis, mutation and the like are caused, and huge damage is caused to human bodies and animals and plants. In order to reduce the adverse effect of the barium-containing waste slag stacking on the environment, a comprehensive utilization way of the barium-containing waste slag must be actively searched.
Barium-containing waste residue generated after dephosphorization of high-phosphorus molten iron by using barium-based slag system and mainly comprising Ba3(PO4)2And also part of BaO and BaF2In order to solve the above problems, there is a need for a process for treating barium-containing waste residues in a harmless manner, because the barium-containing compounds are unstable and easily permeate into groundwater, and are substantially the same as the barium-containing waste residues generated during barium salt production during stacking.
In the prior art, when barium-containing waste residues generated after dephosphorization of high-phosphorus molten iron are treated, a corresponding adding mode is not selected according to the difference between liquid-liquid reaction and solid-liquid reaction, the pertinence is poor, so that the materials are not uniformly mixed, the reaction is not thorough, the treatment efficiency of the barium residues is reduced, and simultaneously, the barium carbonate generated after the reaction is not recycled, so that the resource waste is caused.
Disclosure of Invention
In order to solve the problems, the invention provides a method for harmlessly recycling barium carbonate from barium slag.
The technical scheme of the invention is as follows: a method for harmlessly and synchronously recovering barium carbonate from barium slag, wherein the barium slag is barium-containing waste slag generated after dephosphorization is carried out on high-phosphorus molten iron by utilizing a barium-based slag system, and the main component of the barium slag is Ba3(PO4)2And a soluble barium salt comprising the steps of:
s1, putting the barium-containing waste residue into a grinder, grinding and sieving to obtain 80-100 mesh barium residue fine powder, and fully dissolving the barium residue fine powder in water to obtain soluble barium salt solution and Ba3(PO4)2A precipitated mixed slurry;
s2, separating the soluble barium salt solution in the mixed slurry, mixing the soluble barium salt solution with excessive dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 35-45 deg.C for 30min to obtain barium chloride solution A, and mixing (NH)4)2CO3Dissolving in deionized water to obtain (NH) solution of 0.8-1.2mol/L4)2CO3The solution is finally mixed in a molar ratio of 1:0.8-1.2Mixing barium chloride solution A with (NH)4)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3Precipitating A;
s3, separating Ba in the mixed slurry3(PO4)2Precipitating and drying, and mixing Ba with solid-liquid ratio of 1g to 3ml3(PO4)2Mixing the precipitate with dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 35-45 deg.C for 30min to obtain barium chloride solution B, and mixing barium chloride solution B and (NH) at a molar ratio of 1:0.8-1.24)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3B, precipitation;
s4, mixing BaCO3Precipitate A and BaCO3Uniformly mixing the precipitate B, and then utilizing a vibrating screen to mix the mixed BaCO3Precipitating, crushing and grinding into BaCO with particle size less than or equal to 4mm3Powder, magnetic attraction equipment is utilized to absorb and remove iron impurities, and then the BaCO treated by the method is mixed according to the weight ratio of 1:2:0.23Mixing the powder, water and the modified wet grinding agent to prepare a mixed solution, and putting the mixed solution into wet grinding equipment for grinding to obtain barium carbonate powder with the particle size of 2-4 mu m.
As an alternative of the present invention, in step S2, when the soluble barium salt solution and the excess diluted hydrochloric acid solution are mixed, the soluble barium salt solution and the excess diluted hydrochloric acid solution are simultaneously added into the mixer, and nitrogen is simultaneously introduced into the mixer at a rate of 0.2-0-3L/min for 30-40min, so that the soluble barium salt solution, the excess diluted hydrochloric acid solution and the nitrogen are subjected to air flow impact mixing, the introduction pressure of the nitrogen is 0.5MPa, the mass concentration of the diluted hydrochloric acid solution is 13%, nitrogen air flow impact mixing is adopted, such that uniformity of mixing of the soluble barium salt solution and the diluted hydrochloric acid solution can be maximally improved, meanwhile, exhaust of a reaction process of the soluble barium salt solution and the excess diluted hydrochloric acid is efficiently achieved, and reaction efficiency is improved.
As an alternative of the invention, when the nitrogen gas flow is added into the mixer, the nitrogen gas flow is uniformly dispersed through the gas distribution plate, and the nitrogen gas flow can be dispersed to all places in the mixer, so that the mixing uniformity of the soluble barium salt solution and the dilute hydrochloric acid solution is increased.
As an alternative of the present invention, in step S3, Ba3(PO4)2The specific process of mixing the precipitate with the excess dilute hydrochloric acid solution is as follows:
s3-1, separating Ba3(PO4)2The precipitate was put into a grinder, ground and sieved to obtain Ba of 90 mesh3(PO4)2Powder slag, then, adding Ba3(PO4)2Drying and dehydrating the powder residue for 20-30min, and scattering in a depolymerization scattering device to obtain depolymerized powder residue, and sieving with Ba3(PO4)2The powder slag is ground, depolymerized and scattered, and on the one hand, Ba can be added3(PO4)2The contact area of the precipitate and hydrochloric acid is increased, the reaction rate is improved, and on the other hand, Ba is avoided3(PO4)2The particles are agglomerated, increasing the difficulty of mixing with dilute hydrochloric acid, resulting in Ba3(PO4)2The dispersion process of the precipitate in the dilute hydrochloric acid has the problems of low speed, high energy consumption, poor efficiency and the like;
s3-2, placing the dilute hydrochloric acid solution into a stirring container, stirring for 30min at the stirring speed of 850-3(PO4)2The precipitate is fully mixed with dilute hydrochloric acid, so that the reaction rate is improved;
s3-3, putting the depolymerized powder slag into an adding device and adding the depolymerized powder slag into the stirring container in a rotating manner along the circumferential direction while stirring in the step S3-2, so that the depolymerized powder slag falls into the stirring container in a divergent manner, the adding speed of the depolymerized powder slag is 0.2-0.5g/S, and Ba is ensured by controlling the adding angle and the adding speed of the depolymerized powder slag3(PO4)2The precipitate is fully mixed with dilute hydrochloric acid, the reaction is thorough, and the generation amount of calcium carbonate is increased.
As an alternative of the invention, the depolymerization breaking up device in the step S3-1 comprises a breaking up box body, a reaction box body positioned at the bottom end of the breaking up box body, a depolymerization breaking up element arranged in the breaking up box body, and the depolymerization breaking up element is broken upThe chamber is broken up to the first chamber and the second of breaing up that down including mutual intercommunication of box from the last, first chamber top of breaing up is equipped with and adds the mouth, and the second is broken up the chamber bottom and is equipped with out the powder mouth, the reaction box is broken up the chamber with the second and is connected, and the junction is equipped with the interpolation disc, and the reaction box lateral wall is equipped with pan feeding mouth and discharge gate, is equipped with through positive and negative motor drive's impeller in the reaction box, it is equipped with the retainer plate to add the disc center, add between disc and the retainer plate and along radially evenly being equipped with a plurality of slope guide pieces, the component is broken up in the depolymerization is including locating the vertical section of thick bamboo of breaing up of first breaing up the intracavity, locating the level of second breaing up the section of thick bamboo of loosing, two are used for the drive respectively the vertical section of thick bamboo of beating up and the level drive motor who breaks up a section of thick bamboo of beating up when needs with Ba3(PO4)2When the sediment is mixed with the dilute hydrochloric acid, the dilute hydrochloric acid is added into the reaction box body through the feeding port, meanwhile, the positive and negative motors are started, the stirring impellers are driven by the positive and negative motors to stir alternately according to clockwise and anticlockwise repetition, and then the Ba after grinding and sieving is added through the adding port3(PO4)2Powder slag is added into the first scattering cavity, and a corresponding driving motor is started to drive the vertical scattering cylinder pair Ba3(PO4)2The powder slag is scattered in the vertical direction and then Ba3(PO4)2The powder slag enters a second scattering cavity, and a corresponding driving motor is started to drive a horizontal scattering cylinder pair Ba3(PO4)2The powder slag is scattered along the horizontal direction, and the problem of easy agglomeration of powder is solved through scattering in all directions, so that the scattered raw materials are more uniform, the scattering effect is better, and the scattered Ba is3(PO4)2The powder slag falls into the reaction box body through the gaps of the plurality of inclined guide vanes to react with the dilute hydrochloric acid, and the inclined angles of the inclined guide vanes are different, so that Ba is enabled to be contained3(PO4)2The powder slag falls into dilute hydrochloric acid along different directions simultaneously to increase Ba3(PO4)2The dispersibility of the powder slag avoids the influence of deposition on the reaction efficiency.
As an alternative of the invention, a material homogenizing sieve is arranged at the joint of the first scattering cavity and the second scattering cavity, and the material homogenizing sieve isThe material homogenizing screen is characterized in that a plurality of annular sleeves which are communicated up and down are sleeved to form the material homogenizing screen, the bottom ends of the annular sleeves are connected through the same screen, the bottom end of the material homogenizing screen is provided with a miniature vibration motor used for driving the material homogenizing screen to vibrate, and Ba after scattering in the vertical direction3(PO4)2The powder slag falls into the annular sleeves and is vibrated by a miniature vibration motor to mix Ba3(PO4)2The powder slag is scattered into the second scattering cavity from the screen mesh to avoid Ba3(PO4)2When the powder slag falls into the second scattering cavity, the powder slag is deposited in the second scattering cavity, so that a working blind area exists in the horizontal scattering cylinder, and the scattering effect is reduced.
As an alternative scheme of the invention, the feeding port and the discharging port are connected through a return pipe, the return pipe is provided with an electromagnetic valve, the discharging port is provided with a filter screen, and when Ba is used as the filter screen, Ba is added to the filter screen3(PO4)2BaCO produced after the reaction of the powder slag and the excessive dilute hydrochloric acid is finished3The precipitate is discharged after being filtered by the filter screen, and the residual dilute hydrochloric acid flows into the reaction box again through the return pipe for recycling, so that the method has the advantages of energy conservation and emission reduction.
As an alternative of the present invention, in step S4, the raw materials for forming the modified wet grinding agent include, by weight: 170 portions of polyether alcohol amine 165-containing material, 170 portions of polyethylene glycol polyethyleneimine copolymer 165-containing material, 55-65 portions of sucrose, 15-20 portions of sodium sulfite and 200 portions of deionized water 180-containing material, wherein the raw materials have the functions of grinding aid and dispersing BaCO3The grinding efficiency is effectively improved by the action of precipitation, and the obtained BaCO3The slurry is dispersed evenly and stably and has extremely high particle fineness.
As an alternative of the invention, the preparation method of the modified wet grinding agent comprises the following steps: firstly, dissolving the polyether alcohol amine, the sucrose and the sodium sulfite in parts by weight in deionized water, uniformly stirring, and reacting at the temperature of 45-55 ℃ for 20-35min to obtain a reaction solution; then, measuring the temperature of the reaction liquid, dissolving the polyethylene glycol polyethyleneimine copolymer in the reaction liquid after the temperature of the reaction liquid is stable, continuously stirring, and finally concentrating by adopting a reduced pressure distillation method until the solid phase content is 15-50 wt%.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, barium carbonate precipitation is recycled after barium slag is subjected to harmless treatment, so that the toxicity of barium-containing waste slag can be greatly reduced, the environmental pollution is reduced, in the treatment process, the process is optimized according to different addition modes of liquid-liquid reaction and solid-liquid reaction, the pertinence is strong, the mixing uniformity of different reactants can be improved to the maximum extent, the maximum recycling of barium carbonate is facilitated, and the advantages of energy conservation and emission reduction are achieved.
Drawings
FIG. 1 is a schematic view of the internal structure of the depolymerization breaking-up apparatus of the present invention;
FIG. 2 is a top view of the add-on disk of the present invention;
FIG. 3 is a top view of the homogenizing screen of the present invention.
The device comprises a scattering box body 1, a first scattering cavity 10, an adding port 100, a second scattering cavity 11, a powder outlet 110, a homogenizing sieve 12, an annular sleeve 120, a screen 121, a micro vibration motor 122, a reaction box body 2, an adding disc 20, a fixing ring 200, an inclined guide sheet 201, a feeding port 21, a discharging port 22, a positive and negative motor 23, a stirring impeller 24, a return pipe 25, an electromagnetic valve 26, a filter screen 27, a de-polymerization scattering element 3, a vertical scattering cylinder 30, a horizontal scattering cylinder 31 and a driving motor 33.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof for better understanding the advantages of the invention.
Example 1
A method for harmlessly and synchronously recovering barium carbonate from barium slag, wherein the barium slag is barium-containing waste slag generated after dephosphorization is carried out on high-phosphorus molten iron by utilizing a barium-based slag system, and the main component of the barium slag is Ba3(PO4)2And a soluble barium salt comprising the steps of:
s1, putting the barium-containing waste residue into a grinder, grinding and sieving to obtain 80-mesh barium residue fine powder, and fully dissolving the barium residue fine powder in water to obtain a soluble barium salt solution and Ba3(PO4)2A precipitated mixed slurry;
s2, separating the soluble barium salt solution in the mixed slurry, mixing 3.5g of the soluble barium salt solution with 15ml of dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 35 ℃ for 30min to obtain a barium chloride solution A, and then adding (NH)4)2CO3Dissolving in deionized water to prepare 0.8mol/L (NH)4)2CO3Solution, and finally, mixing the barium chloride solution A and (NH) according to the molar ratio of 1:0.84)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3Precipitating A;
s3, separating Ba in the mixed slurry3(PO4)2Precipitating and drying, and mixing Ba with solid-liquid ratio of 1g to 3ml3(PO4)2Mixing the precipitate with dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 35 deg.C for 30min to obtain barium chloride solution B, and mixing barium chloride solution B and (NH) at a molar ratio of 1:0.84)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3B, precipitation;
s4, mixing BaCO3Precipitate A and BaCO3Uniformly mixing the precipitate B, and then utilizing a vibrating screen to mix the mixed BaCO3Precipitating, crushing and grinding into BaCO with particle size less than or equal to 4mm3Powder, magnetic attraction equipment is utilized to absorb and remove iron impurities, and then the BaCO treated by the method is mixed according to the weight ratio of 1:2:0.23Mixing the powder, water and glycerol to obtain a mixed solution, and grinding the mixed solution in a wet grinding device to obtain barium carbonate powder with the particle size of 2 mu m.
Example 2
A method for harmlessly and synchronously recovering barium carbonate from barium slag, wherein the barium slag is barium-containing waste slag generated after dephosphorization is carried out on high-phosphorus molten iron by utilizing a barium-based slag system, and the main component of the barium slag is Ba3(PO4)2And a soluble barium salt comprising the steps of:
s1, putting the barium-containing waste residue into a grinder, grinding and sieving to obtain barium residue fine powder with 90 meshes, and mixing the fine powder with the barium residueDissolving the fine powder of barium residue in water to obtain soluble barium salt solution and Ba3(PO4)2A precipitated mixed slurry;
s2, separating the soluble barium salt solution in the mixed slurry, mixing 3.5g of the soluble barium salt solution with 15ml of dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 40 ℃ for 30min to obtain a barium chloride solution A, and then adding (NH)4)2CO3Dissolving in deionized water to prepare 1mol/L (NH)4)2CO3Solution, and finally, mixing the barium chloride solution A and (NH) according to the molar ratio of 1:14)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3Precipitating A;
s3, separating Ba in the mixed slurry3(PO4)2Precipitating and drying, and mixing Ba with solid-liquid ratio of 1g to 3ml3(PO4)2Mixing the precipitate with dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 40 deg.C for 30min to obtain barium chloride solution B, and mixing the barium chloride solution B and (NH) at a molar ratio of 1:14)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3B, precipitation;
s4, mixing BaCO3Precipitate A and BaCO3Uniformly mixing the precipitate B, and then utilizing a vibrating screen to mix the mixed BaCO3Precipitating, crushing and grinding into BaCO with particle size less than or equal to 4mm3Powder, magnetic attraction equipment is utilized to absorb and remove iron impurities, and then the BaCO treated by the method is mixed according to the weight ratio of 1:2:0.23Mixing the powder, water and glycerol to obtain a mixed solution, and grinding in a wet grinding device to obtain barium carbonate powder with a particle size of 3 μm.
Example 3
A method for harmlessly and synchronously recovering barium carbonate from barium slag, wherein the barium slag is barium-containing waste slag generated after dephosphorization is carried out on high-phosphorus molten iron by utilizing a barium-based slag system, and the main component of the barium slag is Ba3(PO4)2And a soluble barium salt comprising the steps of:
s1, putting the barium-containing waste residue into the furnaceGrinding in a grinder, sieving to obtain 100 mesh barium residue fine powder, dissolving the barium residue fine powder in water to obtain soluble barium salt solution and Ba3(PO4)2A precipitated mixed slurry;
s2, separating the soluble barium salt solution in the mixed slurry, mixing 3.5g of the soluble barium salt solution with 15ml of dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 45 ℃ for 30min to obtain a barium chloride solution A, and then adding (NH)4)2CO3Dissolving in deionized water to prepare (NH) with the concentration of 1.2mol/L4)2CO3Solution, and finally, mixing the barium chloride solution A and (NH) according to the molar ratio of 1:1.24)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3Precipitating A;
s3, separating Ba in the mixed slurry3(PO4)2Precipitating and drying, and mixing Ba with solid-liquid ratio of 1g to 3ml3(PO4)2Mixing the precipitate with dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 45 deg.C for 30min to obtain barium chloride solution B, and mixing barium chloride solution B and (NH) at a molar ratio of 1:1.24)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3B, precipitation;
s4, mixing BaCO3Precipitate A and BaCO3Uniformly mixing the precipitate B, and then utilizing a vibrating screen to mix the mixed BaCO3Precipitating, crushing and grinding into BaCO with particle size less than or equal to 4mm3Powder, magnetic attraction equipment is utilized to absorb and remove iron impurities, and then the BaCO treated by the method is mixed according to the weight ratio of 1:2:0.23The powder, water and glycerol were mixed to prepare a mixed solution, and the mixed solution was put into a wet milling apparatus to be milled, thereby obtaining barium carbonate powder having a particle size of 4 μm.
Example 4
This example is substantially the same as example 3, except that:
when the soluble barium salt solution and the excessive dilute hydrochloric acid solution are mixed in the step S2, the soluble barium salt solution and the excessive dilute hydrochloric acid solution are added into a mixer at the same time, nitrogen is filled into the mixer for 30min at the speed of 0.2L/min, the soluble barium salt solution, the excessive dilute hydrochloric acid solution and the nitrogen are subjected to air flow impact mixing, the filling pressure of the nitrogen is 0.5MPa, the mass concentration of the dilute hydrochloric acid solution is 13%, and when the nitrogen air flow is added into the mixer, the nitrogen air flow is uniformly dispersed through a gas distribution plate.
Example 5
This example is substantially the same as example 3, except that:
when the soluble barium salt solution and the excessive dilute hydrochloric acid solution are mixed in the step S2, the soluble barium salt solution and the excessive dilute hydrochloric acid solution are added into a mixer at the same time, nitrogen is filled into the mixer for 40min at the speed of 0.3L/min, the soluble barium salt solution, the excessive dilute hydrochloric acid solution and the nitrogen are subjected to air flow impact mixing, the filling pressure of the nitrogen is 0.5MPa, the mass concentration of the dilute hydrochloric acid solution is 13%, and when the nitrogen air flow is added into the mixer, the nitrogen air flow is uniformly dispersed through a gas distribution plate.
Example 6
This example is substantially the same as example 4, except that:
ba in step S33(PO4)2The specific process of mixing the precipitate with the excess dilute hydrochloric acid solution is as follows:
s3-1, separating Ba3(PO4)2The precipitate was put into a grinder, ground and sieved to obtain Ba of 90 mesh3(PO4)2Powder slag, then, adding Ba3(PO4)2Drying and dehydrating the powder slag for 20min, and putting the powder slag into depolymerization scattering equipment for scattering to obtain depolymerized powder slag;
s3-2, placing the dilute hydrochloric acid solution into a stirring container, stirring for 30min at a stirring speed of 850r/min, and repeatedly and alternately stirring clockwise and anticlockwise in the stirring direction;
s3-3, putting the depolymerized powder slag into an adding device while stirring in the step S3-2, and adding the depolymerized powder slag into the stirring container in a rotating manner along the circumferential direction, so that the depolymerized powder slag falls into the stirring container in a divergent manner, wherein the adding speed of the depolymerized powder slag is 0.2 g/S;
as shown in fig. 1, the depolymerization scattering apparatus in step S3-1 includes a scattering box 1, a reaction box 2 located at the bottom end of the scattering box 1, and a depolymerization scattering element 3 located in the scattering box 1, the scattering box 1 includes a first scattering cavity 10 and a second scattering cavity 11 communicated with each other from top to bottom, the top of the first scattering cavity 10 is provided with an addition port 100, the bottom of the second scattering cavity 11 is provided with a powder outlet 110, the reaction box 2 is connected with the second scattering cavity 11, and an addition disc 20 is provided at the connection position, the side wall of the reaction box 2 is provided with a feeding port 21 and a discharging port 22, a stirring impeller 24 driven by a positive and negative motor 23 is provided in the reaction box 2, as shown in fig. 2, a fixed ring 200 is provided at the center of the addition disc 20, eight inclined guide vanes 201 are uniformly provided between the addition disc 20 and the fixed ring 200 along the radial direction, the depolymerization scattering element 3 includes a vertical scattering cylinder 30, a vertical scattering cylinder is provided in the first scattering cavity 10, A horizontal scattering cylinder 31 arranged in the second scattering cavity 11, and two driving motors 33 respectively used for driving the vertical scattering cylinder 30 and the horizontal scattering cylinder 31, when Ba is required to be dispersed3(PO4)2When the sediment is mixed with the dilute hydrochloric acid, the dilute hydrochloric acid is added into the reaction box body 2 through the feeding port 21, meanwhile, the positive and negative motors 23 are started, the stirring impellers 24 are driven by the positive and negative motors 23 to stir alternately according to clockwise and anticlockwise repetition, and then the ground and sieved Ba is added through the adding port 1003(PO4)2Powder slag is added into the first scattering cavity 10, and a corresponding driving motor 33 is started to drive the vertical scattering cylinders 30 to Ba3(PO4)2The powder slag is scattered in the vertical direction and then Ba3(PO4)2The powder slag enters the second scattering cavity 11, and a corresponding driving motor 33 is started to drive the horizontal scattering cylinder 31 to scatter Ba3(PO4)2Scattering the powder slag along the horizontal direction, and scattering the scattered Ba3(PO4)2The powder slag falls into the reaction box body 2 through the gaps of the eight inclined guide vanes 201 to react with the dilute hydrochloric acid;
as shown in fig. 1 and 3, a homogenizing sieve 12 is arranged at the joint of the first scattering cavity 10 and the second scattering cavity 11, the homogenizing sieve 12 is formed by sleeving three vertically-through annular sleeves 120, the bottom ends of the annular sleeves 120 are connected through a same screen 121, and a micro vibration motor 122 for driving the homogenizing sieve 12 to vibrate is arranged at the bottom end of the homogenizing sieve 12;
the feeding port 21 and the discharging port 22 are connected through a return pipe 25, the return pipe 25 is provided with an electromagnetic valve 26, and the discharging port 22 is provided with a filter screen 27.
Example 7
This embodiment is substantially the same as embodiment 6 except that:
ba in step S33(PO4)2The specific process of mixing the precipitate with the excess dilute hydrochloric acid solution is as follows:
s3-1, separating Ba3(PO4)2The precipitate was put into a grinder, ground and sieved to obtain Ba of 90 mesh3(PO4)2Powder slag, then, adding Ba3(PO4)2Drying and dehydrating the powder slag for 30min, and putting the powder slag into depolymerization scattering equipment for scattering to obtain depolymerized powder slag;
s3-2, placing the dilute hydrochloric acid solution into a stirring container, stirring for 30min at a stirring speed of 1200r/min, and repeatedly and alternately stirring clockwise and anticlockwise in the stirring direction;
s3-3, stirring in step S3-2, putting the depolymerized powder slag into an adding device, adding the depolymerized powder slag into the stirring container in a rotating mode along the circumferential direction, and making the depolymerized powder slag fall into the stirring container in a divergent mode, wherein the adding speed of the depolymerized powder slag is 0.5 g/S.
Example 8
This example is substantially the same as example 4, except that:
in step S4, the raw materials for the composition of the modified wet grinding agent include, by weight: 165 parts of polyether alcohol amine, 165 parts of polyethylene glycol-polyethyleneimine copolymer, 55 parts of cane sugar, 15 parts of sodium sulfite and 180 parts of deionized water;
the preparation method of the modified wet grinding agent comprises the following steps: firstly, dissolving the polyether alcohol amine, the sucrose and the sodium sulfite in parts by weight in deionized water, uniformly stirring, and reacting for 20min at the temperature of 45 ℃ to obtain a reaction solution; then, measuring the temperature of the reaction liquid, dissolving the polyethylene glycol polyethyleneimine copolymer in the reaction liquid after the temperature of the reaction liquid is stable, continuously stirring, and finally concentrating by adopting a reduced pressure distillation method until the solid phase content is 15 wt%.
Example 9
This example is substantially the same as example 4, except that:
in step S4, the raw materials for the composition of the modified wet grinding agent include, by weight: 170 parts of polyether alcohol amine, 170 parts of polyethylene glycol-polyethyleneimine copolymer, 65 parts of cane sugar, 20 parts of sodium sulfite and 200 parts of deionized water;
the preparation method of the modified wet grinding agent comprises the following steps: firstly, dissolving the polyether alcohol amine, the sucrose and the sodium sulfite in parts by weight in deionized water, uniformly stirring, and reacting for 35min at the temperature of 55 ℃ to obtain a reaction solution; then, measuring the temperature of the reaction liquid, dissolving the polyethylene glycol polyethyleneimine copolymer in the reaction liquid after the temperature of the reaction liquid is stable, continuously stirring, and finally concentrating by adopting a reduced pressure distillation method until the solid phase content is 50 wt%.
Claims (10)
1. A method for harmlessly and synchronously recovering barium carbonate from barium slag, wherein the barium slag is barium-containing waste slag generated after dephosphorization is carried out on high-phosphorus molten iron by utilizing a barium-based slag system, and the main component of the barium slag is Ba3(PO4)2And a soluble barium salt, characterized by comprising the steps of:
s1, putting the barium-containing waste residue into a grinder, grinding and sieving to obtain 80-100 mesh barium residue fine powder, and fully dissolving the barium residue fine powder in water to obtain soluble barium salt solution and Ba3(PO4)2A precipitated mixed slurry;
s2, separating the soluble barium salt solution in the mixed slurry, mixing the soluble barium salt solution with excessive dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 35-45 deg.C for 30min to obtain barium chloride solution A, and mixing (NH)4)2CO3Dissolving in deionized water to obtain (NH) solution of 0.8-1.2mol/L4)2CO3Solution, finally, in a molar ratio of 1:0.8-1.2Mixing barium chloride solution A and (NH)4)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3Precipitating A;
s3, separating Ba in the mixed slurry3(PO4)2Precipitating and drying, and mixing Ba with solid-liquid ratio of 1g to 3ml3(PO4)2Mixing the precipitate with dilute hydrochloric acid solution, performing ultrasonic vibration treatment at 35-45 deg.C for 30min to obtain barium chloride solution B, and mixing barium chloride solution B and (NH) at a molar ratio of 1:0.8-1.24)2CO3Mixing the solution, stirring uniformly, and filtering to obtain BaCO3B, precipitation;
s4, mixing BaCO3Precipitate A and BaCO3Uniformly mixing the precipitate B, and then utilizing a vibrating screen to mix the mixed BaCO3Precipitating, crushing and grinding into BaCO with particle size less than or equal to 4mm3Powder, magnetic attraction equipment is utilized to absorb and remove iron impurities, and then the BaCO treated by the method is mixed according to the weight ratio of 1:2:0.23Mixing the powder, water and the modified wet grinding agent to prepare a mixed solution, and putting the mixed solution into wet grinding equipment for grinding to obtain barium carbonate powder with the particle size of 2-4 mu m.
2. The method for harmless recycling of barium carbonate of claim 1, wherein in step S2, when the soluble barium salt solution is mixed with the excess diluted hydrochloric acid solution, the soluble barium salt solution and the excess diluted hydrochloric acid solution are simultaneously added into the mixer, and nitrogen is simultaneously filled into the mixer at a rate of 0.2-0-3L/min for 30-40min, so that the soluble barium salt solution, the excess diluted hydrochloric acid solution and the nitrogen are subjected to air flow impact mixing, the filling pressure of the nitrogen is 0.5MPa, and the mass concentration of the diluted hydrochloric acid solution is 13%.
3. The method for harmlessly recycling barium carbonate according to claim 2, wherein the nitrogen gas flow is uniformly dispersed through a gas distribution plate when being added to the mixer.
4. The method for harmlessly recycling barium carbonate according to claim 1, wherein in step S3, Ba is added3(PO4)2The specific process of mixing the precipitate with the excess dilute hydrochloric acid solution is as follows:
s3-1, separating Ba3(PO4)2The precipitate was put into a grinder, ground and sieved to obtain Ba of 90 mesh3(PO4)2Powder slag, then, adding Ba3(PO4)2Drying and dehydrating the powder slag for 20-30min, and putting the powder slag into depolymerization scattering equipment for scattering to obtain depolymerized powder slag;
s3-2, placing the dilute hydrochloric acid solution into a stirring container, stirring for 30min at the stirring speed of 850-;
and S3-3, stirring in the step S3-2, simultaneously putting the depolymerized powder slag into an adding device, adding the depolymerized powder slag into the stirring container in a rotating manner along the circumferential direction, and making the depolymerized powder slag fall into the stirring container in a divergent manner, wherein the adding speed of the depolymerized powder slag is 0.2-0.5 g/S.
5. The method for harmlessly recycling barium carbonate as claimed in claim 4, wherein the depolymerization scattering equipment in step S3-1 comprises a scattering box body (1), a reaction box body (2) located at the bottom end of the scattering box body (1), and a depolymerization scattering element (3) arranged in the scattering box body (1), the scattering box body (1) comprises a first scattering cavity (10) and a second scattering cavity (11) which are communicated with each other from top to bottom, the top of the first scattering cavity (10) is provided with an addition port (100), the bottom of the second scattering cavity (11) is provided with a powder outlet (110), the reaction box body (2) is connected with the second scattering cavity (11), the connection position is provided with an addition disc (20), the side wall of the reaction box body (2) is provided with a feeding port (21) and a discharging port (22), and the reaction box body (2) is internally provided with a stirring impeller (24) driven by a positive and negative motor (23), add disc (20) center and be equipped with retainer plate (200), add between disc (20) and retainer plate (200) and evenly be equipped with a plurality of slope guide vanes (201) along radial, the component (3) is broken up in the depolymerization is including locating vertical a section of thick bamboo (30) of breaing up in first breaing up chamber (10), locating horizontal a section of thick bamboo (31) of breaing up in second breaing up chamber (11), two driving motor (33) that are used for driving respectively a vertical section of thick bamboo (30) of breaing up and horizontal a section of thick bamboo (31) of breaing up.
6. The method for harmless recycling of barium carbonate slag and simultaneous recycling of barium carbonate according to claim 5, wherein a homogenizing screen (12) is arranged at the joint of the first scattering cavity (10) and the second scattering cavity (11), the homogenizing screen (12) is formed by sleeving a plurality of annular sleeves (120) which are communicated up and down, the bottom ends of the annular sleeves (120) are connected through the same screen (121), and a micro vibration motor (122) for driving the homogenizing screen (12) to vibrate is arranged at the bottom end of the homogenizing screen (12).
7. The method for harmless recycling of barium carbonate slag and simultaneous recycling of barium carbonate according to claim 5, wherein the feeding port (21) and the discharging port (22) are connected through a return pipe (25), the return pipe (25) is provided with an electromagnetic valve (26), and the discharging port (22) is provided with a filter screen (27).
8. The method for harmlessly recycling barium carbonate from barium slag according to claim 1, wherein in step S4, the raw materials for preparing the modified wet grinding agent comprise, by weight: 170 portions of polyether alcohol amine 165-containing material, 170 portions of polyethylene glycol polyethyleneimine copolymer 165-containing material, 55-65 portions of sucrose, 15-20 portions of sodium sulfite and 200 portions of deionized water 180-containing material.
9. The method for harmlessly recycling barium carbonate slag and synchronously recycling barium carbonate according to claim 8, wherein the preparation method of the modified wet grinding agent comprises the following steps: firstly, dissolving the polyether alcohol amine, the sucrose and the sodium sulfite in parts by weight in deionized water, uniformly stirring, and reacting at the temperature of 45-55 ℃ for 20-35min to obtain a reaction solution; then, measuring the temperature of the reaction liquid, dissolving the polyethylene glycol polyethyleneimine copolymer in the reaction liquid after the temperature of the reaction liquid is stable, continuously stirring, and finally concentrating by adopting a reduced pressure distillation method until the solid phase content is 15-50 wt%.
10. The method for harmlessly recycling barium carbonate according to claim 1, wherein the barium carbonate powder in step S4 has a mesh size of 80-100.
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| CN114956616A (en) * | 2022-06-14 | 2022-08-30 | 生态环境部华南环境科学研究所(生态环境部生态环境应急研究所) | Method and device for preparing mixed material for cement plant by recycling barium slag |
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