Barium slag full-resource utilization method

Abstract

The invention provides a barium slag full-resource utilization method, and belongs to the technical field of solid waste resource utilization. The barium sulfate in the barium slag is converted into the conversion slag by using the conversion agent. The conversion slag is subjected to acid treatment to obtain acid leaching slag and separation liquid. By adding carbonate, a small amount of metal ions or non-metals are precipitated and separated, and a primary barium chloride solution and first separation residues are obtained; forming a precipitate by utilizing sulfide and part of metal ions in the primary barium chloride solution to obtain a primary barium chloride refined solution and second separation slag; hydroxides and part of metal ions in the primary barium chloride refined liquid are utilized to form precipitates, and barium chloride refined liquid and third separation residues are obtained. The barium chloride refined liquid is subjected to evaporation, concentration and crystallization, and barium chloride dihydrate can be obtained. The acid leaching residues are used for coal dressing, the first separation residues, the second separation residues and the third separation residues are used for active building materials, and full resource utilization of the barium residues is achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of solid waste resource utilization, and particularly relates to a method for full resource utilization of barium residue. BACKGROUND

[0002] Barium residue is a solid waste discharged in the process of producing barium salt from barite and coal, and a large amount of barium residue is produced in China every year. The pH value of the barium residue is greater than 12.5, and the barium residue has strong corrosiveness. Meanwhile, the water-soluble barium concentration in the barium residue is more than 10 times of the discharge standard, and the barium residue generally has leaching toxicity. When the barium residue is stored, the water-soluble barium will seep into groundwater, causing water pollution. Therefore, the barium residue belongs to hazardous solid waste, and long-term storage not only occupies a large amount of land, but also pollutes the environment, so the barium residue needs to be treated urgently.

[0003] In the prior art, the treatment of the barium residue is mainly aimed at the residual solid waste with barium sulfide as the main component left after the preparation of barium salt from barite in the process of producing barium salt. For example, a related patent discloses a method for preparing industrial barium chloride by using barium-containing waste residue. The method discloses a method for treating barium-containing waste residue by using hydrochloric acid to treat barium sulfate, barium carbonate, barium silicate, barium sulfite, barium ferrite and trace barium sulfide, and then using sodium hydroxide to absorb waste gas. Although this method can treat the barium residue, the barium sulfate and coal in the barium residue cannot be utilized, and the full resource utilization of the barium residue cannot be realized. SUMMARY

[0004] The present application aims to provide a method for full resource utilization of barium residue.

[0005] In order to achieve the above-mentioned application purposes, the present application provides the following technical solutions: The present application provides a method for full resource utilization of barium residue, comprising the following steps: Wet grinding the barium residue to obtain barium residue slurry; Mixing the barium residue slurry with carbonate and water to obtain mixed slurry, and then performing conversion treatment to obtain conversion residue and conversion liquid; the liquid in the mixed slurry is a carbonate saturated solution; the conversion liquid is regenerated to obtain recovered conversion agent and sulfate; Mixing the conversion residue with hydrochloric acid solution to perform acid leaching treatment, to obtain acid leaching residue and separation liquid; the acid leaching residue is used for coal separation; Mixing the separation liquid with carbonate to perform primary impurity removal, to obtain primary barium chloride solution and first separation residue; Mixing the primary barium chloride solution with sulfide to perform secondary impurity removal, to obtain primary barium chloride refined liquid and second separation residue; Mixing the primary barium chloride refined liquid with hydroxide to perform third impurity removal, to obtain barium chloride refined liquid and third separation residue; The barium chloride refining liquid is evaporated, concentrated and crystallized to obtain barium chloride dihydrate; The first, second and third separation residues are used for active building material residues.

[0006] Preferably, the fineness of the solids in the barium residue material is 200 mesh ≧ 70%.

[0007] Preferably, the mass ratio of barium residue to water in the mixed slurry is 1:3-6.

[0008] Preferably, the number of conversion treatments is 2-4; the temperature of each conversion treatment is independently 5-30℃, and the time of each conversion treatment is independently 100-130 min.

[0009] Preferably, the mass ratio of the conversion residue to the hydrochloric acid solution is 1:2-5.

[0010] Preferably, the temperature of the acid leaching treatment is 0-50℃; the acid leaching treatment time is 15-30 min.

[0011] Preferably, the mass ratio of the separation liquid to the carbonate is 1:0.045-0.07.

[0012] Preferably, the temperature of the primary, secondary and tertiary impurity removal is independently ≧ 10℃; the time of the primary, secondary and tertiary impurity removal is independently 20-40 min.

[0013] Preferably, the mass ratio of the primary barium chloride solution to the sulfide is 1:0.035-0.05.

[0014] Preferably, the temperature of the evaporation concentration is 80-100℃.

[0015] The application provides a method for full resource utilization of barium residue, which can make barium sulfate in the obtained barium residue fully react with a carbonate saturated solution by wet grinding of the barium residue, so as to improve the recovery rate of barium. The application uses the carbonate saturated solution as a conversion agent, which can react with the barium sulfate in the barium residue to generate barium carbonate, so that a conversion residue mainly composed of barium carbonate and a conversion liquid mainly composed of sulfates are formed; the conversion liquid can be regenerated to obtain a recovered conversion agent and sulfates for recycling; the conversion residue is treated by acid leaching to be converted into an acid leaching residue and a separation liquid mainly composed of barium chloride; the acid leaching residue can be used for coal separation. The application mixes the separation liquid with carbonates, uses the carbonates to change the pH value of the separation liquid, and then makes a small amount of metal ions (or non-metal ions) form a precipitate to be separated from the barium chloride solution, so as to obtain a primary barium chloride solution and a first separation residue. The application mixes the primary barium chloride solution with sulfides, uses the sulfides to react with the ions in the primary barium chloride solution, so that a metal sulfide precipitate is formed to be separated from the barium chloride solution, so as to obtain a primary barium chloride refined liquid and a second separation residue. The application mixes the primary barium chloride refined liquid with hydroxides, uses the hydroxides to react with trace metal ions in the primary barium chloride refined liquid, so that a precipitate is formed to be separated from the barium chloride solution, so as to obtain a barium chloride refined liquid and a third separation residue. The application evaporates and concentrates the barium chloride refined liquid to be crystallized, so as to obtain barium chloride dihydrate. The application uses the first separation residue, the second separation residue and the third separation residue for active building material residue. The method provided by the application can use barium residue to prepare high-purity barium chloride dihydrate, and at the same time, other generated solid waste is used for coal separation or active building material residue, so that full resource utilization of barium residue is realized. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 A schematic diagram of the method for full resource utilization of barium residue. DETAILED DESCRIPTION

[0017] The application provides a method for full resource utilization of barium residue, which comprises the following steps: Wet grinding of barium residue to obtain barium residue slurry; Mixing the barium residue slurry with carbonates and water to obtain mixed slurry, and then performing conversion treatment to obtain conversion residue and conversion liquid; the liquid in the mixed slurry is a carbonate saturated solution; the conversion liquid is regenerated to obtain a recovered conversion agent and sulfates; Mixing the conversion residue with a hydrochloric acid solution to perform acid leaching treatment, so as to obtain an acid leaching residue and a separation liquid; the acid leaching residue is used for coal separation; Mixing the separation liquid with carbonates to perform primary impurity removal, so as to obtain a primary barium chloride solution and a first separation residue; Mixing the primary barium chloride solution with sulfides to perform secondary impurity removal, so as to obtain a primary barium chloride refined liquid and a second separation residue; Mixing the primary barium chloride refining liquid with hydroxide, three times of impurity removal are carried out to obtain barium chloride refining liquid and third separation residue; Evaporating, concentrating and crystallizing the barium chloride refining liquid to obtain barium chloride dihydrate; The first separation residue, the second separation residue and the third separation residue are used for active building material residue.

[0018] The barium residue is wet ground to obtain barium residue slurry.

[0019] The source of the barium residue is not particularly limited in the present application, and conventional barium residue can be fully utilized by the method provided by the present application. In the embodiments of the present application, the source of the barium residue can be Guizhou Hongxing Development Co., Ltd.

[0020] The specific operation of the wet grinding is not particularly limited in the present application, and the barium residue can be converted into barium residue slurry by using conventional wet grinding method. The present application can improve the contact area between the barium residue and the conversion agent by wet grinding the barium residue into barium residue slurry, so that the barium sulfate in the barium residue is fully converted into barium carbonate, and the barium in the barium residue is fully recovered.

[0021] In the present application, the fineness of the solid in the barium residue slurry is preferably 200 mesh >= 70%, and more preferably 200 mesh >= 85%. The fineness of the solid in the barium residue is controlled in the above range in the present application, which has a larger specific surface area and is more easily to fully recover the barium in the barium residue.

[0022] After obtaining the barium residue slurry, the present application mixes the barium residue slurry with carbonate and water to obtain a mixed slurry, and then carries out conversion treatment to obtain conversion residue and conversion liquid.

[0023] In the present application, the liquid in the mixed slurry is a carbonate saturated solution. The present application uses carbonate saturated solution as conversion agent, which can react with barium sulfate in the barium residue to generate conversion residue with barium carbonate as the main component. In the embodiments of the present application, the carbonate saturated solution can be a sodium carbonate saturated solution.

[0024] In the present application, the mass ratio of barium residue to water in the mixed slurry is preferably 1:3~6. As an embodiment of the present application, the mass ratio of barium residue to water in the mixed slurry can be 1:3, 1:4, 1:5 or 1:6.

[0025] The specific amount of the carbonate is not particularly limited in the present application, which can be adjusted according to the amount of barium residue slurry and water, so that the liquid in the mixed slurry forms a saturated carbonate saturated solution. The present application uses carbonate saturated solution as conversion agent, which can fully convert barium sulfate in the barium residue into barium carbonate.

[0026] The method for mixing the barium residue slurry with the carbonate and water is not particularly limited in the present application, and the three can be mixed uniformly. In the present application, the mixing of the barium residue slurry with the carbonate and water is preferably performed in a conversion tank.

[0027] In the present application, the number of conversion treatments is preferably 2 to 4, more preferably 2 to 3. When the number of conversion treatments is one in the present application, about 70% of the barium sulfate in the barium residue can be converted into barium carbonate; when the number of conversion treatments is two, about 20% of the barium sulfate in the barium residue can be converted into barium carbonate; and when the number of conversion treatments is three, about 10% of the barium sulfate in the barium residue can be converted into barium carbonate. Therefore, by limiting the number of conversion treatments to the above range in the present application, the barium sulfate in the barium residue can be sufficiently converted into barium carbonate.

[0028] In the present application, the temperature of each conversion treatment is independently preferably 5 to 30°C, and the time of each conversion treatment is independently preferably 100 to 130 min. As an embodiment of the present application, the temperature of each conversion treatment can be 5°C, 10°C, 15°C, 20°C, 25°C or 30°C, and the time of each conversion treatment can be 100 min, 110 min, 120 min or 130 min. The conversion treatment is performed at the above temperature and time in the present application, which is more conducive to improving the reaction rate of the barium sulfate in the barium residue with the conversion agent.

[0029] In the present application, the conversion slurry obtained by the conversion treatment is preferably subjected to solid-liquid separation to obtain filter residue and conversion liquid; and the filter residue is washed to obtain conversion residue.

[0030] In the present application, the conversion liquid is regenerated to obtain recovered conversion agent and sulfate; the recovered conversion agent is used for subsequent batches of conversion treatment, and the sulfate is used for industrial and agricultural production. In the present application, since the conversion agent is a saturated solution of carbonate, the main component of the obtained conversion liquid is waste sulfate. The method for regeneration is not particularly limited in the present application, and any conventional method for regeneration of waste sulfate can be used. In the present application, when the conversion agent is a saturated solution of sodium carbonate, the method for regeneration can be the method of CN120793966A to regenerate sodium carbonate and ammonium sulfate.

[0031] In the present application, the solid-liquid separation is preferably performed in a plate-and-frame filter.

[0032] In the embodiment of the present application, the washing method can be in-situ two-blowing-two-washing-two-pressing, and the operation method of the in-situ two-blowing-two-washing-two-pressing can be: sequentially performing one high-pressure blowing, one high-pressure washing, two high-pressure blowings and two high-pressure washings on the filter residue on the plate-and-frame filter. In the present application, the reagent for the one high-pressure washing and the two high-pressure washings can be water. In the present application, the total water amount of the one high-pressure washing and the two high-pressure washings is preferably 5-8 times of the filter residue. In the present application, the washing water obtained after the one high-pressure washing and the two high-pressure washings can be used to flow into a buffer tank, as process circulating water for recycling, thereby reducing the generation of waste water.

[0033] After obtaining the conversion residue, the present application mixes the conversion residue with a hydrochloric acid solution to perform acid leaching treatment, thereby obtaining acid leaching residue and a separation liquid.

[0034] In the present application, the concentration of the hydrochloric acid solution is preferably 25-37%, and more preferably 31%. The present application uses the hydrochloric acid solution with the above-mentioned concentration, which can fully convert the barium carbonate in the conversion residue into soluble barium salt.

[0035] In the present application, the mass ratio of the conversion residue to the hydrochloric acid solution is preferably 1:2-5. As an embodiment of the present application, the mass ratio of the conversion residue to the hydrochloric acid solution can be 1:2, 1:3, 1:4 or 1:5. The present application controls the mass ratio of the conversion residue to the hydrochloric acid solution in the above-mentioned range, which can make the pH value of the mixed system be 2-4, and more preferably 2.5-3. This is more conducive to fully dissolving the barium carbonate and other soluble barium in the conversion residue.

[0036] The present application does not have special limitation on the method for mixing the conversion residue with the hydrochloric acid solution, and a conventional mixing method can be used to mix the two to be uniform.

[0037] In the present application, the temperature of the acid leaching treatment is preferably 0-50℃, and the time of the acid leaching treatment is preferably 15-30 min. As an embodiment of the present application, the temperature of the acid leaching treatment can be 0℃, 5℃, 10℃, 15℃, 20℃, 25℃, 30℃, 35℃, 40℃, 45℃ or 50℃, and the time of the acid leaching treatment can be 15 min, 20 min, 25 min or 30 min. The present application performs the acid leaching treatment at the above-mentioned temperature and time, which can promote the barium carbonate in the conversion residue to be fully dissolved.

[0038] The present application preferably performs solid-liquid separation on the acid leaching slurry after the acid leaching treatment, thereby obtaining filter residue and a separation liquid. In the embodiment of the present application, the solid-liquid separation can be performed in a plate-and-frame filter.

[0039] The acid leaching residue is preferably washed to obtain a leaching residue in the present application. In an embodiment of the present application, the washing method can be in-situ blowing-washing-pressing, and the operation method of the in-situ blowing-washing-pressing can be that the filter residue in the plate and frame filter is sequentially subjected to high-pressure blowing, high-pressure washing and pressure filtration. In an embodiment of the present application, the reagent for high-pressure washing can be water, and the washing liquid obtained by high-pressure washing is preferably flowed into a washing liquid buffer tank, and the washing liquid is reused as process circulating water.

[0040] In the present application, the acid leaching residue is used for coal separation, realizing the resource utilization of coal in the barium residue and reducing the generation of solid waste.

[0041] After obtaining the separation liquid, the separation liquid is mixed with a carbonate in the present application to perform primary impurity removal, to obtain a primary barium chloride solution and a first separation residue.

[0042] In the present application, the carbonate preferably includes one or more of ammonium carbonate, ammonium bicarbonate and a material containing carbonate. By adding the carbonate, the pH value of the separation liquid can be changed, the acidity is reduced, and then a small amount of metal ions or non-metal ions in the separation liquid is precipitated, to reduce the impurities in the barium chloride. In an embodiment of the present application, the pH value can be 5.

[0043] In the present application, the mass ratio of the separation liquid to the carbonate is preferably 1:0.045-0.07, and more preferably 1:0.05-0.06.

[0044] The mixing method of the separation liquid and the carbonate in the present application is not particularly limited, and a conventional mixing method can be used. In an embodiment of the present application, the mixing can be performed in an impurity removal tank.

[0045] In the present application, the temperature of the primary impurity removal is preferably ≥10℃, and more preferably 23-25℃; and the time of the primary impurity removal is preferably 20-40 min, and more preferably 25-30 min. Under the above temperature and time, the pH value of the system can reach 5, and a small amount of metal and non-metal impurities in the separation liquid can form a precipitate.

[0046] The impurity removal liquid after the primary impurity removal is preferably subjected to solid-liquid separation to obtain a primary barium chloride solution and a first separation residue. In an embodiment of the present application, the solid-liquid separation can be performed in a plate and frame filter.

[0047] In the present application, the first separation residue is used for active building material residue, to realize the resource utilization of solid waste in the barium residue.

[0048] After obtaining the primary barium chloride solution, the primary barium chloride solution is mixed with a sulfide in the present application to perform secondary impurity removal, to obtain a primary barium chloride refined solution and a second separation residue.

[0049] In the present application, the sulfide preferably includes one or more of potassium sulfide, sodium sulfide, and sulfide-containing materials. The present application can react with metal or non-metal ions in the primary barium chloride solution to form a metal sulfide precipitate by adding a sulfide.

[0050] In the present application, the mass ratio of the primary barium chloride solution to the sulfide is preferably 1:0.035~0.05, and more preferably 1:0.045~0.05.

[0051] The present application does not have special restrictions on the method of mixing the primary barium chloride solution with the sulfide, and a conventional mixing method can be used. In the embodiments of the present application, the mixing can be performed in a removal tank.

[0052] In the present application, the temperature of the secondary removal is preferably ≥10℃, and more preferably 23~25℃; and the time of the secondary removal is preferably 20~40min, and more preferably 25~30min. The present application can sufficiently remove precipitated impurities in the primary barium chloride solution at the above-mentioned temperature and time.

[0053] The present application preferably performs solid-liquid separation on the removal material solution after the secondary removal to obtain a primary barium chloride refined solution and a second separation residue. In the embodiments of the present application, the solid-liquid separation can be performed in a plate-and-frame filter press.

[0054] In the present application, the second separation residue is used as an active building material residue, realizing the resource utilization of solid waste in the barium residue.

[0055] After obtaining the primary barium chloride refined solution, the present application mixes the primary barium chloride refined solution with a hydroxide to perform tertiary removal, obtaining a barium chloride refined solution and a third separation residue.

[0056] In the present application, the hydroxide preferably includes a hydroxide-containing material, and more preferably one or more of ammonium hydroxide or a hydroxide-containing material. The present application can react with trace amounts of metal ions in the primary barium chloride refined solution to form a precipitate by adding an appropriate amount of hydroxide, reducing impurities in the barium chloride.

[0057] In the present application, the mass ratio of the primary barium chloride refined solution to the hydroxide is preferably 1:0.005~0.015, and more preferably 1:0.010~0.011.

[0058] The present application does not have special restrictions on the method of mixing the primary barium chloride refined solution with the hydroxide, and a conventional mixing method can be used. In the embodiments of the present application, the mixing can be performed in a removal tank.

[0059] In this invention, the temperature for the three purification processes is preferably ≥10℃, more preferably 23~25℃; the time for the three purification processes is preferably 20~40min, more preferably 20~25min. Under the above temperature and time conditions, this invention can effectively remove trace amounts of metallic impurities from the primary barium chloride refining solution.

[0060] The present invention preferably involves solid-liquid separation of the purified liquid after the three impurity removal processes to obtain a refined barium chloride solution and a third separation residue. In an embodiment of the present invention, the solid-liquid separation can be performed in a fine filter.

[0061] In this invention, the third separation residue is used as active building material residue to realize the resource utilization of solid waste in barium slag.

[0062] After obtaining the refined barium chloride solution, the present invention evaporates, concentrates, and crystallizes the refined barium chloride solution to obtain barium chloride dihydrate.

[0063] In this invention, the evaporation, concentration, and crystallization are preferably carried out in an evaporator. The evaporation and concentration temperature is preferably 80-100°C. As one embodiment of this invention, the evaporation and concentration temperature can be 80°C, 85°C, 90°C, 95°C, or 100°C. This invention does not have a particular limitation on the evaporation and concentration time; it is sufficient to concentrate the barium chloride purified solution and form crystals.

[0064] The present invention preferably dries the crystals obtained by evaporation, concentration and crystallization to obtain barium chloride dihydrate.

[0065] A preferred schematic diagram of the method provided by the present invention is shown below. Figure 1 As shown. From Figure 1 As can be seen, this invention wet-mills barium slag into a pulp, then mixes it with a conversion agent for a three-stage conversion process to obtain conversion slag and conversion liquid. The conversion liquid is regenerated to obtain a conversion agent and ammonium sulfate (i.e., sulfate). The obtained conversion slag is mixed with hydrochloric acid and acidified to obtain a separation liquid and acid leaching slag. The acid leaching slag can be used for coal preparation after washing. The separation liquid undergoes three-stage impurity removal, and the resulting refined liquid (i.e., barium chloride refined liquid) is evaporated and crystallized to obtain barium chloride dihydrate. The method provided by this invention can utilize barium slag to prepare high-purity barium chloride dihydrate, while also separating clean coal from the acid leaching slag. Other solid waste generated is active building material slag, realizing the full resource utilization of barium slag.

[0066] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0067] The barium residue used in the embodiments of the present application is from Guizhou Hongxing Development Co., Ltd.; according to the inspection report of Hunan Changsha Mining and Metallurgy Institute Detection Center and the detection report issued by Guizhou Non-ferrous Geological Center Laboratory; the barium residue composition analysis is shown in Table 1 below: Table 1 Main components of barium residue

[0068] Example 1 A method for full resource utilization of barium residue, comprising the following steps: (1) The barium residue is sent into a wet mill for wet grinding, and wet grinding is performed at a mass ratio of barium residue to water of 1:1, and the coarse material is returned for continuous wet grinding to obtain barium residue material with a fineness of 200 meshes of 90%.

[0069] (2) The barium residue material obtained in step (1) is mixed with sodium carbonate and water in a conversion tank to obtain a mixed slurry, the mass ratio of barium residue to water is controlled to be 1:4, the liquid in the mixed slurry is a saturated sodium carbonate solution, and then conversion treatment is performed at 25°C for 120 min, the conversion slurry is sent into a plate and frame filter for separation, the separated liquid flows into a primary conversion liquid buffer tank, and the primary conversion liquid is used for conversion agent regeneration; the separated residue is sent into a secondary conversion tank; In the secondary conversion tank, the barium residue and the conversion agent are stirred at a mass ratio of 1:5 in the conversion tank, conversion treatment is performed at 25°C for 120 min, the conversion slurry is sent into a plate and frame filter for separation, the separated liquid flows into a secondary conversion liquid buffer tank, and the secondary conversion liquid is process circulating water for recycling; the separated residue is sent into a tertiary conversion tank; In the tertiary conversion tank, the barium residue and the conversion agent are stirred at a mass ratio of 1:6 in the conversion tank, conversion treatment is performed at 25°C for 120 min, the conversion slurry is sent into a plate and frame filter for separation, the separated liquid is sent into a tertiary conversion liquid buffer tank, and the tertiary conversion liquid is process circulating water for recycling; the separated conversion residue is washed in situ; The filter residue is subjected to two blowing-two washing-two pressing in the plate and frame filter: after the third conversion filtration, the filter residue is not unloaded, and is subjected to high-pressure blowing once, then high-pressure washing with water once, the first washing liquid flows into a first washing liquid buffer tank, and the first washing liquid is process circulating water for recycling; the filter residue is subjected to high-pressure blowing once and high-pressure washing with water once, the second washing liquid flows into a second washing liquid buffer tank, and the second washing liquid is process circulating water for recycling; the washing water is tap water (condensate water), and the total washing water amount is 6 times that of the conversion residue. After washing, the filter residue is unloaded after high-pressure filtration to obtain the conversion residue.

[0070] (3) The conversion residue obtained in step (2) is added to an acid leaching tank with hydrochloric acid solution (31%) at a mass ratio of 1:3, then the pH value is adjusted to 3, and then acid leaching treatment is performed at 30°C for 30 min, and the acid leaching slurry is sent into a plate and frame filter for separation to obtain filter residue and separated liquid; The filter residue is washed in situ in a plate and frame filter once, namely in-situ one blowing-one washing-one pressing. After the acid leaching residue is treated, the filter residue is not unloaded, is blown once with high pressure, and is then washed once with water (condensed water) with high pressure, the washing liquid flows into a washing liquid buffer tank, and the washing liquid is recycled process water; after washing is completed, the filter residue is unloaded after being pressed with high pressure, and the washed acid leaching residue is used for coal separation.

[0071] (4) The separated liquid obtained in step (3) is mixed with carbonate (ammonium bicarbonate) in a mass ratio of 1:0.06 in a impurity removal tank 1, and after the pH value is adjusted to 5, one-time impurity removal is performed at 25°C for 25 min, the impurity removal liquid is sent to a plate and frame filter for filtration, to obtain a primary barium chloride solution and first separated residue; the first separated residue is used as active building material residue; The primary barium chloride solution is mixed with sulfide (sodium sulfide) in a mass ratio of 1:0.045 in a impurity removal tank 2, and secondary impurity removal is performed at 25°C for 25 min, the impurity removal liquid is sent to a plate and frame filter for filtration, to obtain a primary barium chloride refined liquid and second separated residue; the second separated residue is used as active building material residue; The primary barium chloride refined liquid is mixed with hydroxide (ammonium hydroxide) in a mass ratio of 1:0.011 in a impurity removal tank 3, and after reaction at 25°C for 25 min, three-time impurity removal is performed, the impurity removal liquid is sent to a filter for filtration, to obtain a barium chloride refined liquid and third separated residue; the third separated residue is used as active building material residue.

[0072] (5) The barium chloride refined liquid obtained in step (4) is sent to a preheater, preheated with condensed water, and the preheated barium chloride refined solution is sent to an evaporator, evaporated and concentrated at 80-100°C, and separated by crystallization, to obtain hydrous barium chloride dihydrate, which is dried to obtain barium chloride dihydrate, and the analysis results are shown in Table 2.

[0073] Table 2 Detection results of barium chloride dihydrate

[0074] As can be seen from Table 2, in the method provided by the application: the quality of refined impurity removal twice (conversion residue without washing) reaches the first-class product of industrial grade II, the quality of refined impurity removal three times (conversion residue has been washed) reaches the first-class product of industrial grade I, and the product obtained by using the method provided by the application can meet the industrial grade I product standard of barium chloride dihydrate. The barium recovery rate of barium residue can reach ≧90%.

[0075] Example 2 A method for full resource utilization of barium residue, comprising the following steps: (1) The barium residue is sent to a grinder for wet grinding, and wet grinding is performed at a mass ratio of barium residue to water of 1:1, and the coarse material is returned for continuous wet grinding after being classified by a cyclone classifier, to obtain barium residue material with fineness of 200 mesh and 85%.

[0076] (2) The barium residue slurry obtained in step (1) is mixed with sodium carbonate and water in a conversion tank to obtain a mixed slurry, the mass ratio of barium residue to water is controlled to be 1:3.5, the liquid in the mixed slurry is a saturated sodium carbonate solution, then conversion treatment is carried out at 30°C for 130 min, the conversion slurry is sent to a plate and frame filter for separation, the separated liquid flows into a primary conversion liquid buffer tank, and the primary conversion liquid is used for conversion agent regeneration; the separated residue is sent to a secondary conversion tank; In the secondary conversion tank, the barium residue slurry and the conversion agent are stirred according to a mass ratio of 1:4.5 in the conversion tank, conversion treatment is carried out at 30°C for 130 min, the conversion slurry is sent to a plate and frame filter for separation, the separated liquid flows into a secondary conversion liquid buffer tank, and the secondary conversion liquid is process circulating water for recycling; the separated residue is sent to a tertiary conversion tank; In the tertiary conversion tank, the barium residue slurry and the conversion agent are stirred according to a mass ratio of 1:6 in the conversion tank, conversion treatment is carried out at 30°C for 130 min, the conversion slurry is sent to a plate and frame filter for separation, the separated liquid is sent to a tertiary conversion liquid buffer tank, and the tertiary conversion liquid is process circulating water for recycling; the separated conversion residue is washed in situ; The filter residue is subjected to two blowing, two washing and two pressing in situ in the plate and frame filter: after the third conversion filtration, the filter residue is not unloaded, is blown once with high pressure, is washed once with high pressure water, the first washing liquid flows into a first washing liquid buffer tank, and the first washing liquid is process circulating water for recycling; is blown once with high pressure, is washed once with high pressure water, the second washing liquid flows into a second washing liquid buffer tank, and the second washing liquid is process circulating water for recycling; the washing water is tap water (condensate water), and the total washing water amount is 7 times that of the conversion residue. After washing, the filter residue is unloaded after high pressure filtration to obtain the conversion residue.

[0077] (3) The conversion residue obtained in step (2) is mixed with a hydrochloric acid solution (31%) according to a mass ratio of 1:3.5 in an acid leaching tank, the pH value is adjusted to 2.8, then acid leaching treatment is carried out at 35°C for 35 min, the acid leaching slurry is sent to a plate and frame filter for separation to obtain filter residue and separated liquid; The filter residue is subjected to one washing in situ in the plate and frame filter, namely one blowing, one washing and one pressing in situ. After the acid leaching residue treatment, the filter residue is not unloaded, is blown once with high pressure, is washed once with high pressure water, the washing liquid flows into a washing liquid buffer tank, and the washing liquid is process circulating water for recycling; after washing, the filter residue is unloaded after high pressure filtration, and the washed acid leaching residue is used for coal separation.

[0078] (4) The separated liquid obtained in step (3) is mixed with a carbonate (ammonium bicarbonate) according to a mass ratio of 1:0.07 in a impurity removal tank 1, the pH value is adjusted to 4.5, then one impurity removal is carried out at 20°C for 30 min, the impurity removal slurry is sent to a plate and frame filter for filtration to obtain a primary barium chloride solution and a first separated residue; the first separated residue is used as an active building material residue. The primary barium chloride solution is mixed with sulfide (sodium sulfide) in a mass ratio of 1:0.04 in a removal tank 2, secondary impurity removal is carried out by reacting for 30 min at 20℃, the impurity removal liquid is filtered in a plate and frame filter press, primary barium chloride refined liquid and second separation residue are obtained; the second separation residue is used as active building material residue; The primary barium chloride refined liquid is mixed with hydroxide (ammonium hydroxide) in a mass ratio of 1:0.01 in a removal tank 3, tertiary impurity removal is carried out by reacting for 30 min at 20℃, the impurity removal liquid is filtered in a precision filter, barium chloride refined liquid and third separation residue are obtained; the third separation residue is used as active building material residue.

[0079] (5) The barium chloride refined liquid obtained in step (4) is sent to a preheater, preheated by condensed water, the preheated barium chloride refined solution is sent to an evaporator, evaporated and concentrated at 80-100℃, and crystallized and separated, to obtain hydrous barium chloride dihydrate, which is dried to obtain barium chloride dihydrate.

[0080] From the above results, it can be seen that the method provided by the present application can prepare industrial-grade barium chloride dihydrate, which meets the requirements of national standard GB / T 1617-2014, and the barium recovery rate of the barium residue is >=90%. The acid leaching residue can be used for coal separation. The coal separation residue and all separation residues are active building material residues, which are used for cement, commercial concrete, wall materials, floor tiles and the like. The method provided by the present application can realize full resource utilization of barium residue, does not need to build a barium residue field, solves the problem of environmental pollution caused by barium residue stacking, can realize high-value cyclic utilization of barium residue resources, resource regeneration, energy saving and emission reduction, and breaks through the bottleneck restricting the development of barium chemical industry.

[0081] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A method for the complete resource utilization of barium slag, characterized in that, Includes the following steps: Barium slag is wet-milled to obtain barium slag slurry; The barium slag slurry is mixed with carbonates and water to obtain a mixed slurry, which is then subjected to conversion treatment to obtain conversion slag and conversion liquid; the liquid in the mixed slurry is a carbonate saturated solution; the conversion liquid is regenerated to obtain a recovered conversion agent and sulfate; The conversion residue is mixed with hydrochloric acid solution and subjected to acid leaching to obtain acid leaching residue and separation liquid; the acid leaching residue is used for coal preparation. The separation liquid is mixed with carbonate and subjected to a first impurity removal process to obtain a primary barium chloride solution and a first separation residue. The primary barium chloride solution is mixed with sulfide and subjected to secondary impurity removal to obtain a primary barium chloride refined solution and a second separation residue. The primary barium chloride refining solution is mixed with hydroxide and subjected to three impurity removal processes to obtain barium chloride refining solution and third separation residue; The refined barium chloride solution was evaporated, concentrated, and crystallized to obtain barium chloride dihydrate. The first, second, and third separated residues are used as active building material residues.

2. The method according to claim 1, characterized in that, The fineness of the solids in the barium slag slurry is ≥70% (200 mesh).

3. The method according to claim 1, characterized in that, The mass ratio of barium slag to water in the mixed slurry is 1:3~6.

4. The method according to claim 1, characterized in that, The conversion process is performed 2 to 4 times; the temperature of each conversion process is independently 5 to 30°C, and the time of each conversion process is independently 100 to 130 minutes.

5. The method according to claim 1, characterized in that, The mass ratio of the conversion residue to the hydrochloric acid solution is 1:2~5.

6. The method according to claim 1, characterized in that, The acid leaching treatment temperature is 0~50℃; the acid leaching treatment time is 15~30min.

7. The method according to claim 1, characterized in that, The mass ratio of the separated liquid to carbonate is 1:0.045~0.

07.

8. The method according to claim 1, characterized in that, The temperatures for the first, second, and third impurity removal processes are independently ≥10℃; the times for the first, second, and third impurity removal processes are independently 20~40min.

9. The method according to claim 1, characterized in that, The mass ratio of the primary barium chloride solution to the sulfide is 1:0.035~0.

05.

10. The method according to claim 1, characterized in that, The evaporation and concentration temperature is 80~100℃.

Images