CN108862351B - Method for comprehensively utilizing strontium-producing waste residues - Google Patents
Method for comprehensively utilizing strontium-producing waste residues Download PDFInfo
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- CN108862351B CN108862351B CN201810868971.6A CN201810868971A CN108862351B CN 108862351 B CN108862351 B CN 108862351B CN 201810868971 A CN201810868971 A CN 201810868971A CN 108862351 B CN108862351 B CN 108862351B
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- chloride
- strontium chloride
- urea
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- 239000002699 waste material Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 49
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 39
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 39
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims abstract description 86
- 229940013553 strontium chloride Drugs 0.000 claims abstract description 74
- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 74
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 62
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 44
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000004202 carbamide Substances 0.000 claims abstract description 42
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 36
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims abstract description 34
- 238000003756 stirring Methods 0.000 claims abstract description 33
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011259 mixed solution Substances 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 23
- 108010046334 Urease Proteins 0.000 claims abstract description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940047908 strontium chloride hexahydrate Drugs 0.000 claims abstract description 12
- AMGRXJSJSONEEG-UHFFFAOYSA-L strontium dichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Sr]Cl AMGRXJSJSONEEG-UHFFFAOYSA-L 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims abstract description 6
- 238000002425 crystallisation Methods 0.000 claims abstract description 5
- 230000008025 crystallization Effects 0.000 claims abstract description 5
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000002893 slag Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001276 controlling effect Effects 0.000 claims description 3
- 239000003832 thermite Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000007935 neutral effect Effects 0.000 abstract 1
- 229940063656 aluminum chloride Drugs 0.000 description 23
- 239000006227 byproduct Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012629 purifying agent Substances 0.000 description 3
- 229910001427 strontium ion Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical group [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- FWGZLZNGAVBRPW-UHFFFAOYSA-N alumane;strontium Chemical compound [AlH3].[Sr] FWGZLZNGAVBRPW-UHFFFAOYSA-N 0.000 description 1
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 1
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 1
- ZJHHPAUQMCHPRB-UHFFFAOYSA-N urea urea Chemical compound NC(N)=O.NC(N)=O ZJHHPAUQMCHPRB-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
- C01F11/186—Strontium or barium carbonate
- C01F11/187—Strontium carbonate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/462—Sulfates of Sr or Ba
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to the technical field of inorganic chemistry, and particularly relates to a method for comprehensively utilizing strontium-producing waste residues. The specific method comprises the following steps: adding water into the strontium-producing waste residues, standing and curing the waste residues; then adding hydrochloric acid to obtain a waste residue mixed solution; and regulating the temperature for crystallization, and performing solid-liquid separation to obtain a crude strontium chloride crystal, and a mixed solution of strontium chloride and aluminum chloride. Adding sulfuric acid or sulfate solution into the mixed solution, and performing solid-liquid separation to obtain a crude strontium sulfate solid and an aluminum chloride solution; redissolving the crude strontium chloride crystal, adjusting the pH to be neutral by using strontium hydroxide, properly stirring and standing, carrying out solid-liquid separation, and concentrating the filtrate to obtain strontium chloride hexahydrate or anhydrous strontium chloride; redissolving strontium chloride hexahydrate or anhydrous strontium chloride to obtain a strontium chloride solution, adding urea into the strontium chloride solution, and then adding urease to decompose the urea to generate the required strontium carbonate. The method has the advantages of low cost, obvious effect, high recovery rate and environmental friendliness, and has important practical significance and guiding value for treating the strontium-producing waste residue.
Description
Technical Field
The invention belongs to the technical field of inorganic chemistry, and particularly relates to a method for comprehensively utilizing strontium-producing waste residues.
Background
At present, most of metal strontium is produced by an aluminothermic reduction method, a large amount of waste residues are generated, and the main components of the waste residues comprise aluminum oxide, strontium carbonate and the like. In the past, the part of waste slag is often used as solid waste to be buried, so that a great deal of resource waste and environmental pollution are caused.
Meanwhile, Chongqing is a region with developed industrial production, local factories and companies can generate a large amount of byproduct hydrochloric acid every year, and the data of the byproduct hydrochloric acid produced in local enterprises in Chongqing every year are as follows: 16 ten thousand tons of byproduct hydrochloric acid is produced annually by Dongan potash fertilizer Co.Ltd; hydrochloric acid is produced as a byproduct of 10 ten thousand tons in Chongqing Tianhui chlor-alkali chemical industry Limited; the morning light group company produces 12 ten thousand tons of hydrochloric acid as a byproduct every year; the Chongqing division company of Basff China produces 10 million tons of hydrochloric acid as a byproduct annually; the byproduct hydrochloric acid produced by Chongqing Tianyuan chemical industry Co Ltd is 12 ten thousand tons every year. However, the by-product hydrochloric acid is mainly used for steel pickling, and the concentrated hydrochloric acid is easy to volatilize, has a very high volatilization speed especially in a high-temperature environment, and is very easy to corrode equipment and pollute the environment. Therefore, how to efficiently and environmentally utilize the hydrochloric acid which is a local existing industrial production byproduct with extremely high yield is a problem of green development of national and regional industries.
If the hydrochloric acid in Chongqing local area and a large amount of strontium-producing waste residues can be jointly utilized according to local conditions, multiple purposes can be achieved, the environmental problem is solved, a large amount of resources can be saved, and a series of high-value byproducts are generated. For example, strontium chloride can be produced for the production of precision instruments and the like; producing strontium sulfate for preparing self-regulating chromium plating solution, etc.; producing aluminum chloride, purifying water resource, etc. In addition, the domestic demand for high-quality strontium carbonate is high, but because the strontium carbonate has high requirements on particle size, morphology and the like, no method for producing the strontium carbonate with high efficiency and low cost exists in China at present. If the waste residue can be used for producing high-quality strontium carbonate, the method has important practical significance.
Disclosure of Invention
The invention aims to provide a method for comprehensively utilizing strontium-producing waste residues. The specific technical scheme is as follows: a method for comprehensively utilizing strontium-producing waste residues is an aluminothermic reduction method, and comprises the following specific steps:
(1) curing: adding water with the weight of 30-60% of the weight of the waste residue into the strontium-producing waste residue, and then standing for 5-10 days to obtain cured waste residue;
(2) acidifying: adding hydrochloric acid with the concentration of 30-35% into the cured waste residues, and uniformly mixing to obtain a waste residue mixed solution with the free acid content of 4-6%;
(3) and (3) crystallization: regulating the temperature of the waste residue mixed solution to be lower than 35 ℃, and performing solid-liquid separation to obtain a crude strontium chloride crystal, strontium chloride and aluminum chloride mixed solution;
(4) and (3) precipitation: adding 25% sulfuric acid or sulfate solution with the concentration being 1.05 times of the stoichiometric relation of strontium chloride into the mixed solution of strontium chloride and aluminum chloride; carrying out solid-liquid separation to obtain a crude strontium sulfate solid and an aluminum chloride solution;
(5) and (3) purification: redissolving the crude strontium chloride crystal obtained in the step (3) in hot water, adjusting the concentration to be 30-40 Baume degrees, heating to 75-90 ℃, adjusting the pH to be 7 by using strontium hydroxide, keeping the temperature, stirring for 0.3-0.6 h, standing for 0.3-0.6 h, carrying out solid-liquid separation, and concentrating the filtrate to obtain strontium chloride hexahydrate or anhydrous strontium chloride.
(6) Preparing strontium carbonate: redissolving the strontium chloride hexahydrate or anhydrous strontium chloride to obtain a strontium chloride solution, adding urea into the strontium chloride solution while stirring at 35-40 ℃, and controlling the concentration of the urea in the solution to be 55-65%; after urea is fully dissolved, gradually cooling to 20-25 ℃, after urea is crystallized, heating to 35-45 ℃ again according to the mol ratio of urea: adding urease while slowly stirring, and reacting for 2-5 min; and filtering and drying the mixed reaction liquid to obtain the required strontium carbonate.
Preferably, the water addition amount in the step (1) is 50% of the weight of the waste residue.
Preferably, the hydrochloric acid concentration in the step (2) is 31%, and the free acid content is 5%.
Preferably, the concentration in the step (5) is 35 Baume degrees, the temperature is increased to 80 ℃, the heat preservation stirring time is 0.5h, and the standing time is 0.5 h.
Preferably, the urea concentration in step (6) is: 60 percent; the urea: urease 1: 1; the stirring reaction time is as follows: 3 min.
Correspondingly, the method for comprehensively utilizing the strontium-producing waste residue is an aluminothermic reduction method, and comprises the following specific steps:
(1) curing: adding water with the weight of 30-60% of the weight of the waste residue into the strontium-producing waste residue, and then standing for 5-10 days to obtain cured waste residue;
(2) acidifying: adding hydrochloric acid with the concentration of 30-35% into the cured waste residues, and uniformly mixing to obtain a waste residue mixed solution with the free acid content of 4-6%;
(3) and (3) crystallization: regulating the temperature of the waste residue mixed solution to be lower than 35 ℃, and performing solid-liquid separation to obtain a crude strontium chloride crystal, strontium chloride and aluminum chloride mixed solution;
(4) and (3) precipitation: adding 25% sulfuric acid or sulfate solution with the concentration being 1.05 times of the stoichiometric relation of strontium chloride into the mixed solution of strontium chloride and aluminum chloride; carrying out solid-liquid separation to obtain a crude strontium sulfate solid and an aluminum chloride solution;
(5) and (3) purification: redissolving the crude strontium chloride crystal obtained in the step (3) in hot water, adjusting the concentration to be 30-40 Baume degrees, heating to 75-90 ℃, adjusting the pH to be 7 by using strontium hydroxide, keeping the temperature, stirring for 0.3-0.6 h, standing for 0.3-0.6 h, carrying out solid-liquid separation, and concentrating the filtrate to obtain strontium chloride hexahydrate or anhydrous strontium chloride.
(6) Preparing strontium carbonate: redissolving the strontium chloride hexahydrate or anhydrous strontium chloride to obtain a strontium chloride solution, wherein the molar ratio of strontium chloride: adding urea at a ratio of 1: 2-5 while stirring; after the urea is fully dissolved, keeping the room temperature, and then adding the following components in molar ratio: adding urease while stirring, and reacting for 4-10 min; and filtering and drying the mixed reaction liquid to obtain the required strontium carbonate.
Preferably, the water addition amount in the step (1) is 50% of the weight of the waste residue.
Preferably, the hydrochloric acid concentration in the step (2) is 31%, and the free acid content is 5%.
Preferably, the concentration in the step (5) is 35 Baume degrees, the temperature is increased to 80 ℃, the heat preservation stirring time is 0.5h, and the standing time is 0.5 h.
Preferably, the strontium chloride in the step (6): urea 1: 3; the urea: urease 1: 1; the stirring reaction time is 4 min.
The invention has the following beneficial effects:
(1) the method utilizes the existing industrial production by-products with extremely large yield in Chongqing places: hydrochloric acid is used for efficiently treating strontium aluminum in the metal strontium waste residue, and meanwhile, the hydrochloric acid is used for assisting environmental protection and solving the problem of local byproduct hydrochloric acid.
(2) The production process is a new process, the production process does not need to be broken, the solid materials are completely converted into liquid in the acidification process, no solid waste is generated, strontium in the metal strontium waste residue is used for producing strontium chloride and strontium sulfate, the recovery rate of strontium is over 95 percent, aluminum in the metal strontium waste residue can be directly used for producing liquid aluminum chloride for sale or producing crystalline aluminum chloride or polyaluminum chloride, and the recovery rate of aluminum is over 95 percent.
(3) The production process adopts closed equipment and a waste gas absorption device, and the production field is safe and environment-friendly.
(4) In the wastewater treatment process, a large amount of water purifying agent is needed; polyaluminium chloride is a water purifying agent with excellent effect, but along with the large-scale exploitation of aluminum ore resources, the aluminum ore resources are less and less, and the price of the water purifying agent is also high; the aluminum salt recovered from the metal strontium waste residue can be used for producing aluminum chloride or polyaluminium chloride, and can be just sold nearby.
(5) The waste residue, the urea and the urease are used as raw materials, the strontium carbonate with high purity, spherical shape and smaller grain diameter is generated, new impurity ions are not introduced, expensive equipment such as a supergravity reactor is not used, and the method has important popularization significance.
In conclusion, the method has the characteristics of low cost, obvious effect, high recovery rate and environmental friendliness, and has important practical significance and guiding value for treatment of the strontium-producing waste residue.
Detailed Description
The method comprises the following specific operation steps:
1. curing waste residues: and adding water with the weight of 30-60% of the weight of the waste residue into the strontium-producing waste residue at the speed of 60ml/min by using a spraying method, and then standing for 5-10 days to obtain the cured waste residue. Because the strontium-producing waste residue obtained by the aluminothermic reduction method is olive-shaped and relatively compact, the waste residue can be naturally dispersed in the process of adding water for curing, and various components in the waste residue can be favorably reacted in the subsequent steps. When water is added, the speed is too high, the absorption of water mist by waste residues is not facilitated, the waste of water resources is easily caused, and the operation environment is influenced; if the water adding speed is too slow, the working efficiency is influenced, and the production cost is increased; through repeated tests, the water adding speed of 60ml/min is preferably selected.
2. Acidifying: slowly adding hydrochloric acid with the concentration of 30-35% into the cured waste residue while stirring to obtain a waste residue solution with the free acid content of about 5%, then stopping adding the acid, and continuously stirring for 1h to obtain a waste residue mixed solution.
3. Cooling and crystallizing: and putting the waste residue mixed solution into a cooling tank, and adjusting the temperature of the waste residue mixed solution to be lower than 35 ℃ while stirring to obtain a crude strontium chloride crystal, and an uncrystallized strontium chloride and aluminum chloride mixed solution. Wherein, a device for exhausting air and absorbing acid liquor is arranged above the cooling tank, so that the hydrochloric acid gas is prevented from volatilizing to pollute the environment; the air draft device and the device for absorbing the acid liquor are conventional commercially available devices capable of absorbing hydrochloric acid gas.
4. Solid-liquid separation for the first time: and (3) carrying out solid-liquid separation on the solid-liquid mixture obtained in the step (3), wherein the separation method can adopt a closed centrifuge or a filter press and other devices to obtain a crude strontium chloride crystal and a mixed solution of strontium chloride and aluminum chloride.
5. Precipitating strontium sulfate: the composition of the strontium chloride/aluminum chloride mixed solution was measured, and a 25% sulfuric acid or sulfate solution (the stoichiometric ratio of 1.05: 1.05 times the amount of strontium chloride theoretically allowed to react completely was added to the mixed solution to ensure completion of the strontium chloride reaction and promote forward progress of the reaction) to precipitate strontium ions in the mixed solution. Although the sulfate solution can theoretically be any salt solution which can provide sulfate ions to precipitate strontium ions, in practice, many sulfate solutions affect the production and subsequent steps of aluminum chloride, and finally, a sodium sulfate solution or an ammonium sulfate solution is preferred.
6. And (3) solid-liquid separation for the second time: and (5) performing centrifugal separation or filter pressing on the product obtained in the step (5) to obtain a crude strontium sulfate solid and an aluminum chloride solution. The aluminum chloride solution can be directly sold or further produced into aluminum chloride hexahydrate or polyaluminium chloride for use according to actual needs.
7. Washing: washing the strontium sulfate solid obtained in step 6 with hot water at a temperature of more than 60 ℃ to remove a small amount of aluminum chloride contained in the crude strontium sulfate solid. And (3) then carrying out solid-liquid separation, wherein the washing liquor can replace the water in the step (1) to cure the waste residue, and drying after separation to obtain the strontium sulfate solid which can be put into industrial use.
8. And (3) dissolving the crude strontium chloride crystal obtained in the step (4) in hot water with the temperature of more than 60 ℃, adjusting the concentration of the solution to 35 Baume degrees, heating to 80 ℃, adding strontium hydroxide to adjust the pH value to 7, keeping the temperature, stirring for 0.5h, stopping stirring, and standing for 0.5h to precipitate aluminum hydroxide. Then the solution is subjected to solid-liquid separation, and the filtrate is concentrated to produce pure strontium chloride hexahydrate or anhydrous strontium chloride (using temperature regulation). And (3) washing the solid phase (filter cake, the main component of which is aluminum hydroxide) by using clean water, wherein the washing liquid can replace hot water and is used for dissolving the crude strontium chloride crystal in the step (step 8) for recycling. The filter cake can be dissolved into the aluminum chloride solution in the step 6 for recycling.
9. The pure strontium chloride obtained in the step 8 can be directly used, and can also be continuously used for producing spherical strontium carbonate. The specific production method has two types.
The method comprises the following steps:
dissolving strontium chloride hexahydrate or anhydrous strontium chloride, measuring the concentration of a strontium chloride solution, calculating the actual concentration (mol/L) of the strontium chloride, adding urea into the strontium chloride solution while stirring at 35-40 ℃, controlling the concentration of the urea in the solution to be 55-65%, gradually cooling to 20-25 ℃ after the urea is fully dissolved, enabling the urea to generate spherical crystals, then heating to 35-45 ℃, slowly stirring while adding urease according to a molar ratio of urea to urease of 1: 1-2, stirring for reaction for 2-5 min, filtering to remove residual urease by using a dialysis method and the like, and filtering and drying the mixed reaction liquid to obtain the spherical strontium carbonate with the crystal form.
The possible main principles of the method are as follows: the spherical crystal of urea is used as a soft template, and the urea crystal is gradually decomposed into CO under the action of urease2And NH4，NH4Volatilization of CO2And Sr2+Reaction to form SrCO3Gradually replace the original urea crystal to form spherical SrCO3Crystallizing; the redundant urea is completely volatilized under the action of urease.
The second method comprises the following steps:
measuring the concentration of a strontium chloride solution, calculating the actual concentration (mol/L) of strontium chloride, adding urea into the strontium chloride solution at room temperature according to the molar ratio, wherein the ratio of strontium chloride to urea is 1: 2-5, adding the urea while stirring, keeping the room temperature after the urea is fully dissolved, adding urease into the solution at the molar ratio, stirring and reacting for 4-10 min, filtering and removing the residual urease by using a dialysis method and other methods, and filtering and drying the mixed reaction solution to obtain the spherical strontium carbonate.
The possible main principles of the method are as follows: the optimum reaction temperature of the urease is 50-60 ℃, the activity is low at room temperature, the urea decomposition rate is slow, and CO is slowly released2The generation and nucleation rates of the strontium carbonate crystals are controlled, so that the produced strontium carbonate crystals are controlled to be spherical.
In order to make the technical effects and methods of the present invention more detailed for those skilled in the art, the following specific examples and corresponding test data are provided.
The first embodiment is as follows: the parameters when the final product is a solution of strontium chloride, strontium sulfate and aluminum chloride are preferably
1. Determination of initial components of waste residue
A batch of waste residues produced by preparing metal strontium by using a thermite reduction method is randomly selected and subjected to component measurement, and the result (average result after 10 times of measurement by random sampling) is shown in Table 1.
TABLE 1 waste residue composition table
2. Using 13 batches of the said slag, 1000 grams each (considered to contain 614.6 grams of SrCO each batch)3、 365g Al2O3) And putting the mixture into a 10L container, and preparing strontium chloride, strontium sulfate and aluminum chloride according to the steps 1-8 of the method, wherein specific parameters of each group are shown in Table 2.
TABLE 2 detailed parameters of the respective groups
3. The mass of the crude strontium chloride, strontium sulfate, aluminum chloride solution and the washing solution prepared in each group was measured, and the results are shown in table 3. Wherein, in order to calculate the total recovery amount of strontium, after the respective weights of anhydrous strontium chloride and strontium sulfate are measured, all the weights are respectively converted into the amounts of strontium carbonate, and the total amount of strontium is reflected after the weights are added; to calculate the total recovery of aluminum, after measuring the respective aluminum chloride contents in the aluminum chloride solution (obtained in step 6) and the washing solution (obtained in step.. times.), all were converted to alumina and added to represent the total amount of aluminum in terms of alumina. Only the total amount, expressed as strontium carbonate and alumina, is shown in table 3.
TABLE 3 determination of the results of the groups
From the above results, it can be seen that the utilization efficiency is the highest when the slag is treated using the parameters of group 3.
Example two: preference of parameters in the preparation of strontium carbonate Using Process one of step 9
1. Using the strontium chloride prepared in example group 3 as a starting material, spherical strontium carbonate was prepared according to the method one of step 9 above, and the specific parameters of each group are shown in table 6.
TABLE 6 specific reaction parameters for each group
| Group of | Concentration of urea | Urea: urease | Length of stirring |
| Group 1 | 55％ | 1:1 | 3min |
| Group 2 | 60％ | 1:1 | 3min |
| Group 3 | 65％ | 1:1 | 3min |
| Group 4 | 60％ | 1:2 | 3min |
| Group 5 | 60％ | 1:1 | 2min |
| Group 6 | 60％ | 1:1 | 5min |
| Group 7 | 60％ | 1:1 | 10min |
2. Observing the crystal form and the grain size of the strontium carbonate in each group by using an electron microscope; the purity of strontium carbonate in each group was measured and the results are shown in table 7.
Table 7 results of each group
| Group of | Strontium carbonate crystal form | Particle size of strontium carbonate | Purity of strontium carbonate |
| Group 1 | Spherical shape | ＜1μm | 99.4％ |
| Group 2 | Spherical shape | ＜1μm | 99.6％ |
| Group 3 | Spherical shape | ＜1μm | 99.4％ |
| Group 4 | Spherical shape | ＜1μm | 99.5％ |
| Group 5 | Spherical shape | ＜1μm | 99.3％ |
| Group 6 | Spherical shape | ＜1μm | 99.4％ |
| Group 7 | Ellipsoid | ＞1μm | 99.2％ |
Example three: preference of parameters in the preparation of strontium carbonate using Process two of step 9
1. The strontium chloride prepared in the first group of example 3 was used as a raw material to prepare spherical strontium carbonate according to the second method in the above step 9, and specific parameters of each group are shown in table 8. Among them, urea in this example: the urease is 1:1, so the relationship between strontium chloride and urea is only shown in the following table.
TABLE 8 specific reaction parameters for each group
| Group of | Strontium chloride: urea | Length of stirring |
| Group 1 | 1:2 | 4min |
| Group 2 | 1:3 | 4min |
| Group 3 | 1:5 | 4min |
| Group 4 | 1:3 | 6min |
| Group 5 | 1:3 | 8min |
| Group 6 | 1:3 | 10min |
| Group 7 | 1:3 | 12min |
2. Observing the crystal form and the grain size of the strontium carbonate in each group by using an electron microscope; the purity of strontium carbonate in each group was measured and the results are shown in table 9.
TABLE 9 respective groups of specific reaction parameters
| Group of | Strontium carbonate crystal form | Particle size of strontium carbonate | Purity of strontium carbonate |
| Group 1 | Spherical shape | ＜1μm | 99.4％ |
| Group 2 | Spherical shape | ＜1μm | 99.7％ |
| Group 3 | Spherical shape | ＜1μm | 99.2％ |
| Group 4 | Spherical shape | ＜1μm | 99.6％ |
| Group 5 | Spherical shape | ＜1μm | 99.5％ |
| Group 6 | Spherical shape | 1μm | 99.6％ |
| Group 7 | Ellipsoid | ＞1μm | 99.6％ |
Claims (10)
1. A method for comprehensively utilizing strontium-producing waste residues is characterized by comprising the following steps: the method for producing strontium is an aluminothermic reduction method, and comprises the following specific steps:
(1) curing: adding water with the weight of 30-60% of the weight of the waste residue into the strontium-producing waste residue, and then standing for 5-10 days to obtain cured waste residue;
(2) acidifying: adding hydrochloric acid with the concentration of 30-35% into the cured waste residues, and uniformly mixing to obtain a waste residue mixed solution with the free acid content of 4-6%;
(3) and (3) crystallization: regulating the temperature of the waste residue mixed solution to be lower than 35 ℃, and performing solid-liquid separation to obtain a crude strontium chloride crystal, strontium chloride and aluminum chloride mixed solution;
(4) and (3) precipitation: adding 25% sulfuric acid or sulfate solution with the concentration being 1.05 times of the stoichiometric relation of strontium chloride into the mixed solution of strontium chloride and aluminum chloride; performing solid-liquid separation to obtain a crude strontium sulfate solid and an aluminum chloride solution;
(5) and (3) purification: redissolving the crude strontium chloride crystal obtained in the step (3) in hot water, adjusting the concentration to be 30-40 Baume degrees, heating to 75-90 ℃, adjusting the pH to be 7 by using strontium hydroxide, keeping the temperature, stirring for 0.3-0.6 h, standing for 0.3-0.6 h, carrying out solid-liquid separation, and concentrating the filtrate to obtain strontium chloride hexahydrate or anhydrous strontium chloride.
(6) Preparing strontium carbonate: redissolving the strontium chloride hexahydrate or anhydrous strontium chloride to obtain a strontium chloride solution, adding urea into the strontium chloride solution while stirring at 35-40 ℃, and controlling the concentration of the urea in the solution to be 55-65%; after urea is fully dissolved, gradually cooling to 20-25 ℃, after urea is crystallized, heating to 35-45 ℃ again according to the mol ratio of urea: adding urease while slowly stirring, and reacting for 2-5 min; and filtering and drying the mixed reaction liquid to obtain the required strontium carbonate.
2. The method for comprehensively utilizing strontium-producing waste slag according to claim 1, characterized by comprising the steps of: the water addition amount in the step (1) is 50% of the weight of the waste residue.
3. The method for comprehensively utilizing strontium-producing waste slag according to claim 1, characterized by comprising the steps of: in the step (2), the concentration of the hydrochloric acid is 31%, and the content of the free acid is 5%.
4. The method for comprehensively utilizing strontium-producing waste slag according to claim 1, characterized by comprising the steps of: and (5) the concentration is 35 Baume degrees, the temperature is increased to 80 ℃, the heat preservation stirring time is 0.5h, and the standing time is 0.5 h.
5. The method for comprehensively utilizing strontium-producing waste slag according to claim 1, characterized by comprising the steps of: the urea concentration in the step (6) is as follows: 60 percent; the urea: urease 1: 1; the stirring reaction time is as follows: 3 min.
6. A method for comprehensively utilizing strontium-producing waste residues is characterized by comprising the following steps: the strontium production is a thermite reduction method, and the method comprises the following specific steps:
(1) curing: adding water with the weight of 30-60% of the weight of the waste residue into the strontium-producing waste residue, and then standing for 5-10 days to obtain cured waste residue;
(2) acidifying: adding hydrochloric acid with the concentration of 30-35% into the cured waste residues, and uniformly mixing to obtain a waste residue mixed solution with the free acid content of 4-6%;
(3) and (3) crystallization: regulating the temperature of the waste residue mixed solution to be lower than 35 ℃, and performing solid-liquid separation to obtain a crude strontium chloride crystal, strontium chloride and aluminum chloride mixed solution;
(4) and (3) precipitation: adding 25% sulfuric acid or sulfate solution with the concentration being 1.05 times of the stoichiometric relation of strontium chloride into the mixed solution of strontium chloride and aluminum chloride; performing solid-liquid separation to obtain a crude strontium sulfate solid and an aluminum chloride solution;
(5) and (3) purification: redissolving the crude strontium chloride crystal obtained in the step (3) in hot water, adjusting the concentration to be 30-40 Baume degrees, heating to 75-90 ℃, adjusting the pH to be 7 by using strontium hydroxide, keeping the temperature, stirring for 0.3-0.6 h, standing for 0.3-0.6 h, carrying out solid-liquid separation, and concentrating the filtrate to obtain strontium chloride hexahydrate or anhydrous strontium chloride.
(6) Preparing strontium carbonate: redissolving the strontium chloride hexahydrate or anhydrous strontium chloride to obtain a strontium chloride solution, wherein the molar ratio of strontium chloride: adding urea at a ratio of 1: 2-5 while stirring; after the urea is fully dissolved, keeping the room temperature, and then adding the following components in molar ratio: adding urease while stirring, and reacting for 4-10 min; and filtering and drying the mixed reaction liquid to obtain the required strontium carbonate.
7. The method for comprehensively utilizing strontium-producing waste slag according to claim 6, characterized by comprising the steps of: the water addition amount in the step (1) is 50% of the weight of the waste residue.
8. The method for comprehensively utilizing strontium-producing waste slag according to claim 6, characterized by comprising the steps of: in the step (2), the concentration of the hydrochloric acid is 31%, and the content of the free acid is 5%.
9. The method for comprehensively utilizing strontium-producing waste slag according to claim 6, characterized by comprising the steps of: and (5) the concentration is 35 Baume degrees, the temperature is increased to 80 ℃, the heat preservation stirring time is 0.5h, and the standing time is 0.5 h.
10. The method for comprehensively utilizing strontium-producing waste slag according to claim 6, characterized by comprising the steps of: the strontium chloride of the step (6): urea 1: 3; the urea: urease 1: 1; the stirring reaction time is 4 min.
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| JP2009001475A (en) * | 2006-12-14 | 2009-01-08 | Sony Corp | Method for manufacturing strontium carbonate fine particle |
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| JP2009001475A (en) * | 2006-12-14 | 2009-01-08 | Sony Corp | Method for manufacturing strontium carbonate fine particle |
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