CN108862351A - A method of comprehensive utilization produces strontium waste residue - Google Patents
A method of comprehensive utilization produces strontium waste residue Download PDFInfo
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- CN108862351A CN108862351A CN201810868971.6A CN201810868971A CN108862351A CN 108862351 A CN108862351 A CN 108862351A CN 201810868971 A CN201810868971 A CN 201810868971A CN 108862351 A CN108862351 A CN 108862351A
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- China
- Prior art keywords
- strontium
- waste residue
- chloride
- urea
- added
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- 239000002699 waste material Substances 0.000 title claims abstract description 78
- 229910052712 strontium Inorganic materials 0.000 title claims abstract description 63
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 44
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 claims abstract description 73
- 229910001631 strontium chloride Inorganic materials 0.000 claims abstract description 65
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000004202 carbamide Substances 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 36
- 229910000018 strontium carbonate Inorganic materials 0.000 claims abstract description 34
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 claims abstract description 31
- 239000000243 solution Substances 0.000 claims abstract description 30
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000012043 crude product Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 22
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 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 10
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 230000009467 reduction Effects 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000012467 final product Substances 0.000 abstract description 2
- 238000010563 solid-state fermentation Methods 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000006210 lotion Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910001427 strontium ion Inorganic materials 0.000 description 3
- PWYYWQHXAPXYMF-UHFFFAOYSA-N strontium(2+) Chemical compound [Sr+2] PWYYWQHXAPXYMF-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 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
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 2
- 229910001570 bauxite Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- UKCFNZXJZBAZFS-UHFFFAOYSA-N carbonic acid;strontium Chemical compound [Sr].OC(O)=O UKCFNZXJZBAZFS-UHFFFAOYSA-N 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- LEDMRZGFZIAGGB-UHFFFAOYSA-L strontium carbonate Chemical compound [Sr+2].[O-]C([O-])=O LEDMRZGFZIAGGB-UHFFFAOYSA-L 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 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
- 229940063656 aluminum chloride Drugs 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
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 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
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000007789 sealing 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
- 239000010959 steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000009156 water cure 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 technical field of inorganic, and in particular to a method of comprehensive utilization produces strontium waste residue.Specific method is：In producing strontium waste residue, water is added and stands the waste residue after curing；Hydrochloric acid is then added, obtains waste residue mixed solution；Temperature crystallization is adjusted again, is separated by solid-liquid separation, is obtained crude product chlorination strontium crystal, strontium chloride and aluminium chloride mixed solution.Sulfuric acid or sulfate liquor are added in mixed solution, is separated by solid-liquid separation to obtain crude product strontium sulfate solid, liquor alumini chloridi；Crude product chlorination strontium crystal is redissolved, adjusts pH neutrality using strontium hydroxide, it is appropriate to stir and stand, it is separated by solid-liquid separation, six water strontium chlorides or anhydrous strontium chloride to obtain the final product is concentrated in filtrate；Six water strontium chlorides or anhydrous strontium chloride are redissolved, strontium chloride solution is obtained, urea is added in strontium chloride solution, adds urase decomposing urea, strontium carbonate needed for generating.The present invention is low in cost, effect is obvious, the rate of recovery is high, environmental-friendly, has practical significance and guiding value to strontium Solid state fermentation is produced.
Description
Technical field
The invention belongs to technical field of inorganic, and in particular to a method of comprehensive utilization produces strontium waste residue.
Background technique
Currently, production Preparation of Metallic Strontium is mostly thermit reduction, a large amount of waste residues can be generated, the main component of waste residue includes oxidation
Aluminium, strontium carbonate etc..Past, this part waste residue are often used as solid waste to be filled, and cause vast resources waste and environmental pollution.
Meanwhile Chongqing is industrial production comparatively developed regions, local each factory, the every annual meeting of company generate a large amount of by-product salt
Acid, it is as follows that part Chongqing domestic enterprise produces by-product hydrochloric acid data per year：Dongan potash fertilizer Co., Ltd produces 160000 tons of by-product hydrochloric acid per year；
Chongqing Ying Tianhui chemical industry for making chlorine and alkali Co., Ltd produces 100000 tons of by-product hydrochloric acid per year；Morning twilight group company produces 120000 tons of by-product hydrochloric acid per year；
BASF Chinese companies Chongqing Branch produces 100000 tons of by-product hydrochloric acid per year；Chongqing Tianyuan Chemical Co., Ltd. produces by-product hydrochloric acid per year
120000 tons.But in general, by-product hydrochloric acid is mainly used for pickling iron and steel etc., and concentrated hydrochloric acid is volatile, especially in hot environment
Under, evaporation rate is exceedingly fast, and is very easy to corrosion equipment, pollution environment.Therefore, how efficiently, environmentally friendlyly using local existing and
The great industrial production by-product of yield -- hydrochloric acid is the problem of countries and regions Industrial Green development.
If energy adaptation to local conditions, joint utilize the hydrochloric acid and big volume production strontium waste residue of Chongqing locality, then can achieve many things at one stroke, no
Environmental problem is only solved, vast resources can be also saved, generate a series of high value by-products.For example, strontium chloride can be produced,
For precision instrument production etc.；Strontium sulfate is produced, for preparing self-regulation Cr-plating Bath etc.；Aluminium chloride is produced, purified water is used for
Resource etc..In addition, domestic higher to the strontium carbonate demand of high quality, but because this kind of strontium carbonate have to partial size, pattern etc. it is higher
It is required that so domestic there is presently no the methods of efficient, inexpensive this kind of strontium carbonate of production.If this part waste residue can be utilized
High quality strontium carbonate is produced, will be had important practical significance.
Summary of the invention
The object of the present invention is to provide a kind of methods that comprehensive utilization produces strontium waste residue.Specifically technical solution is：It is a kind of comprehensive
Close using produce strontium waste residue method, it is described produce strontium method be thermit reduction, the method the specific steps are：
(1) it cures：In producing strontium waste residue, the water that weight is waste residue weight 30~60% is added, is subsequently placed with 5~10 days,
Waste residue after must curing；
(2) it is acidified：The hydrochloric acid that concentration is 30~35% is added in waste residue after curing, mixes, obtaining free acid content is
4~6% waste residue mixed solution；
(3) it crystallizes：It adjusts waste residue mixed solution temperature and is lower than 35 DEG C, be separated by solid-liquid separation, obtain crude product chlorination strontium crystal, chlorination
Strontium and aluminium chloride mixed solution；
(4) it precipitates：1.05 times of strontium chloride stoichiometric relationship are added in the strontium chloride and aluminium chloride mixed solution
The sulfuric acid or sulfate liquor that concentration is 25%；It is separated by solid-liquid separation, obtains crude product strontium sulfate solid, liquor alumini chloridi；
(5) it purifies：Step (3) the crude product chlorination strontium crystal is redissolved in hot water, adjusting concentration is 30~40 Baumes
Degree, is warming up to 75~90 DEG C, adjusts pH=7,0.3~0.6h of insulated and stirred using strontium hydroxide, stands 0.3~0.6h, solid-liquid
Separation, filtrate are concentrated up to six water strontium chlorides or anhydrous strontium chloride.
(6) strontium carbonate is prepared：The six water strontium chloride or anhydrous strontium chloride are redissolved, obtains strontium chloride solution, 35~40 DEG C,
Add urea while stirring in the strontium chloride solution, the concentration for controlling urea in solution is 55~65%；It is abundant to urea
After dissolution, 20~25 DEG C are gradually cooled to, after urea crystals, then is warming up to 35~45 DEG C, in molar ratio, urea：Urase=
1:1~2, urase is added when being slowly stirred, and is stirred to react 2~5min；By mixed reaction solution filtering, drying to get required
Strontium carbonate.
Preferably, step (1) amount of water is the 50% of waste residue weight.
Preferably, step (2) concentration of hydrochloric acid is 31%, and the free acid content is 5%.
Preferably, step (5) concentration is 35 Baume degrees, and the warming temperature is to 80 DEG C, the insulated and stirred duration
For 0.5h, when standing a length of 0.5h.
Preferably, step (6) described urea concentration is：60%；The urea：Urase=1:1；It is described when being stirred to react
It is a length of：3min.
Correspondingly, a kind of method that comprehensive utilization produces strontium waste residue, the production strontium are aluminothermic reduction reduction method, the method
The specific steps are：
(1) it cures：In producing strontium waste residue, the water that weight is waste residue weight 30~60% is added, is subsequently placed with 5~10 days,
Waste residue after must curing；
(2) it is acidified：The hydrochloric acid that concentration is 30~35% is added in waste residue after curing, mixes, obtaining free acid content is
4~6% waste residue mixed solution；
(3) it crystallizes：It adjusts waste residue mixed solution temperature and is lower than 35 DEG C, be separated by solid-liquid separation, obtain crude product chlorination strontium crystal, chlorination
Strontium and aluminium chloride mixed solution；
(4) it precipitates：1.05 times of strontium chloride stoichiometric relationship are added in the strontium chloride and aluminium chloride mixed solution
The sulfuric acid or sulfate liquor that concentration is 25%；It is separated by solid-liquid separation, obtains crude product strontium sulfate solid, liquor alumini chloridi；
(5) it purifies：Step (3) the crude product chlorination strontium crystal is redissolved in hot water, adjusting concentration is 30~40 Baumes
Degree, is warming up to 75~90 DEG C, adjusts pH=7,0.3~0.6h of insulated and stirred using strontium hydroxide, stands 0.3~0.6h, solid-liquid
Separation, filtrate are concentrated up to six water strontium chlorides or anhydrous strontium chloride.
(6) strontium carbonate is prepared：The six water strontium chloride or anhydrous strontium chloride are redissolved, strontium chloride solution is obtained, at room temperature,
In the strontium chloride solution, in molar ratio, strontium chloride：Urea=1:2~5, urea is added while stirring；It is sufficiently molten to urea
Xie Hou keeps room temperature, then in molar ratio, urea：Urase=1:1~1.5, urase is added while stirring, it is stirred to react 4~
10min；By mixed reaction solution filtering, drying to get required strontium carbonate.
Preferably, step (1) amount of water is the 50% of waste residue weight.
Preferably, step (2) concentration of hydrochloric acid is 31%, and the free acid content is 5%.
Preferably, step (5) concentration is 35 Baume degrees, and the warming temperature is to 80 DEG C, the insulated and stirred duration
For 0.5h, when standing a length of 0.5h.
Preferably, step (6) strontium chloride：Urea=1:3；The urea：Urase=1:1；It is described when being stirred to react
A length of 4min.
The invention has the advantages that：
(1) the great industrial production by-product of the local existing and yield in Chongqing is utilized：Hydrochloric acid, in Preparation of Metallic Strontium waste residue
Strontium aluminium has carried out efficient process, while environmental protection being assisted to solve local by-product hydrochloric acid.
(2) new technique is taken, production process is not required to be crushed, and solid material is all switched to liquid, nothing by acidization
Solid waste generates, and the strontium in Preparation of Metallic Strontium waste residue produces strontium chloride, strontium sulfate, and the rate of recovery of strontium reaches 95% or more, Preparation of Metallic Strontium waste residue
In aluminium can directly produce liquid chlorine aluminium and sell or production crystal aluminum chloride or aluminium polychloride, the rate of recovery 95% of aluminium with
On.
(3) using Sealing Arrangement and installation exhaust gas absorption device, production scene safety and environmental protection in production process.
(4) in wastewater treatment process, a large amount of water purification agent is needed；Aluminium polychloride is a kind of water purification of excellent
Agent, but with a large amount of exploitations of bauxite resource, bauxite resource is fewer and fewer, and also when the river rises the boat goes up for water purification agent price；It is useless from Preparation of Metallic Strontium
The aluminium salt production aluminium chloride or aluminium polychloride recycled in slag, can be sold nearby just.
(5) using waste residue, urea and urase as raw material, purity is high, spherical, the lesser strontium carbonate of partial size are generated, and not
New foreign ion is introduced, the expensive devices such as supergravity reactor are not used, there is important dissemination.
To sum up, the present invention has the characteristics that low in cost, effect is obvious, the rate of recovery is high, environmentally friendly, useless to strontium is produced
Slag treatment has practical significance and guiding value.
Specific embodiment
Concrete operation step of the invention is：
1, waste residue is cured：In producing strontium waste residue, with spray-on process, it is waste residue weight that weight, which is added, by the speed of 60ml/min
30~60% water, is subsequently placed with 5~10 days, the waste residue after must curing.Because of the production strontium waste residue obtained using thermit reduction
In olive shape, denser adds the process of water cure, can make waste residue nature dispersion, and facilitates each constituents in waste residue
Reaction in the next steps.When adding water, excessive velocities are unfavorable for absorption of the waste residue to water mist, water are be easy to cause to provide
Source wastes and will affect operating environment；Add water speed to spend slowly, then influence working efficiency, improves production cost；Through repetition test,
It is preferred that go out 60ml/min plus water speed.
2, it is acidified：It stirs on one side, is slowly added to the salt that concentration is 30~35% into the waste residue after the curing on one side
Acid obtains free acid in 5% or so waste residue solution, then stops acid adding, and continues to stir 1h, obtains waste residue mixed solution.
3, crystallisation by cooling：The waste residue mixed solution is put into cooling tank, it is molten that waste residue mixing is adjusted while stirring
Liquid temperature is lower than 35 DEG C, obtains crude product chlorination strontium crystal, uncrystallized strontium chloride and aluminium chloride mixed solution.Wherein, described cold
But it is provided with exhausting above tank and absorbs the device of acid solution, avoid HCl gas volatilization pollution environment；The extractor fan and suction
The device for receiving acid solution is the device that can absorb HCl gas of regular market purchase.
4, it is separated by solid-liquid separation for the first time：The solidliquid mixture that step 3 obtains is separated by solid-liquid separation, separation method can be adopted
With devices such as closed centrifugal machine or filter presses to get crude product chlorination strontium crystal and strontium chloride, aluminium chloride mixed solution.
5, sulfate precipitate strontium：Composition measurement is carried out to the strontium chloride, aluminium chloride mixed solution, in the mixed solution
The sulfuric acid or sulfate liquor that the concentration for being added 1.05 times of strontium chloride stoichiometric relationship is 25% (close by stoichiometry herein
It is 1.05 times of fingers：Theoretically make 1.05 times of the amount of strontium chloride fully reacting, to ensure strontium chloride fully reacting, promotes reaction
Positive carry out), to precipitate strontium chloride, the strontium ion in aluminium chloride mixed solution.Though the sulfate liquor theoretically makes
The salting liquid for precipitating strontium ion with sulfate ion can be provided, but in fact, many sulfate liquors all can be to aluminium chloride
Production and subsequent step have an impact, finally preferably sodium sulphate or ammonium sulfate.
6, it is separated by solid-liquid separation for second：The product of step 5 is centrifuged or filters pressing, crude product strontium sulfate solid is obtained
And liquor alumini chloridi.Liquor alumini chloridi can sell, or according to actual needs, further be produced as Aluminum Chloride Hexahydrate
Or aluminium polychloride uses.
7, it washs：The strontium sulfate solid obtained with 60 DEG C of > of hot water washing step 6, to remove crude product strontium sulfate solid
In a small amount of aluminium chloride for containing.It is then separated by solid-liquid separation, the water in the alternative step 1 of washing lotion cures waste residue, separation
After be drying to obtain strontium sulfate solid, industrial application can be put into.
8, for the crude product strontium chloride dissolution of crystals for obtaining step 4 in 60 DEG C or more of hot water, adjusting solution concentration is 35
Baume degrees is then heated to 80 DEG C, adds strontium hydroxide and adjusts pH=7, insulated and stirred 0.5h, stops stirring, then stand
0.5h, with precipitated aluminium hydroxide.Then solution is separated by solid-liquid separation, to filtrate concentration produce pure six water strontium chlorides or
Anhydrous strontium chloride (is adjusted) using temperature.Solid phase (filter cake, main component are aluminium hydroxide) is washed using clear water, cleaning solution can
Hot water is substituted, dissolves crude product chlorination strontium crystal for this step (step 8), to be recycled.Filter cake can dissolve in step 6
Liquor alumini chloridi be recycled.
9, the pure strontium chloride that step 8 obtains, can be used directly, and can also continue on for producing spherical strontium carbonate.It is specific raw
There are two types of production methods.
Method one：
Six water strontium chlorides or anhydrous strontium chloride are dissolved, the concentration of strontium chloride solution is measured, the reality for calculating strontium chloride is dense
It spends (mol/L), under the conditions of 35~40 DEG C, in the strontium chloride solution, adds urea while stirring, control and urinated in solution
The concentration of element is 55~65%；After completely dissolution to urea, 20~25 DEG C are gradually cooled to, urea is made to generate spheroidal cementite.Again
It is warming up to 35~45 DEG C, in molar ratio, urea：Urase=1:1~2, urase is added when being slowly stirred, it is stirred to react 2~
5min.Remaining urase is filtered to remove using the methods of dialysis；It is spherical that mixed reaction solution, which is filtered, is dried to get crystal form
Strontium carbonate.
The possible cardinal principle of this method is：It is soft template using the spheroidal cementite of urea, under the action of urase, urine
Element crystallization is gradually decomposed into CO2And NH4, NH4Volatilization, CO2With Sr2+Reaction generates SrCO3, gradually replace original urea knot
Crystalline substance forms spherical SrCO3Crystallization；Extra urea total overall reaction under urase effect is volatilized.
Method two：
The concentration for measuring strontium chloride solution, calculates the actual concentrations (mol/L) of strontium chloride, under room temperature, described
In strontium chloride solution, in molar ratio, strontium chloride：Urea=1:2~5, urea is added while stirring；After completely dissolution to urea,
Room temperature is kept, then in molar ratio, urea：Urase=1:1~1.5, urase is added while stirring, is stirred to react 4~10min.Make
Remaining urase is filtered to remove with the methods of dialysis；Mixed reaction solution is filtered, the dry carbonic acid to get crystal form for spherical shape
Strontium.
The possible cardinal principle of this method is：The optimal reactive temperature of urase be 50~60 DEG C, in room temperature activity compared with
Low, urea decomposition rate is slower, slow release CO2, generation and the nucleation rate of carbonic acid strontium crystal are controlled, to control life
The carbonic acid strontium crystal of production is spherical.
To make those skilled in the art understand implementation method and technical effect of the invention in more detail, following tool is provided
Body embodiment and corresponding detection data.
Embodiment one：Parameter when final product is strontium chloride, strontium sulfate and liquor alumini chloridi is preferred
1, waste residue Initial Composition measures
The waste residue for randomly selecting a collection of thermit reduction preparation Preparation of Metallic Strontium production, carries out composition measurement to it, as a result (with
Machine samples the average result after 10 measurements) as shown in table 1.
1 waste residue component list of table
2, using 13 groups of the waste residue, every group of 1000g (is considered as every group and contains 614.6g SrCO3、 365g Al2O3), it puts
Enter in 10L container, step 1 according to the above method~8, prepares strontium chloride, strontium sulfate and aluminium chloride.Wherein, each group is other specific
Parameter is as shown in table 2.
The other design parameter of 2 each group of table
3, the crude product strontium chloride of above-mentioned each group preparation, the quality of strontium sulfate, liquor alumini chloridi and washing lotion are measured, as a result
As shown in table 3.It wherein, is the overall recovery for calculating strontium, after measuring the weight of anhydrous strontium chloride and strontium sulfate respectively, all
It is converted into the amount of strontium carbonate respectively, and embodies the total amount of strontium after being added；It is molten measuring aluminium chloride for the overall recovery for calculating aluminium
Liquid (obtained by step 6) and washing lotion (step.Gained) in after chlorination aluminium content respectively, be all converted into aluminium oxide and phase
Add, to embody the total amount of aluminium, in terms of aluminium oxide.The total amount after being converted into strontium carbonate and aluminium oxide is only embodied in table 3.
The measurement of each group result of table 3
It can be seen from the results above that using the parameter processing waste residue of group 3, utilization efficiency highest.
Embodiment two：Parameter when preparing strontium carbonate using step 9 method one is preferred
1, the strontium chloride prepared using one group 3 of embodiment is raw material, prepares spherical carbonic acid by 9 method one of above-mentioned steps
Strontium, the other design parameter of each group are as shown in table 6.
The other specific response parameter of 6 each group of table
| Group | Urea concentration | Urea：Urase | Stir duration |
| 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, the other strontium carbonate crystal form of above-mentioned each group, partial size are observed using Electronic Speculum；Measure the purity of strontium carbonate in each group, knot
Fruit is as shown in table 7.
Each group result of table 7 is shown
| Group | Strontium carbonate crystal form | Strontium carbonate partial size | Strontium carbonate purity |
| Group 1 | It is spherical | 1 μm of < | 99.4% |
| Group 2 | It is spherical | 1 μm of < | 99.6% |
| Group 3 | It is spherical | 1 μm of < | 99.4% |
| Group 4 | It is spherical | 1 μm of < | 99.5% |
| Group 5 | It is spherical | 1 μm of < | 99.3% |
| Group 6 | It is spherical | 1 μm of < | 99.4% |
| Group 7 | Ellipsoid | 1 μm of > | 99.2% |
Embodiment three：Parameter when preparing strontium carbonate using step 9 method two is preferred
1, selecting with the strontium chloride of one group 3 of embodiment preparation is raw material, prepares spherical carbon by 9 method two of above-mentioned steps
Sour strontium, the other design parameter of each group are as shown in table 8.Wherein, because of urea in the present embodiment：Urase=1:1, in institute's following table only
Embody the relationship of strontium chloride and urea.
The other specific response parameter of 8 each group of table
| Group | Strontium chloride：Urea | Stir duration |
| 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, the other strontium carbonate crystal form of above-mentioned each group, partial size are observed using Electronic Speculum；Measure the purity of strontium carbonate in each group, knot
Fruit is as shown in table 9.
The 9 specific response parameter of each group of table
| Group | Strontium carbonate crystal form | Strontium carbonate partial size | Strontium carbonate purity |
| Group 1 | It is spherical | 1 μm of < | 99.4% |
| Group 2 | It is spherical | 1 μm of < | 99.7% |
| Group 3 | It is spherical | 1 μm of < | 99.2% |
| Group 4 | It is spherical | 1 μm of < | 99.6% |
| Group 5 | It is spherical | 1 μm of < | 99.5% |
| Group 6 | It is spherical | 1μm | 99.6% |
| Group 7 | Ellipsoid | 1 μm of > | 99.6% |
Claims (10)
1. a kind of method that comprehensive utilization produces strontium waste residue, it is characterised in that：The method for producing strontium is thermit reduction, the side
Method the specific steps are：
(1) it cures：In producing strontium waste residue, the water that weight is waste residue weight 30~60% is added, is subsequently placed with 5~10 days, obtains ripe
Waste residue after change；
(2) it is acidified：In waste residue after curing be added concentration be 30~35% hydrochloric acid, mix, obtain free acid content be 4~
6% waste residue mixed solution；
(3) it crystallizes：It adjusts waste residue mixed solution temperature and is lower than 35 DEG C, be separated by solid-liquid separation, obtain crude product chlorination strontium crystal, strontium chloride and chlorine
Change aluminium mixed solution；
(4) it precipitates：1.05 times of strontium chloride stoichiometric relationship of concentration is added in the strontium chloride and aluminium chloride mixed solution
For 25% sulfuric acid or sulfate liquor；It is separated by solid-liquid separation, obtains crude product strontium sulfate solid, liquor alumini chloridi；
(5) it purifies：Step (3) the crude product chlorination strontium crystal is redissolved in hot water, adjusting concentration is 30~40 Baume degrees, is risen
Temperature adjusts pH=7,0.3~0.6h of insulated and stirred to 75~90 DEG C, using strontium hydroxide, stands 0.3~0.6h, is separated by solid-liquid separation,
Filtrate is concentrated up to six water strontium chlorides or anhydrous strontium chloride.
(6) strontium carbonate is prepared：The six water strontium chloride or anhydrous strontium chloride are redissolved, obtains strontium chloride solution, 35~40 DEG C, described
Urea is added in strontium chloride solution while stirring, the concentration for controlling urea in solution is 55~65%；After completely dissolution to urea,
20~25 DEG C are gradually cooled to, after urea crystals, then is warming up to 35~45 DEG C, in molar ratio, urea：Urase=1:1~2,
Urase is added when being slowly stirred, and is stirred to react 2~5min；By mixed reaction solution filtering, drying to get required strontium carbonate.
2. the method that comprehensive utilization according to claim 1 produces strontium waste residue, it is characterised in that：Step (1) described amount of water
It is the 50% of waste residue weight.
3. the method that comprehensive utilization according to claim 1 produces strontium waste residue, it is characterised in that：Step (2) described hydrochloric acid is dense
Degree is 31%, and the free acid content is 5%.
4. the method that comprehensive utilization according to claim 1 produces strontium waste residue, it is characterised in that：Step (5) described concentration is
35 Baume degrees, the warming temperature to 80 DEG C, when insulated and stirred a length of 0.5h, when standing a length of 0.5h.
5. the method that comprehensive utilization according to claim 1 produces strontium waste residue, it is characterised in that：Step (6) described urea is dense
Degree is：60%；The urea：Urase=1:1；It is described a length of when being stirred to react：3min.
6. a kind of method that comprehensive utilization produces strontium waste residue, it is characterised in that：The production strontium is aluminothermic reduction reduction method, the method
The specific steps are：
(1) it cures：In producing strontium waste residue, the water that weight is waste residue weight 30~60% is added, is subsequently placed with 5~10 days, obtains ripe
Waste residue after change；
(2) it is acidified：In waste residue after curing be added concentration be 30~35% hydrochloric acid, mix, obtain free acid content be 4~
6% waste residue mixed solution；
(3) it crystallizes：It adjusts waste residue mixed solution temperature and is lower than 35 DEG C, be separated by solid-liquid separation, obtain crude product chlorination strontium crystal, strontium chloride and chlorine
Change aluminium mixed solution；
(4) it precipitates：1.05 times of strontium chloride stoichiometric relationship of concentration is added in the strontium chloride and aluminium chloride mixed solution
For 25% sulfuric acid or sulfate liquor；It is separated by solid-liquid separation, obtains crude product strontium sulfate solid, liquor alumini chloridi；
(5) it purifies：Step (3) the crude product chlorination strontium crystal is redissolved in hot water, adjusting concentration is 30~40 Baume degrees, is risen
Temperature adjusts pH=7,0.3~0.6h of insulated and stirred to 75~90 DEG C, using strontium hydroxide, stands 0.3~0.6h, is separated by solid-liquid separation,
Filtrate is concentrated up to six water strontium chlorides or anhydrous strontium chloride.
(6) strontium carbonate is prepared：The six water strontium chloride or anhydrous strontium chloride are redissolved, strontium chloride solution is obtained, at room temperature, in the chlorine
Change in strontium solution, in molar ratio, strontium chloride：Urea=1:2~5, urea is added while stirring；After completely dissolution to urea, it protects
Room temperature is held, then in molar ratio, urea：Urase=1:1~1.5, urase is added while stirring, is stirred to react 4~10min；It will mix
Reaction solution filtering, drying are closed to get required strontium carbonate.
7. the method that comprehensive utilization according to claim 6 produces strontium waste residue, it is characterised in that：Step (1) described amount of water
It is the 50% of waste residue weight.
8. the method that comprehensive utilization according to claim 6 produces strontium waste residue, it is characterised in that：Step (2) described hydrochloric acid is dense
Degree is 31%, and the free acid content is 5%.
9. the method that comprehensive utilization according to claim 6 produces strontium waste residue, it is characterised in that：Step (5) described concentration is
35 Baume degrees, the warming temperature to 80 DEG C, when insulated and stirred a length of 0.5h, when standing a length of 0.5h.
10. the method that comprehensive utilization according to claim 6 produces strontium waste residue, it is characterised in that：Step (6) described chlorination
Strontium：Urea=1:3；The urea：Urase=1:1；The 4min a length of when being stirred to react.
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| CN1609242A (en) * | 2004-02-03 | 2005-04-27 | 祁顺东 | Process for recovering strontium and aluminium from metal strontium residue |
| JP2009001475A (en) * | 2006-12-14 | 2009-01-08 | Sony Corp | Method for manufacturing strontium carbonate fine particle |
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| CN1609242A (en) * | 2004-02-03 | 2005-04-27 | 祁顺东 | Process for recovering strontium and aluminium from metal strontium residue |
| JP2009001475A (en) * | 2006-12-14 | 2009-01-08 | Sony Corp | Method for manufacturing strontium carbonate fine particle |
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