CN100519419C - Method for preparing strontium chloride - Google Patents
Method for preparing strontium chloride Download PDFInfo
- Publication number
- CN100519419C CN100519419C CN 200710018050 CN200710018050A CN100519419C CN 100519419 C CN100519419 C CN 100519419C CN 200710018050 CN200710018050 CN 200710018050 CN 200710018050 A CN200710018050 A CN 200710018050A CN 100519419 C CN100519419 C CN 100519419C
- Authority
- CN
- China
- Prior art keywords
- strontium
- chloride
- solution
- magnesium
- coal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention offers a new method of strontium chloride preparation, the method uses breeze to deoxidize celestite which is dipped into hot water and get solution of strontium sulfide, put sulfureted hydrogen gas into solution of strontium sulfide to make solution of strontium hydrosulphide which reacts with magnesium chloride to get products of strontium chloride and magnesium hydrate, sulfureted hydrogen gas formed in the reaction is used to make strontium hydrosulphide, thus, it circulates like these steps above. The flow of the invention id short, it no need to consume chemical raw material, the raw material used in this invention is simple to get and is cheap, the quality of the product is high; it can get byproduct of magnesium hydrate at the same time and avoid pollution of sulfureted hydrogen, therefore, it has good economical and social benefits, and it is especially suitable for area where the sources of magnesium chloride is abundant.
Description
Technical field
The invention belongs to chemical field, relate to a kind of preparation method of strontium chloride, the SrS solution and the salt lake magnesium chloride that are characterized in adopting carbon reduction method to prepare and obtain in the Strontium carbonate powder technology prepare strontium chloride as reactant.
Background technology
Strontium chloride is one of main strontium product salt, is mainly used in the preparation raw material of producing high-purity strontium carbonate, magneticsubstance, electrolytic metal strontium and other strontium salt, also is applied to produce the fusing assistant of electrolytic metal sodium and the catalyzer of organic synthesis etc.; And making fireworks, producing aspects such as toothpaste, pigment application is also arranged.Along with progress of science and technology, the purposes of strontium chloride will be expanded more, and the market requirement increases fast.The production of Strontium carbonate powder is mainly with hydrochloric acid and Strontium carbonate powder prepared in reaction at present, and wherein the source of Strontium carbonate powder is the waste residue that industrial magnesium strontium, strontianite or carbon reduction method prepare Strontium carbonate powder.Because hydrochloric acid has very strong corrodibility, very high to the material requirement of production unit, this just brings very big difficulty to its production.
" sea lake salt and chemical industry " the 3rd volume the 1st interim page 4 " applied research of flocculation agent in producing strontium chloride-magnesium hydroxide " has been reported a kind of method for preparing strontium chloride.This method is by strontium hydroxide and salt lake magnesium chloride generation replacement(metathesis)reaction, generates magnesium hydrate precipitate and strontium chloride solution.Its emphasis has carried out adding flocculation agent to the strainability of magnesium hydroxide and the research of quality product influence." sea lake salt and chemical industry " the 33rd volume the 5th interim the 14th page " magnesium chloride-Strontium carbonate powder is produced strontium chloride and magnesium hydroxide technical study " reported the similar method for preparing strontium chloride, the main difference point of this method is, strontium hydroxide is to prepare strontium oxide by the calcining Strontium carbonate powder, obtain strontium hydroxide solution or crystal by the hot water leaching then, prepare strontium chloride and magnesium hydroxide with magnesium chloride generation replacement(metathesis)reaction again.
In above-mentioned first piece of report, the source of not pointing out strontium hydroxide, in second piece of report, strontium hydroxide obtains by the calcining Strontium carbonate powder, and Strontium carbonate powder can transform the thick Strontium carbonate powder that celestite ore obtains from industrial magnesium strontium or metathesis.Strontium hydroxide can also be analysed method by the molten alkali of Strontium carbonate powder acid and be obtained, and promptly the thick Strontium carbonate powder that industrial magnesium strontium or double decomposition are obtained adds caustic soda again and separates out strontium hydroxide by adding strong acid solution.All there is the industrial chemicals that preparation flow is long, energy consumption is high, needs consumption is a large amount of in these methods that prepare strontium hydroxide, and this can make production cost increase undoubtedly, and economic benefit descends, and practicality also descends.
Summary of the invention
The purpose of this invention is to provide a kind of strontium sulfide (SrS) solution that adopts carbon reduction method to prepare to obtain in the Strontium carbonate powder technology and salt lake magnesium chloride prepare strontium chloride as reactant method.
The present invention prepares the method for strontium chloride, comprises following processing step:
1. the lazurite breeze is mixed with the part by weight of reduction coal dust with 1:0.5～1:5, obtained grey black in 0.5～12 hour, again grey black water counter-current extraction is obtained strontium sulfide solution at 900～1300 ℃ of roasting temperatures.The carbon reduction lazurite generally adopts the rotary kiln continuous production, and wherein to select Strontium Sulphate content for use be 55～100% lazurite breeze to lazurite; Also raw coal is for can select coking coal, non-caking coal, lean coal, bottle coal, rich coal for use, and long-flame coal, hard coal etc. are any; The concentration of the strontium sulfide solution of leaching is controlled at 50～150g/L;
2. get sulphur hydrogenation strontium solution to the logical hydrogen sulfide of strontium sulfide solution;
3. add magnesium chloride to sulphur hydrogenation strontium solution, reacted 0.5～2 hour down, obtain containing the slip of magnesium hydrate precipitate and strontium chloride solution, and emit hydrogen sulfide at 80～90 ℃; Wherein magnesium chloride is that the salt lake magnesium chloride gets by the ordinary method purification, and its add-on is 0.85～1.15 times of strontium sulfide molar weight;
4. slip is obtained magnesium hydrate precipitate and strontium chloride solution by solid-liquid separation, strontium chloride solution is the strontium chloride product through evaporation, crystallization, separation, drying; Magnesium hydroxide is byproduct through washing, oven dry; The hydrogen sulfide that generates return step 2. with strontium sulfide solution prepared in reaction sulphur hydrogenation strontium, so circulation is carried out, and has both solved the pollution problem of hydrogen sulfide, also makes this process to carry out smoothly.
It is to obtain sulphur magnesium hydride and strontium chloride by sulphur hydrogenation strontium and magnesium chloride generation replacement(metathesis)reaction that method of the present invention prepares strontium chloride, and the sulphur magnesium hydride complete hydrolysis takes place in the aqueous solution obtains magnesium hydroxide and hydrogen sulfide, and the chemical reaction of this process comprises:
SrS+H
2S→Sr(HS)
2
Sr(HS)
2+MgCl
2→Mg(HS)
2+SrCl
2
Mg(HS)
2+2H
2O→Mg(OH)
2↓+2H
2S↑
Above-mentioned reaction gained strontium chloride solution is limpid transparent, and the evaporation concentration postcooling is separated out the strontium chloride crystal, filters and is drying to obtain white crystal hydration strontium chloride product at 80～100 ℃, and molecular formula is SrCl
26H
2O.Ca, Sr, Ba, Mg resultant adopt the EDTA titration measuring in the strontium chloride product, are indicator with the eriochrome black T, and Mg-EDTA solution is auxiliary; Ba in the strontium chloride product, Ca, Mg use aas determination respectively, and Fe content adopts spectrophotometric determination o-phenanthroline, SO
4Content adopts barium sulfate turbidimetry to measure, and water-insoluble adopts ordinary method to measure, and Pb content adopts the lead sulfide colorimetric method for determining, and pH value employing standard test paper is measured, and Na content adopts atomic absorption spectroscopy determination.Analytical results sees Table 1.
The contrast (%) of table 1 strontium chloride product chemical analysis results and standard
The result who measures from table 1 as can be seen, the every analysis indexes contrast of the strontium chloride crystalline of the present invention's preparation Q/JS j0101-2004 standard is qualified industrial strontium chloride product.
The magnesium hydrate precipitate crystallization that above-mentioned reaction generates is tiny, and settling velocity is very slow, filtration difficulty.Adopt flocculation agent can make magnesium hydroxide that cohesion takes place and with the clear phase-splitting of solution, adopt press filtration, vacuum filtration or centrifugation to be easy to make Solid-Liquid Separation.Flocculation agent is an organic polymer, and as starch, polyacrylamide etc., the consumption of flocculation agent is 0.5～50g/L.The magnesium hydroxide that filtration obtains is by the washing fixed number of 1～10 times of weight, and then 100～150 ℃ of oven dry are magnesium hydroxide products.It is indicator that MgO content in the magnesium hydroxide products adopts EBT, uses the EDTA titration measuring; CaO content calcium carboxylate indicator is used the EDTA titration measuring; Mg (OH)
2Middle Fe Determination on content adopts phenanthroline spectrophotometry (GB3049-1986), and Cl content adopts mercurimetry (GB/T 3051-2000), and Sr content adopts aas determination; Acid non-soluble substance, moisture, loss on ignition, screenings are measured according to a conventional method.Analytical results sees Table 2.
The contrast of table 2 magnesium hydroxide products chemical analysis results and standard (%)
The result who measures from table 2 as can be seen, every analysis indexes contrast HG/T 3607-2000 " industrial hydrogen magnesium oxide " chemical industry standard of byproduct magnesium hydroxide of the present invention reaches first grade.
The present invention compared with prior art has the following advantages:
1, the quality of the strontium chloride product of the present invention's preparation is good, and its every analysis indexes contrast Q/JS j0101-2004 standard is qualified industrial strontium chloride product.
2, the present invention's strontium sulfide (SrS) solution and salt lake magnesium chloride of adopting carbon reduction method to prepare to obtain in the Strontium carbonate powder technology prepares strontium chloride as reactant, do not use strontium hydroxide to produce strontium chloride as raw material or intermediate product, do not need hydrochloric acid to participate in turning over gushing yet, not only avoided using hydrochloric acid to the burn into of equipment but also need not prepare strontium hydroxide and make Production Flow Chart short, cost is minimized.
When 3, the present invention prepares strontium chloride, the strontium hydroxide product that by-product is high-quality.
4, the present invention is in the process of preparation strontium chloride, the hydrogen sulfide that generates turns back to the operation with strontium sulfide solution prepared in reaction sulphur hydrogenation strontium, so circulation is carried out, both solved the pollution problem of hydrogen sulfide, also make this process to carry out smoothly, reduce production cost, had good social benefit and economic benefit.
5, the magnesium chloride of the present invention's employing is that the salt lake magnesium chloride gets by the ordinary method purification, has made full use of salt lake resources, has effectively saved resource, has reduced cost.
Embodiment
Embodiment 1, be that 55～75% lazurite breeze mixes with the part by weight of reduction coal dust with 1:0.5～1:2.0 with Strontium Sulphate content, obtained grey black in 1.0～3.0 hours at 1100～1200 ℃ roasting temperatures, with the solid-liquid weight ratio is the water counter-current extraction 3 times of 1:1～1:5, obtain leaching liquid A, with soak slag a, use another part of leaching liquid A counter-current extraction grey black again, obtain leaching liquid B and soak slag b, leach the 3rd part of grey black once more with leaching liquid B and obtain leaching liquid C and soak slag c; Merge and soak slag a, b, c, stack for always soaking slag; Resulting leaching liquid C makes the leach liquor of strontium sulfide present yellow owing to generate many strontium sulfides with the strontium sulfide reaction in the water leaching process, so be commonly called as yellow water, adding its concentration of water management (in SrS) is 100g/L.
Get yellow water 500mL, logical H
2S gas under agitation slowly adds the MgCl of 170g through purifying to saturated
26H
2O (can be purified by ordinary method by the salt lake magnesium chloride and get), reaction system maintains 90 ℃, 1.5 hours reaction times.The hydrogen sulfide that produces in the reaction is used for the saturated yellow water in front and prepares sulphur hydrogenation strontium.After reaction finishes, in system, add the 2.0g polyacrylamide flocculant, magnesium hydroxide take place cohesion and with the solution layering; The filtration under diminished pressure magnesium hydroxide is used the 50mL water washing respectively 3 times, and oven dry is magnesium hydroxide products, and yield is 99.3%.Mother liquor is a clear solution, and heating evaporation to liquor capacity is 50mL, and crystallisation by cooling 100 ℃ of oven dry 3 hours, obtains crystallization strontium chloride product, and yield is 85.5%.Crystalline mother solution is incorporated next time in the filtrate evaporation into and is reclaimed strontium chloride, and total recovery is greater than 95%.Content of strontium in the magnesium hydroxide products (in Sr)≤0.05%, other index meet the requirement of HG/T 3607-2000 " industrial hydrogen magnesium oxide " chemical industry standard first grade.Mg content in the strontium chloride product (in Mg)≤0.10%, the requirement of other index accord with Q/JS j0101-2004 " industrial strontium chloride " company standard.
Embodiment 2, be that 55～70% lazurite breeze mixes with the part by weight of reduction coal dust with 1:0.5～1:2.0 with Strontium Sulphate content, obtained grey black in 1.0～3.0 hours at 1100～1200 ℃ roasting temperatures, with the solid-liquid weight ratio is the water counter-current extraction 3 times of 1:1～1:5, obtain leaching liquid, with soak slag, resulting leaching liquid makes the leach liquor of strontium sulfide present yellow, so be commonly called as yellow water owing to generate many strontium sulfides with the strontium sulfide reaction in the water leaching process.Adding its concentration of water management (in SrS) is 50g/L.
Get yellow water 500mL, logical H
2S gas under agitation slowly adds the MgCl of 90g through purifying to saturated
26H
2O (can be purified by ordinary method by the salt lake magnesium chloride and get), reaction system maintains 85 ℃, 1 hour reaction times.The hydrogen sulfide that produces in the reaction is used for the saturated yellow water in front and prepares sulphur hydrogenation strontium.After reaction finishes, in system, add the 2.0g polyacrylamide flocculant, magnesium hydroxide take place cohesion and with the solution layering; The filtration under diminished pressure magnesium hydroxide is used the 50mL water washing respectively 3 times, and oven dry is magnesium hydroxide products, and yield is 99.0%.Mother liquor is a clear solution, and heating evaporation to liquor capacity is 30mL, and crystallisation by cooling 100 ℃ of oven dry 3 hours, obtains crystallization strontium chloride product, and yield is 80.5%.Crystalline mother solution discards.Content of strontium in the magnesium hydroxide products (in Sr)≤0.05%, other index meet the requirement of HG/T 3607-2000 " industrial hydrogen magnesium oxide " chemical industry standard first grade.Mg content in the strontium chloride product (in Mg)≤0.10%, the requirement of other index accord with Q/JS j0101-2004 " industrial strontium chloride " company standard.
Embodiment 3, be that 55～70% lazurite breeze mixes with the part by weight of reduction coal dust with 1:0.5～1:2.0 with Strontium Sulphate content, obtained grey black in 1.0～3.0 hours at 1100～1200 ℃ roasting temperatures, with 1:1～1:3 water counter-current extraction 3 times, obtain leaching liquid A, with soak slag a, use another part of leaching liquid A counter-current extraction grey black again, obtain leaching liquid B and soak slag b, leach the 3rd part of grey black once more with leaching liquid B and obtain leaching liquid C and soak slag c; Merge and soak slag a, b, c, stack for always soaking slag; Resulting leaching liquid C makes the leach liquor of strontium sulfide present yellow, so be commonly called as yellow water owing to generate many strontium sulfides with the strontium sulfide reaction in the water leaching process.Add water and reconcile yellow water concentration (in SrS) at 150g/L.
Get yellow water 500mL, logical H
2S gas under agitation slowly adds the MgCl of 275g through purifying to saturated
26H
2O (can be purified by ordinary method by the salt lake magnesium chloride and get), reaction system maintains 80 ℃, 2 hours reaction times.The hydrogen sulfide that produces in the reaction is used for the saturated yellow water in front and prepares sulphur hydrogenation strontium.After reaction finishes, in system, add the 2.0g polyacrylamide flocculant, magnesium hydroxide take place cohesion and with the solution layering; The filtration under diminished pressure magnesium hydroxide is used the 50mL water washing respectively 3 times, and oven dry is magnesium hydroxide products, and yield is 99.0%.Mother liquor is a clear solution, and heating evaporation to liquor capacity is 30mL, and crystallisation by cooling 100 ℃ of oven dry 3 hours, obtains crystallization strontium chloride product, and yield is 80.5%.Crystalline mother solution discards.Content of strontium in the magnesium hydroxide products (in Sr)≤0.05%, other index meet the requirement of HG/T 3607-2000 " industrial hydrogen magnesium oxide " chemical industry standard first grade.Mg content in the strontium chloride product (in Mg)≤0.10%, the requirement of other index accord with Q/JS j0101-2004 " industrial strontium chloride " company standard.
Claims (2)
1, a kind of preparation method of strontium chloride comprises following processing step:
1. the lazurite breeze is mixed with the part by weight of reduction coal dust with 1:0.5～1:5, obtained grey black in 0.5～12 hour, again grey black water counter-current extraction is got strontium sulfide solution at 900～1300 ℃ roasting temperatures; Strontium Sulphate content is 55～100% in the described celestite ore; The strontium sulfide solution concentration that leaching obtains is controlled at 50～150g/L;
2. to the logical hydrogen sulfide of strontium sulfide solution, get sulphur hydrogenation strontium solution;
3. add magnesium chloride to sulphur hydrogenation strontium solution, reacted 0.5～2 hour down, obtain containing the slip of magnesium hydrate precipitate and strontium chloride solution, and emit hydrogen sulfide at 80～90 ℃; Wherein magnesium chloride is that the salt lake magnesium chloride gets by the ordinary method purification; The add-on of magnesium chloride is 0.85～1.15 times of strontium sulfide molar weight;
4. slip is obtained magnesium hydrate precipitate and strontium chloride solution by solid-liquid separation, strontium chloride solution is the strontium chloride product through evaporation, crystallization, separation, drying; Magnesium hydroxide is byproduct through washing, oven dry; Hydrogen sulfide return step 2. with the process of strontium sulfide solution prepared in reaction sulphur hydrogenation strontium.
2, the preparation method of strontium chloride according to claim 1, it is characterized in that: the described raw coal of going back is coking coal, non-caking coal, lean coal, bottle coal, rich coal, any in long-flame coal, the hard coal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710018050 CN100519419C (en) | 2007-05-24 | 2007-05-24 | Method for preparing strontium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710018050 CN100519419C (en) | 2007-05-24 | 2007-05-24 | Method for preparing strontium chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101070179A CN101070179A (en) | 2007-11-14 |
| CN100519419C true CN100519419C (en) | 2009-07-29 |
Family
ID=38897621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200710018050 Expired - Fee Related CN100519419C (en) | 2007-05-24 | 2007-05-24 | Method for preparing strontium chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100519419C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW201141789A (en) * | 2010-05-21 | 2011-12-01 | Guizhou Redstar Developing Co | Method for preparing strontium chloride hexahydrate |
| CN106745150B (en) * | 2017-03-06 | 2018-12-25 | 中国科学院青海盐湖研究所 | The preparation method of toothpaste strontium chloride |
| CN114541330A (en) * | 2021-12-16 | 2022-05-27 | 四川恒高新型建材有限公司 | Preparation and construction method of Roller Compacted Concrete (RCC) surface auxiliary anti-seepage coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104559A (en) * | 1987-06-26 | 1988-01-20 | 自贡市轻工业设计研究院 | The method of production of strontium salt using strontianite |
| CN1104608A (en) * | 1993-12-30 | 1995-07-05 | 梁义勋 | Production of strontium carbonate |
| CN1884086A (en) * | 2005-06-24 | 2006-12-27 | 朱作远 | Technology for combined production of barium chloride, potassium carbonate, potassium sulfate, and hydrochloric acid by potassium chloride method |
-
2007
- 2007-05-24 CN CN 200710018050 patent/CN100519419C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87104559A (en) * | 1987-06-26 | 1988-01-20 | 自贡市轻工业设计研究院 | The method of production of strontium salt using strontianite |
| CN1104608A (en) * | 1993-12-30 | 1995-07-05 | 梁义勋 | Production of strontium carbonate |
| CN1884086A (en) * | 2005-06-24 | 2006-12-27 | 朱作远 | Technology for combined production of barium chloride, potassium carbonate, potassium sulfate, and hydrochloric acid by potassium chloride method |
Non-Patent Citations (1)
| Title |
|---|
| 氯化镁-碳酸锶制取氯化锶和氢氧化镁工艺研究. 王树轩.海湖盐与化工，第33卷第5期. 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101070179A (en) | 2007-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101041450B (en) | Clean production technique for preparation of aluminium oxide and white carbon black by using high-alumina coal ash | |
| CN102225775A (en) | Process for producing magnesium hydroxide and calcium carbonate by dolomite conversion method | |
| CN104445311B (en) | Clean poly-generation preparation method for flyash with high-content silicon dioxide | |
| CA2756763C (en) | Process for simultaneous production of potassium sulphate, ammonium sulfate, magnesium hydroxide and/or magnesium oxide from kainite mixed salt and ammonia | |
| CN101327942A (en) | Method for preparing light magnesium carbonate and magnesium oxide from dolomite sea water bittern | |
| EP0038891B1 (en) | Process for the production of magnesium oxide from brine or bittern | |
| CN101760641A (en) | Technology for recovering magnesium from magnesium sulfate solution | |
| CN101863500A (en) | Method for producing alumina with aluminum-containing metallurgical material | |
| CN100560500C (en) | The preparation method of high-quality strontium carbonate | |
| CN114180603A (en) | Method for producing active magnesium oxide from waste residues of spices | |
| CN112093814A (en) | Method for preparing aluminum oxide by using aluminum ash without slagging | |
| CN102126734A (en) | Process for removing calcium from magnesite | |
| CN109384254A (en) | The method that crystal aluminum chloride and white carbon black are prepared by flyash or gangue | |
| CN103979584A (en) | Process for preparing light magnesium carbonate from boron mud | |
| CN100519419C (en) | Method for preparing strontium chloride | |
| CN114180604A (en) | Comprehensive utilization method of waste residues in spice production and synthetic ammonia purge gas | |
| CN101264904A (en) | Method for producing sodium bicarbonate and sulfur from mirabilite by wet process | |
| CN101215108A (en) | Method for producing series function magnesium chemical products by using magnesite | |
| CN102531016A (en) | Production method of food-grade calcium hydroxide | |
| CN101559965B (en) | Method for using medium and low-grade celestite ore to produce strontium carbonate under plateau conditions | |
| CN101857258A (en) | Method for preparing light calcium carbonate and magnesium hydroxide from magnesium tailings | |
| CN101760638B (en) | Method for recovering magnesium from magnesium sulfate solution | |
| CN100368298C (en) | Method for preparing strontium carbonate in high purity from celestite ore in mid and low grades | |
| CN102838141A (en) | Process for producing magnesium hydrate by removing silicon and aluminum from magnesite | |
| CN101760643B (en) | Improved method for recovering magnesium from magnesium sulfate solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090729 Termination date: 20120524 |