CN101229923A - Novel technique for producing large-particle high-grade soft leonite from potassium mixed salt by hot crystallization - Google Patents
Novel technique for producing large-particle high-grade soft leonite from potassium mixed salt by hot crystallization Download PDFInfo
- Publication number
- CN101229923A CN101229923A CNA2007100342920A CN200710034292A CN101229923A CN 101229923 A CN101229923 A CN 101229923A CN A2007100342920 A CNA2007100342920 A CN A2007100342920A CN 200710034292 A CN200710034292 A CN 200710034292A CN 101229923 A CN101229923 A CN 101229923A
- Authority
- CN
- China
- Prior art keywords
- schoenite
- salt
- sodium
- potassium
- mixed salt
- 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.)
- Pending
Links
Images
Abstract
The invention relates to method for extracting schoenite of high purity from the raw material such as potassium magnesium sulfate subtype brine, sea salt bitter brine, lake salt, well salt brine, belonging to the salt chemistry industry, characterized in that potassium mixed with salt is wetly ground and crushed to remove the free magnesium chloride; potassium compound is discomposed by adding water; the magnesium chloride is dissolved and removed to obtain crude schoenite with sodium; the thermosol recrystallizing method is adopted to obtain large particle schoenite and at the same time separate sodium salt under the condition that compound growth substance and denaturant are added,. The novel process adopts the crystallization method to remove magnesium chloride in liquid phase and sieve the sodium salt in solid phase; developing a new conception for preparing the schoenite from the potassium mixed salt. Recycling rate of the potassium is higher than that of all kings of methods known at present and product grade can reach 99.5 percent with the best product quality in the world; the prepared large particle schoenite with high purity can be used as the raw material for producing potassium sulfate with high purity.
Description
One, technical field
The invention belongs to the salt chemical engineering technical field, relate in particular to the method that potassium mixed salt that a kind of utilization contains the potassium magnesium sulfate bittern system of shining is produced the schoenite of higher-grade, big particle diameter.Be applicable to from containing raw materials such as potassium magnesium sulfate bittern, bittern, lake salt and well salt bittern and produce the high purity schoenite.
Two, background technology
From containing potassium magnesium sulfate bittern through the system of shining resulting potassium mixed salt, the mainly mixture of forming by multi mineral such as sylvite, carnallitite, kainite, schoenite, halite, epsom salts.
The method of producing schoenite from sulfate type salt lake bittern is more, but realizes the industrialized following a few class that mainly contains: (1) flotation process: with flotation reagent sodium-chlor is removed, or schoenite is selected, the water-soluble magnesium chloride that removes; (2) machinery takes off sodium: utilize the sodium-chlor principle bigger than newly-generated schoenite particle, remove most of sodium-chlor with method of sieving, water-soluble magnesium chloride and the sodium-chlor of removing.(3) saltpan method: at the water of salt Tanaka increasing amount with the dissolving of potassium mixed salt, crystallisation by cooling at low temperatures again.
But existing all resulting schoenites of method all are the products of finely powdered, and granularity is generally 0.1mm. grade generally is no more than 98%, and impurity is more.The disposable rate of recovery of potassium is between 40 to 60%.
Three, summary of the invention
This technology provides a kind of production granularity big, of high grade, the method for the measured schoenite product of matter, and technology is simple.The single rate of recovery of potassium is between 60 to 80%.
The present invention realizes as follows:
1. wet-milling workshop section: the raw material potassium ores, by weight composed as follows: K
+5～11%, Mg
2+5～8.5%, Na
+5～8%, SO
4 2-15～25%, C1
-25～30%, H
2O 25～40%, and the raw material potassium ores at first carries out wet-milling with the mother liquor that comes self-watering to transform workshop section, is crushed to certain order number, below 40 orders (or 60 orders or 80 orders or 100 orders), solid-liquid separation, the beach, field of desalting after the dense sedimentation of the unnecessary mother liquor of this workshop section is shone and is reclaimed, Gu material is washing potassium mixed salt.In the wet-milling process, free magnesium chloride is dissolved in liquid phase, the mother liquor sylvite and separates out in the potassium mixed salt raw ore, and the rate of recovery of potassium was about 110% during this workshop section expected admittedly, and the grade of potassium generally can rise more than 2 percentage points.2. add water and transform workshop section: the solid material after the drying adds the sodium salt washing water from the screening washing room under stirring state, other adds part hot water, total amount of water is in 10～50% of raw ore amount, and temperature is controlled at 20～50 ℃, guarantees the certain reaction time, make in the potassium mixed salt compound decomposition such as carnallitite, kainite complete, centrifugal solid-liquid separates, the mother liquor grinder section of drying, and solid material is the thick schoenite that contains sodium, contain magnesium chloride below 1.5%, sodium chloride-containing is 20～30%.3. thermosol workshop section: the thick schoenite that will contain sodium mixes with the crystallisation by cooling circulating mother liquor, carry out the thermosol recrystallization, the mother liquor amount is 0.5～2 times of thick schoenite, is heated to 75～90 ℃, insolubles is a sodium salt, merges with sodium salt slip under the sieve behind the crystallisation by cooling and handles.4. cool off workshop section: hot mother liquor is joined in the cooling crystallizer of specially made structure, add compound growth substance and denaturing agent, sodium-chlor is not grown up, schoenite can be grown up fast, cools, and controlled temperature is low more good more, and crystallizer is by the certain flow blowing.5. sieve washing room: the ore pulp behind the crystallisation by cooling sieves with the sieve of certain order number (as 20 orders), and screen overflow is a schoenite, and particle diameter is generally greater than 3mm, and butt grade 99% is dried and is product; Sieve is the sodium salt slip down, and it is dense that the sodium salt slip after dissolving with thermosol merges the back, and clear mother liquor returns again thermosol and dissolves thick schoenite, dense slip adds an amount of water washing, and centrifugal or sedimentation solid-liquid separation is Gu major ingredient is a sodium-chlor in the material, discard, washing water remove to add water and transform workshop section.
The technological core of this technology is to add water magnesium chloride is discharged with liquid phase, and in the crystallisation by cooling process, add compound growth substance, sodium chloride crystal is not grown up, the schoenite crystal can be grown up fast, when guaranteeing that residence time of material is more than 45 minutes, can obtain the above macrobead schoenite crystal of particle diameter 3mm, the longest macrocrystal that obtains 10mm.Final by method of sieving, be easy to macrobead schoenite crystal is separated with tiny sodium salt.
Existing some other technology is to adopt flotation process or add the water washing method to remove sodium-chlor, because sodium salt is to remove with solid phase form in this technology, the single rate of recovery of this technology potassium is higher, different according to the height of potassium mixed salt grade and quality, adopt certain working method, from potassium mixed salt meter, the single rate of recovery of potassium is up to more than 85% between 60 to 80%.And add various denaturing agents simultaneously, can obtain difform schoenite product, as oblique tetragonal body, square, long column shape, short cylinder, rectangular laminar, water chestnut side's slab-like or the like.
This Technology is applicable to that also bittern, lake salt and well salt bittern etc. produce high purity schoenite production process.All compositions belong to K
+, Na
+, Mg
2+∥ SO
4 2-, Cl
-H
2Five yuan of salt-water systems of O, centre or the finished product are schoenite, all can use present technique, especially adopt method of evaporation to produce schoenite in the bittern chemical industry, more can obtain high-quality schoenite, thereby further obtain high-purity sulphuric acid potassium.Used various growth substances, activator, inhibitor and denaturing agent is by the development and production of Changsha Yuhua District positizing Chemical Industry Science Co., Ltd.
Laboratory of the present invention lab scale has been finished 3000 tons of pilot scales of annual output since in February, 2002 from containing the thick schoenite production of the low magnesium of sodium macrobead high purity schoenite.And to have finished with the high-purity big particle schoenite be raw material, produces the pilot scale of 500 ton of 99.5% higher-grade vitriolate of tartar per year.
Four, description of drawings
Figure of description is that the present invention produces macrobead higher-grade schoenite technical process schematic diagram from the potassium mixed salt.
Five, embodiment:
The potassium mixed salt 1000g that certain salt lake brine shines system amounts to sodium chloride-containing 16%, magnesium chloride 12%, and sal epsom 8%, schoenite 32%, water 30%, total mass component are 98%.Add and to be crushed to below 80 orders after washing mother liquor that last time, reaction process obtained is sized mixing, solid-liquid separation, unnecessary mother liquor discards, and solid material washs to amount in the potassium mixed salt and contains magnesium chloride 7%; In solid material, add the sodium salt washing water, and add a certain amount of hot water, stir certain hour, solid-liquid separation, mother liquor makes to pulverize next time the raw material usefulness of sizing mixing, and solid material is the thick schoenite that contains sodium 20%; Thick schoenite mixes with the crystallisation by cooling circulating mother liquor, be heated to 75～90 ℃, insolubles is a sodium salt, tipping is with solid-liquid separation, add compound growth substance 30g in hot mother liquor, cooling is cooled to 20 ℃ naturally, with 20 mesh sieve slip is sieved, macrobead expects to dry with whizzer admittedly on the sieve, promptly obtains consisting of 96% wet schoenite product 213g; Minus mesh slurry solid-liquid separation, liquid is made next thermosol circulating mother liquor usefulness, and insolubles merges when solid and thermosol, and with a spot of water agitator treating, solid-liquid separation, liquid scrubbing water gives over to produce next time and adds water conversion usefulness, and solid is a sodium salt.The rate of recovery of this experiment potassium is 64%.
Claims (10)
1. a thermosol crystallization process is produced macrobead higher-grade schoenite novel process from the potassium mixed salt, it is characterized in that may further comprise the steps:
1. wet-milling workshop section: the raw material potassium ores at first carries out wet-milling with mother liquor from thermal conversion workshop section, is crushed to certain order number, below 40 orders (or 60 orders or 80 orders or 100 orders), and solid-liquid separation, the beach, field of desalting after the dense sedimentation of the unnecessary mother liquor of this workshop section is shone and is reclaimed.2. add water and transform workshop section: the solid material after the drying adds the sodium salt washing water from the screening washing room under stirring state, other adds part hot water, total amount of water is in 10～50% of raw ore amount, temperature is controlled at 20～50 ℃, guarantee the certain reaction time, make in the potassium mixed salt compound decomposition such as carnallitite, kainite complete, centrifugal solid-liquid separates, the mother liquor grinder section of drying is Gu material is for containing the thick schoenite of sodium.3. thermosol workshop section: the thick schoenite that will contain sodium mixes with the crystallisation by cooling circulating mother liquor, carry out the thermosol recrystallization, the mother liquor amount is 0.5～2 times of thick schoenite, is heated to 75～90 ℃, insolubles is sodium salt and silt impurity, merges with sodium salt slip under the sieve behind the crystallisation by cooling and handles.4. cool off workshop section: hot mother liquor is joined in the cooling crystallizer of specially made structure, add compound growth substance and denaturing agent, sodium-chlor is not grown up, schoenite can be grown up fast, cool, controlled temperature is low more good more, and the material crystallization residence time, crystallizer was by the certain flow blowing about one hour.5. sieve washing room: the ore pulp behind the crystallisation by cooling sieves with the sieve of certain order number (as 20 orders), and screen overflow is a schoenite, and particle diameter is generally greater than 3mm, and oven dry is product, butt grade 99%; Sieve is the sodium salt slip down, it is dense that insolubles sodium salt slip after dissolving with thermosol merges the back, clear mother liquor returns again thermosol and dissolves thick schoenite, dense slip adds an amount of water washing, centrifugal or settling process solid-liquid separation, Gu major ingredient is a sodium-chlor in the material, discards, washing water go to thermal conversion workshop section.
2. thermosol crystallization process according to claim 1 is produced macrobead higher-grade schoenite novel process from the potassium mixed salt, it is characterized in that the mother liquor that wet-milling workshop section adds to come self-watering to transform workshop section carries out wet-milling, being potassium mixed salt levigated process on the one hand, is that free magnesium chloride dissolves in the potassium mixed salt, sylvite is separated out the process of recovery in the mother liquor on the one hand.
3. thermosol crystallization process according to claim 1 is produced macrobead higher-grade schoenite novel process from the potassium mixed salt, it is characterized in that the potassium mixed salt after drying expected to stir down admittedly adding water, and always amount of water is in 10～50% of raw ore amount, 20～50 ℃ of temperature.Guarantee the certain reaction time, make in the potassium mixed salt compound decomposition such as carnallitite, kainite complete, obtain containing the thick schoenite of sodium behind the centrifuge dripping.
4. produce macrobead higher-grade schoenite novel process according to the described thermosol crystallization process of claim 1 from the potassium mixed salt, it is characterized in that the thick schoenite that will contain sodium mixes with the cold crystallization circulating mother liquor, the mother liquor amount is 0.5～2 times of thick schoenite, is heated to 75～90 ℃, isolates the insolubles sodium salt.
5. thermosol crystallization process according to claim 1 is produced macrobead higher-grade schoenite novel process from the potassium mixed salt, add a small amount of compound growth substance when it is characterized in that crystallisation by cooling, compound growth substance is made up of growth substance, crystal activator and inhibitor, sodium-chlor is not grown up, schoenite can be grown up fast, the material crystallization in crystallizer the residence time about one hour.
6. thermosol crystallization process according to claim 1 is produced macrobead higher-grade schoenite novel process from the potassium mixed salt, and the growth substance that is added when it is characterized in that crystallisation by cooling is one of following several materials: stearate, quaternary amine, alkylbenzene sulfonate, alkyl-sulphate, oleate, tween.
7. thermosol crystallization process according to claim 1 is produced macrobead higher-grade schoenite novel process from the potassium mixed salt, it is characterized in that adding in the crystallisation by cooling process crystal activator and inhibitor, the crystal activator is one of following several materials: tertiary sodium phosphate, Sodium phosphate dibasic, borax, salt of wormwood, pyrosulfite, dimethylbenzene etc., inhibitor is one of following several materials: hydrochloric acid stearylamine, alkylthio carbonate, sapn, Fatty Alcohol(C12-C14 and C12-C18).
8. thermosol crystallization process according to claim 1 is produced macrobead higher-grade schoenite novel process from the potassium mixed salt, it is characterized in that adding in the crystallisation by cooling process different denaturing agents, can obtain difform product, as short cylinder, rectangular sheet, water chestnut side's slab-like, long column shape, oblique tetragonal body etc.
9. thermosol crystallization process according to claim 1 is produced macrobead higher-grade schoenite novel process from the potassium mixed salt, it is characterized in that the ore pulp behind the crystallisation by cooling sieves with the sieve of certain order number, and screen overflow is a schoenite, and particle diameter is generally greater than 3mm; Sieve is the sodium salt slip down, and solid-liquid separation Gu major ingredient is a sodium-chlor in the material, discards.
10. thermosol crystallization process according to claim 1 is produced macrobead higher-grade schoenite novel process from the potassium mixed salt, it is characterized in that in entire reaction course, magnesium chloride is discharged with liquid phase, sodium salt can exist with solid phase form, not influencing the schoenite crystalline grows up, because the sodium salt particle diameter is little more than the product schoenite, be easy to separated going out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100342920A CN101229923A (en) | 2007-01-22 | 2007-01-22 | Novel technique for producing large-particle high-grade soft leonite from potassium mixed salt by hot crystallization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100342920A CN101229923A (en) | 2007-01-22 | 2007-01-22 | Novel technique for producing large-particle high-grade soft leonite from potassium mixed salt by hot crystallization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101229923A true CN101229923A (en) | 2008-07-30 |
Family
ID=39896806
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100342920A Pending CN101229923A (en) | 2007-01-22 | 2007-01-22 | Novel technique for producing large-particle high-grade soft leonite from potassium mixed salt by hot crystallization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101229923A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253685A (en) * | 2013-03-04 | 2013-08-21 | 云南省化工研究院 | Method for producing industrial potassium chloride through hot melting crystallization of underground embedded solid potassium salt mine |
| CN103420401A (en) * | 2013-07-10 | 2013-12-04 | 河北工业大学 | Method for preparing large-particle picromerite |
| CN104692420A (en) * | 2015-03-26 | 2015-06-10 | 茫崖兴元钾肥有限责任公司 | Potassium sulphate preparing method through thermal melting, refrigeration and double decomposition crystallization method |
| CN107324849A (en) * | 2017-08-31 | 2017-11-07 | 化工部长沙设计研究院 | A kind of method for preparing potash magnesium sulphate fertilizer |
| CN107382381A (en) * | 2017-08-31 | 2017-11-24 | 化工部长沙设计研究院 | A kind of production technology of high-quality potash magnesium sulphate fertilizer |
| CN107963914A (en) * | 2017-11-10 | 2018-04-27 | 国投新疆罗布泊钾盐有限责任公司 | A kind of method that pyrolytic conversion legal system takes top grade high-grade potassic-magnesian fertilizer |
| CN108323745A (en) * | 2018-03-20 | 2018-07-27 | 天津长芦汉沽盐场有限责任公司 | A kind of refined crushing washing salt production method of the reparing process containing crystal form |
| CN109052432A (en) * | 2018-11-07 | 2018-12-21 | 河北工业大学 | The method for preparing picromerite with salt-mixture |
| CN109415218A (en) * | 2016-06-24 | 2019-03-01 | 雅拉达洛尔有限公司 | The method that rock salt is reduced in potassium sulfate is prepared from phosphate-containing ore at a high ambient temperature |
| CN109574043A (en) * | 2019-02-11 | 2019-04-05 | 青海盐湖工业股份有限公司 | A kind of food grade sodium chloride and its production method |
| CN112047364A (en) * | 2020-09-22 | 2020-12-08 | 青海省柴达木综合地质矿产勘查院 | Method for preparing picromerite from magnesium sulfate subtype brine |
-
2007
- 2007-01-22 CN CNA2007100342920A patent/CN101229923A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103253685A (en) * | 2013-03-04 | 2013-08-21 | 云南省化工研究院 | Method for producing industrial potassium chloride through hot melting crystallization of underground embedded solid potassium salt mine |
| CN103420401A (en) * | 2013-07-10 | 2013-12-04 | 河北工业大学 | Method for preparing large-particle picromerite |
| CN104692420A (en) * | 2015-03-26 | 2015-06-10 | 茫崖兴元钾肥有限责任公司 | Potassium sulphate preparing method through thermal melting, refrigeration and double decomposition crystallization method |
| CN109415218A (en) * | 2016-06-24 | 2019-03-01 | 雅拉达洛尔有限公司 | The method that rock salt is reduced in potassium sulfate is prepared from phosphate-containing ore at a high ambient temperature |
| CN107324849B (en) * | 2017-08-31 | 2020-09-15 | 化工部长沙设计研究院 | Method for preparing potash magnesium sulphate fertilizer |
| CN107324849A (en) * | 2017-08-31 | 2017-11-07 | 化工部长沙设计研究院 | A kind of method for preparing potash magnesium sulphate fertilizer |
| CN107382381A (en) * | 2017-08-31 | 2017-11-24 | 化工部长沙设计研究院 | A kind of production technology of high-quality potash magnesium sulphate fertilizer |
| CN107382381B (en) * | 2017-08-31 | 2020-09-15 | 化工部长沙设计研究院 | Production process of high-quality potassium magnesium sulfate fertilizer |
| CN107963914A (en) * | 2017-11-10 | 2018-04-27 | 国投新疆罗布泊钾盐有限责任公司 | A kind of method that pyrolytic conversion legal system takes top grade high-grade potassic-magnesian fertilizer |
| CN108323745A (en) * | 2018-03-20 | 2018-07-27 | 天津长芦汉沽盐场有限责任公司 | A kind of refined crushing washing salt production method of the reparing process containing crystal form |
| CN109052432A (en) * | 2018-11-07 | 2018-12-21 | 河北工业大学 | The method for preparing picromerite with salt-mixture |
| CN109574043A (en) * | 2019-02-11 | 2019-04-05 | 青海盐湖工业股份有限公司 | A kind of food grade sodium chloride and its production method |
| CN112047364A (en) * | 2020-09-22 | 2020-12-08 | 青海省柴达木综合地质矿产勘查院 | Method for preparing picromerite from magnesium sulfate subtype brine |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101229923A (en) | Novel technique for producing large-particle high-grade soft leonite from potassium mixed salt by hot crystallization | |
| JP6687608B2 (en) | Collection method | |
| CN104532339B (en) | A kind of method that calcium sulfate crystal whiskers are prepared using low grade natural gypsum or gypsum mine | |
| CN106185994B (en) | A kind of production technology that high-quality potassium chloride is produced using carnallite | |
| CN105271347A (en) | Method for preparing high-purity barium salt by using witherite-barytocalcite industrial waste residues | |
| CN101993256A (en) | Method for preparing agricultural potassium sulfate from potassium-rich rock | |
| CN108975348A (en) | A kind of method of production of 4 A molecular sifter | |
| US4129642A (en) | Process for the production of potassium sulfate | |
| CN106335910B (en) | A kind of preparation method of potassium sulfate and ammonium chloride | |
| CN100515946C (en) | Technique producing potassium muriate by using potassium mixed salt and aged halogen produced by vitriolate type bittern | |
| AU2003300706B2 (en) | Simultaneous recovery of potassium chloride and KCl enriched edible salt | |
| CN1094466C (en) | Method of extracting potassium chloride from mixed ore of sylvine and carnallite | |
| CN105366701B (en) | A kind of technique of continuous production cesium rubidium alum and potassium alum | |
| CN113751190A (en) | Method and system for preparing potassium chloride from carnallite raw ore | |
| US6464736B1 (en) | Recrystallization process | |
| CN108658097A (en) | A method of utilizing carnallite preparing potassium chloride | |
| CN1171794C (en) | Preparation method of potassium sulfate with sulfate-type salt lake bittern containing potassium salt | |
| CN100402426C (en) | Process of preparing refined salt with sodium-containing bittern | |
| CN102432042B (en) | Method for directly producing potassium nitrate end product from complex nitrate bittern | |
| US20210180153A1 (en) | Process and method for refining lithium carbonate starting from an impure lithium chloride solution | |
| CN102336418A (en) | Method for extracting potassium salt from potassium-ion-containing brine | |
| CN108147433B (en) | A kind of low-sulfur potassium mixed salt proposes potassium processing technology | |
| EP0742175B1 (en) | Process for production of dense soda ash from soda ash fines | |
| RU2566414C1 (en) | Method of producing potassium sulphate from polyhalite ore | |
| RU2795224C1 (en) | Process and method for lithium carbonate purification based on a lithium chloride solution with impurities |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Open date: 20080730 |