CN101172623A - Technique producing potassium muriate by using potassium mixed salt and aged halogen produced by vitriolate type bittern - Google Patents
Technique producing potassium muriate by using potassium mixed salt and aged halogen produced by vitriolate type bittern Download PDFInfo
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- CN101172623A CN101172623A CNA2007101344730A CN200710134473A CN101172623A CN 101172623 A CN101172623 A CN 101172623A CN A2007101344730 A CNA2007101344730 A CN A2007101344730A CN 200710134473 A CN200710134473 A CN 200710134473A CN 101172623 A CN101172623 A CN 101172623A
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- mixed salt
- potassium mixed
- potassium
- old halogen
- carnallitite
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Abstract
The invention discloses a process of producing sylvite by using sulfate brine and potassium chloride by aged brine. Sylvite and aged brine are converted under high temperature; clear solution can be achieved by the solid liquid separation of ground paste which is converted completely under high temperature; carnallite can be crystallized after the cooling of the clear solution; and the product, potassium chloride, is finally achieved by decomposing and washing the carnallite. The invention can adapt to all sylvite with different qualities made from sulfate brine, thereby solving the problem that domestic sylvite can not produce potassium chloride. The invention has the advantages of high material adaptability, high acquisition rate, mature equipment, less investment, low energy consumption, large controllable scope of parameter of production process, simple operation, no limit to production scale, etc., thereby providing a new way of producing potash fertilizer in our country.
Description
Technical field
The invention belongs to the inorganic chemicals industry field, particularly relating to a kind of potassium mixed salt with vitriolate type bittern production is the production technique that raw material is produced Repone K.
Background technology
At present, the main method of producing Repone K in the domestic inorganic chemicals industry is: with the bittern behind the production sea salt is that raw material is with converting the halogen method of evaporation, with the natural carnallitite in salt lake, regeneration carnallitite and sylvite is raw material, main with flotation process, inverse flotation method, thermosol crystallization process, decomposition and separation method etc., above-mentioned all methods have a common ground, be raw material with carnallitite or sylvite exactly, different according to the composition of carnallitite and sylvite again, and adopt various processes to produce Repone K.
Its major ingredient of vitriolate type bittern is KCl, NaCl, MgSO
4, MgCl
2, the potassium mixed salt of being produced at home and abroad all is used as produces vitriolate of tartar or potash magnesium sulphate fertilizer (schoenite), but is raw material production Repone K with the potassium mixed salt, does not still have report at home and abroad.
The potassium mixed salt is the mixture of multiple single salt and double salt, and its major ingredient has: halite (NaCl), epsom salt (MgSO
44～7H
2O), sylvite (KCl, NaCl), kainite (KClMgSO
43H
2O), schoenite (K
2SO
4MgSO
46H
2O), bischofite (MgCl
26H
2O), carnallitite (KClMgCl
26H
2O) etc., use vitriolate type bittern, potassium mixed salt through salt pan Exposure to Sunlight production, be subjected to all multifactor influences such as bittern composition, weather condition (temperature, humidity, steam output, rainfall amount), salt pan area, structure, it is also very big that it forms variation, is difficult to determine with quantitative data the main compositing range of potassium mixed salt.
Summary of the invention
The purpose of this invention is to provide and a kind ofly utilize old halogen that the potassium ion in the potassium mixed salt is dissolved and isolate sodium-chlor and sal epsom, thereby produce the production technique of Repone K.
Purpose of the present invention can reach by following measure:
A kind of potassium mixed salt of vitriolate type bittern production and technology that old halogen is produced Repone K utilized comprises the steps:
A, potassium mixed salt and old halogen are carried out pyrolytic conversion; The pyrolytic conversion temperature is 68～127 ℃, and preferred 100～115 ℃, the time is 5min～1h, preferred 5～40min; Wherein the potassium mixed salt is 1: 1～4.5 with the mass ratio of old halogen, preferred 1: 1.6～3.6.
B, the slip that pyrolytic conversion is finished carry out solid-liquid separation separate clear liquid; Temperature when solid-liquid separation is separated is corresponding with the temperature of pyrolytic conversion, is 68～127 ℃.
C, with clear liquid cooling, crystallization goes out carnallitite; Cooling temperature is 0～50 ℃, is preferably 20～30 ℃.
D, carnallitite is decomposed washing, product Repone K; This step is existing sophisticated technology.
Purpose of the present invention specifically can reach by following measure:
The production technique of a kind of usefulness " pyrolytic conversion " legal system potassium chloride:
A, be raw material,, calculate the add-on of old halogen, carry out pyrolytic conversion, make the MgCl in the potassium mixed salt according to the content of potassium ion in the potassium mixed salt with the potassium mixed salt
2All enter liquid phase with potassium ion, and the NaCl in the potassium mixed salt and become MgSO with the sal epsom of a plurality of crystal water
4H
2O is present in the solid phase.
B, the slip after pyrolytic conversion finished carry out settlement separate in the insulation settling vessel, and that discharge the settling vessel lower end is NaCl and MgSO
4H
2The O mixing salt, and the top of settling vessel is heavy clear liquid.(or carry out solid-liquid separation get clear liquid) with other method.
C, the clear liquid (or clear liquid) that will sink carry out crystallisation by cooling, and xln is the higher carnallitite of purity.
D, carnallitite is added water decomposition washing (or use other several different methods) promptly get technical grade high-quality Repone K (this belong to have maturation process now, see Tianjin Light Industry College for details: now be Tianjin skill university " salinization engineering science ").
The present invention is according to Na
+, K
+, Mg
2+/ Cl
-, SO
4 2--H
2The equilibrium phase diagram (110 ℃, 25 ℃ phasor see Fig. 2, Fig. 3) of O salt-water system under differing temps done the pyrolytic conversion analysis: with 25 ℃, 110 ℃ is example, a certain amount of old halogen will be added in the potassium mixed salt raw material, the add-on of potassium mixed salt and old halogen then goes out a suitable proportioning according to its composition by 110 ℃, 25 ℃ calphad, with a certain amount of potassium mixed salt and old halogen mixing post-heating to 110 ℃, reach that solid phase is NaCl and MgSO when balancing each other
4H
2O, liquid phase be to carnallitite near saturated heavy clear liquid, when the composition of heavy clear liquid was controlled at heavy clear liquid is cooled to 25 ℃, liquid phase consisted of old halogen, and the solid phase that obtains at this moment is the maximum value of the carnallitite amount of separating out.The mass ratio that the present invention draws potassium mixed salt and old halogen according to the difference of K content in weighing apparatus mutually between pyrolytic conversion and the crystallisation by cooling and the raw material is can reach reasonable effect at 1: 1.5～4.5 o'clock.
Technology elaborates:
1, raw material:
1.1 potassium mixed salt: potassium mixed salt chemical constitution complexity, generally weigh the grade of potassium mixed salt with the potassium content in the potassium mixed salt, its potassium content of potassium ores that is used for suitability for industrialized production at home is generally between 5～10%.
1.2 old halogen: be meant that generally the mother liquor behind the extraction carnallitite is referred to as old halogen, the major ingredient of old halogen is MgCl
2With a small amount of other salt, the MgCl in the old halogen
2Content is generally between 420～450g/l.
2, (macrobead will be pulverized with the potassium mixed salt, granularity is controlled in the 5mm) and old halogen (being heated to boiling), mix stirring heating by a certain percentage, be referred to as " pyrolytic conversion ", best invert point is selected to be controlled at 110 ℃, transformation time is according to potassium mixed salt granular size, generally at 5～40 minutes.
3, the variation tendency of each salt during pyrolytic conversion:
3.1 sodium-chlor: sodium-chlor changes in solubility owing to sodium-chlor when pyrolytic conversion is little, when having magnesium chloride to exist in a large number, the rising of the solubility with temperature of sodium-chlor and decreasing is so the sodium-chlor in the potassium mixed salt is when transforming, can think not participate in transforming, keep original physical features.
3.2 sal epsom: sal epsom is to be with 4,5,6,7 crystal water and KClMgSO in the potassium mixed salt
43H
2O and a small amount of K
2SO
4MgSO
46H
2The O form exists, but MgSO
4Two Main physical characteristics are arranged, the one, its solubleness is maximum value at 69 ℃, the 2nd, be to exist at 67.5～300 ℃ with the magnesium sulfate monohydrate form, when definite potassium mixed salt invert point scope, mainly be to consider the characteristic of sal epsom and the solubleness of Repone K, on the basis of test, determine that the pyrolytic conversion temperature is: in the highlands, the boiling point of solution is low, is 68～118 ℃; In the plains region is 68～127 ℃, because above-mentioned two top temperatures are potassium mixed salt slip boiling points when pyrolytic conversion, if raise again, pyrolytic conversion and solid-liquid separation will have been carried out in encloses container, there is no need in the suitability for industrialized production, determine on the technology that 2 minimum temperatures all are 68 ℃, be because more than 67.5 ℃, the sal epsom that contains different a plurality of crystal water in the potassium mixed salt just can change into magnesium sulfate monohydrate, and has only a water in the Industrial products, three kinds of seven water and anhydrides, but two water, four water, five water, six water things are all unstable, so under 110 ℃ of high temperature, all sal epsom that contain the different quantities crystal water will lose unnecessary crystal water and become magnesium sulfate monohydrate, because old halogen is smaller to the solubleness of sal epsom, magnesium sulfate monohydrate will separately exist in the slip.
3.3 Repone K: Repone K can Repone K form Individual existence in the potassium mixed salt, or exist with the form of kainite and carnallitite, when potassium mixed salt after old halogen mixes with heat, along with the solubleness of the rising Repone K of temperature significantly raises, Repone K in the potassium mixed salt will all enter liquid phase, be present in the old halogen of high temperature with ionic species.
3.4 magnesium chloride: the solubleness of magnesium chloride raises along with temperature and increases, and its variation is maximum in the potassium mixed salt, so the magnesium chloride in the old halogen is undersaturated when old halogen rises to high temperature, it can dissolve magnesium chlorides all in the potassium mixed salt.
3.5 after pyrolytic conversion was finished, the sodium-chlor state in the former potassium mixed salt was constant, sal epsom is present in the slip with the magnesium sulfate monohydrate form, and Repone K and magnesium chloride lay the first stone for going on foot down to separate promptly by in the pass into solution.
4, insulation sedimentation (or carry out solid-liquid separation with other method): after the slip after pyrolytic conversion finished is delivered to and is incubated settling vessel, optimum temps is controlled at about 105 ℃, sodium-chlor in the slip and magnesium sulfate monohydrate are because the action of gravity of self, sink to the bottom of settling vessel, separated draining, and the upper clear supernate of settling vessel (being referred to as heavy clear liquid) (or clear liquid) is admitted to subsequent processing.
5, crystallisation by cooling: the clear liquid that will sink cools off, the cooling optimum temps generally is controlled at about 25 ℃, the refrigerative mode is commonly used in existing salinization industry naturally cooling, vacuum cooling, a cooling of partition sleeve etc., heavy clear liquid in process of cooling since the Repone K in the heavy clear liquid of the reduction of temperature and the solubleness of magnesium chloride also reduce thereupon, they will be separated out with the form of carnallitite, be core technology of the present invention to this.
6, solid-liquid separation is carried out solid-liquid separation with the slip behind the crystallisation by cooling, promptly gets solid---carnallitite and the old halogen of liquid that purity is higher, and old halogen can recycle again.
With the potassium mixed salt is raw material, make solvent with old halogen, through pyroprocess, solid-phase chlorination sodium and magnesium sulfate monohydrate are separated, make the potassium mixed salt change into carnallitite, carnallitite is decomposed wash the Repone K that gets product, a lot of with the method for producing potassium chloride from carnallite, all be maturation process, just repeat no more.
Four main points during pyrolytic conversion:
1, in pyrolytic conversion and the high temperature solid-liquid separation process, do not allow any sylvite and separate out, old exactly halogen can not add less, and the solid-liquid separation temperature can not be low excessively.
2, should as far as possible when the high temperature solid-liquid separation, the solid phase of sodium-chlor and magnesium sulfate monohydrate be separated, to guarantee the quality of carnallitite.
3, resulting heavy clear liquid after the high temperature solid-liquid separation, wherein carnallitite should be tried one's best near saturated, with saturated and do not separate out and exceed just.
4, the pyrolytic conversion time, the specimen test of the potassium mixed salt of producing according to a plurality of salt lakes and saltern vitriolate type bittern, the pyrolytic conversion time just can finish between 5～40 minutes, but the potassium mixed salt that indivedual salt lakes vitriolate type bittern is produced is big because of particle, most of particle diameter is at 1～3cm, pyrolytic conversion can't be finished at 40 minutes, moreover the wearing and tearing to equipment when pyrolytic conversion of macrobead potassium mixed salt are also big, can consider before pyrolytic conversion the potassium mixed salt to be carried out break process.
4 technology points to pyrolytic conversion, concluding its core mainly is before pyrolytic conversion, according to the quality (content of magnesium chloride) of old halogen and the quality (content of potassium ion) of potassium mixed salt, control its ratio and time, if old halogen add-on is little, in the pyrolytic conversion process, old halogen is to the potassium ion supersaturation, and the residue potassium ion in the potassium mixed salt can not CL and is caused sylvite with sodium-chlor with magnesium sulfate monohydrate is separated loses, if the add-on of old halogen is excessive, old halogen is after intensification, the rising of the magnesium chloride solubility with temperature in the old halogen and increasing, all dissolved fall of magnesium chloride during pyrolytic conversion in the potassium mixed salt and sylvite and carnallitite be not also near saturated, cause dissolving in again in the old halogen sodium-chlor and sal epsom, final output and the quality that directly influences carnallitite, according to processing requirement, the Repone K in the heavy clear liquid in the settlement separate back of pyrolytic conversion insulation, magnesium chloride is saturated for well near carnallitite.
On the whole, the present invention is a raw material with the potassium mixed salt of vitriolate type bittern production, utilize old halogen to be solvent, at high temperature, potassium ion in the potassium mixed salt and magnesium chloride dissolving are entered in the old halogen, and sodium-chlor in the potassium mixed salt and magnesium sulfate monohydrate are still stayed in the solid phase, then separate sodium-chlor and magnesium sulfate monohydrate solid, with the liquid of gained through crystallisation by cooling, the higher carnallitite of purity, again carnallitite is promptly got the Repone K product through decomposing washing.
The present invention can both adapt to the potassium mixed salt of the different mass that vitriolate type bittern is produced, thereby solved the difficult problem that at present domestic and international potassium mixed salt can not be produced Repone K, it has adaptability to raw material strong, obtains the rate height, the equipment maturation, less investment, energy consumption is low, and the processing parameter controlled range is big, and is easy to operate, industrial scale such as does not limit at advantage, for China's potash fertilizer (Repone K) production provide one new by way of.
Description of drawings
Fig. 1 is a kind of technological process of production figure of the present invention.
Fig. 2 is Na
+, K
+, Mg
2+/ Cl
-, SO
4 2--H
2The equilibrium phase diagram of O salt-water system under 110 ℃.
Fig. 3 is Na
+, K
+, Mg
2+/ Cl
-, SO
4 2--H
2The equilibrium phase diagram of O salt-water system under 25 ℃.
Among Fig. 2 and Fig. 3, A--potassium mixed salt is formed point, and the old halogen of B--is formed point, and M--potassium mixed salt mixes back complex point with old halogen, and the C--magnesium sulfate monohydrate is formed point, and D--110 ℃ of clear liquor formed point, and the E--carnallitite is formed point, B '--old halogen point, Van--3Na
2SO
4MgSO
4Crystallizing field, Gla--Na
2SO
43K
2SO
4Crystallizing field, Lan--K
2SO
42MgSO
4Crystallizing field, M
1-7--be respectively the MgSO of 1-7 crystal water of band
4Crystallizing field, Low--Na
2SO
4MgSO
42.5H
2The crystallizing field of O, Car--KClMgCl
26H
2The crystallizing field of O, Bis--MgCl
26H
2The crystallizing field of O, Ast--Na
2SO
4MgSO
44H
2The crystallizing field of O, Pic--K
2SO
4MgSO
46H
2The crystallizing field of O, Leo--K
2SO
4MgSO
44H
2The crystallizing field of O, Kai--KClMgSO
43H
2The crystallizing field of O.
Embodiment
Get the old halogen of 2700g (composition sees Table 1-1), be heated to (115 ℃ of boilings, annotate: the test of doing in Part of Qinghai Plateau), add 1000g potassium mixed salt (composition sees Table 1-2) while stirring, heated constant temperature is at 110 ℃ under whipped state, allow slip pyrolytic conversion 40 minutes, stop to stir, slip constant temperature 105 ℃ of sedimentations 1 hour, is taken out slip, quick solid-liquid separation, must sink clear liquid 2930g, (composition sees Table 1-3), separated salt 490g (composition sees Table 1-4), whole pyrolytic conversion process loss moisture content 280g, the clear liquid that will sink naturally cools to 25 ℃, and carnallitite is separated out from heavy clear liquid, through solid-liquid separation, must hang down sodium higher-grade carnallitite 536g (composition sees Table 1-5), get old halogen 2397g (old halogen composition sees Table 1-6), carnallitite is added the water decomposition washing, must contain pure 90.55% Repone K 106g, pyrolytic conversion to Repone K whole process is carried out material balance calculate, the result is:
1, by the potassium mixed salt through pyrolytic conversion to carnallitite, the transformation efficiency of potassium is 92.6%;
2, the rate that obtains of producing Repone K by carnallitite is 76.35%;
3, be 70.69% by potassium mixed salt to the rate that always obtains of Repone K.
Each material of table 1: embodiment is formed
| Numbering | Title | Form (%) | |||||
| K + | Mg 2+ | SO 4 2- | Cl - | Na + | H 2O | ||
| 1-1 | Old halogen | 0.09 | 9.14 | 1.90 | 25.44 | 0.05 | 63.38 |
| 1-2 | The potassium mixed salt | 6.87 | 7.92 | 15.97 | 27.98 | 6.71 | 34.64 |
| 1-3 | Heavy clear liquid | 2.33 | 9.26 | 1.77 | 28.37 | 0.36 | 57.91 |
| 1-4 | Separated salt | 0.55 | 10.32 | 32.38 | 25.00 | 11.87 | 19.88 |
| 1-5 | Carnallitite | 12.30 | 8.47 | 0.17 | 38.00 | 1.68 | 39.38 |
| 1-6 | Old halogen | 0.10 | 9.49 | 1.96 | 26.41 | 0.06 | 61.96 |
Claims (8)
1. one kind is utilized the potassium mixed salt of vitriolate type bittern production and the technology that old halogen is produced Repone K, it is characterized in that comprising the steps:
A, potassium mixed salt and old halogen are carried out pyrolytic conversion;
B, the slip that pyrolytic conversion is finished carry out solid-liquid separation, get clear liquid;
C, with clear liquid cooling, crystallization goes out carnallitite;
D, carnallitite is decomposed washing, product Repone K.
2. technology according to claim 1 is characterized in that among the step a that the pyrolytic conversion temperature is 68～127 ℃, and the time is 5min～1h.
3. technology according to claim 2 is characterized in that the pyrolytic conversion temperature is 100～115 ℃, and the time is 5～40min.
4. technology according to claim 1 is characterized in that among the step a, and the potassium mixed salt is 1: 1.5～4.5 with the mass ratio of old halogen.
5. technology according to claim 1 is characterized in that the potassium mixed salt and the mass ratio of old halogen are 1: 1.6～3.6.
6. the technology of utilizing potassium mixed salt and old halogen to produce Repone K according to claim 1 is characterized in that among the step b, adopts the settled method of insulation to carry out solid-liquid separation, and separation temperature is 68～127 ℃.
7. technology according to claim 1 is characterized in that among the step c that cooling temperature is 0～50 ℃.
8. technology according to claim 7 is characterized in that cooling temperature is 20～30 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101344730A CN100515946C (en) | 2007-10-30 | 2007-10-30 | Technique producing potassium muriate by using potassium mixed salt and aged halogen produced by vitriolate type bittern |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101344730A CN100515946C (en) | 2007-10-30 | 2007-10-30 | Technique producing potassium muriate by using potassium mixed salt and aged halogen produced by vitriolate type bittern |
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| Publication Number | Publication Date |
|---|---|
| CN101172623A true CN101172623A (en) | 2008-05-07 |
| CN100515946C CN100515946C (en) | 2009-07-22 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372293A (en) * | 2010-08-16 | 2012-03-14 | 盛骝吾 | Technology of preparing Na2SO4 through salting-out method with NaC1 as salting-out agent, and recovering salting-out agent through water evaporation in salt field |
| CN102417191A (en) * | 2011-09-08 | 2012-04-18 | 中国科学院青海盐湖研究所 | Method for extracting potassium chloride from carbonate type salt lake |
| CN102826874A (en) * | 2012-09-04 | 2012-12-19 | 青海中信国安科技发展有限公司 | Method for producing potash magnesium sulphate fertilizers with unsaturation brine serving as flotation medium |
| CN104477941A (en) * | 2014-12-16 | 2015-04-01 | 中国科学院青海盐湖研究所 | Method for preparing carnallite from potassium mixed salts by low-temperature refrigeration |
| CN106083221A (en) * | 2016-06-15 | 2016-11-09 | 古舜起 | Carnallite is utilized to produce the method for potassium sulphate fertilizer magnesium metal PVC and liquid chlorine hydrochloric acid |
| CN109541127A (en) * | 2018-12-19 | 2019-03-29 | 青海盐湖工业股份有限公司 | The method that a kind of pair of saturated potassium chloride solution carries out assay |
-
2007
- 2007-10-30 CN CNB2007101344730A patent/CN100515946C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102372293A (en) * | 2010-08-16 | 2012-03-14 | 盛骝吾 | Technology of preparing Na2SO4 through salting-out method with NaC1 as salting-out agent, and recovering salting-out agent through water evaporation in salt field |
| CN102372293B (en) * | 2010-08-16 | 2013-10-30 | 盛骝吾 | Technology of preparing Na2SO4 through salting-out method with NaC1 as salting-out agent, and recovering salting-out agent through water evaporation in salt field |
| CN102417191A (en) * | 2011-09-08 | 2012-04-18 | 中国科学院青海盐湖研究所 | Method for extracting potassium chloride from carbonate type salt lake |
| CN102826874A (en) * | 2012-09-04 | 2012-12-19 | 青海中信国安科技发展有限公司 | Method for producing potash magnesium sulphate fertilizers with unsaturation brine serving as flotation medium |
| CN102826874B (en) * | 2012-09-04 | 2014-01-01 | 青海中信国安科技发展有限公司 | Method for producing potash magnesium sulphate fertilizers with unsaturation brine serving as flotation medium |
| CN104477941A (en) * | 2014-12-16 | 2015-04-01 | 中国科学院青海盐湖研究所 | Method for preparing carnallite from potassium mixed salts by low-temperature refrigeration |
| CN104477941B (en) * | 2014-12-16 | 2016-02-03 | 中国科学院青海盐湖研究所 | A kind of method utilizing potassium mixed salt cryogenic freezing to produce carnallite |
| CN106083221A (en) * | 2016-06-15 | 2016-11-09 | 古舜起 | Carnallite is utilized to produce the method for potassium sulphate fertilizer magnesium metal PVC and liquid chlorine hydrochloric acid |
| CN109541127A (en) * | 2018-12-19 | 2019-03-29 | 青海盐湖工业股份有限公司 | The method that a kind of pair of saturated potassium chloride solution carries out assay |
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|---|---|
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