CN101927214B - Technology for extracting potassium from potassium mixed salt containing picromerite, KCL and carnallite - Google Patents
Technology for extracting potassium from potassium mixed salt containing picromerite, KCL and carnallite Download PDFInfo
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- CN101927214B CN101927214B CN2010101982818A CN201010198281A CN101927214B CN 101927214 B CN101927214 B CN 101927214B CN 2010101982818 A CN2010101982818 A CN 2010101982818A CN 201010198281 A CN201010198281 A CN 201010198281A CN 101927214 B CN101927214 B CN 101927214B
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- potassium
- picromerite
- kcl
- mixed salt
- carnallite
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Abstract
The invention relates to a technology for extracting potassium from potassium mixed salt containing picromerite, KCL and carnallite. An extraction method comprises the following steps of: (1), adding the potassium mixed salt containing the picromerite, KCL and the carnallite to co-saturated mother solution of the picromerite, KCL and epsomite to grind ore; (2), transmitting the material obtained in step (1) into a flotation machine for floating and separating potassium salt, NaCl and the epsomite, wherein a cation ether amine collector and an anion sodium sulfonate collector are adopted in the floatation with the utilization quantity of 20 g/t to 60 g/t of crude ore and 50 g/t to 100 g/t of crude ore respectively and the chemicals are added at the same time; and (3) washing the floatation concentrates obtained in step (2) by using fresh water or the mother solution of potassium sulfate to obtain a picromerite product which can be used as a magnesian fertilizer for direct sale, wherein the magnesian fertilizer reaches the first-grade product standard of GB/T20937-2007.
Description
Technical field
The present invention relates to a kind of from the potassium mixed salt that contains picromerite, KCl and carnallite Potassium process.
Background technology
[0002] up to now, from the potassium mixed salt, carrying potassium all is meant from the potassium mixed salt that contains sylvite and carries potassium.Existing potassium mixed salt is put forward the potassium method and can be divided three classes.One type is to utilize the pure soft potassium magnesium of crystallization path of preparing vanadium; The mode that is thermosol or forced evaporation-cooling-crystallization is isolated soft potassium; The existing disclosed technical scheme of related patent U.S. Patent No. document, their distinguishing characteristics is that the order of the raw ore type of use, crystallization mode, adding potassium chloride and the type of end product are different (referring to CN 98108686.1, CN 97123278.4, CN 200410038989; CN 93105556.3, CN 87103934 etc.).The shortcoming of these class methods is that the single cycle yield is lower, force the heating evaporation energy consumption big and adopt solar pond to evaporate overlong time, crystallization processes and cause line clogging, most of process route product gas purity lower easily.Second class methods are that the solid phase that on first kind method, grows up is sieved the technology of removing sodium chloride; Be about to take after soft potassium and sodium chloride crystallize out the mechanical means screening (referring to CN 200410069545.4; CN200510085831.4; CN200510091865.4 etc.), the product purity that these class methods obtain is higher, but the shortcoming that exists in the first kind method still fails to solve fully.The 3rd class methods are flotation or reverse flotation method: these class methods roughly are divided into two kinds; A kind of is to transform after the first flotation; Promptly kainite is separated with impure mineral NaCl and epsomite in the mixed salt through method for floating; The kainite flotation concentrate that obtains adds fresh water again, accompanies by mechanical agitation simultaneously and transforms, and obtains picromerite product (referring to CN200910042726.0, CN200610008786.7 etc.).Floatation process wherein is the one thick two single-minded flow process of sweeping, and beneficiation reagent adopts anion collecting agent and foaming agent.Second kind is to transform the back flotation earlier; Promptly add fresh water earlier and accompany by mechanical agitation; Kainite is changed into picromerite, carry out flotation again, use flotation agent that picromerite is floated; The realization picromerite separates with NaCl and epsomite, thereby obtains picromerite product (seeing CN011136421, CN200810135849.4, CN200610008787.1, CN03134289.2, CN200610008785.2).These class methods are simpler slightly than first and second class methods technology, and energy consumption is lower, and is with short production cycle, and product gas purity is higher, relatively are fit to suitability for industrialized production.
From salt lake resources; Why can form this potassium mixed salt that contains kainite, the one, form decision by the salt lake, the 2nd, relevant by salt pan crystallization and local climate, temperature; Picture area, Lop Nur, Xinjiang annual high temperature drying except that winter, potassium mixed salt pond mainly generated kainite during shone on the beach, salt pan.
But some area, like the part salt lake in Qinghai, the potassium mixed salt composition that (below 25 ℃) salt lake crystallization went out when temperature was relatively low is picromerite and carnallite and KCl, does not have kainite.The existence of carnallite has been shone carnallite owing to the salt pond hysteresis of falling halogen makes in potassium mixed salt pond and has been caused.Therefore, the potassium mixed salt of more than introducing that is not suitable for containing picromerite, KCl and carnallite to the floatation process route of the potassium mixed salt invention that contains kainite and Potassium process is carried potassium.
Summary of the invention
The object of the present invention is to provide a kind of step simple, yield is high, and energy consumption is low, the technology of from the potassium mixed salt that contains picromerite, KCl and carnallite, carrying potassium that production cost is low.
The present invention's the technology of from the potassium mixed salt that contains picromerite, KCl and carnallite, carrying potassium may further comprise the steps:
The full altogether mother liquor that (1) will contain the adding of potassium mixed salt raw ore picromerite, KCl and the epsomite of picromerite, KCl and carnallite carries out ore grinding; Ore milling concentration is 40～60wt% (preferred 50=55wt%), and the potassium mixed salt granularity behind the ore grinding accounts for 50～70wt% (preferred 58-62wt%) for-100 order content.
(2) material that step (1) is obtained is sent into flotation device; Carry out the FLOTATION SEPARATION of sylvite and NaCl and epsomite; The mother liquor that flotation is used is an one roughing as the common saturated mother liquor of picromerite, KCl and epsomite, flotation process, flotation time 6～10 minutes; Floating agent is cation ether amine collector and anion sulfoacid sodium class collecting agent; Cation ether amine collector consumption is 20～60g/t raw ore, and anion sulfoacid sodium class collector dosage is 50～100g/t raw ore, and dosing method is for add simultaneously;
Adopt the benefit of two kinds of floating agents of zwitterion to be effectively to tackle the variation that various potassium-bearing minerals are formed in the raw material simultaneously, yield is higher; Use cation ether amine collector or anion sulfoacid sodium class collecting agent separately, yield can hang down;
(3) flotation concentrate that step (2) is obtained washs with fresh water or potassium sulfate mother liquid, and used washing lotion total amount is 10%～15% of a flotation concentrate quality, divides and washs for 2～4 times, and Separation of Solid and Liquid promptly gets solid picromerite product.
Step (2) wherein, said cation ether amine collector can be decyl ethers amine or ten diether amine, or the mixture (mixing match is not limit) of decyl ethers amine and ten diether amine; Anion sulfoacid sodium class collecting agent is sodium alkyl sulfonate or their mixture (preferred sodium cetanesulfonate or the octadecyl sodium sulfonate, or the mixture (mixing match do not limit) of sodium cetanesulfonate and octadecyl sodium sulfonate of alkyl chain carbon atomicity between 10～20.
Gained picromerite product both can be used as the raw material of producing potassium sulfate, also can be used as potassic-magnesian fertilizer and sold.Said potassic-magnesian fertilizer reaches GB/T20937-2007 primes standard.
Step of the present invention is simple, and yield is high, and energy consumption is low, and production cost is low.Potassium mixed salt with salt lake, China Qinghai Province is an example, and its mineral composition is KCl and carnallite 17.28 wt%, picromerite 13.17 wt%, NaCl 28.12 wt%, epsomite 30.01 wt%, and (C point bittern refers to Na to the C that carries secretly some bittern 11.42 wt%
+, K
+, Mg
2+//SO
4 2-, Cl
--H
2The bittern of the full altogether point of picromerite, epsomite, KCl in five yuan of water salt of O phasor), use ore grinding → flotation (one roughing) technology of the present invention, can obtain sylvite concentrate grade K
+17.21%, the good technique index of flotation yield 93.98% (referring to embodiment 2).
The specific embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
(1) Qinghai potassium mixed salt raw ore is consisted of K
+5.07%, Mg
2+5.78%, Na
+10.60%, SO
4 2-18.70%, Cl
-24.07% potassium mixed salt, adding picromerite, epsomite and KCl saturated mother liquor altogether carry out ore grinding, and ore milling concentration is 50wt%, and the potassium mixed salt granularmetric composition behind the ore grinding accounts for 58.71wt% for-100 order content;
(2) material that step (1) is obtained is sent into flotation device; Carry out the FLOTATION SEPARATION of sylvite and NaCl and epsomite; The flotation mother liquor is the common saturated mother liquor of picromerite, epsomite and KCl, and flotation process is an one roughing, flotation time 10 minutes; The floating agent cation-collecting agent is ten diether amine, and consumption is a 40g/t potassium mixed salt raw ore; The anion collecting agent is a sodium cetanesulfonate, and consumption is a 80g/t potassium mixed salt raw ore, and dosing method is for add simultaneously;
(3) flotation concentrate that step (2) is obtained divides with the fresh water of concentrate quality 12% and washs for 3 times, the picromerite product, product quality is K
+16.33%, Mg
2+5.71%, Cl
-2.48, SO
4 2-41.75%, the flotation-washing total recovery is 92.45%.
Embodiment 2
(1) the Qinghai raw ore is consisted of K
+5.05%, Mg
2+6.12%, Na
+10.62%, SO
4 2-17.84%, Cl
-25.63% potassium mixed salt adds the full altogether mother liquor of picromerite, epsomite and KCl and carries out ore grinding, and ore milling concentration is 52wt%, and the potassium mixed salt granularmetric composition behind the ore grinding accounts for 60.00% for-100 order content.
(2) material that step (1) is obtained is sent into flotation device; Carry out the FLOTATION SEPARATION of sylvite and NaCl and epsomite; The flotation mother liquor is the full altogether mother liquor of picromerite, epsomite and KCl, and flotation process is an one roughing, flotation time 8 minutes; The floating agent cation-collecting agent is a decyl ethers amine, and consumption is a 40g/t potassium mixed salt raw ore; The anion collecting agent is the octadecyl sodium sulfonate, and consumption is a 100g/ potassium mixed salt raw ore, and dosing method is for add simultaneously;
(3) flotation concentrate that step (2) is obtained divides with the potassium sulfate mother liquid of concentrate quality 14% and washs for 3 times, the picromerite product, product quality is K
+17.21%, Mg
2+6.23%, Cl
-2.71, SO
4 2-42.98%, flotation-washing total recovery 93.98%.
Embodiment 3
(1) the Qinghai raw ore is consisted of K
+5.09%, Mg
2+6.73%, Na
+10.45%, SO
4 2-17.90%, Cl
-25.74% potassium mixed salt adds the full altogether mother liquor of picromerite, epsomite and KCl and carries out ore grinding, and ore milling concentration is 55wt%, and the potassium mixed salt granularmetric composition behind the ore grinding accounts for 61.4% for-100 order content.
(2) material that step (1) is obtained is sent into flotation device; Carry out the FLOTATION SEPARATION of sylvite and NaCl and epsomite; The flotation mother liquor is the full altogether mother liquor of picromerite, epsomite and KCl, and flotation process is an one roughing, flotation time 8 minutes; The floating agent cation-collecting agent is the mixture (ratio of 1:1) of decyl ethers amine and ten diether amine, and consumption is a 40g/t potassium mixed salt raw ore; The anion collecting agent is the mixture (ratio of 1:1) of sodium cetanesulfonate octadecyl sodium sulfonate, and consumption is a 100g/ potassium mixed salt raw ore, and dosing method is for add simultaneously;
(3) flotation concentrate that step (2) is obtained divides with the potassium sulfate mother liquid of concentrate quality 13% and washs for 3 times, the picromerite product, product quality is K
+17.47%, Mg
2+5.16%, Cl
-3.25, SO
4 2-41.47%, flotation-washing total recovery 92.17%.
Claims (5)
1. Potassium process from the potassium mixed salt that contains picromerite, KCl and carnallite is characterized in that, may further comprise the steps:
(1) the common saturated mother liquor to the adding of potassium mixed salt raw ore picromerite, KCl and the epsomite that contain picromerite, KCl and carnallite carries out ore grinding, and ore milling concentration is 40-60wt%, and the potassium mixed salt granularity behind the ore grinding accounts for 50-70wt% for-100 order content;
(2) material that step (1) is obtained is sent into flotation device; Carry out the FLOTATION SEPARATION of sylvite and NaCl and epsomite; The mother liquor that flotation is used is an one roughing as the common saturated mother liquor of picromerite, KCl and epsomite, flotation process, flotation time 6～10 minutes; Floating agent is cation ether amine collector and anion sulfoacid sodium class collecting agent; Cation ether amine collector consumption is 20～60g/t raw ore, and anion sulfoacid sodium class collector dosage is 50～100g/t raw ore, and dosing method is for add simultaneously;
(3) flotation concentrate that step (2) is obtained washs with fresh water or potassium sulfate mother liquid, and the washing lotion total amount is 10%～15% of a flotation concentrate quality, washs 2～4 times, and Separation of Solid and Liquid promptly gets solid picromerite product.
According to claim 1 said from the potassium mixed salt of picromerite, KCl and carnallite Potassium process, it is characterized in that, said step (1), ore milling concentration is 50wt%, the potassium mixed salt granularity behind the ore grinding accounts for 58～62wt% for-100 order content.
According to right 1 or 2 said from the potassium mixed salt that contains picromerite, KCl and carnallite Potassium process, it is characterized in that said cation ether amine collector is decyl ethers amine or ten diether amine, or the mixture of decyl ethers amine and ten diether amine; Said anion sulfoacid sodium class collecting agent is sodium alkyl sulfonate or their mixture of alkyl chain carbon atomicity between 10～20.
According to right 3 said from the potassium mixed salt that contains picromerite, KCl and carnallite Potassium process, it is characterized in that the sodium alkyl sulfonate of said alkyl chain carbon atomicity between 10～20 is sodium cetanesulfonate or octadecyl sodium sulfonate.
According to right 3 said from the potassium mixed salt that contains picromerite, KCl and carnallite Potassium process; It is characterized in that the mixture of the sodium alkyl sulfonate of said alkyl chain carbon atomicity between 10～20 is the mixture of sodium cetanesulfonate and octadecyl sodium sulfonate.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102744142A (en) * | 2012-07-18 | 2012-10-24 | 中蓝连海设计研究院 | Floatation medium and floatation method for potassium-containing sulfate floatation |
| CN104998748A (en) * | 2015-06-19 | 2015-10-28 | 化工部长沙设计研究院 | Technology for extracting potassium and removing sodium from high-sodium polyhalite ore |
| CN106082279B (en) * | 2016-06-21 | 2017-12-26 | 化工部长沙设计研究院 | A kind of method that potassium sulfate is produced using carnallite as raw material |
| CN107954750B (en) * | 2017-11-10 | 2021-03-09 | 国投新疆罗布泊钾盐有限责任公司 | Method for preparing top-grade potash magnesium sulphate fertilizer by using carnallite and potassium mixed salt ore |
| CN108147433B (en) * | 2018-01-30 | 2019-09-17 | 中蓝长化工程科技有限公司 | A kind of low-sulfur potassium mixed salt proposes potassium processing technology |
| CN111533140B (en) * | 2020-05-06 | 2022-08-02 | 中国科学院青海盐湖研究所 | Method for preparing potash magnesium sulphate fertilizer, potassium chloride and potassium sulfate by using sulfate type carnallite |
| CN111533139B (en) * | 2020-05-06 | 2022-08-02 | 中国科学院青海盐湖研究所 | Method for co-producing potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate |
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|---|---|---|---|---|
| RU2079378C1 (en) * | 1994-06-16 | 1997-05-20 | Акционерное общество открытого типа "Сильвинит" | Method of processing carnallite ores |
| CN1548372A (en) * | 2003-05-23 | 2004-11-24 | 中国科学院青海盐湖研究所 | Potassium sulfate preparing process from sulfate-type salt lake bittern |
| CN101327941A (en) * | 2008-07-16 | 2008-12-24 | 化工部长沙设计研究院 | Potassium extraction production process of low grade potassium-containing mixing salt |
| CN101481265A (en) * | 2009-02-25 | 2009-07-15 | 化工部长沙设计研究院 | Production process for extracting potash fertilizer form low grade potassium mixed salt |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060226051A1 (en) * | 2005-04-07 | 2006-10-12 | The Mosaic Company | Use of urea-formaldehyde resin in potash ore flotation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2079378C1 (en) * | 1994-06-16 | 1997-05-20 | Акционерное общество открытого типа "Сильвинит" | Method of processing carnallite ores |
| CN1548372A (en) * | 2003-05-23 | 2004-11-24 | 中国科学院青海盐湖研究所 | Potassium sulfate preparing process from sulfate-type salt lake bittern |
| CN101327941A (en) * | 2008-07-16 | 2008-12-24 | 化工部长沙设计研究院 | Potassium extraction production process of low grade potassium-containing mixing salt |
| CN101481265A (en) * | 2009-02-25 | 2009-07-15 | 化工部长沙设计研究院 | Production process for extracting potash fertilizer form low grade potassium mixed salt |
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