CN111533139A - Method for co-producing potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate - Google Patents
Method for co-producing potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/08—Preparation by working up natural or industrial salt mixtures or siliceous minerals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/04—Fertilisers containing potassium from minerals or volcanic rocks
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a method for co-producing a potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate. It includes: firstly, carrying out flotation treatment on sulfate type potassium mixed salt ores by using an anionic flotation agent to obtain potassium-sulfur mixed salt concentrates and chloride type tailings; then, contacting a hot solvent with the chloride type tailings, carrying out selective hot-dissolving treatment, and carrying out solid-liquid separation on the obtained mixture to obtain high-temperature potassium-rich saturated liquid, sodium chloride and kieserite; then, while replenishing fresh water, carrying out stepped closed cooling crystallization and refining treatment on the obtained high-temperature potassium-rich saturated liquid to prepare potassium chloride; finally, the obtained potassium-sulfur mixed salt concentrate is converted and refined to obtain a potash magnesium sulphate fertilizer, and the potash magnesium sulphate fertilizer is reacted with the obtained potassium chloride and fresh water to prepare the potassium sulphate. According to the invention, through anionic flotation agent flotation, selective hot melting and stepped closed cooling crystallization, the high-efficiency and high-quality precipitation of potassium chloride is ensured; meanwhile, the invention has simple process flow and is convenient for the popularization and implementation of the technology.
Description
Technical Field
The invention belongs to the technical field of inorganic salt industry, and particularly relates to a method for co-producing a potash magnesium sulphate fertilizer, potassium chloride and potassium sulfate, in particular to a method for co-preparing the potash magnesium sulphate fertilizer, the potassium chloride and the potassium sulfate by using sulfate type mixed potassium salt ores.
Background
The potash fertilizer is a basic material for the stable growth of grain production, can effectively improve the quality of agricultural products and the stress resistance of crops, and is one of the nutrients necessary for the growth of the crops. With the reduction of the cultivated land area and the continuous increase of population, the potassium resource is developed on a large scale, the yield of the potassium fertilizer is improved, and the method has important food safety significance.
The potassium fertilizer product type is mainly potassium chloride fertilizer, and accounts for more than 90% of the total amount of the potassium fertilizer; there are also various chlorine-free potassium fertilizers such as sulfate type (potassium sulfate, potash magnesium sulfate fertilizer), nitrate type (potassium nitrate), carbonate type (potassium carbonate), phosphate type (monopotassium phosphate) and the like. The sulfate type potash fertilizer contains a nutrient element K necessary for crop growth and also contains a nutrient element S, Mg which plays a role in promoting crop growth, has stronger adaptability compared with KCl, is known as a 'golden partner' of crop fertilization, has obvious effects on balancing fertilization, improving crop yield, improving crop quality and the like, and is mainly used for planting various economic crops. In view of the current situation that agricultural farmland in China is generally lack of magnesium and sulfur, the popularization of the application of the sulfate type potash fertilizer has important significance.
Most of the raw materials for preparing the sulfate type potash fertilizer at the present stage are sulfate type potassium mixed salt ores (solid ores, sulfate type brine, seawater bittern, potassium mixed salt ores obtained by evaporation and the like), potassium magnesium sulfate fertilizer is prepared according to the raw materials, and then potassium sulfate is prepared by reaction of the potassium magnesium sulfate fertilizer and potassium chloride; or the raw material directly reacts with potassium chloride to prepare potassium sulfate. The sulfate type potassium mixed salt ore is a mixture of various single salts and complex salts, and mainly comprises the following components: halite (NaCl), epsomite (MgSO)4Hydrated salt), sylvite (KCl), kainite (KCl MgSO)4·3H2O), picromerite (K)2SO4·MgSO4·6H2O), Kalium magnesium alum (K)2SO4·MgSO4·4H2O), potassium magnesium anhydrous alum (K)2SO4·2MgSO4) Carnallite (KCl. MgCl)2·6H2O) and bischofite (MgCl)2·6H2O), etc., the composition ranges of the components are NaCl 10-30%, KCl 15-20%, K2SO42％～5％，MgSO418％～30％，MgCl20％～20％。
At present, the technology for preparing the sulphate potash fertilizer by sulphate type potassium mixed salt is mainly completed by combining conversion and flotation technology. The patent CN100488874C adopts the technology of 'transformation + self decomposition' to obtain the potash magnesium sulphate fertilizer and the potash potassium sulphate product in turn. In patents CN1255320C, CN1810730B, CN104477943B and CN107963914A, potassium mixed salt is treated by "conversion + anion collector flotation" technology to obtain potash magnesium sulphate fertilizer, and the potash magnesium sulphate fertilizer is continuously decomposed or reacted with potassium chloride to obtain potash sulphate product. The potassium mixed salt can be treated by the technology of 'conversion and reverse flotation' to prepare the potassium sulphate magnesium fertilizer. In order to reduce the influence of sodium chloride in the conversion, the patents CN1197833C and CN1288084C adopt mechanical screening to remove sodium chloride. The potash magnesium sulphate fertilizer can also be prepared by a technology of reverse flotation sodium removal and conversion. In patents CN1065213C and CN1038833C, sodium chloride is removed by hot-melt technology, and then cooled and crystallized to obtain picromerite or potassium mixed salt concentrate to prepare potash magnesium sulphate fertilizer or potassium chloride. In patents CN1810729B, CN101927214B and CN104193425B, potassium mixed salt ore is subjected to take-over or mixed flotation by using positive and negative ion collectors to obtain potassium salt concentrate, and potassium magnesium sulfate fertilizer or potassium sulfate product is prepared by conversion. In patents CN1179882C and CN1275857C, potassium mixed salt is adopted to be fully dissolved, brine composition points are adjusted to enter picromerite or potassium sulfate phase region, and natural evaporation is performed to obtain potash magnesium sulphate fertilizer or potassium sulfate product.
The key of the technology for preparing the potassium chloride by using the sulfate type potassium mixed salt ore is to avoid the influence of sulfate radicals. In patents US20110008243a1, CN102421707B and CN103073029B, desulfurizing agents (calcium hydroxide, calcium chloride, ammonia evaporation waste liquid, etc.) are used for desulfurization modification to change the desulfurizing agents into chloride type, so as to obtain carnallite or potassium chloride, and prepare potassium chloride products. In patent CN104477941B, potassium chloride is prepared by separating out epsomite of different crystal water by low-temperature freezing or high-temperature evaporation, and then evaporating to obtain carnallite. In patents CN100515946C and CN104891532A, saturated magnesium chloride solution is used to convert potassium mixed salt at high temperature or low temperature to convert it into carnallite, and then potassium chloride is prepared. Patent CN1248966C adopts halogen blending technology to obtain low-sodium carnallite, and then potassium chloride products are obtained. In patents CN106517250B, CN106430248B and CN106517251B, a nanofiltration membrane is used to separate sulfate radicals at a high retention rate of divalent ions, and a reverse flotation or hot melt crystallization technology is combined to prepare a potassium chloride product.
The process technology for simultaneously preparing the potash magnesium sulphate fertilizer, the potassium chloride and the potassium sulphate by utilizing the sulfate type potassium mixed salt is less. In patents CN1321893C and CN105692657B, the potassium mixed salt is divided into two stages, the high sulfur-potassium ratio stage is used for preparing potash magnesium sulphate fertilizer, the high carnallite content stage is used for preparing potassium chloride, and the potassium sulphate is prepared by converting the two. In patent CN100383045C, potassium mixed salt is firstly used for conversion to prepare a potash magnesium sulphate fertilizer, then the potash magnesium sulphate fertilizer conversion mother liquor is mixed with magnesium chloride old brine to obtain low-sodium carnallite for preparing potassium chloride, and then potassium sulphate is prepared subsequently. And performing flotation on the CN201810089886.X by adopting a technology of conversion, anion collector flotation and tailing cation collector flotation to obtain a potash magnesium sulphate fertilizer and a potassium chloride product.
At present, in the prior art, potassium mixed salt can be prepared into potash magnesium sulphate fertilizer or potassium chloride respectively by adopting different processes according to the content of magnesium sulphate in the potassium mixed salt, and then another raw material is introduced to further prepare potassium sulphate. And few reports on the process technology for simultaneously preparing the potash magnesium sulphate fertilizer, the potassium chloride and the potassium sulfate by using the potassium mixed salt are reported. The potash fertilizer prepared by converting the sulfate type potash mixed salt ore mainly comprises a potash magnesium sulphate fertilizer and a potash fertilizer, but the conversion effect is closely related to the phase proportion of magnesium chloride containing substances such as carnallite, bischofite and the like in the potash mixed salt ore, and the higher the content of magnesium chloride is, the lower the yield of the converted potash magnesium sulphate fertilizer is. Similarly, the yield of the potassium chloride obtained by conversion is related to the proportion of the sulfate phase, and the higher the sulfate content is, the lower the potassium chloride yield is. Meanwhile, the introduced flotation technology has almost no flotation capacity on the carnallite phase, so that the risk that the carnallite stays in tailings and is abandoned is easily caused, and the potassium resource is lost.
Disclosure of Invention
The invention mainly aims to provide a method for co-producing a potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate, so as to overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a method for co-producing a potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate, which comprises the following steps:
(1) carrying out flotation treatment on sulfate type potassium mixed salt ores by using an anionic flotation agent to obtain potassium-sulfur mixed salt concentrates and chloride type tailings, wherein the potassium-sulfur mixed salt concentrates comprise the following components in percentage by mass: 1.0-2.5 wt% of NaCl, 23-28 wt% of KCl and K2SO43～11wt％、MgSO442～47wt％、MgCl20-1.5 wt%, wherein the chloride type tailings comprise the following components in percentage by mass: 16-76 wt% of NaCl, 6.5-11.0 wt% of KCl, and K2SO40.2～0.7wt％、MgSO42.0～5.5wt％、MgCl24.0～32.5wt％；
(2) Enabling a hot solvent to contact with the chloride type tailings, carrying out selective hot-dissolving treatment at 75-100 ℃, and then carrying out solid-liquid separation on the obtained mixture to obtain high-temperature potassium-rich saturated liquid, sodium chloride and kieserite, wherein the hot solvent is rich in MgCl2The high-temperature potassium-rich saturated liquid is prepared by mixing the following components in percentage by mass: 1.2-1.4 wt% of NaCl, 4-5 wt% of KCl and MgSO41.0～1.4wt％、MgCl229～31wt％；
(3) And (3) while supplementing fresh water, performing stepped closed cooling crystallization and refining treatment on the high-temperature potassium-rich saturated liquid obtained in the step (2) to prepare potassium chloride, wherein the potassium chloride comprises the following components in percentage by mass: 1-2 wt% of NaCl, 92-95 wt% of KCl, and MgCl22～3wt％。
Further, the method further comprises: and (2) after the flotation treatment in the step (1) is finished, converting and refining the obtained potassium-sulfur mixed salt concentrate to obtain a potash magnesium sulphate fertilizer, and then reacting the potash magnesium sulphate fertilizer with the potassium chloride and fresh water obtained in the step (3) to obtain potassium sulphate.
In the invention, (1) the sulfate type potassium mixed salt ore is floated by using an anionic flotation agent, so that the sodium chloride and magnesium chloride type phases are separated from the sulfate type phase, the mutual transformation reaction influence between the sodium chloride and magnesium chloride type phases is avoided, and the potassium chloride and magnesium sulfate fertilizer products are respectively and efficiently preparedA raw material supply base; (2) the high-sodium chloride type tailings are subjected to high-temperature selective hot melting treatment, so that the advantage of increased solubility of potassium chloride and magnesium chloride can be fully exerted, and carnallite and bischofite are fully dissolved; meanwhile, the solid-to-mass ratio of the hot solution is controlled, so that only a small amount of sodium chloride and magnesium sulfate enter the saturated solution, and selective dissolution of different phases in the high-sodium chloride type tailings is realized, and the aim of separating sodium chloride from potassium chloride is fulfilled; (3) the heat in the step-type closed cooling crystallization process is recycled, the temperature of the initial hot solvent is increased, and the high-concentration MgCl is ensured2The type thermal solvent (near saturation) has extremely strong uniformity and stability; (4) the control of the concentration of the hot solvent and the liquid-solid mass ratio in the hot dissolving process is beneficial to the composition of high-temperature potassium-rich saturated liquid obtained by hot dissolving to be close to the three-phase common saturation point of carnallite, potassium chloride and sodium chloride, the composition stability of the saturated liquid is strong, and the independent separation of potassium chloride in the cooling crystallization process is facilitated; (5) the temperature difference between the hot melting and the cooling crystallization is large, so that the maximum separation of potassium chloride in the high-temperature potassium-rich saturated solution is ensured; (6) the cooling crystallization process adopts stepped slow cooling in a closed space, and simultaneously controls the proportion of supplemented fresh water (or potassium chloride washing liquid), so that other salts such as sodium chloride, magnesium chloride and the like in the high-temperature saturated liquid can be always stably remained in a liquid phase in the cooling process, and only potassium chloride is separated out; (7) the fresh water consumption in the relevant conversion and reaction is calculated by utilizing the phase diagram data, which is beneficial to the corresponding regulation of the recycling of various mother liquids and ensures the quality of the obtained product.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, the anionic flotation agent is used for flotation separation of the magnesium chloride type phase and the sulfate type phase in the sulfate type potassium mixed salt ore, so that the mutual influence of the magnesium chloride type phase and the sulfate type phase in conversion is avoided, and the efficient preparation of the magnesium potassium sulfate fertilizer and the potassium chloride is realized;
(2) the invention utilizes the characteristics of different solubility change trends of potassium chloride and magnesium chloride, sodium chloride and magnesium sulfate to cooperate with MgCl2And (3) a type solvent, wherein the high-sodium type chloride tailings are subjected to selective hot-melting treatment, and the mass ratio of sodium chloride to potassium chloride in the obtained potassium-rich saturated liquid is only 0.25: 1-0.30:1, the separation of sodium chloride and carnallite is quickly realized, and compared with the traditional process for preparing potassium chloride by carnallite ore, the selective hot melting process has better separation effect, saves the decomposition stage of carnallite, saves water resources and achieves three purposes at one time;
(3) the invention ensures the stability of the composition of the high-temperature potassium-rich saturated solution in the hot melting process and the unsaturation degree of other salts such as sodium chloride, magnesium chloride and the like in the cooling crystallization process through process control, and is beneficial to the high-efficiency and high-quality precipitation of potassium chloride;
(4) the invention has the advantages of no strict technological conditions, no setting of extremely high or low temperature and other special conditions, simple technological process and convenient popularization and implementation of the technology.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a schematic flow chart of a method for jointly preparing a potash magnesium sulphate fertilizer, potassium chloride and potassium sulfate by using sulphate type mixed potassium salt ore in one embodiment of the invention.
Detailed Description
The potash fertilizer prepared by converting the sulfate type potash mixed salt ore mainly comprises a potash magnesium sulphate fertilizer and a potash fertilizer, but the conversion effect is closely related to the phase proportion of magnesium chloride containing substances such as carnallite, bischofite and the like in the potash mixed salt ore, and the higher the content of magnesium chloride is, the lower the yield of the converted potash magnesium sulphate fertilizer is. Similarly, the yield of the potassium chloride obtained by conversion is related to the proportion of the sulfate phase, and the higher the sulfate content is, the lower the potassium chloride yield is. Meanwhile, the introduced flotation technology has almost no flotation capacity on the carnallite phase, so that the risk that the carnallite stays in tailings and is abandoned is easily caused, and the potassium resource is lost.
In view of the defects of the prior art, the inventor of the present invention provides a technical scheme of the present invention through long-term research and a large amount of practice, and the present invention aims to avoid the mutual influence of magnesium chloride type phases such as carnallite, bischofite, etc. and sulfate type phases in the conversion, efficiently prepare a potash magnesium sulphate fertilizer and potassium chloride respectively, obtain a potassium sulphate product, and realize the comprehensive development and utilization of potassium resources of sulfate type potassium mixed salt ore. The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
One aspect of an embodiment of the present invention provides a method for co-producing a potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate, comprising:
(1) carrying out flotation treatment on sulfate type potassium mixed salt ores by using an anionic flotation agent to obtain potassium-sulfur mixed salt concentrates and chloride type tailings, wherein the potassium-sulfur mixed salt concentrates comprise the following components in percentage by mass: 1.0-2.5 wt% of NaCl, 23-28 wt% of KCl and K2SO43～11wt％、MgSO442～47wt％、MgCl20-1.5 wt%, wherein the chloride type tailings comprise the following components in percentage by mass: 16-76 wt% of NaCl, 6.5-11.0 wt% of KCl, and K2SO40.2～0.7wt％、MgSO42.0～5.5wt％、MgCl24.0～32.5wt％；
(2) Enabling a hot solvent to contact with the chloride type tailings, carrying out selective hot-dissolving treatment at 75-100 ℃, and then carrying out solid-liquid separation on the obtained mixture to obtain high-temperature potassium-rich saturated liquid, sodium chloride and kieserite, wherein the hot solvent is rich in MgCl2The high-temperature potassium-rich saturated liquid is prepared by mixing the following components in percentage by mass: 1.2-1.4 wt% of NaCl, 4-5 wt% of KCl and MgSO41.0～1.4wt％、MgCl229～31wt％；
(3) While replenishing fresh water, carrying out stepped closed cooling crystallization and refining on the high-temperature potassium-rich saturated liquid obtained in the step (2)Preparing potassium chloride, wherein the potassium chloride comprises the following components in percentage by mass: 1-2 wt% of NaCl, 92-95 wt% of KCl, and MgCl22～3wt％。
In some more specific embodiments, the anionic flotation agent in step (1) includes any one or a combination of two of alkyl sulfonate anionic collectors and alkyl sulfate anionic collectors, and is not limited thereto.
Further, the flotation medium used in the flotation treatment is a saturated solution of sodium chloride, schoenite, potassium chloride and epsomite.
In some more specific embodiments, the method for preparing the thermal solvent in step (2) comprises: will be rich in MgCl2Mixing the substances with fresh water and preheating to 40-50 ℃ to obtain a hot solvent, wherein MgCl is contained in the hot solvent2The concentration of (A) is 25-30 wt%.
In some specific embodiments, the mass ratio of the hot solvent to the chloride-type tailings in the step (2) is 1.3:1 to 1.5: 1.
Further, the mass ratio of sodium chloride to potassium chloride in the high-temperature potassium-rich saturated liquid is 0.25: 1-0.30: 1.
Further, the MgCl is enriched2The substance (b) includes any one or a combination of two or more of old brine and bischofite, and is not limited thereto.
In some more specific embodiments, step (3) specifically includes: and (3) while supplementing fresh water, performing stepped closed cooling crystallization on the high-temperature potassium-rich saturated liquid obtained in the step (2), performing solid-liquid separation treatment to obtain crude potassium chloride and low-temperature potassium saturated liquid, and then performing refining treatment on the obtained crude potassium chloride to obtain potassium chloride.
Further, the step-type closed cooling crystallization treatment comprises the following steps: and (3) cooling the high-temperature potassium-rich saturated liquid to a cooling crystallization temperature at a selected cooling rate while replenishing fresh water, and performing stepped cooling and closed cooling crystallization, wherein the cooling crystallization temperature is 10-15 ℃, and the selected cooling rate is 0.3-0.5 ℃/min.
Further, the mass ratio of the fresh water to the high-temperature potassium-rich saturated liquid is 0.20: 1-0.25: 1;
further, the content of potassium chloride in the crude potassium chloride is 85-90 wt%;
further, the low-temperature potassium saturated liquid comprises the following components in percentage by mass: NaCl 0.8-0.9 wt%, KCl 2.2-2.7 wt%, MgSO40.7～1.0wt％、MgCl223～26wt％。
Further, the method further comprises: recovering the low-temperature potassium saturated solution to prepare the hot solvent.
Further, the method further comprises: and preheating the hot solvent by using the heat released in the stepped closed cooling crystallization treatment process.
In some more specific embodiments, the crude potassium chloride refining process comprises: and washing, solid-liquid separation and drying the obtained crude potassium chloride.
Further, the washing liquid used in the washing process includes fresh water, and is not limited thereto.
Further, the liquid-solid mass ratio of the washing liquid to the crude potassium chloride is 0.20: 1-0.30: 1.
Further, the temperature of the washing treatment is 10-15 ℃.
Further, the method further comprises: and adding a potassium chloride washing solution generated by the washing treatment into the closed cooling crystallization system while performing the stepped closed cooling crystallization treatment.
Furthermore, the mass ratio of the potassium chloride washing liquid to the high-temperature potassium-rich saturated liquid is 0.20: 1-0.25: 1.
In some more specific embodiments, the method further comprises: after the flotation treatment in the step (1) is finished, carrying out conversion and refining treatment on the obtained potassium-sulfur mixed salt concentrate to obtain a potassium magnesium sulfate fertilizer; and (4) reacting the potash magnesium sulphate fertilizer with the potassium chloride and fresh water obtained in the step (3) to obtain potassium sulphate.
In some more specific embodiments, the method specifically includes:
mixing the potassium-sulfur mixed salt concentrate obtained in the step (1) with fresh water for conversion treatment, separating to obtain crude picromerite and picromerite conversion mother liquor, and refining the obtained crude picromerite to obtain a potash magnesium sulphate fertilizer, wherein the potash magnesium sulphate fertilizer comprises the following components in percentage by mass: NaCl 0.2-0.5 wt%, K2SO450～55wt％、MgSO423～27wt％；
And (3) reacting a mixed reaction system containing the potash magnesium sulphate fertilizer, the potassium chloride obtained in the step (3) and fresh water to obtain crude potassium sulphate, and then refining to obtain the potassium sulphate, wherein the potassium sulphate comprises the following components in percentage by mass: NaCl 0.5-1.0 wt%, KCl 0.5-1.0 wt%, and K2SO492～95wt％、MgSO42～4wt％。
Furthermore, the fresh water consumption of the potassium-sulfur mixed salt concentrate conversion treatment is 1.10-1.15 times of the amount obtained through phase diagram calculation.
Further, the method further comprises: and (4) recovering the picromerite conversion mother liquor, mixing with the low-temperature potassium saturated liquor obtained in the step (3), and solarizing to form potassium mixed salt.
Further, the method further comprises: and recovering the picromerite conversion mother liquor as a flotation medium used in flotation treatment.
In the invention, the flotation medium is sodium chloride, schoenite, potassium chloride and epsomite saturated solution, and the schoenite conversion mother liquor can also be used as the flotation medium.
Further, the refining treatment of the crude schoenite comprises the following steps: and washing, separating and drying the obtained crude picromerite to obtain the potash magnesium sulphate fertilizer.
Furthermore, the washing liquid adopted in the washing treatment comprises fresh water; more preferably, the liquid-solid mass ratio of the washing liquid to the crude schoenite is 0.15:1 to 0.25: 1.
Still further, the method further comprises: the picromerite washing liquid generated by the recovery washing treatment is mixed with fresh water for conversion treatment to prepare crude picromerite.
Furthermore, the amount of the fresh water in the mixed reaction system is 1.1-1.2 times of the amount obtained by calculating through a phase diagram.
Further, the content of potassium sulfate in the crude potassium sulfate is 85-90 wt%.
Further, the crude potassium sulfate refining treatment comprises the following steps: and washing, separating and drying the crude potassium sulfate to obtain the potassium sulfate.
Further, the washing liquid adopted by the washing treatment comprises fresh water.
Furthermore, the liquid-solid mass ratio of the washing liquid to the crude potassium sulfate is 0.20: 1-0.30: 1.
Still further, the method further comprises: the potassium sulfate washing liquid generated by the washing treatment is recycled for preparing potassium sulfate.
As one of more specific embodiments of the present invention, referring to fig. 1, the method for jointly preparing a potash magnesium sulphate fertilizer, potassium chloride and potassium sulfate by using a sulfate type potash mixed salt ore may specifically include the following steps:
(1) stage one: and (3) carrying out flotation separation on the sulfate type potassium mixed salt ore to obtain potassium-sulfur mixed salt concentrate and chloride type tailings. The flotation agent is alkyl sulfonate or sulfate and other anionic collectors, and the flotation medium is sodium chloride, picromerite, potassium chloride and epsomite saturated solution. The potassium-sulfur mixed salt concentrate obtained by flotation comprises 1.0-2.5 percent of NaCl, 23-28 percent of KCl and K2SO43％～11％、MgSO442％～47％、MgCl20 to 1.5 percent of the total amount of the tailings, the chloride tailings comprise 16 to 76 percent of NaCl, 6.5 to 11.0 percent of KCl and K2SO40.2％～0.7％、MgSO42.0％～5.5％、MgCl24.0 to 32.5 percent of high-sodium chloride mineral.
(2) And a second stage: and (4) converting the potassium-sulfur mixed salt concentrate to obtain coarse picromerite, washing and refining to prepare a potash magnesium sulphate fertilizer product. Converting the potassium-sulfur mixed salt concentrate by using fresh water, the picromerite washing solution and the potassium sulfate conversion mother solution to obtain crude picromerite, wherein the conversion water amount is 1.10-1.15 times of the theoretical fresh water input amount (the theoretical fresh water input amount passes through)Calculated phase diagram); returning the separated picromerite conversion mother liquor to the first stage as a flotation medium, or mixing the picromerite conversion mother liquor with low-temperature potassium saturated liquid and solarizing the mixture to obtain potassium mixed salt ore. And continuously washing and drying the coarse picromerite to obtain the potash magnesium sulphate fertilizer product. The liquid-solid mass ratio of the fresh water added in the washing to the crude schoenite is 0.15: 1-0.25: 1, the washing solution of the schoenite obtained by the washing is returned to the potassium-sulfur mixed salt concentrate conversion stage for recycling, and the obtained potash magnesium sulphate fertilizer comprises 0.2-0.5% of NaCl and K2SO450％～55％、MgSO423％～27％。
(3) And a third stage: and (3) selectively carrying out hot melting separation on the chloride type tailings to obtain sodium chloride and kieserite, thereby obtaining high-temperature potassium-rich saturated solution. The hot solvent is prepared from aged brine, bischofite or low-temperature potassium saturated solution rich in MgCl2The salt ore body is mixed with fresh water, wherein MgCl is contained in the hot solvent2The percentage concentration of (A) is 25-30%. And absorbing energy released by cooling the high-temperature potassium-rich saturated liquid, and preheating the hot solvent, wherein the temperature of the preheated hot solvent is 40-50 ℃. And (3) selectively hot-dissolving the chloride tailings by using a hot solvent, wherein the hot-dissolving temperature is 75-100 ℃, the liquid-solid mass ratio of the hot solvent to the chloride tailings is controlled to be 1.3: 1-1.5: 1, and the hot solution phase composition is kept stable to serve as a sign for hot-dissolving completion. After the selective hot dissolving is finished, carrying out solid-liquid separation to obtain high-temperature potassium-rich saturated solution which comprises 1.2-1.4 percent of NaCl, 4-5 percent of KCl and MgSO41.0％～1.4％、MgCl229-31 percent, the rest solid phase is sodium chloride and kieserite, and the potassium in the tailings enters into high-temperature potassium-rich saturated solution.
(4) And a fourth stage: closing, cooling and crystallizing the high-temperature potassium-rich saturated liquid to obtain crude potassium chloride, and washing and refining to obtain a potassium chloride product. Controlling the cooling crystallization temperature to be 10-15 ℃, the cooling rate to be 0.3-0.5 ℃/min, carrying out stepped closed cooling crystallization on the high-temperature potassium-rich saturated liquid, and simultaneously supplementing a certain amount of fresh water (or potassium chloride washing liquid), wherein the mass ratio of the supplemented fresh water (or potassium chloride washing liquid) to the high-temperature potassium-rich saturated liquid is controlled to be 0.20: 1-0.25: 1. The solid phase obtained after solid-liquid separation is crude potassium chloride, and the content of potassium chloride is 85-90%; the residual liquid is low-temperature potassium saturated liquid with the composition of NaCl 0.8% ~ up to0.9％、KCl 2.2％～2.7％、MgSO40.7％～1.0％、MgCl223% -26%, and the potassium mixed salt ore is obtained by mixing the potassium mixed salt ore with a hot solvent preparation or schoenite conversion mother liquor and solarizing the mixture. And washing and drying the crude potassium chloride to obtain a potassium chloride product. Wherein the liquid-solid mass ratio of the fresh water added in the washing to the crude potassium chloride is 0.20: 1-0.30: 1, and the washing temperature is the same as the crystallization temperature. Returning the washed potassium chloride washing liquid to the fourth stage for reuse, wherein the obtained potassium chloride comprises 1-2% of NaCl, 92-95% of KCl and MgCl22％～3％。
(5) And a fifth stage: the potassium chloride reacts with potassium magnesium sulfate fertilizer to obtain coarse potassium sulfate, which is washed and refined to obtain potassium sulfate product. And adding fresh water into the potash magnesium sulphate fertilizer and the potassium chloride product obtained in the second stage and the fourth stage for mixing reaction to obtain crude potassium sulphate. Wherein the reaction water amount is 1.1-1.2 times of the theoretical fresh water input amount (the theoretical fresh water input amount is obtained by phase diagram calculation); the potassium sulfate content is 85-90%; and returning the residual potassium sulfate conversion mother liquor to the potassium-sulfur mixed salt concentrate conversion stage for recycling. And washing and drying the coarse potassium sulfate to obtain a potassium sulfate product. Wherein the liquid-solid mass ratio of the fresh water added in the washing to the crude potassium sulfate is 0.20: 1-0.30: 1, the potassium sulfate washing liquid obtained by the washing is returned to the reaction stage of the potash magnesium sulphate fertilizer and the potassium chloride for recycling, and the obtained potassium sulfate comprises 0.5-1.0% of NaCl0, 0.5-1.0% of KCl and K2SO492％～95％、MgSO42％～4％。
In the invention, (1) an anionic flotation agent is used for flotation of the sulfate type potassium mixed salt ore, so that sodium chloride and magnesium chloride type phases in the sulfate type potassium mixed salt ore are separated from the sulfate type phases, the mutual transformation reaction influence between the sodium chloride and magnesium chloride type phases is avoided, and a raw material basis is provided for respectively and efficiently preparing potassium chloride and potassium magnesium sulfate fertilizer products; (2) the high-sodium chloride type tailings are subjected to high-temperature selective hot melting treatment, so that the advantage of increased solubility of potassium chloride and magnesium chloride can be fully exerted, and carnallite and bischofite are fully dissolved; meanwhile, the solid-to-mass ratio of the hot solution is controlled, so that only a small amount of sodium chloride and magnesium sulfate enter the saturated solution, and the selective dissolution of different phases in the high-sodium chloride tailings is realized to achieve the aim ofThe purpose of separating sodium chloride and potassium chloride; (3) control of the Hot solvent MgCl2The concentration is 25-30%, the solid-to-solid mass ratio of the concentrated solution to the hot solution is 1.3: 1-1.5: 1, the composition of a high-temperature potassium-rich saturated solution obtained by hot melting is close to a three-phase common saturation point of carnallite, potassium chloride and sodium chloride, the composition stability of the saturated solution is high, and the potassium chloride can be separated out independently in the cooling crystallization process; (4) in the cooling crystallization process, the temperature is slowly reduced in a stepped manner in a closed space, and meanwhile, the mass ratio of the supplemented fresh water (or potassium chloride washing liquid) to the high-temperature potassium-rich saturated liquid is controlled to be 0.20: 1-0.25: 1, so that sodium chloride, magnesium chloride and other salts in the high-temperature saturated liquid can be always stably remained in a liquid phase in the temperature reduction process, and only potassium chloride is separated out. The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.
The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.
The following examples (examples 1-3) were all obtained by the following steps:
(1) and (3) carrying out flotation separation on the sulfate type potassium mixed salt ore to obtain potassium-sulfur mixed salt concentrate and chloride type tailings. The flotation agent is alkyl sulfonate or sulfate and other anionic collectors, and the flotation medium is sodium chloride, schoenite, potassium chloride and epsomite saturated solution;
(2) and (4) converting the potassium-sulfur mixed salt concentrate to obtain coarse picromerite, washing and refining to prepare a potash magnesium sulphate fertilizer product. And (3) converting the potassium-sulfur mixed salt concentrate by using fresh water, the picromerite washing liquid and the potassium sulfate conversion mother liquor to obtain crude picromerite, and returning the separated picromerite conversion mother liquor to the first stage to be used as a flotation medium or mixing the separated picromerite conversion mother liquor with low-temperature potassium saturated liquid and solarizing the mixture to obtain potassium mixed salt ore. And continuously washing and drying the coarse picromerite to obtain the potash magnesium sulphate fertilizer product. Returning the washed picromerite washing liquid to the potassium-sulfur mixed salt concentrate conversion stage for recycling;
(3) selective thermosol separation of chloride type tailingsSeparating sodium chloride and kieserite to obtain high-temperature potassium-rich saturated solution, wherein the hot solvent is prepared from old brine, bischofite or low-temperature potassium-rich saturated solution rich in MgCl2Mixing the salt ore body with fresh water to obtain a mixture, wherein the rest solid phases are sodium chloride and kieserite, and potassium in the tailings enters a high-temperature potassium-rich saturated solution;
(4) closing, cooling and crystallizing the high-temperature potassium-rich saturated liquid to obtain crude potassium chloride, and washing and refining the crude potassium chloride to prepare a potassium chloride product;
(5) and (3) reacting potassium chloride with the potash magnesium sulphate fertilizer to obtain crude potassium sulphate, washing and refining to prepare a potassium sulphate product, and adding fresh water into the potash magnesium sulphate fertilizer and the potassium chloride product obtained in the step (2) and the step (4) to perform mixed reaction to obtain the crude potassium sulphate. And returning the residual potassium sulfate conversion mother liquor to the potassium-sulfur mixed salt concentrate conversion stage for recycling. And washing and drying the coarse potassium sulfate to obtain a potassium sulfate product.
Example 1
Example 2
Example 3
In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (10)
1. A method for coproducing a potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate is characterized by comprising the following steps:
(1) carrying out flotation treatment on sulfate type potassium mixed salt ore by using an anionic flotation agent to obtain potassium-sulfur mixed salt concentrate and chloride typeThe tailings comprise the following components in percentage by mass: 1.0-2.5 wt% of NaCl, 23-28 wt% of KCl and K2SO43～11wt％、MgSO442～47wt％、MgCl20-1.5 wt%, wherein the chloride type tailings comprise the following components in percentage by mass: 16-76 wt% of NaCl, 6.5-11.0 wt% of KCl, and K2SO40.2～0.7wt％、MgSO42.0～5.5wt％、MgCl24.0～32.5wt％；
(2) Enabling a hot solvent to contact with the chloride type tailings, carrying out selective hot-dissolving treatment at 75-100 ℃, and then carrying out solid-liquid separation on the obtained mixture to obtain high-temperature potassium-rich saturated liquid, sodium chloride and kieserite, wherein the hot solvent is rich in MgCl2The high-temperature potassium-rich saturated liquid is prepared by mixing the following components in percentage by mass: 1.2-1.4 wt% of NaCl, 4-5 wt% of KCl and MgSO41.0～1.4wt％、MgCl229～31wt％；
(3) And (3) while supplementing fresh water, performing stepped closed cooling crystallization and refining treatment on the high-temperature potassium-rich saturated liquid obtained in the step (2) to prepare potassium chloride, wherein the potassium chloride comprises the following components in percentage by mass: 1-2 wt% of NaCl, 92-95 wt% of KCl, and MgCl22～3wt％。
2. The method of claim 1, wherein: the anionic flotation agent in the step (1) comprises an alkyl sulfonate anionic collector and/or an alkyl sulfate anionic collector;
and/or the flotation medium used in the flotation treatment is a saturated solution of sodium chloride, schoenite, potassium chloride and epsomite.
3. The method of claim 1, wherein: the preparation method of the thermal solvent in the step (2) comprises the following steps: will be rich in MgCl2Mixing the substances with fresh water and preheating to 40-50 ℃ to obtain a hot solvent, wherein MgCl is contained in the hot solvent2The concentration of (A) is 25-30 wt%.
4. The method according to claim 1, wherein the mass ratio of the hot solvent to the chloride-type tailings in the step (2) is 1.3:1 to 1.5: 1;
and/or the mass ratio of sodium chloride to potassium chloride in the high-temperature potassium-rich saturated liquid is 0.25: 1-0.30: 1;
and/or, said enriched MgCl2The substance(s) of (a) include old brine and/or bischofite.
5. The method according to claim 1, wherein step (3) comprises in particular: step-type closed cooling crystallization is carried out on the high-temperature potassium-rich saturated liquid obtained in the step (2) while fresh water is supplemented, then solid-liquid separation treatment is carried out to obtain crude potassium chloride and low-temperature potassium saturated liquid, and then the obtained crude potassium chloride is refined to obtain potassium chloride;
preferably, the step-type closed cooling crystallization treatment comprises the following steps: cooling the high-temperature potassium-rich saturated liquid to a cooling crystallization temperature at a selected cooling rate while replenishing fresh water, and performing stepped cooling and closed cooling crystallization, wherein the cooling crystallization temperature is 10-15 ℃, and the selected cooling rate is 0.3-0.5 ℃/min;
preferably, the mass ratio of the fresh water to the high-temperature potassium-rich saturated liquid is 0.20: 1-0.25: 1;
preferably, the content of potassium chloride in the crude potassium chloride is 85-90 wt%;
preferably, the low-temperature potassium saturated liquid comprises the following components in percentage by mass: NaCl 0.8-0.9 wt%, KCl 2.2-2.7 wt%, MgSO40.7～1.0wt％、MgCl223～26wt％；
Preferably, the method further comprises: recovering the low-temperature potassium saturated solution to prepare the hot solvent;
preferably, the method further comprises: and preheating the hot solvent by using the heat released in the stepped closed cooling crystallization treatment process.
6. The method of claim 5, wherein the crude potassium chloride refining process comprises: washing, solid-liquid separation and drying the obtained crude potassium chloride;
preferably, the washing liquid used in the washing treatment comprises fresh water; preferably, the liquid-solid mass ratio of the washing liquid to the crude potassium chloride is 0.20: 1-0.30: 1; preferably, the temperature of the washing treatment is 10-15 ℃;
preferably, the method further comprises: adding a potassium chloride washing solution generated by washing treatment into a closed cooling crystallization system while performing the stepped closed cooling crystallization treatment; more preferably, the mass ratio of the potassium chloride washing solution to the high-temperature potassium-rich saturated solution is 0.20: 1-0.25: 1.
7. The method of claim 1, further comprising: after the flotation treatment in the step (1) is finished, carrying out conversion and refining treatment on the obtained potassium-sulfur mixed salt concentrate to obtain a potassium magnesium sulfate fertilizer; and (4) reacting the potash magnesium sulphate fertilizer with the potassium chloride and fresh water obtained in the step (3) to obtain potassium sulphate.
8. The method according to claim 7, characterized in that it comprises in particular:
mixing the potassium-sulfur mixed salt concentrate obtained in the step (1) with fresh water for conversion treatment, separating to obtain crude picromerite and picromerite conversion mother liquor, and refining the obtained crude picromerite to obtain a potash magnesium sulphate fertilizer, wherein the potash magnesium sulphate fertilizer comprises the following components in percentage by mass: NaCl 0.2-0.5 wt%, K2SO450～55wt％、MgSO423～27wt％；
And (3) reacting a mixed reaction system containing the potash magnesium sulphate fertilizer, the potassium chloride obtained in the step (3) and fresh water to obtain crude potassium sulphate, and then refining to obtain the potassium sulphate, wherein the potassium sulphate comprises the following components in percentage by mass: NaCl 0.5-1.0 wt%, KCl 0.5-1.0 wt%, and K2SO492～95wt％、MgSO42～4wt％。
9. The method according to claim 8, wherein the fresh water used in the potassium-sulfur mixed salt concentrate conversion treatment is 1.10-1.15 times of the fresh water obtained by phase diagram calculation;
and/or, the method further comprises: recovering the picromerite conversion mother liquor, mixing with the low-temperature potassium saturated liquor obtained in the step (3), and solarizing to form potassium mixed salt;
and/or, the method further comprises: recovering the picromerite conversion mother liquor as a flotation medium used in flotation treatment;
and/or the refining treatment of the crude schoenite comprises the following steps: washing, separating and drying the obtained crude picromerite to obtain a potash magnesium sulphate fertilizer; preferably, the washing liquid used in the washing treatment comprises fresh water; more preferably, the liquid-solid mass ratio of the washing liquid to the crude schoenite is 0.15: 1-0.25: 1; preferably, the method further comprises: the picromerite washing liquid generated by the recovery washing treatment is mixed with fresh water for conversion treatment to prepare crude picromerite.
10. The method according to claim 8, wherein the amount of the fresh water in the mixed reaction system is 1.1 to 1.2 times of the amount calculated by a phase diagram;
and/or the content of potassium sulfate in the crude potassium sulfate is 85-90 wt%;
and/or the crude potassium sulfate refining treatment comprises the following steps: washing, separating and drying the crude potassium sulfate to obtain potassium sulfate; preferably, the washing liquid used in the washing treatment comprises fresh water; more preferably, the liquid-solid mass ratio of the washing liquid to the crude potassium sulfate is 0.20: 1-0.30: 1; preferably, the method further comprises: the potassium sulfate washing liquid generated by the washing treatment is recycled for preparing potassium sulfate.
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| CN113247920A (en) * | 2021-05-24 | 2021-08-13 | 青海联宇钾肥有限公司 | Method for co-producing potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate |
| CN113526529A (en) * | 2021-04-02 | 2021-10-22 | 青海联宇钾肥有限公司 | Comprehensive recycling method of potassium sulfate high-potassium mother liquor |
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