CN111362731A - Potassium magnesium sulfate fertilizer, potassium chloride and preparation method of potassium sulfate - Google Patents
Potassium magnesium sulfate fertilizer, potassium chloride and preparation method of potassium sulfate Download PDFInfo
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- CN111362731A CN111362731A CN202010371578.3A CN202010371578A CN111362731A CN 111362731 A CN111362731 A CN 111362731A CN 202010371578 A CN202010371578 A CN 202010371578A CN 111362731 A CN111362731 A CN 111362731A
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- potassium
- chloride
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- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 title claims abstract description 351
- 239000001103 potassium chloride Substances 0.000 title claims abstract description 175
- 235000011164 potassium chloride Nutrition 0.000 title claims abstract description 175
- 229910052939 potassium sulfate Inorganic materials 0.000 title claims abstract description 81
- 239000003337 fertilizer Substances 0.000 title claims abstract description 72
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 title claims abstract description 66
- 235000011151 potassium sulphates Nutrition 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- WZISDKTXHMETKG-UHFFFAOYSA-H dimagnesium;dipotassium;trisulfate Chemical compound [Mg+2].[Mg+2].[K+].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O WZISDKTXHMETKG-UHFFFAOYSA-H 0.000 title description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 153
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 145
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims abstract description 142
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000011591 potassium Substances 0.000 claims abstract description 103
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 103
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims abstract description 83
- 239000011780 sodium chloride Substances 0.000 claims abstract description 79
- 150000003839 salts Chemical class 0.000 claims abstract description 72
- 239000013505 freshwater Substances 0.000 claims abstract description 66
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 65
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 63
- 229940072033 potash Drugs 0.000 claims abstract description 63
- 235000015320 potassium carbonate Nutrition 0.000 claims abstract description 63
- 239000011555 saturated liquid Substances 0.000 claims abstract description 59
- 235000019341 magnesium sulphate Nutrition 0.000 claims abstract description 51
- 238000001816 cooling Methods 0.000 claims abstract description 45
- 238000005188 flotation Methods 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 39
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 238000002425 crystallisation Methods 0.000 claims abstract description 33
- 230000008025 crystallization Effects 0.000 claims abstract description 33
- 239000012141 concentrate Substances 0.000 claims abstract description 26
- LFZAXBDWELNSEE-UHFFFAOYSA-N [S].[K] Chemical compound [S].[K] LFZAXBDWELNSEE-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 23
- 238000001704 evaporation Methods 0.000 claims abstract description 18
- 239000001120 potassium sulphate Substances 0.000 claims abstract description 18
- 125000000129 anionic group Chemical group 0.000 claims abstract description 11
- 239000008396 flotation agent Substances 0.000 claims abstract description 9
- 229910052928 kieserite Inorganic materials 0.000 claims abstract description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L magnesium chloride Substances [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 77
- 238000006243 chemical reaction Methods 0.000 claims description 65
- 238000005406 washing Methods 0.000 claims description 65
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 58
- PALNZFJYSCMLBK-UHFFFAOYSA-K magnesium;potassium;trichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-].[Cl-].[K+] PALNZFJYSCMLBK-UHFFFAOYSA-K 0.000 claims description 55
- 239000007788 liquid Substances 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 24
- 239000012047 saturated solution Substances 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 239000012452 mother liquor Substances 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 20
- 229910052708 sodium Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 238000007670 refining Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000000354 decomposition reaction Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 239000012267 brine Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 11
- 230000008020 evaporation Effects 0.000 claims description 11
- GMLLYEDWRJDBIT-UHFFFAOYSA-J magnesium;dipotassium;disulfate Chemical compound [Mg+2].[K+].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GMLLYEDWRJDBIT-UHFFFAOYSA-J 0.000 claims description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 11
- 238000010587 phase diagram Methods 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims description 9
- 229910052564 epsomite Inorganic materials 0.000 claims description 7
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- 238000004364 calculation method Methods 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 abstract description 17
- 239000012071 phase Substances 0.000 description 24
- 235000011147 magnesium chloride Nutrition 0.000 description 18
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000004064 recycling Methods 0.000 description 10
- 239000007790 solid phase Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910021653 sulphate ion Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 235000015097 nutrients Nutrition 0.000 description 3
- -1 picromerite Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000005227 alkyl sulfonate group Chemical group 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000004720 fertilization Effects 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 150000003109 potassium Chemical class 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052930 hexahydrite Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- SWHAQEYMVUEVNF-UHFFFAOYSA-N magnesium potassium Chemical compound [Mg].[K] SWHAQEYMVUEVNF-UHFFFAOYSA-N 0.000 description 1
- BMQVDVJKPMGHDO-UHFFFAOYSA-K magnesium;potassium;chloride;sulfate;trihydrate Chemical compound O.O.O.[Mg+2].[Cl-].[K+].[O-]S([O-])(=O)=O BMQVDVJKPMGHDO-UHFFFAOYSA-K 0.000 description 1
- OJXVUEMVNWMNCR-UHFFFAOYSA-L magnesium;potassium;sulfate Chemical compound [Mg+2].[K+].[O-]S([O-])(=O)=O OJXVUEMVNWMNCR-UHFFFAOYSA-L 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052929 starkeyite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- 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
- C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- 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
-
- 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
- C01D3/14—Purification
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; Specified applications
- B03D2203/02—Ores
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses a potash magnesium sulphate fertilizer, potassium chloride and a preparation method of potash. The method comprises the following steps: 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, a hot solvent is contacted with the chloride type tailings for selective hot-dissolving treatment to obtain high-temperature potassium-rich saturated liquid, sodium chloride and kieserite; then, while replenishing fresh water, carrying out stepped closed cooling crystallization treatment on the obtained high-temperature potassium-rich saturated liquid to prepare potassium chloride; meanwhile, evaporating and decomposing fresh water on the low-temperature potassium saturated liquid obtained by the cooling crystallization treatment 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. The invention has high separation efficiency, simple technological condition and flow and convenient 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 potash magnesium sulphate fertilizer, potassium chloride and a preparation method of potassium sulphate.
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 mixture of various single salts and double salts comprises the following main 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 MgC)l2·6H2O) and bischofite (MgCl)2·6H2O), etc., the composition ranges of the components are 10 to 30 percent of NaCl, 78 to 20 percent of KCl15 and 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 preparation method of 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 preparation method of a potash magnesium sulphate fertilizer, potassium chloride and potassium sulfate, 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) When fresh water is supplemented, performing stepped closed cooling crystallization treatment on the high-temperature potassium-rich saturated liquid obtained in the step (2) to obtain crude potassium chloride and low-temperature potassium saturated liquid; 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％、MgCl223-26 wt%, wherein the content of potassium chloride in the crude potassium chloride is 85-90 wt%;
(4) evaporating the low-temperature potassium saturated solution to obtain ultra-low-sodium carnallite, and then performing fresh water decomposition on the ultra-low-sodium carnallite to obtain crude potassium chloride and low-temperature carnalliteSaturated liquid of stone; the low-temperature carnallite saturated liquid comprises the following components in percentage by mass: NaCl 1.5-2.0 wt%, KCl 2.5-3.5 wt%, MgSO40.5～1.0wt％、MgCl225-26 wt%, wherein the content of potassium chloride in the crude potassium chloride is 90-92 wt%.
Further, the preparation method further comprises the following steps: mixing the crude potassium chloride obtained in the steps (3) and (4) and refining to obtain potassium chloride, wherein the potassium chloride comprises the following components in percentage by mass: NaCl 0.8-1.5 wt%, KCl 93-96 wt%, MgCl21～2wt％。
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 obtained potassium chloride and fresh water to obtain potassium sulphate.
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 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) thermal melting and cooling crystallization "The temperature difference 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) compared with pure chloride type low-temperature potassium saturated liquid, the low-temperature potassium saturated liquid has lower sodium chloride content under the influence of hot melting and magnesium sulfate introduction, so that carnallite obtained by evaporation is very low-sodium carnallite, and crude potassium chloride can be obtained by direct decomposition without further process treatment; (8) the fresh water consumption in the relevant conversion, decomposition and reaction is calculated by utilizing the phase diagram data, thereby being beneficial to the corresponding regulation of the recycling of various mother liquids and ensuring 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 MgCl2The selective hot-dissolving process is used for selectively hot-dissolving the high-sodium chloride tailings, and the mass ratio of sodium chloride to potassium chloride in the obtained potassium-rich saturated solution is only 0.25: 1-0.30: 1, so that the separation of sodium chloride and carnallite is rapidly realized, and compared with the traditional process for preparing potassium chloride from carnallite ore, the selective hot-dissolving process has the advantages of better separation effect, water resource saving and two purposes;
(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 technical process ensures the extreme low property of sodium chloride in carnallite, crude potassium chloride can be obtained by decomposition, and unnecessary process flows are reduced while high yield and high quality of potassium chloride are ensured;
(5) the invention has the advantages of no strict technological conditions, no setting of extremely high or low temperature and other special conditions, 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 preparing a potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate by using sulphate type mixed potassium salt ore according to an embodiment of the present 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 the embodiments of the present invention provides a potash magnesium sulphate fertilizer, a potassium chloride and a preparation method of potassium sulphate, which includes:
(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) When fresh water is supplemented, performing stepped closed cooling crystallization treatment on the high-temperature potassium-rich saturated liquid obtained in the step (2) to obtain crude potassium chloride and low-temperature potassium saturated liquid; 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％、MgCl223-26 wt%, wherein the content of potassium chloride in the crude potassium chloride is 85-90 wt%;
(4) evaporating the low-temperature potassium saturated liquid to obtain the ultra-low sodium carnallite, and then performing fresh water separation on the ultra-low sodium carnallitePerforming decomposition treatment to obtain crude potassium chloride and low-temperature carnallite saturated liquid; the low-temperature carnallite saturated liquid comprises the following components in percentage by mass: NaCl 1.5-2.0 wt%, KCl 2.5-3.5 wt%, MgSO40.5～1.0wt％、MgCl225-26 wt%, wherein the content of potassium chloride in the crude potassium chloride is 90-92 wt%.
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%.
Further, the mass ratio of the hot solvent to the chloride type tailings in the step (2) is 1.3: 1-1.5: 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, bischofite, and low-temperature carnallite saturated solution, but 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), and performing solid-liquid separation treatment to obtain crude potassium chloride and low-temperature potassium saturated liquid.
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.
Furthermore, the mass ratio of the fresh water to the high-temperature potassium-rich saturated liquid is 0.20: 1-0.25: 1.
Further, the preparation method further comprises the following steps: and preheating the hot solvent by using the heat released in the stepped closed cooling crystallization treatment process.
In some more specific embodiments, the very low sodium carnallite used in step (4) comprises the following components in percentage by mass: 1-2 wt% of NaCl, 20-22 wt% of KCl and MgSO40.3～0.8wt％、MgCl230～35wt％。
Further, the temperature of the evaporation treatment is 75-100 ℃.
Further, the preparation method further comprises the following steps: recovering the old brine generated by the evaporation treatment to prepare the hot solvent.
Further, the old brine comprises the following components in percentage by mass: NaCl 0.6-1.2 wt%, KCl 0.1-0.5 wt%, MgSO41.0～1.5wt％、MgCl226～29wt％。
Further, the temperature of the fresh water decomposition treatment is 10-15 ℃.
Furthermore, the amount of the fresh water in the fresh water decomposition treatment is 1.1-1.2 times of the amount obtained by calculating through a phase diagram.
Further, the preparation method further comprises the following steps: and recovering the low-temperature carnallite saturated liquid generated by the fresh water decomposition treatment to prepare the hot solvent.
In some more specific embodiments, the preparation method further comprises: mixing the crude potassium chloride obtained in the steps (3) and (4) and refining to obtain potassium chloride, wherein the potassium chloride comprises the following components in percentage by mass: NaCl 0.8-1.5 wt%, KCl 93-96 wt%, MgCl21～2wt％。
Further, the crude potassium chloride refining treatment comprises the following steps: and washing, solid-liquid separation and drying the obtained crude potassium chloride.
Further, the washing liquid used in the washing process includes, but is not limited to, fresh water.
Furthermore, the liquid-solid mass ratio of the washing liquid to the crude potassium chloride is 0.20: 1-0.25: 1.
Furthermore, the temperature of the washing treatment is 10-15 ℃.
Still further, the preparation 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 preparation method further comprises:
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 reacting a mixed reaction system containing the potash magnesium sulphate fertilizer, the potassium chloride obtained in the claim 6 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 preparation method further comprises the following steps: and (4) recovering the picromerite conversion mother liquor, mixing the picromerite conversion mother liquor with the low-temperature carnallite saturated liquid obtained in the step (4), and solarizing the mixture to form potassium mixed salt.
Further, the preparation method further comprises the following steps: 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 preparation method further comprises the following steps: and recovering the potassium sulfate conversion mother liquor reacted in the mixed reaction system, mixing the potassium sulfate conversion mother liquor with fresh water, and performing conversion treatment to prepare the crude picromerite.
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 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 reagent 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 weight 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. And (3) converting the fresh water, the picromerite washing solution and the potassium sulfate conversion mother solution into potassium-sulfur mixed salt concentrate to obtain the crude picromerite. Wherein the converted water amount is 1.10-1.15 times of the theoretical fresh water input amount (the theoretical fresh water input amount is obtained by phase diagram calculation); 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 carnallite saturated liquor 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, and the washing solution of the schoenite obtained by washing is returned to the potassium-sulfur mixed salt concentrate conversion stage for recycling. The obtained potash magnesium sulphate fertilizer consists of NaCl 0.2-0.5% 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 carnallite 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 ℃. Selectively hot-dissolving chloride tailings by using hot solvent at hot-dissolving temperatureThe temperature is 75-100 ℃, the liquid-solid mass ratio of the hot solvent to the chloride type 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 of hot melting 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 MgSO 441.0％～1.4％，MgCl229 to 31 percent; the remaining solid phases are sodium chloride and kieserite, and potassium in the tailings completely enters high-temperature potassium-rich saturated liquid.
(4) And a fourth stage: closing the high-temperature potassium-rich saturated liquid, cooling and crystallizing to obtain crude potassium chloride. 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 saturated potassium solution comprising NaCl 0.8-0.9 wt%, KCl 2.2-2.7 wt% and MgSO40.7％～1.0％，MgCl223％～26％。
(5) And a fifth stage: evaporating the low-temperature potassium saturated solution to separate out the ultra-low sodium carnallite. The low-temperature saturated potassium solution is continuously evaporated, and the residual solution consists of 0.6-1.2 percent of NaCl, 0.1-0.5 percent of KCl and MgSO41.0％～1.5％，MgCl2And stopping evaporation when the concentration is between 26 and 29 percent. Solid-liquid separation, namely the residual liquid at the moment is the aged brine, and the residual liquid is returned to the hot solvent preparation stage for recycling; the separated solid phase is carnallite ore which comprises 1-2 percent of NaCl, 20-22 percent of KCl and MgSO40.3％～0.8％，MgCl230 to 35 percent of the sodium halide is very low sodium carnallite.
(6) And a sixth stage: decomposing the ultra-low sodium carnallite to obtain crude potassium chloride. And (3) decomposing the low-sodium carnallite by the fresh water, wherein the decomposition temperature is the same as the cooling crystallization temperature in the fourth stage, and the adding amount of the fresh water is 1.1-1.2 times of the theoretical fresh water amount (the theoretical fresh water amount is obtained by calculating through a phase diagram). After solid-liquid separation, the obtained solid phase is crude potassium chloride, and the content of the potassium chloride is 90-92 percent; the liquid phase is low-temperature carnallite saturated liquid, the composition of the liquid phase is 1.5-2.0 percent of NaCl,KCl 2.5％～3.5％，MgSO40.5％～1.0％，MgCl225 to 26 percent of the potassium mixed salt ore can be returned to the hot solvent preparation stage for recycling or is mixed with the picromerite conversion mother liquor and is solarized to obtain the potassium mixed salt ore.
(7) Stage seven: refining the crude potassium chloride to prepare a potassium chloride product. And mixing the crude potassium chloride obtained in the fourth stage and the crude potassium chloride obtained in the sixth stage, washing and drying to prepare 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: 1-0.25: 1, and the washing temperature is the same as the crystallization temperature in the fourth stage. And returning the potassium chloride washing liquid obtained by washing to the fourth stage for recycling. The obtained potassium chloride comprises 0.8-1.5% of NaCl, 93-96% of KCl and MgCl21％～2％。
(8) And step eight: 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 seventh 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, and the potassium sulfate washing liquid obtained by washing is returned to the reaction stage of the potassium magnesium sulfate fertilizer and potassium chloride for recycling. The potassium sulfate comprises NaCl0.5-1.0%, KCl 0.5-1.0%, 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; simultaneously controlling the solid mass of the hot solutionIn comparison, only a small amount of sodium chloride and magnesium sulfate enter the saturated solution, so that 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) 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) the cooling crystallization process adopts stepped slow cooling in a closed space, and simultaneously 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 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; (5) compared with pure chloride type low-temperature potassium saturated liquid, the low-temperature potassium saturated liquid has lower sodium chloride content under the influence of hot melting and magnesium sulfate introduction, so that carnallite obtained by evaporation is very low-sodium carnallite, and crude potassium chloride can be obtained by direct decomposition without further process treatment.
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 reagent is alkyl sulfonate or sulfate and other anionic collectors, and the flotation medium is sodium chloride, picromerite, 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 fresh water, the picromerite washing solution and the potassium sulfate conversion mother solution into potassium-sulfur mixed salt concentrate to obtain the crude picromerite. And (3) returning the separated picromerite conversion mother liquor to the step (1) to be used as a flotation medium, or mixing the picromerite conversion mother liquor with the low-temperature carnallite saturated liquor and solarizing the mixture to obtain the potassium mixed salt mine. Continuously washing and drying the coarse picromerite to obtain a potash magnesium sulphate fertilizer product;
(3) 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. Carrying out solid-liquid separation after the selective hot melting is finished to obtain high-temperature potassium-rich saturated liquid, wherein the rest solid phases are sodium chloride and kieserite, and potassium in the tailings completely enters the high-temperature potassium-rich saturated liquid;
(4) closing the high-temperature potassium-rich saturated liquid, cooling and crystallizing to obtain crude potassium chloride. The solid phase obtained after solid-liquid separation is crude potassium chloride, and the residual liquid is low-temperature potassium saturated liquid;
(5) evaporating the low-temperature potassium saturated solution to separate out extremely low-sodium carnallite;
(6) decomposing the ultra-low sodium carnallite to obtain crude potassium chloride; after solid-liquid separation, the obtained solid phase is crude potassium chloride, the liquid phase is low-temperature carnallite saturated liquid, and the liquid phase can return to a hot solvent preparation stage for recycling or be mixed with picromerite conversion mother liquor for solarization to obtain potassium mixed salt ore;
(7) refining the crude potassium chloride to prepare a potassium chloride product. And (5) mixing the crude potassium chloride obtained in the step (4) and the step (6), washing and drying to prepare a potassium chloride product. Returning the washed potassium chloride washing liquid to the step (4) for recycling;
(8) 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 (3) adding fresh water into the potash magnesium sulphate fertilizer and the potassium chloride product obtained in the step (2) and the step (7) for mixing reaction to obtain crude potassium sulphate. And returning the residual potassium sulfate conversion mother liquor to the potassium-sulfur mixed salt concentrate conversion stage for recycling.
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 potash magnesium sulphate fertilizer, potassium chloride and a preparation method of potassium sulphate are characterized by comprising 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) When fresh water is supplemented, performing stepped closed cooling crystallization treatment on the high-temperature potassium-rich saturated liquid obtained in the step (2) to obtain crude potassium chloride and low-temperature potassium saturated liquid; 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％、MgCl223-26 wt%, wherein the content of potassium chloride in the crude potassium chloride is 85-90 wt%;
(4) evaporating the low-temperature potassium saturated solution to obtain ultra-low-sodium carnallite, and then performing fresh water decomposition on the obtained ultra-low-sodium carnallite to obtain crude potassium chloride and low-temperature carnallite saturated solution; the low-temperature carnallite saturated liquid comprises the following components in percentage by mass: NaCl 1.5-2.0 wt%, KCl 2.5-3.5 wt%, MgSO40.5～1.0wt％、MgCl225-26 wt%, wherein the content of potassium chloride in the crude potassium chloride is 90-92 wt%.
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%;
and/or the mass ratio of the hot solvent to the chloride type tailings in the step (2) is 1.3: 1-1.5: 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 of (A) comprisesAny one or the combination of more than two of brine, bischofite and low-temperature carnallite saturated liquid.
4. The method according to claim 1, wherein the step (3) specifically comprises: 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, and then solid-liquid separation treatment is carried out to obtain crude potassium chloride and low-temperature potassium saturated liquid;
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 preparation method further comprises: and preheating the hot solvent by using the heat released in the stepped closed cooling crystallization treatment process.
5. The method according to claim 1, wherein the very low sodium carnallite used in the step (4) comprises the following components in percentage by mass: 1-2 wt% of NaCl, 20-22 wt% of KCl and MgSO40.3～0.8wt％、MgCl230～35wt％；
And/or the temperature of the evaporation treatment is 75-100 ℃;
and/or, the preparation method further comprises the following steps: recovering the old brine generated by the evaporation treatment to prepare the hot solvent; preferably, the old brine comprises the following components in percentage by mass: NaCl 0.6-1.2 wt%, KCl 0.1-0.5 wt%, MgSO41.0～1.5wt％、MgCl226～29wt％；
And/or the temperature of the fresh water decomposition treatment is 10-15 ℃;
and/or the amount of the fresh water in the fresh water decomposition treatment is 1.1-1.2 times of the amount obtained by calculating through a phase diagram;
and/or, the preparation method further comprises the following steps: and recovering the low-temperature carnallite saturated liquid generated by the fresh water decomposition treatment to prepare the hot solvent.
6. The method of claim 1, further comprising: mixing the crude potassium chloride obtained in the steps (3) and (4) and refining to obtain potassium chloride, wherein the potassium chloride comprises the following components in percentage by mass: NaCl 0.8-1.5 wt%, KCl 93-96 wt%, MgCl21～2wt％。
7. The production method according to claim 6, the crude potassium chloride refining treatment comprising: 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: 1-0.25: 1;
preferably, the temperature of the washing treatment is 10-15 ℃;
preferably, the preparation 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.
8. The method of claim 1, further comprising:
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, allowing to contain said sulfuric acidReacting a potash magnesium fertilizer, the potassium chloride obtained in the claim 6 and a mixed reaction system of fresh water to obtain crude potassium sulfate, and then refining to obtain the potassium sulfate, wherein the potassium sulfate 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 preparation method according to claim 8, wherein the fresh water used in the conversion treatment of the potassium-sulfur mixed salt concentrate is 1.10 to 1.15 times of the fresh water used in the conversion treatment of the potassium-sulfur mixed salt concentrate calculated by a phase diagram;
and/or, the preparation method further comprises the following steps: recovering the picromerite conversion mother liquor, mixing the picromerite conversion mother liquor with the low-temperature carnallite saturated liquid obtained in the step (4), and solarizing the mixture to form potassium mixed salt;
and/or, the preparation method further comprises the following steps: 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 preparation method further comprises: and recovering the picromerite washing liquid generated by the washing treatment, mixing the picromerite washing liquid with fresh water, and performing conversion treatment to prepare the crude picromerite.
10. The preparation method according to claim 8, wherein the amount of fresh water in the mixed reaction system is 1.1 to 1.2 times of the amount obtained by phase diagram calculation;
and/or, the preparation method further comprises the following steps: recovering potassium sulfate conversion mother liquor reacted in the mixed reaction system, mixing the potassium sulfate conversion mother liquor with fresh water, and performing conversion treatment to prepare coarse schoenite;
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 preparation method further comprises: the potassium sulfate washing liquid generated by the washing treatment is recycled for preparing potassium sulfate.
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