CN105668594B - A kind of technique with polyhalite leaching mother liquor production potassium sulfate - Google Patents
A kind of technique with polyhalite leaching mother liquor production potassium sulfate Download PDFInfo
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- CN105668594B CN105668594B CN201610045396.0A CN201610045396A CN105668594B CN 105668594 B CN105668594 B CN 105668594B CN 201610045396 A CN201610045396 A CN 201610045396A CN 105668594 B CN105668594 B CN 105668594B
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- mother liquor
- polyhalite
- potassium sulfate
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 90
- 229910052939 potassium sulfate Inorganic materials 0.000 title claims abstract description 46
- OTYBMLCTZGSZBG-UHFFFAOYSA-L Potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 title claims abstract description 45
- 235000011151 potassium sulphates Nutrition 0.000 title claims abstract description 42
- 238000002386 leaching Methods 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 55
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium monoxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000197 pyrolysis Methods 0.000 claims abstract description 30
- 238000003763 carbonization Methods 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 22
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011591 potassium Substances 0.000 claims abstract description 19
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000005712 crystallization Effects 0.000 claims abstract description 18
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000292 calcium oxide Substances 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- ZLNQQNXFFQJAID-UHFFFAOYSA-L Magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000011776 magnesium carbonate Substances 0.000 claims abstract description 14
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 20
- JLVVSXFLKOJNIY-UHFFFAOYSA-N magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 11
- 238000009993 causticizing Methods 0.000 claims description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000005255 carburizing Methods 0.000 claims description 7
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 23
- 239000000047 product Substances 0.000 abstract description 23
- 239000000395 magnesium oxide Substances 0.000 abstract description 14
- 239000006227 byproduct Substances 0.000 abstract description 8
- 229910052602 gypsum Inorganic materials 0.000 abstract description 8
- 239000010440 gypsum Substances 0.000 abstract description 8
- 229940037179 Potassium Ion Drugs 0.000 abstract description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 19
- 239000011777 magnesium Substances 0.000 description 17
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 10
- 235000019341 magnesium sulphate Nutrition 0.000 description 9
- VTHJTEIRLNZDEV-UHFFFAOYSA-L Magnesium hydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 238000003837 high-temperature calcination Methods 0.000 description 5
- 239000000347 magnesium hydroxide Substances 0.000 description 5
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L Calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- -1 potassium magnesium Chemical compound 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 229910052925 anhydrite Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001095 magnesium carbonate Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N Ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- WZISDKTXHMETKG-UHFFFAOYSA-N dimagnesium;dipotassium;sulfuric acid Chemical compound [Mg+2].[Mg+2].[K+].[K+].OS(O)(=O)=O.OS(O)(=O)=O.OS(O)(=O)=O WZISDKTXHMETKG-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940072033 potash Drugs 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000000153 supplemental Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C01D5/16—Purification
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/02—Magnesia
- C01F5/06—Magnesia by thermal decomposition of magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/24—Magnesium carbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Abstract
A kind of technique with polyhalite leaching mother liquor production potassium sulfate, comprise the following steps：（1）Adjust pH value：It is 10.0~12.0 that ammonia, which is passed through in polyhalite leaching mother liquor to pH value, obtains Mg (OH)2Slurry；（2）CO2Carbonization：It is passed through CO2It is 7.5~8.0 to pH value, obtains carbonization mother liquor；（3）Pyrolysis separation：Heat resolve, separation of solid and liquid, obtain MgCO3·3H2O solid salts and pyrolysis separation mother liquor；（4）Causticization separates：Calcium oxide slurry or calcium hydroxide slurry are added in pyrolysis separates mother liquor, is heated, stirring, separation of solid and liquid, obtains causticization separation mother liquor；（5）Evaporative crystallization：Forced evaporation, crystallization separate out potassium product.Potassium product K obtained by present invention process2O content is up to 51.9%, and potassium ion high income is up to 91.7%；Can two kinds of byproducts of co-producing high-purity magnesia and gypsum；Technological process, required equipment are simple, are easy to industrialized production, and cost is low.
Description
Technical field
The present invention relates to a kind of production technology of potassium sulfate, and in particular to a kind of polyhalite leaching mother liquor production potassium sulfate
Technique.
Background technology
Polyhalite（K2SO4·MgSO4·2CaSO4·2H2O）, it is that a kind of important slightly solubility contains sylvite ore, its reserves is rich
Richness, it is maximum with Sichuan, Hubei ore deposit amount, only（Four）Chuan Dong（Portion）Polyhalite resource converts into K2O reserves about more than 20,000,000,000 tons,
It is the important supplemental resources of China's potash fertilizer industry.It is available high-quality containing potassium money with the exploitation of high-grade salt lake bittern resource
Source is increasingly deficient, and the polyhalite ore resources containing sylvite of slightly solubility certainly will turn into the focus and research work of the exploitation of following sylvite
The study hotspot of person.
At present, the research on polyhalite leaching technology is quite ripe, and leaching mother liquor is mainly sulfur acid potassium and sulfuric acid
The solution of magnesium, K+Extraction rate can reach more than 90%.Research for leaching mother liquor extraction potassium sulfate, mostly using evaporation and concentration
The technique of crystallization, but the yield of potassium sulfate is minimum, and most potassium sulfate is to crystallize to separate out in the form of potassium magnesium mixed salt, potassium magnesium point
It is big from difficulty, it is difficult to realize being completely separated for potassium sulfate and magnesium sulfate.If sold directly as potassic-magnesian fertilizer product, not only product
Grade is low, and market outlet is also undesirable；If carrying out secondary conversion preparing potassium sulfate, outsourcing potassium chloride raw material is not only needed to be used for
Potassium magnesium mixed salt converts the reaction raw materials of preparing potassium sulfate, increases production cost, but also can produce a large amount of high potassium constantly expanded
Mother liquor is difficult to digest, and influences Business Economic Benefit.
The method of potassium sulfate and related is produced as CN104755426A discloses a kind of potassium sulfate and Adlerika processed
System, it is to be mixed using sulfur acid potassium after circulating crystal structure and leaching polyhalite with the mother liquor of magnesium sulfate, so that first is dense
Contracting liquid enrichment, the evaporation energy consumption of the first concentrate can be reduced to a certain extent, increase the yield of potassium sulfate, but can not be from root
Realize being completely separated for potassium sulfate and magnesium sulfate in sheet, no matter low-temperature evaporation or forced evaporation, substantial amounts of sylvite be also all with
The form of leonite or langbeinite separates out, and reduces product grade and the market price, and back dissolving is big again for evaporative crystallization repeatedly
Add energy consumption cost greatly.CN102030487A discloses a kind of new technology of normal temperature carbonization low temperature pyrogenation high-purity magnesium oxide, profit
It can realize that the precipitation of magnesium separates with pyrolysis process integration with carbonization, but gained thermal decomposition product magnesium carbonate is easily hydrolyzed as solubility
Lower magnesium hydrate precipitate, particle is thin, and separation is difficult, and mother liquor entrainment is big, leaches mother liquor according to technology separation polyhalite,
Precipitation magnesium salts mother liquor entrainment is big, and potassium product yield is low.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing for prior art, there is provided a kind of potassium magnesium point
From efficiency high, precipitation strainability is good, and mother liquor entrainment is small, and product purity, yield, added value are high, cost it is low use polyhalite
The technique for leaching mother liquor production potassium sulfate.
The technical solution adopted for the present invention to solve the technical problems is as follows：
（1）Adjust pH value：Ammonia is passed through in polyhalite leaching mother liquor, is 10.0~12.0 to pH value, obtains Mg (OH)2Material
Slurry；
（2）CO2Carbonization：By CO2It is passed through step（1）Gained Mg (OH)2Normal temperature carburizing reagent is carried out in slurry, is to pH value
7.5~8.0, obtain carbonization mother liquor；
（3）Pyrolysis separation：By step（2）Gained carbonization mother liquor carries out heat resolve, separation of solid and liquid, obtains MgCO3·3H2O consolidates
Body salt and pyrolysis separation mother liquor；
（4）Causticization separates：In step（3）Calcium oxide slurry or calcium hydroxide slurry are added in gained pyrolysis separation mother liquor,
Heating, stirring, causticizing reaction is carried out, separation of solid and liquid, obtains causticization separation mother liquor；
（5）Evaporative crystallization：By step（4）Gained causticization separation mother liquor carries out forced evaporation, and crystallization separates out potassium product.
Further, step（1）In, K in the polyhalite leaching mother liquor+Mass concentration be 1.0~7.5wt%, Mg2+'s
Mass concentration is 0.5~2.5wt%, Ca2+Mass concentration ＜ 0.1wt%.
Further, step（1）In, speed that the ammonia is passed through is 20~30L/L solution h, the volumetric concentration of ammonia
≥90%.Ammoniacal liquor basicity adjusts pH value than relatively low, with it, is unlikely to make solution ph change too fast as strong base reagent, limits
The speed that ammonia is passed through can further control reaction speed, allow solution ph slowly to raise, and be unlikely to because solution ph is uprushed
And make it that precipitated particle size is uneven；It is 10.0~12.0 to be passed through ammonia to pH value, is the Mg in order that in polyhalite leaching mother liquor2+
Completely with Mg (OH)2Form precipitates, and so as to provide preferable raw material for carbonisation, is easy to promote Mg (OH)2Colloid pair
CO2Absorption to ensure the complete of carburizing reagent.
Further, step（2）In, the CO2The pressure being passed through is 0.1~0.5MPa, the speed being passed through is 0.5~
5.0L/L solution h, CO2Volumetric concentration >=80%.In carbonisation, CO2Pressure and dosage it is the most key, with pressure be passed through is
In order to ensure preferable extent of reaction and degree, preferable CO is controlled2Dosage, which can not only be realized, makes Mg more difficult to filter (OH)2
Colloid is completely converted into readily soluble Mg (HCO3)2, and raw material is saved, and when solution ph is 7.5~8.0, Mg (OH)2Colloid
Basic carbonization is complete, in this, as the Rule of judgment of carbonization terminal.
Further, step（2）In, the normal temperature is 20~30 DEG C.
Further, step（3）In, the temperature of the heat resolve is 80 DEG C of 30~＜（It is preferred that 35~75 DEG C）, the time is
10~60min（It is preferred that 20~50min）.Separating technology is pyrolyzed using the medium temperature of mild condition, can effectively control Mg (HCO3)2Heat
Solve as MgCO3·3H2O extent of reaction, obtain the MgCO that particle diameter is big, crystal type is good3·3H2O is precipitated, if temperature Tai Gaoyi
Form basic magnesium carbonate crystallization, the strainability of precipitation can be influenceed, pyrolysis effect is influenceed if temperature is too low, in the temperature and
Under the combination of time conditions, bigger yield, the precipitated product of more excellent strainability can be just obtained.
Step（3）MgCO obtained by separation of solid and liquid3·3H2O can utilize existing known technology, through 450~600 DEG C, high-temperature calcination
20~120min（It is preferred that 25~80min）, obtain the higher high-purity magnesium oxide product of added value.
Further, step（4）In, the calcium oxide slurry or calcium hydroxide slurry are with calcium oxide or calcium hydroxide and miscellaneous halogen
NH in stone pyrolysis separation mother liquor4 +Mol ratio be 1.2~1.5:1 ratio adds.Mainly contain in polyhalite pyrolysis separation mother liquor
There is K2SO4(NH4)2SO4, it is to promote itself and (NH to add calcium oxide slurry or calcium hydroxide slurry4)2SO4In heating condition
Lower fast reaction, generates sl. sol. CaSO4Precipitation, and ammonia is discharged, to realize K2SO4(NH4)2SO4Separation, K2SO4It is pure
Change and the recovery of ammonia, CaSO4After separation of solid and liquid, it can be used as by-produced gypsum, step is can return to after Ammonia recovery（1）Enter
Row recycles, and this also complies with green requirement.The selection of additional proportion is more beneficial for ensuring to separate NH in mother liquor4 +It is complete
Full response.Selection adds calcium oxide slurry or calcium hydroxide slurry after separating magnesium is precipitated, rather than directly in polyhalite
Added in leaching mother liquor is because of if in step（1）Direct causticizing reaction, then calcium sulfate precipitated simultaneously with magnesium hydroxide, rear
In continuous carbonisation, excessive calcium or sl. sol. calcium sulfate can it is partially carbonized with magnesium salts coprecipitation in thermal decomposition product, influence
The purity of magnesium salts.
Further, step（4）In, the mass concentration of the calcium oxide slurry or calcium hydroxide slurry is 10~30wt%.
Further, step（4）In, the temperature of the causticizing reaction is 60~100 DEG C, and the time is 1~12h（It is preferred that 2~
8h）.Inventor, which studies, to be found, in the causticization temperature, under the time, it is ensured that in a heated condition, in calcic slurry and mother liquor
(NH4)2SO4Fully reaction, gained byproduct of reaction ammoniacal liquor is fully decomposed into ammonia and overflow and reclaim.
Further, step（5）In, the temperature of the forced evaporation is 80~120 DEG C.Causticization separation mother liquor is potassium sulfate
Single solute mother liquor, the higher potassium product of purity can be separated out by 80~120 DEG C of forced evaporations of high temperature.
Polyhalite leaching mother liquor used in the present invention is to carry out conventional leaching to polyhalite using calcining Hydrolyze method
Obtain, such as CN103930371A.
In present invention process will carbonization demagging be combined with evaporative crystallization, solve polyhalite leaching mother liquor in potassium sulfate and
The difficult technical barrier of magnesium sulfate separation, realizes the purifying of potassium sulfate mother liquid by magnesium sinking, at the same can by-product multiple product, its
Beneficial effect is specific as follows：
（1）It can realize that potassium sulfate is completely separated with magnesium sulfate according to present invention process, break away from conventional polyhalite leaching liquid
It is only suitable for producing the technique predicament of potassic-magnesian fertilizer, gained potassium product purity is high, K2O content may be up to 51.9%, reach
GB20406-2006 agriculturals require that potassium ion yield may be up to 91.7%, and potassium sulfate yield and added value are high with Grade A；
（2）Present invention process, can also co-producing high-purity magnesia and gypsum two while the production of potassium sulfate high-purity is realized
Kind byproduct, wherein, content of MgO may be up to 93.8% in high-purity magnesium oxide, and magnesium ion yield may be up to 89.2%, the purity of gypsum
Up to 89.1%, yield may be up to 87.6%, high financial profit；
（3）Present invention process flow is simple, and required equipment is simple, is easy to industrialized production, ammonia used, CO2, lime or
Ca(OH)2It is easy to get Deng raw material, and ammonia recoverable, process costs are low.
Embodiment
With reference to embodiment, the invention will be further described.
Polyhalite leaching mother liquor used in the embodiment of the present invention is to calcining using technique described in CN103930371A
Polyhalite carries out fresh water leaching and obtained；Chemical reagent used in other, unless otherwise specified, passes through routine business approach
Obtain.
Embodiment 1
（1）Adjust pH value：The ammonia of volumetric concentration 92% is passed through 2000g with 22L/L solution h speed（Volume
1750mL）Polyhalite leaching mother liquor（K+：2.2wt%, Mg2+：0.8wt%, Ca2+：0.03wt%）In, it is 10.85 to pH value, obtains
1800mL Mg(OH)2Slurry；
（2）CO2Carbonization：By the CO of volumetric concentration 95%2Step is passed through with the speed of 0.3MPa pressure and 4.8L/L solution h
Suddenly（1）Gained 1800mL Mg (OH)2In slurry, at 20 DEG C carry out normal temperature carburizing reagent, to pH value be 7.6 when terminating reaction,
Obtain carbonization mother liquor；
（3）Pyrolysis separation：By step（2）Gained carbonization mother liquor heat resolve 40min, separation of solid and liquid, obtains at 45 DEG C
MgCO3·3H2O solid salts and pyrolysis separation mother liquor；
（4）Causticization separates：In step（3）NH in mother liquor is separated with pyrolysis with calcium oxide in gained pyrolysis separation mother liquor4 +'s
Mol ratio is 1.3:1 ratio adds calcium oxide slurry（Pulp quality concentration is 15wt%）, at 80 DEG C, stirring, carry out causticization
2h is reacted, separation of solid and liquid, obtains causticization separation mother liquor；
（5）Evaporative crystallization：By step（4）Gained causticization separates mother liquor at 85 DEG C, carries out forced evaporation, and crystallization separates out
94.5g potassium products.
Gained potassium product purity is high, K2O content is 50.2%, reaches GB20406-2006 agricultural Grade A requirements,
Potassium ion yield is 89.5%, and potassium sulfate yield and added value are high.
Meanwhile by step（3）Gained MgCO3·3H2O high-temperature calcination 60min, it is high-purity to obtain byproduct 25.33g through 450 DEG C
Magnesia, its content of MgO are 92.8%, and magnesium ion yield is 88.6%, realize the thorough of potassium sulfate and magnesium sulfate in leachate
Separation；Step（4）The purity of gained by-produced gypsum is 84.8%, yield 80.9%；Collection step（4）The ammonia of effusion, is returned
Return step（1）Recycled.
Embodiment 2
（1）Adjust pH value：The ammonia of volumetric concentration 95% is passed through 1000g with 30L/L solution h speed（Volume
850mL）Polyhalite leaching mother liquor（K+：4.48wt%, Mg2+：1.63wt%, Ca2+：0.08wt%）In, it is 11.3 to pH value, obtains
910mL Mg(OH)2Slurry；
（2）CO2Carbonization：By the CO of volumetric concentration 88%2Step is passed through with the speed of 0.2MPa pressure and 0.8L/L solution h
Suddenly（1）Gained 910mL Mg (OH)2In slurry, at 30 DEG C carry out normal temperature carburizing reagent, to pH value be 7.8 when terminating reaction,
Obtain carbonization mother liquor；
（3）Pyrolysis separation：By step（2）Gained carbonization mother liquor heat resolve 30min, separation of solid and liquid, obtains at 70 DEG C
MgCO3·3H2O solid salts and pyrolysis separation mother liquor；
（4）Causticization separates：In step（3）NH in mother liquor is separated with pyrolysis with calcium oxide in gained pyrolysis separation mother liquor4 +'s
Mol ratio is 1.5:1 ratio adds calcium oxide slurry（Pulp quality concentration is 28wt%）, at 60 DEG C, stirring, carry out causticization
4h is reacted, separation of solid and liquid, obtains causticization separation mother liquor；
（5）Evaporative crystallization：By step（4）Gained causticization separates mother liquor at 115 DEG C, carries out forced evaporation, and crystallization separates out
95.9g potassium products.
Gained potassium product purity is high, K2O content is 50.8%, reaches GB20406-2006 agricultural Grade A requirements,
Potassium ion yield is 90.3%, and potassium sulfate yield and added value are high.
Meanwhile by step（3）Gained MgCO3·3H2O high-temperature calcination 30min, it is high-purity to obtain 25.12g byproducts through 580 DEG C
Magnesia, its content of MgO are 93.3%, and magnesium ion yield is 86.7%, realize the thorough of potassium sulfate and magnesium sulfate in leachate
Separation；Step（4）The purity of gained by-produced gypsum is 87.2%, yield 85.4%；Collection step（4）The ammonia of effusion, is returned
Return step（1）Recycled.
Embodiment 3
（1）Adjust pH value：The ammonia of volumetric concentration 99% is passed through 1000g with 26L/L solution h speed（Volume
900mL）Polyhalite leaching mother liquor（K+：3.29wt%, Mg2+：1.50wt%, Ca2+：0.05wt%）In, it is 11.5 to pH value, obtains
940mL Mg(OH)2Slurry；
（2）CO2Carbonization：By the CO of volumetric concentration 85%2Step is passed through with the speed of 0.5MPa pressure and 3.6L/L solution h
Suddenly（1）Gained 940mL Mg (OH)2In slurry, at 25 DEG C carry out normal temperature carburizing reagent, to pH value be 7.9 when terminating reaction,
Obtain carbonization mother liquor；
（3）Pyrolysis separation：By step（2）Gained carbonization mother liquor heat resolve 40min, separation of solid and liquid, obtains at 60 DEG C
MgCO3·3H2O solid salts and pyrolysis separation mother liquor；
（4）Causticization separates：In step（3）NH in mother liquor is separated with pyrolysis with calcium hydroxide in gained pyrolysis separation mother liquor4 +
Mol ratio be 1.2:1 ratio adds calcium hydroxide slurry（Pulp quality concentration is 23wt%）, at 80 DEG C, stir, carry out
Causticizing reaction 6h, separation of solid and liquid, obtain causticization separation mother liquor；
（5）Evaporative crystallization：By step（4）Gained causticization separates mother liquor at 105 DEG C, carries out forced evaporation, and crystallization separates out
67.8g potassium products.
Gained potassium product purity is high, K2O content is 51.9%, reaches GB20406-2006 agricultural Grade A requirements,
Potassium ion yield is 88.8%, and potassium sulfate yield and added value are high.
Meanwhile by step（3）Gained MgCO3·3H2O high-temperature calcination 45min, it is high-purity to obtain 22.80g byproducts through 520 DEG C
Magnesia, its content of MgO are 92.5%, and magnesium ion yield is 84.8%, realize the thorough of potassium sulfate and magnesium sulfate in leachate
Separation；Step（4）The purity of gained by-produced gypsum is 88.6%, yield 84.7%；Collection step（4）The ammonia of effusion, is returned
Return step（1）Recycled.
Embodiment 4
（1）Adjust pH value：The ammonia of volumetric concentration 95% is passed through 1000g with 23L/L solution h speed（Volume
885mL）Polyhalite leaching mother liquor（K+：6.50wt%, Mg2+：2.12wt%, Ca2+：0.06wt%）In, it is 10.95 to pH value, obtains
915mL Mg(OH)2Slurry；
（2）CO2Carbonization：By the CO of volumetric concentration 90%2Step is passed through with the speed of 0.1MPa pressure and 2.4L/L solution h
Suddenly（1）Gained 915mL Mg (OH)2In slurry, at 25 DEG C carry out normal temperature carburizing reagent, to pH value be 7.7 when terminating reaction,
Obtain carbonization mother liquor；
（3）Pyrolysis separation：By step（2）Gained carbonization mother liquor heat resolve 30min, separation of solid and liquid, obtains at 70 DEG C
MgCO3·3H2O solid salts and pyrolysis separation mother liquor；
（4）Causticization separates：In step（3）NH in mother liquor is separated with pyrolysis with calcium hydroxide in gained pyrolysis separation mother liquor4 +
Mol ratio be 1.3:1 ratio adds calcium hydroxide slurry（Pulp quality concentration is 25wt%）, at 100 DEG C, stirring, enter
Row causticizing reaction 2h, separation of solid and liquid, obtain causticization separation mother liquor；
（5）Evaporative crystallization：By step（4）Gained causticization separates mother liquor at 95 DEG C, carries out forced evaporation, and crystallization separates out
139.9g potassium product.
Gained potassium product purity is high, K2O content is 51.3%, reaches GB20406-2006 agricultural Grade A requirements,
Potassium ion yield is 91.7%, and potassium sulfate yield and added value are high.
Meanwhile by step（3）Gained MgCO3·3H2O high-temperature calcination 50min, it is high-purity to obtain 33.43g byproducts through 480 DEG C
Magnesia, its content of MgO are 93.8%, and magnesium ion yield is 89.2%, realize the thorough of potassium sulfate and magnesium sulfate in leachate
Separation；Step（4）The purity of gained by-produced gypsum is 89.1%, yield 87.6%；Collection step（4）The ammonia of effusion, is returned
Return step（1）Recycled.
Claims (12)
1. a kind of technique with polyhalite leaching mother liquor production potassium sulfate, it is characterised in that comprise the following steps：
（1）Adjust pH value：Ammonia is passed through in polyhalite leaching mother liquor, is 10.0~12.0 to pH value, obtains Mg (OH)2Slurry；Institute
State K in polyhalite leaching mother liquor+Mass concentration be 1.0~7.5wt%, Mg2+Mass concentration be 0.5~2.5wt%, Ca2+'s
Mass concentration ＜ 0.1wt%；The speed that the ammonia is passed through is 20~30L/L solution h, volumetric concentration >=90% of ammonia；
（2）CO2Carbonization：By CO2It is passed through step（1）Gained Mg (OH)2In slurry carry out normal temperature carburizing reagent, to pH value be 7.5~
8.0, obtain carbonization mother liquor；The CO2The pressure being passed through is 0.1~0.5MPa, and the speed being passed through is 0.5~5.0L/L solution h,
CO2Volumetric concentration >=80%；
（3）Pyrolysis separation：By step（2）Gained carbonization mother liquor carries out heat resolve, separation of solid and liquid, obtains MgCO3·3H2O solid salts
Mother liquor is separated with pyrolysis；The temperature of the heat resolve is 80 DEG C of 30~＜, and the time is 10~40min；
（4）Causticization separates：In step（3）Calcium oxide slurry or calcium hydroxide slurry are added in gained pyrolysis separation mother liquor, is heated,
Stirring, causticizing reaction is carried out, separation of solid and liquid, obtains causticization separation mother liquor；
（5）Evaporative crystallization：By step（4）Gained causticization separation mother liquor carries out forced evaporation, and crystallization separates out potassium product.
2. according to claim 1 with the technique of polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（2）In,
The normal temperature is 20~30 DEG C.
3. the technique according to claim 1 or claim 2 with polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（4）
In, the calcium oxide slurry or calcium hydroxide slurry separate NH in mother liquor with calcium oxide or calcium hydroxide with polyhalite pyrolysis4 +'s
Mol ratio is 1.2~1.5:1 ratio adds.
4. the technique according to claim 1 or claim 2 with polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（4）
In, the mass concentration of the calcium oxide slurry or calcium hydroxide slurry is 10~30wt%.
5. according to claim 3 with the technique of polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（4）In,
The mass concentration of the calcium oxide slurry or calcium hydroxide slurry is 10~30wt%.
6. the technique according to claim 1 or claim 2 with polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（4）
In, the temperature of the causticizing reaction is 60~100 DEG C, and the time is 1~12h.
7. according to claim 3 with the technique of polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（4）In,
The temperature of the causticizing reaction is 60~100 DEG C, and the time is 1~12h.
8. according to claim 4 with the technique of polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（4）In,
The temperature of the causticizing reaction is 60~100 DEG C, and the time is 1~12h.
9. the technique according to claim 1 or claim 2 with polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（5）
In, the temperature of the forced evaporation is 80~120 DEG C.
10. according to claim 3 with the technique of polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（5）
In, the temperature of the forced evaporation is 80~120 DEG C.
11. according to claim 4 with the technique of polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（5）
In, the temperature of the forced evaporation is 80~120 DEG C.
12. according to claim 6 with the technique of polyhalite leaching mother liquor production potassium sulfate, it is characterised in that：Step（5）
In, the temperature of the forced evaporation is 80~120 DEG C.
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| CN101760638A (en) * | 2008-12-24 | 2010-06-30 | 中国恩菲工程技术有限公司 | Method for recovering magnesium from magnesium sulfate solution |
| CN101760641A (en) * | 2008-12-24 | 2010-06-30 | 中国恩菲工程技术有限公司 | Technology for recovering magnesium from magnesium sulfate solution |
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| CN101125670A (en) * | 2007-09-04 | 2008-02-20 | 中盐制盐工程技术研究院 | Method for producing light magnesium carbonate |
| CN101760638A (en) * | 2008-12-24 | 2010-06-30 | 中国恩菲工程技术有限公司 | Method for recovering magnesium from magnesium sulfate solution |
| CN101760641A (en) * | 2008-12-24 | 2010-06-30 | 中国恩菲工程技术有限公司 | Technology for recovering magnesium from magnesium sulfate solution |
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