CN1321893C - Method for preparing potassium sulfate from bittern containing potassium and magnesium sulfate - Google Patents

Method for preparing potassium sulfate from bittern containing potassium and magnesium sulfate Download PDF

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Publication number
CN1321893C
CN1321893C CNB02143641XA CN02143641A CN1321893C CN 1321893 C CN1321893 C CN 1321893C CN B02143641X A CNB02143641X A CN B02143641XA CN 02143641 A CN02143641 A CN 02143641A CN 1321893 C CN1321893 C CN 1321893C
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potassium
salt
bittern
halogen
mixed salt
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CN1439602A (en
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李�浩
唐中凡
尹新斌
汤建良
雷光元
贺其华
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SDIC XINJIANG LUOBUPO POTASH CO Ltd
China Bluestar Chonfar Engineering and Technology Co Ltd
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SDIC XINJIANG LUOBUPO POTASH CO Ltd
China Bluestar Changsha Design and Research Institute
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Abstract

The invention discloses a method for preparing potassium sulfate by using potassium-containing magnesium sulfate subtype brine. The process comprises the steps of firstly, sun-drying raw brine to extract most of sodium chloride, then, brine blending, sequentially introducing the brine into a epsomite salt field, a kainite potassium mixed salt field and a carnallite potassium mixed salt field, sun-drying the kainite potassium mixed salt and the carnallite potassium mixed salt respectively, then respectively introducing the raw brine into a picromerite selection plant and a potassium chloride selection plant, and carrying out conversion, decomposition, selective washing and dehydration to respectively obtain picromerite and potassium chloride. Adding brackish water into picromerite and potassium chloride to prepare brine, and then preparing potassium sulfate by drying in the sun, evaporating and dehydrating in a salt field or converting picromerite and potassium chloride in a device to obtain a potassium sulfate product.

Description

Produce the method for vitriolate of tartar with containing potassium magnesium sulfate bittern
One, technical field
The present invention relates to a kind of utilization and contain the method that potassium magnesium sulfate bittern is produced vitriolate of tartar.
Two, background technology
Vitriolate of tartar is the indispensable few potash fertilizer of agriculture production.China is a large agricultural country, and the expense of potash fertilizer is big.In present prior art, the production technique of vitriolate of tartar mainly is to utilize commodity Repone K and the various compound (as sulfuric acid, ammonium sulfate, sal epsom, sodium sulfate, calcium sulfate etc.) that contains sulfate radical to carry out conversion method production.This kind method is to the specification of quality height of raw material Repone K, the raw materials cost height, produce required various device in addition, expenses such as transportation make investment strengthen product cost and increase, and easy contaminate environment, and at the landlocked arid biogeographic zone of northern China and northwest, be distributed with a large amount of salt lakes, there is the abundant potassium vitriolate type bittern resource that contains in some salt lake, and these salt lakes are not exploited mostly as yet.
Three, summary of the invention
The purpose of this invention is to provide that a kind of cost is low, less investment, free of contamination utilization contain the method that potassium magnesium sulfate bittern is produced vitriolate of tartar.
In order to achieve the above object, the technical solution adopted in the present invention is characterized in need not adding any raw material, make full use of sylvite contained in the magnesium sulfate bittern and vitriol and produce vitriolate of tartar at the scene, concrete technology is as follows: operation 1, elder generation import the NaCI salt pan with former halogen, separate out most of NaCI through solar evaporation; Operation 2, will extract bittern behind the NaCI and the old halogen after the operation 3 is converted halogen; Operation 3, the bittern of converting after the halogen import epsom salt salt pan, kainite potassium mixed salt salt pan and carnallitite potassium mixed salt salt pan successively, obtain epsom salt, kainite potassium mixed salt and carnallitite potassium mixed salt respectively behind solar evaporations, bittern behind the system carnallitite potassium mixed salt is old halogen, halogen is converted in the sodium salt pond that is used for shining next time after the system NaCI salt, and chloromagnesite is produced in unnecessary discharge; Operation 4: the kainite potassium mixed salt of the system of shining enters one section mother liquor and the slightly salty of workshop after with the thick KCI of washing kainite is formed slurry and transforms through ore grinding earlier, produces schoenite through the flotation dehydration again; Operation 5: carnallitite potassium mixed salt enters the Repone K enrichment plant, and the C point bittern decomposition carnallitite potassium mixed salt with beginning to separate out kainite passes through flotation, dehydration again, and obtains Repone K with two commentaries on classics mother liquors washings, the dehydration of vitriolate of tartar operation; Operation 6: with schoenite and Repone K is that raw material and slightly salty are joined halogen, after the bittern sedimentation for preparing, shine through the beach, salt pan, dehydration produces vitriolate of tartar, or is that raw material is a medium with the slightly salty with schoenite and Repone K, obtains potassium product after conversion in device, separation, the drying.
Said that (C point) bittern that in crystallisation process takes place, begins to separate out sylvite that preferably adopts in order to the bittern that decomposes carnallitite potassium mixed salt in the above-mentioned operation 5.
The said halogen of joining is preferably by K in the above-mentioned operation 6 +, Mg 2+//C1 -, SO 4 2-The proportion scale of 25 ℃ of calphad of quaternary salt-water system carries out.
The salinity of said slightly salty 3-10g/L preferably in the above-mentioned operation.
All take from from technique scheme raw material of the present invention as can be seen and to contain potassium magnesium sulfate bittern, do not need outsourcing Repone K, and adopt the saltpan method equipment used simple, save energy, thereby facility investment is few, production cost has only about half of prior art, uses or convert halogen repeatedly, no waste discharge thereby non-environmental-pollution because mother liquor that the per pass operation produces and bittern all return the front operation.Its chemical ingredients of high-quality vitriolate of tartar and the relative national standards HG/T3279-1990 that produce contrast as following table:
The order item Measure unit Index Examination and test of products result Individual event is judged
Premium grads Acceptable end product Salable product
Potassium oxide (K 2O) content ≥50.0 ≥45.0 ≥33.0 50.7 Meet the premium grads index
Chlorine (CI -) content ≤1.5 ≤2.5 - 0.8 Meet the premium grads index
Water content ≤1.0 ≤3.0 ≤3.0 0.1 Meet the premium grads index
Free acid (H 2SO 4) content ≤0.5 ≤3.0 - Do not detect Meet the premium grads index
Basicity (NaOH) content - - ≤1.0 0.1 Meet index
Four, description of drawings and embodiment
Fig. 1 utilizes to contain the process route chart that potassium magnesium sulfate bittern is produced the vitriolate of tartar saltpan method.As shown in Figure 1, earlier former halogen is imported the sodium-chlor salt pan, after solar evaporation is separated out most of sodium-chlor, bittern is imported secondary sodium salt pond convert halogen (not converting halogen when producing for the first time) with the old halogen that shines behind the system carnallitite potassium mixed salt, the bittern of converting after the halogen imports the epsom salt salt pan, kainite potassium mixed salt salt pan and carnallitite potassium mixed salt salt pan successively.After shining, the beach, salt pan obtains epsom salt respectively, kainite potassium mixed salt and carnallitite potassium mixed salt, and the bittern that shines behind the system carnallitite potassium mixed salt is old halogen, is used for and secondary sodium salt field bittern that former halogen shines behind the system sodium-chlor is converted halogen, and unnecessary old halogen row storage is stand-by.The kainite potassium mixed salt input schoenite that solarization is made selects factory to add conversion fluid (adding two behind the washing Repone K with slightly salty changes mother liquors and be made into), behind the ball milling pulping, squeeze into one section reactive tank and transform, the slurry after the conversion obtains schoenite through flotation, dehydration, and the liquid that removes is E 1Mother liquor.The carnallitite potassium mixed salt input Repone K obtain is shone on the beach select factory, the E that itself and schoenite are deviate from 1The point mother liquor is squeezed into decomposer, after decomposing with C point bittern, carries out dense, flotation, dehydration promptly obtains Repone K.The mother liquor that removes returns the salt pan recycle of kainite potassium mixed salt, and schoenite and the Repone K that makes with above-mentioned technology is produced vitriolate of tartar at last.Earlier slightly salty (salinity 3.02g/L) is squeezed into and joined the halogen groove, under agitation condition, press K +, Mg 2+∥ Cl -, SO 4 2--H 2The proportion scale of 25 ℃ of calphad of O quaternary salt-water system, add Repone K successively and schoenite is joined halogen, join halogen after sedimentation pumps into the salt pan solar evaporation with clear halogen, when being evaporated to bittern proportion near 1.20, when liquid phase was formed point and is positioned near the terminal point, dewatering promptly obtained potassium product.
Fig. 2 utilizes to contain the installation method process route chart that potassium magnesium sulfate bittern is produced vitriolate of tartar, among the figure as can be seen, compare with saltpan method, installation method is all identical with saltpan method to operation 5 from operation 1, the operation 6 of installation method is behind the schoenite and Repone K uniform mixing produced, add the slightly salty that salinity is 3.02g/L again, enter two sections convertors, dewater after in convertor, transforming and be drying to obtain vitriolate of tartar.

Claims (3)

1, a kind of utilization contains the method that potassium magnesium sulfate bittern is produced vitriolate of tartar, and it comprises operation 1: former halogen is imported the sodium-chlor salt pan, separate out most of sodium-chlor behind solar evaporation; Operation 2: will extract bittern behind the sodium-chlor and the old halogen after the operation 3 and convert halogen, it is characterized in that: it also comprises operation 3: the bittern of converting after the halogen imports the epsom salt salt pan successively, sylvite magnesium vanadium potassium mixed salt salt pan and carnallitite potassium mixed salt salt pan, behind solar evaporation, obtain epsom salt respectively, kainite potassium mixed salt and carnallitite potassium mixed salt, remaining bittern is old halogen, and the bittern after being used for next time and shining the system sodium chloride salt is converted halogen; Operation 4: the kainite potassium mixed salt of the system of shining enters mother liquor and the slightly salty of workshop after with the thick Repone K of washing kainite potassium mixed salt is obtained schoenite through the conversion again of ore grinding formation slurry, flotation, dehydration earlier; Operation 5: the carnallitite potassium mixed salt of the system of will shining decomposes dense, the flotation in back with the bittern in salt pan kainite stage, obtains Repone K with dehydration after the two commentaries on classics mother liquor washings of vitriolate of tartar operation again; Operation 6: with schoenite and Repone K is that raw material and slightly salty are joined halogen, the bittern for preparing shines through the beach, salt pan to be produced vitriolate of tartar or is that raw material is made conversion medium with slightly salty with schoenite and Repone K, produces vitriolate of tartar through conversion, separation, drying in device.
2, said utilization contains potassium magnesium sulfate bittern and produces the vitriolate of tartar method according to claim 1, it is characterized in that: said in the operation 5 is that the C point bittern that begins to separate out sylvite in evaporation and crystal process in order to the bittern that decomposes carnallitite potassium mixed salt.
3, produce the method for vitriolate of tartar according to claim 1 is said to contain potassium magnesium sulfate bittern, the salinity that it is characterized in that said slightly salty is 3-10g/L.
CNB02143641XA 2002-09-25 2002-09-25 Method for preparing potassium sulfate from bittern containing potassium and magnesium sulfate Expired - Lifetime CN1321893C (en)

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Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100488874C (en) * 2004-05-12 2009-05-20 国投新疆罗布泊钾盐有限责任公司 Method for preparing potassium sulfate by using potassium mixed salt
CN100383045C (en) * 2005-08-16 2008-04-23 青海中信国安科技发展有限公司 Method for preparing potassium sulfate by utilizing brine pan potassium as raw material
CN1789129B (en) * 2005-12-12 2010-10-06 中国科学院青海盐湖研究所 Method for extracting potassium sulphate by magnesium sulfate sub-type potassium-containing salt lake brine water
CN1810729B (en) * 2006-02-11 2011-04-27 国投新疆罗布泊钾盐有限责任公司 Process of preparing magnesium potassium sulfate fertilizer with bittern potassium containing magnesium sulfite
CN1810644B (en) * 2006-02-11 2010-06-16 国投新疆罗布泊钾盐有限责任公司 Improved process of preparing potassium sulfate with bittern containing potassium and magnesium sulfite
CN1810730B (en) * 2006-02-11 2010-12-01 国投新疆罗布泊钾盐有限责任公司 Improved process of preparing magnesium potassium sulfate fertilizer with bittern containing potassium and magnesium sulfite
CN100503440C (en) * 2007-03-30 2009-06-24 中国科学院青海盐湖研究所 Process of preparing potassium sulfate with potassium containing bittern of magnesium sulfate subtype
CN101602617B (en) * 2009-06-30 2011-11-30 雅泰实业集团有限公司 Method for producing potash magnesium sulphate fertilizer
CN102249268B (en) * 2011-05-04 2013-06-05 中国科学院青海盐湖研究所 Method for enriching trace elements in saturated magnesium chloride brine by natural evaporation
CN102921553B (en) * 2012-11-23 2014-03-19 化工部长沙设计研究院 Method for flotation of lithium potassium sulfate in mixture of lithium potassium sulfate and sodium chloride
CN103771460B (en) * 2013-03-22 2015-03-11 新疆安华矿业投资有限公司 Method for preparing potassium mixed salt mine by using nitrate contained magnesium sulphate subtype bittern and potassium nitrate production
CN103204521B (en) * 2013-04-16 2014-11-05 青海省茫崖兴元钾肥有限责任公司 Method for obtaining potassium chloride from low-grade potassium-containing sulphate salt lake ores
CN104628017A (en) * 2015-02-13 2015-05-20 中国科学院青海盐湖研究所 Method for preparing kainite ore from sulfate-type brine
CN105000578B (en) * 2015-08-03 2017-03-15 化工部长沙设计研究院 The production technology of potassium chloride is reclaimed in a kind of glaserite mother liquor from saturation
CN105692657B (en) * 2016-04-14 2017-07-28 化工部长沙设计研究院 A kind of method of use low-sulfur potassium than bittern preparing potassium sulfate
CN107188208B (en) * 2017-07-06 2019-11-22 化工部长沙设计研究院 A method of Shoenite is extracted with the carnallite of containing magnesium sulfate
CN107244680B (en) * 2017-07-06 2020-03-31 化工部长沙设计研究院 Process for producing potassium sulfate by using halite ore containing epsomite in salt field
CN107265482B (en) * 2017-07-06 2020-03-31 化工部长沙设计研究院 Method for producing potassium sulfate from magnesium sulfate-meta-chloride type potassium-containing brine
CN107935638A (en) * 2017-11-10 2018-04-20 国投新疆罗布泊钾盐有限责任公司 A kind of method for producing top grade potash magnesium sulphate fertilizer using thick potassium chloride and thick picromerite
CN107954750B (en) * 2017-11-10 2021-03-09 国投新疆罗布泊钾盐有限责任公司 Method for preparing top-grade potash magnesium sulphate fertilizer by using carnallite and potassium mixed salt ore
CN111170338A (en) * 2020-03-10 2020-05-19 青海中信国安锂业发展有限公司 Process for preparing fully water-soluble potassium sulfate from magnesium sulfate subtype salt lake brine
CN113247920A (en) * 2021-05-24 2021-08-13 青海联宇钾肥有限公司 Method for co-producing potash magnesium sulphate fertilizer, potassium chloride and potassium sulphate

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CN1077434A (en) * 1993-05-14 1993-10-20 中国石油天然气总公司工程技术研究所 A kind of method of producing vitriolate of tartar with bittern and Repone K
CN1131639A (en) * 1995-11-27 1996-09-25 中国科学院青海盐湖研究所 Method for preparing potassium sulfate with sulfate type bittern
CN1281822A (en) * 2000-08-29 2001-01-31 化学工业部连云港设计研究院 Method for preparing potassium sulfate by using sulfate type potassium-containing bittern
CN1318515A (en) * 2001-05-24 2001-10-24 化学工业部连云港设计研究院 Preparation method of potassium sulfate with sulfate-type salt lake bittern containing potassium salt
CN1335260A (en) * 2001-09-07 2002-02-13 中信国安锂业科技有限责任公司 Halogenation process of preparing KCl

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1077434A (en) * 1993-05-14 1993-10-20 中国石油天然气总公司工程技术研究所 A kind of method of producing vitriolate of tartar with bittern and Repone K
CN1131639A (en) * 1995-11-27 1996-09-25 中国科学院青海盐湖研究所 Method for preparing potassium sulfate with sulfate type bittern
CN1281822A (en) * 2000-08-29 2001-01-31 化学工业部连云港设计研究院 Method for preparing potassium sulfate by using sulfate type potassium-containing bittern
CN1318515A (en) * 2001-05-24 2001-10-24 化学工业部连云港设计研究院 Preparation method of potassium sulfate with sulfate-type salt lake bittern containing potassium salt
CN1335260A (en) * 2001-09-07 2002-02-13 中信国安锂业科技有限责任公司 Halogenation process of preparing KCl

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