WO2005063626A1 - Procede de recuperation de sulfate de potasse - Google Patents

Procede de recuperation de sulfate de potasse Download PDF

Info

Publication number
WO2005063626A1
WO2005063626A1 PCT/IN2003/000463 IN0300463W WO2005063626A1 WO 2005063626 A1 WO2005063626 A1 WO 2005063626A1 IN 0300463 W IN0300463 W IN 0300463W WO 2005063626 A1 WO2005063626 A1 WO 2005063626A1
Authority
WO
WIPO (PCT)
Prior art keywords
bittern
nacl
mgcl
carnallite
kcl
Prior art date
Application number
PCT/IN2003/000463
Other languages
English (en)
Inventor
Pushpito Kumar Ghosh
Kaushik Jethalal Langalia
Maheshkumar Ramniklal Gandhi
Rohit Harshadray Dave
Himanshu Labshanker Joshi
Rajinder Nath Vohra
Vadakke Puthoor Mohandas
Sohanlal Daga
Koushik Halder
Hasina Hajibhai Deraiya
Ramjibhai Devjibhai Rathod
Abdulhamid Usmanbhai Hamdani
Original Assignee
Council Of Scientific And Industrial Research
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Council Of Scientific And Industrial Research filed Critical Council Of Scientific And Industrial Research
Priority to CA002552104A priority Critical patent/CA2552104C/fr
Priority to AU2003300719A priority patent/AU2003300719B2/en
Priority to PCT/IN2003/000463 priority patent/WO2005063626A1/fr
Priority to JP2005512762A priority patent/JP4516023B2/ja
Priority to CNB2003801109302A priority patent/CN100439248C/zh
Priority to BRPI0318666A priority patent/BRPI0318666B1/pt
Priority to GB0614762A priority patent/GB2427190B8/en
Publication of WO2005063626A1 publication Critical patent/WO2005063626A1/fr
Priority to IL176482A priority patent/IL176482A/en

Links

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
    • 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
    • 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
    • Y02P20/10—Process efficiency

Definitions

  • the present invention provides an integrated process for the recovery of sulphate of potash (SOP) from sulphate-rich bittern.
  • SOP sulphate of potash
  • the process requires only bittern and lime as raw materials and affords, besides SOP, low boron containing Mg(OH) 2 , gypsum and salt, as co-products, all of which are obtained in pure form.
  • Background of the invention SOP is a dual fertilizer containing 50% K 2 O and 18% S. It has the lowest salt index and is virtually free of chloride, which makes it a superior fertilizer to muriate of potash (MOP).
  • MOP is easy to produce, especially, when brine/bittern is low in sulphate content such as in the Dead Sea and this accounts for its lower price compared to SOP.
  • countries such as India, which do not have low sulphate bittern, but which have adequate bittern of sea and sub-soil origin, would be greatly benefited if SOP can be produced economically from such bittern sources.
  • potassium sulphate has numerous industrial applications as well.
  • Mg(OH) 2 is commercially used in pulp and paper industries and also as antacid and fire retardant. Waste water and acidic effluent treatment represent additional high growth areas for its application.
  • Mg(OH) 2 is also used for production of magnesia (MgO), magnesium carbonate and other magnesium chemicals. Mg(OH) 2 that is low in B O 3 impurity is especially suitable for production of refractory grade MgO.
  • High quality gypsum (CaSO 4 .2H O) finds applications in the white cement industry and for manufacture of high strength ⁇ and ⁇ Plaster of Paris.
  • Sodium chloride that contains small quantities of potassium chloride finds application in the edible salt industry. Reference is made to the well-known Mannheim process involving reaction of
  • MOP through reaction with gypsum in presence of ammonia.
  • the principle of the process is double decomposition reaction between gypsum and potassium chloride in presence of ammonia at 0°C.
  • the main disadvantage of the process is that it is energy intensive and necessitates careful, design of the reactor for safe operation.
  • H. Scherzberg et al. ('Messo pilots new potassium sulphate process', Phosphorous & Potassium, 178, March- April 1992, p-20) describe the successful trials on a process involving reaction of MOP with sodium sulphate to produce the double salt glaserite (3K SO 4 .Na 2 SO 4 ). The glaserite is in turn reacted with MOP to produce SOP.
  • the main disadvantage of the process is that it would be unsuitable for those who do not have access to such raw materials. Moreover, the process involves several complex unit operations including the need for chilling. Such processes have their limitation on large scale. H. Scherzberg and R. Schmitz ('Duisberg's alternative to Mannheim', Phosphorous & Potassium, 178, March- April 1992, p-20), describe an integrated process for production of SOP from KC1 and MgSO 4 or Na SO 4 . The main drawback of the process is that the amount of NaCl in raw materials has a critical effect on the process and, as such, is less applicable to crude mixed salt as obtained from sea bittern. Another disadvantage is that the process involves heating and cooling which makes it energy intensive.
  • K. P. Patel, R. P. Vyas and K. Seshadri disclose a process for preparation of SOP by leaching syngenite (K 2 SO 4 .CaSO 4 .H O) with hot water and then recovering it by solar evaporation.
  • the main drawback of the process is that it is energy intensive.
  • production of syngenite from mixed salt is itself an involved affair.
  • K. Sehsadri et al "Manufacture of Potassium chloride and byproducts from Sea
  • Bittern " Salt Research and Industry, April-July 1970, Vol. 7, page 39-44) disclose a process wherein mixed salt (NaCl and kainite) obtained from bittern is dispersed with high density bittern in proper proportion and heated to a temperature of 110°C when kieserite (MgSO 4 .H 2 O) is formed which is separated by filtering the slurry under hot conditions. The filtrate is cooled to ambient temperature, when carnallite crystallizes out. Carnallite is decomposed with water to get a solid mixture of sodium chloride and potassium chloride while magnesium chloride goes into solution. Solid mixture of potassium chloride and sodium chloride is purified using known techniques to produce pure potassium chloride.
  • the main drawback of the patent application is that the process is less attractive when distiller waste is not available in the vicinity and the process becomes less economical when carnallite has to be obtained from bittern without production of industrial grade salt. Moreover, as in the case referred to above, it is desirable to utilize the sulphate content in bittern and produce SOP in preference to MOP.
  • Michael Freeman ('Great Salt Lake- A fertile harvest for IMC in Phosphorus & Potassium, 225, Jan-Feb, 2000) describe a process comprising concentrating the brine containing 0.2-0.4% KCl, harvesting mixed salt, separation of high sodium chloride fraction through floatation, leaching with sulphate rich brine to produce schoenite, hot water dissolution of schoenite, fractional crystallization of SOP and recycling of mother liquor containing up to 30% of original K to evaporation pond.
  • the method comprises concentrating the bittern, separating NaCl, concentrating to obtain crude K-Mg salt containing 10-45% NaCl, crushing, mixing with saturated bittern to obtain a solution with concentration of 20-40%, removing NaCl by back-floatation, concentrating, dewatering to obtain refined K-Mg salt containing less than 5% NaCl, mixing the K-Mg salt and water at specified ratio, allowing the mixture to react at 10-60°F for 0.5-3hr, separating to obtain schoenite, mixing with KCl and water at specified ratio, allowing the mixture to react at 10-70°F for 0.25-3hr and separating to obtain K 2 SO 4 .
  • the drawbacks of the process are (i) need for elaborate method of purification of mixed salt that includes removing NaCl by the less desirable method of back floatation that involves use of organic chemicals, (ii) lack of any mention of the manner in which the various effluent streams are dealt with, and (iii) dependence on outsourced KCl since no mention is made of any process for KCl production as part of the process.
  • J. H. Hildebrand ('Extraction of Potash and other Constituents from sea water Bittern' in Journal of Industrial and Engineering Chemistry, Vol. 10, No. 2, 1918, pp 96-106) describe theoretical aspects of the recovery of potash from sea bittern and propose a process for extraction.
  • bittern is evaporated at a temperature between 100-120°C, thereby forming a solid mixture of sodium chloride and kieserite (MgSO 4 .H 2 O), separating this mixture under hot conditions in a heated centrifuge, and cooling the mother liquor in a cooler for separation of carnallite.
  • Carnallite is decomposed and washed with water to produce potassium chloride.
  • the drawback of this process is that it is demanding in terms of energy requirement and sufficiently pure, carnallite cannot be obtained.
  • the main drawback of the process is the contamination of kieserite with NaCl, which would necessitate further purification to obtain products in saleable form.
  • Patent Application No. 423211, CA 1203666, by Wendling et al titled, "Process for the manufacture of potassium sulphate by treatment of solution containing magnesium chloride and potassium chloride" describes a process for the production of potassium sulphate from solutions containing magnesium chloride, such as solutions of carnallite ore and, in particular, the equilibrium mother liquors of a unit for the treatment of carnallite.
  • A. S. Mehta Indian Chemical Engineer, 45(2), 2003, p. 73 describes a process of bromine manufacture from bittern. Bittern is acidified with sulphuric acid to a pH of 3.0-3.5 and the bromide ion is then oxidized with chlorine and stripped off with the help of steam. The acidic de-brominated bittern is neutralized with lime, the sludge thus formed removed, and the effluent discharged. Bromine plants located in the vicinity of natural salt beds in the Greater Rann of Kutch in Gujarat, India utilize natural bittern for bromine production by the above method and discharge their effluent back into the Rann.
  • Mg(OH) 2 produced directly from raw bittern has much higher B 2 O 3 content compared to Mg(OH) 2 prepared from the Mg 2+ source of the present invention, which is linked to production of SOP.
  • Chinese Patent No. 1084492, Lu Zheng describes a process of manufacture of SOP from bittern and potassium chloride. In this process, bittern is processed by evaporation, cooling, floatation, and is then reacted with potassium chloride to make potassium sulfate and by-products of industrial salt and residual brine.
  • SOP superior fertilizer
  • Another object is to dispense with the need for floatation to remove NaCl from mixed salt and instead to leach away NaCl in the mother liquor (SEL) and simultaneously convert kainite into schoenite.
  • Another object is to produce SOP from schoenite under ambient conditions through the known method of reaction with KCl in presence of water and wherein the
  • MOP is generated from SEL eliminating the need to source it externally. Another object is to maximize recovery of potash in the form of SOP from mixed salt. Another object is to desulphate the SEL cost-effectively to promote carnallite formation. Another object is to evaporate desulphated SEL in a multiple effect evaporator to recover water for reuse. Another object is to utilize the NaCl separated as edible salt. Another object is to utilize the MgCl 2 -rich carnallite decomposed liquor (CDL) for cost- effective production of CaCl 2 and Mg(OH) 2 through treatment with lime. Another object is to utilize the washings from Mg(OH) 2 filtration for preparation of slaked lime from quick lime which conserves water and recycles residual
  • Another object is to utilize the CaCl 2 solution above for desulphatation of SEL. Another object is to recover KCl that is lost in CDL by recycling the latter in the manner described above. Another object is to show that MgO produced from the above Mg(OH) 2 contains very low ( ⁇ 0.03 %) levels of B 2 O 3 impurity. Another object is to minimize effluent generation in the process and instead to utilize effluent to enhance potash recovery or to convert into value-added products. Another object is to replace conventionally employed slaked lime with
  • the present invention provides an integrated process for the preparation of sulphate of potash from bitterns, comprising:
  • step (i) subjecting bittern to fractional crystallization to obtain kainite type mixed salt with high kainite content and MgCl 2 -rich end bittern, and . subjecting the MgC12 rich end bittern to desulphation; (ii) treating the kainite type mixed salt with water and mother liquor obtained in step (xiii) below to leach out substantially all NaCl from the mixed salt and simultaneously convert kainite into schoenite; (iii) filtering the schoenite and separating the filtrate; (iv) desulphating the filtrate with aqueous CaCl 2 ;
  • step (v) filtering the gypsum produced in step (iv) and mixing the filtrate with the MgCl 2 -rich filtrate obtained in step (vii) below,
  • step (vi) evaporating the resultant solution of step (v) and cooling to ambient temperature to crystallize crude carnallite, (vii) centrifuging the crude carnallite and recycling the required quantity of filtrate to step (v), (viii) decomposing the crude carnallite with appropriate quantity of water from step (vi) to yield crude KCl and carnallite decomposed liquor; (ix) filtering the crude KCl, and washing with water to remove adhering MgCl 2 and subjecting to hot leaching for production of MOP and NaCl, (x) mixing the carnallite decomposed liquor from step (viii) and washing from step (ix) and treating with hydrated lime,
  • step (xi) filtering the slurry and washing the cake to produce Mg(OH) 2 and CaCl 2 - containing filtrate for the desulphatation process of step (iv).
  • step (xii) treating by known method the schoenite produced in step (iii) with MOP produced in step (ix) to produce SOP under ambient condition, (xiii) filtering the SOP and collecting separately the mother liquor hereinafter referred to as KEL, (xiv) recycling the KEL of step (xiii) in the process of step (ii). It may be noted that certain steps of the above process are triggered initially with CaCl 2 and water procured externally and thereafter these are largely generated in the process of the invention as described above.
  • bittern of density in the range of 29- 34°Be (sp. gr. 1.25-1.31) is used for production of mixed salt as described in the prior art and then converted into schoenite with simultaneous teaching of NaCl from the solid mass.
  • mixed salt is treated with a 0.3-
  • schoenite is reacted with MOP and water in the ratio of 1:0.3-0.6:1-2 to produce SOP and KEL and wherein the MOP is produced in situ from SEL.
  • MOP is produced from carnallite which, in turn, is obtained through desulphatation of SEL, treatment with 400-440 g/L
  • MgCl 2 liquor into the ratio of 1 part of desulphated bittern and 0.7-0.9 parts of MgCl 2 liquor, and forced evaporation till the solution attains a temperature of 120-128 °C at atmospheric pressure.
  • the filtrate obtained after removal of NaCl is cooled to room temperature whereupon carnallite is obtained upon filtration while the filtrate contains 400-440 g/L of MgCl 2 and is recycled back into a fresh lot of desulphated SEL for further production of carnallite.
  • the wet carnallite is treated with water in the ratio of 1 :0.4-0.6 to obtain crude KCl.
  • the magnesium chloride in carnallite decomposed liquor is supplemented with MgCl 2 in the end liquor and treated with lime to produce Mg(OH) and required quantity of calcium chloride solution (20-
  • the Mg(OH) 2 is calcined in the temperature range of 800-900°C to produce MgO with ⁇ 0.04% B 2 O 3 .
  • fresh water requirement is kept to a minimum by recycling water from forced evaporation step along with washing generated in the purification of gypsum, Mg(OH) 2 and KCl.
  • acidified de-brominated bittern which is an ideal raw material for mixed production, is neutralized with crude Mg(OH) 2 instead of with lime to eliminate sludge formation.
  • the main inventive step is the recognition that the step of transforming kainite in mixed salt into schoenite and leaching of NaCl from mixed salt can be simultaneously performed in a single operation with minimum loss of KCl in mixed salt.
  • Another inventive step is self reliance wherein the need for outsourced MOP is minimized by producing it instead from the waste filtrate of schoenite manufacture.
  • Another inventive step is the desulphatation of SEL required for MOP production using calcium chloride generated in situ from the MgCl 2 in desulphated SEL that shows up as MgCl 2 -rich streams of carnallite decomposed liquor and end liquor.
  • Another inventive step is the coupling of Mg(OH) 2 production with desulphatation of SEL and thereby eliminating the problem of CaCl 2 waste management otherwise encountered in production of Mg(OH) 2 from brine or bittern.
  • Another inventive step is the use of CDL primarily for Mg(OH) 2 production which greatly reduces B O 3 impurity in Mg(OH) 2 and, as a result, in MgO obtained there from.
  • Another inventive step is the local use of crude Mg(OH) 2 for neutralization of acidified de-brominated bittern prior to production of mixed salt.
  • Another inventive step is the recycling of liquid effluents to minimize requirement of fresh water while simultaneously enhancing recoveries and addressing the problem of effluent disposal.
  • EXAMPLE-1 In a typical process, 200 M 3 of 29.5° Be' (sp. gr. 1.255) sea bittern was subjected to solar evaporation in a lined pan. The first fraction (20 Tons) containing mainly crude salt was removed at 34° Be' (sp. gr. 1.306). The bittern was further evaporated to 35.5° Be' (sp. gr. 1.324) and sels Mixt. fraction (15 tons) was separated. The resultant bittern (100 M 3 ) was transferred to a second lined pan and solar evaporation was continued whereupon 16 tons of kainite type mixed salt and 26 M 3 of end bittern were obtained.
  • the mixed salt was further processed for production of schoenite as described in subsequent examples while a part of the end bittern was desulphated with outsourced calcium chloride to generate desulphated end bittern. A part of the desulphated end bittern was subsequently treated with hydrated lime to produce calcium chloride and magnesium hydroxide.
  • the calcium chloride solution was filtered and used for desulphatation of SEL of Example-6.
  • the other part of the desulphated end bittern was used as MgCl 2 source in the same example to promote carnallite formation from desulphated SEL. Similar experiments were also conducted with other sources of bittern such as sub-soil bittern and bittern obtained after bromine recovery.
  • EXAMPLE-2 142.0 kg of kainite type mixed salt, having chemical composition: KCl -
  • EXAMPLE-3 60.0 kg of the mixed salt having the same composition as in Example-2 was taken along with the KEL obtained in Example-2. 27 L of water was additionally added and the contents were stirred for 2.5 hr. The slurry was filtered in a centrifuge to obtain 26.0 kg of schoenite analysing K 2 SO 4 - 39.7%, MgSO 4 - 29.5%, NaCl - 0.7%, and MgCl 2 - 0.6%, and 95.0 L of filtrate (SEL), analysing as KCl - 9.9%, NaCl - 13.0%, MgSO 4 - 18.6%, and MgCl 2 - 6.0%d.
  • the schoenite was reacted with solution of 10.4 kg of MOP in 38 L of water in a vessel under stirring for 3.5 hr.
  • the resultant sluny was filtered using centrifuge to obtain 14.5 kg SOP analyzing K 2 SO - 98.1, NaCl - 0.2%, MgSO 4 - 1.4%, and 45 L of filtrate (KEL) analysing as K 2 SO 4 - 12.4%, KCl - 6.15%, NaCl - 0.9%, MgSO 4 - 1.0%, and MgCl 2 - 10.2%,
  • EXAMPLE-4 104 kg of mixed salt analyzing KCl - 14.1%, NaCl - 16.5%, MgSO 4 - 41.6%, was reacted with 100 L of KEL analysing as K 2 SO 4 - 13.9%, NaCl - 2.8%, and MgCl 2
  • the schoenite was reacted with a solution of 19.0 kg of MOP in 75 L of water for 3.5 hr in a vessel with continuous stirring.
  • the slurry was centrifuged to get 27.0 kg of SOP analysed as K 2 SO - 94.3%, NaCl - 0.2%, and MgSO 4 - 3.7%, and 85 L of filtrate (KEL), analysing as KCl - 15.5%, NaCl - 0.8%, MgSO 4 - 10.5%, and MgCl 2 - 3.0%.
  • EXAMPLE-6 59 L of desulphated end bittern obtained in Example- 1 having chemical composition: KCl - 1.15 %, NaCl 1.3%, MgCl 2 - 41.2%, CaSO - traces was diluted with 40 L of water and treated with 14.7 kg of freshly prepared hydrated lime (87.7 % active strength) for 1 hr. The resultant slurry was filtered and the cake was washed with 30 L of water. 90 L of total filtrate containing CaCl 2 -22.3% and MgCl 2 - 3.0% was obtained. The solid magnesium hydroxide was further washed with 100 L of water to make it free from soluble impurities.
  • the resultant solution was subjected to forced evaporation in an open pan evaporator till the solution attained a boiling point of 120°C.
  • the hot liquor was filtered to separate 5.5 kg of crude NaCl having composition: NaCl- 85%, KCl-2.9% and MgCl 2 -12.1%.
  • the filtrate was cooled in a tank to crystallize carnallite.
  • the resultant slurry was filtered to obtain 11.3 kg of carnallite analysing as KCl -21.7%, NaCl-9.7 %, MgCl 2 -31.4%, and CaSO 4 - 2.7%, and 48 L of end bittern analyzing as MgCl 2 -40.2%, KCl - 0.8 %, NaCl - 1.1 %.
  • the CDP was treated with 1.9L of water at ambient temperature (30 °C) to obtain 2.0 kg KCl having composition : KCl - 90.0 %, NaCl - 3.3% ; MgCl 2 - 0.4% and CaSO 4 - 6.0 and 2.2 L of saturated solution having chemical composition KCl - 14.0% and NaCl - 20.0%.
  • EXAMPLE-7 Of 10 L of CDL obtained in above experiment, 5.7 L of cold leachate with which crude salt produced in the previous example was also washed to recover magnesium content in it, having chemical composition: KCl-7.0%, NaCl-8.2%, MgCl 2 - 21.5%, and CaSO 4 - traces, and 15 L of water was treated with 2.5 Kg of freshly prepared hydrated lime having 90 % activity for 1 hr. The resultant slurry was filtered and solid cake washed with 10 L of water to obtain 34 L of filtrate containing 7.7 % CaCl 2 . The solid magnesium hydroxide was further washed with 30 L of water to make it free from soluble impurities.
  • the Mg(OH) 2 was dried to obtain 2.3 Kg of Mg(OH) 2 which was calcined to get MgO analyzing as 92% MgO containing 0.034% B 2 O 3 as impurity.
  • 34 L of CaCl 2 containing brine was used to desulphate 17 L of SEL having chemical composition KCl - 7.2%, NaCl - 12.4 %, MgSO - 16.0 %, and MgCl - 6.5 % .
  • the resultant slurry was filtered to remove 5.2 kg of wet calcium sulphate and obtain 49 L of desulphated SEL having Mg content of 2.03 %.
  • 75 L of end bittern having Mg concentration of 9.6 % obtained from previous experiment was added to the desulphated SEL.
  • the resultant solution mixture was subjected to forced evaporation in open pan evaporator till the boiling point of the solution is 126°C.
  • the hot liquor was cooled in a tank to crystallize carnallite.
  • the resultant slurry was filtered to obtain 18.8 kg of carnallite having chemical composition: KCl - 14.3 %, NaCl -12.7 %, MgCl 2 - 31.9 % and CaSO 4 - 1.9 % and 46.5 L of end bittern having chemical composition.
  • EXAMPLE-8 15.5 L of CDL obtained in above experiment having chemical composition: KCl - 5.0%, NaCl - 3.2%, MgCl 2 - 32.5% and CaSO 4 - traces; and 15 L of water was treated with 3.0 kg of freshly prepared hydrated lime having 90.0 % activity for 1 hr. The resultant slurry was filtered and solids washed with 10 L of water to obtain 27.5 L of filtrate containing 10.60 % CaCl 2 . The solid magnesium hydroxide was further washed with 30 L of water to make it free from soluble impurities.
  • the Mg(OH) was dried to obtain 2.9 kg of Mg(OH) 2 and subsequently calcined to obtain caustic calcined MgO having 95% MgO content and 0.03 % B 2 O 3 impurity.
  • the CaCl containing solution was used to desulphate 25 L of SEL having chemical composition KCl - 7.2%, NaCl - 12.4 %, MgSO 4 16.0 % and MgCl 2 - 6.5 %.
  • the resultant slurry was filtered to remove 5.7 kg of calcium sulphate and obtain 46 L of desulphated SEL having Mg content of 3.05 %. 33 L of end bittern having Mg concentration of 11.8 % obtained from previous experiment was added to the desulphated SEL.
  • the resultant solution mixture was subjected to forced evaporation in an open pan evaporator till the boiling point of the solution is 125°C.
  • the hot liquor was cooled in a tank to crystallize carnallite.
  • the resultant slurry was filtered to obtain 14 kg of carnallite having chemical composition: KCl - 15.0 %, NaCl - 24.7 %, MgCl 2 - 25.1%, and CaSO 4 - 4.0% and 33.8 L of end bittern having chemical composition.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Fertilizers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention a trait à un procédé de récupération de sulfate de potasse à partir d'eau mère riche en sulfate. Le procédé nécessite seulement de l'eau mère et de la chaux comme matières premières. Du sel de type kaïnite en mélange est obtenu par la cristallisation fractionnaire de l'eau mère. La kaïnite est convertie en picromérite avec l'élimination simultanée de NaCl par son traitement avec de l'eau et de liqueur terminale obtenue par la réaction de picromérite avec du chlorure de potasse pour sa conversion en sulfate de potasse. La liqueur terminale dérivée de la conversion de la kaïnite en picromérite est utilisée pour la récupération de chlorure de potasse. La kaïnite convertie en picromérite est désulfurée et additionnée de MgCl2 à l'aide d'eau mère terminale générée dans le procédé de production de carnallite. La liqueur décomposée de carnallite produite lors de la décomposition de carnallite est soumise à une réaction avec de la chaux hydratée pour la préparation de solution de CaCl2 et de Mg(OH) de pureté élevée avec une faible teneur en bore. La solution de CaCl2 est utilisée pour la désulfatation de la kaïnite convertie en picromérite produisant un gypse de haute pureté comme sous-produit. Il a été démontré que les flux liquides contenant de la potasse sont recyclés dans le procédé, la récupération de potasse sous forme de sulfate de potasse est quantitative.
PCT/IN2003/000463 2003-12-31 2003-12-31 Procede de recuperation de sulfate de potasse WO2005063626A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
CA002552104A CA2552104C (fr) 2003-12-31 2003-12-31 Procede de recuperation de sulfate de potasse
AU2003300719A AU2003300719B2 (en) 2003-12-31 2003-12-31 Process for recovery of sulphate of potash
PCT/IN2003/000463 WO2005063626A1 (fr) 2003-12-31 2003-12-31 Procede de recuperation de sulfate de potasse
JP2005512762A JP4516023B2 (ja) 2003-12-31 2003-12-31 硫酸カリの回収方法
CNB2003801109302A CN100439248C (zh) 2003-12-31 2003-12-31 硫酸钾回收方法
BRPI0318666A BRPI0318666B1 (pt) 2003-12-31 2003-12-31 processo integrado para a preparação de sulfato de potássio
GB0614762A GB2427190B8 (en) 2003-12-31 2003-12-31 Process for recovery of sulphate of potash
IL176482A IL176482A (en) 2003-12-31 2006-06-21 Process for recovery of sulphate of potash

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IN2003/000463 WO2005063626A1 (fr) 2003-12-31 2003-12-31 Procede de recuperation de sulfate de potasse

Publications (1)

Publication Number Publication Date
WO2005063626A1 true WO2005063626A1 (fr) 2005-07-14

Family

ID=34717580

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2003/000463 WO2005063626A1 (fr) 2003-12-31 2003-12-31 Procede de recuperation de sulfate de potasse

Country Status (8)

Country Link
JP (1) JP4516023B2 (fr)
CN (1) CN100439248C (fr)
AU (1) AU2003300719B2 (fr)
BR (1) BRPI0318666B1 (fr)
CA (1) CA2552104C (fr)
GB (1) GB2427190B8 (fr)
IL (1) IL176482A (fr)
WO (1) WO2005063626A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007054953A1 (fr) * 2005-11-10 2007-05-18 Council Of Scientific & Industrial Research Procede ameliorepour la recuperation de sulfate de potasse (sop) a partir d'une eau-mere riche en sulfate
WO2016059651A1 (fr) * 2014-10-16 2016-04-21 Council Of Scientific And Industrial Research Procédé de production peu coûteux d'un engrais composé de sulfate d'ammonium et de potassium directement à partir d'eaux-mères des salines concentrées
WO2016180692A1 (fr) 2015-05-08 2016-11-17 Yara Dallol Bv Procédés de production de sulfate de potassium à partir de minerais contenant du potassium à des températures ambiantes élevées
WO2017220709A1 (fr) 2016-06-24 2017-12-28 Yara Dallol Bv Procédé de réduction d'halite dans la préparation de sulfate de potassium à partir de minerais contenant du potassium à températures ambiantes élevées.
CN107673372A (zh) * 2017-11-15 2018-02-09 河北工业大学 一种基于耦合技术的大型富钾的方法及其装置
US10815130B2 (en) 2017-10-13 2020-10-27 Novopro Projects Inc. Systems and methods of producing potassium sulfate

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102503619B (zh) * 2011-09-02 2013-11-06 天津科技大学 由制盐母液制取复合肥的方法
CN103397201B (zh) * 2013-07-26 2014-12-17 中国科学院青海盐湖研究所 从杂卤石矿中静态溶浸提取钾以及制备硫酸钾的方法
CN104628017A (zh) * 2015-02-13 2015-05-20 中国科学院青海盐湖研究所 一种用硫酸盐型卤水制备钾盐镁矾矿的方法
CN107285283B (zh) * 2017-06-01 2019-10-15 中国中轻国际工程有限公司 一种硫化碱黑液、液体烧碱联产小苏打、铬酸钠、硫化碱工艺
CN114560480A (zh) * 2022-03-01 2022-05-31 天津长芦海晶集团有限公司 钙法除硫后苦卤的多元素提取方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634041A (en) * 1969-02-14 1972-01-11 Great Salt Lake Minerals Method for the production of potassium sulfate from potassium-containing double salts of magnesium sulfate
CN1084492A (zh) * 1992-09-12 1994-03-30 国家海洋局天津海水淡化与综合利用研究所 苦卤与氯化钾制备硫酸钾的方法
CN1188076A (zh) * 1997-04-10 1998-07-22 中国石油天然气总公司工程技术研究院 一种苦卤综合利用的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL50873A (en) * 1976-11-09 1979-11-30 Sadan A Process for the production of potassium chloride and magnesium chloride from carnallite
CN1027883C (zh) * 1993-05-14 1995-03-15 中国石油天然气总公司工程技术研究所 一种用苦卤和氯化钾制取硫酸钾的方法
CN1130152A (zh) * 1995-04-26 1996-09-04 国家海洋局天津海水淡化与综合利用研究所 用苦卤与氯化钾制取硫酸钾的方法
CN1128760C (zh) * 2000-08-29 2003-11-26 化学工业部连云港设计研究院 一种硫酸盐型含钾卤水制取硫酸钾的方法
CN1171794C (zh) * 2001-05-24 2004-10-20 化学工业部连云港设计研究院 一种硫酸盐型含钾盐湖卤水制取硫酸钾的方法
JP2005537202A (ja) * 2001-10-22 2005-12-08 カウンシル オブ サイエンティフィク アンド インダストリアル リサーチ ブラインからの塩化ナトリウムおよび他の塩類の回収
CN100439247C (zh) * 2003-12-31 2008-12-03 科学与工业研究委员会 同时回收氯化钾和富含KCl的食用盐

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3634041A (en) * 1969-02-14 1972-01-11 Great Salt Lake Minerals Method for the production of potassium sulfate from potassium-containing double salts of magnesium sulfate
CN1084492A (zh) * 1992-09-12 1994-03-30 国家海洋局天津海水淡化与综合利用研究所 苦卤与氯化钾制备硫酸钾的方法
CN1188076A (zh) * 1997-04-10 1998-07-22 中国石油天然气总公司工程技术研究院 一种苦卤综合利用的方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
DATABASE CA NIU, Z. ET.AL.: "Manufacture of potassium sulfate and other inorganic materials from bittern brine", XP002294205 *
MEHTA, D.J.: "Production of Potassium Sulphate from Mixed Salt obtained from Salt Works of Little Rann Of Kutch", SALT RESEARCH AND INDUSTRY, vol. 2, no. 4, 1965, pages 139 - 140, XP009035774 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007054953A1 (fr) * 2005-11-10 2007-05-18 Council Of Scientific & Industrial Research Procede ameliorepour la recuperation de sulfate de potasse (sop) a partir d'une eau-mere riche en sulfate
CN1962443B (zh) * 2005-11-10 2010-05-12 科学与工业研究委员会 从富含硫酸盐的盐卤中回收硫酸钾的改进方法
US8182784B2 (en) 2005-11-10 2012-05-22 Council Of Scientific & Industrial Research Process for the time recovery of sulphate of potash (SOP) from sulphate rich bittern
WO2016059651A1 (fr) * 2014-10-16 2016-04-21 Council Of Scientific And Industrial Research Procédé de production peu coûteux d'un engrais composé de sulfate d'ammonium et de potassium directement à partir d'eaux-mères des salines concentrées
WO2016180692A1 (fr) 2015-05-08 2016-11-17 Yara Dallol Bv Procédés de production de sulfate de potassium à partir de minerais contenant du potassium à des températures ambiantes élevées
WO2017220709A1 (fr) 2016-06-24 2017-12-28 Yara Dallol Bv Procédé de réduction d'halite dans la préparation de sulfate de potassium à partir de minerais contenant du potassium à températures ambiantes élevées.
US10815130B2 (en) 2017-10-13 2020-10-27 Novopro Projects Inc. Systems and methods of producing potassium sulfate
US10954133B2 (en) 2017-10-13 2021-03-23 Novopro Projects Inc. Systems and methods of producing potassium sulfate
CN107673372A (zh) * 2017-11-15 2018-02-09 河北工业大学 一种基于耦合技术的大型富钾的方法及其装置
CN107673372B (zh) * 2017-11-15 2023-09-08 河北工业大学 一种基于耦合技术的大型富钾的方法及其装置

Also Published As

Publication number Publication date
IL176482A0 (en) 2006-10-05
JP4516023B2 (ja) 2010-08-04
IL176482A (en) 2012-06-28
GB2427190B (en) 2009-04-15
GB2427190A (en) 2006-12-20
CA2552104C (fr) 2009-11-24
CA2552104A1 (fr) 2005-07-14
BRPI0318666B1 (pt) 2015-12-15
JP2007528333A (ja) 2007-10-11
GB2427190B8 (en) 2009-07-22
AU2003300719B2 (en) 2008-06-12
BR0318666A (pt) 2006-11-28
CN1886339A (zh) 2006-12-27
AU2003300719A1 (en) 2005-07-21
GB0614762D0 (en) 2006-09-06
CN100439248C (zh) 2008-12-03

Similar Documents

Publication Publication Date Title
US6776972B2 (en) Recovery of common salt and marine chemicals from brine
IL176482A (en) Process for recovery of sulphate of potash
EP1440036B1 (fr) Extraction du chlorure de sodium et des autres sels contenus dans de la saumure
US7041268B2 (en) Process for recovery of sulphate of potash
CA2538493C (fr) Procede ameliore pour la recuperation de sulfate de potasse (sop) dans des eaux salees riches en sulfate
AU2002212675A1 (en) Recovery of sodium chloride and other salts from brine
IL176481A (en) Integrated process for the simultaneous recovery of industrial grade potassium chloride and low sodium edible salt from bittern
US7014832B2 (en) Simultaneous recovery of potassium chloride and KCL enriched edible salt
JP5336408B2 (ja) ブラインからの塩化ナトリウムおよび他の塩類の回収
US4210626A (en) Manufacture of magnesium carbonate and calcium sulphate from brine mud
Niu Bhavnagar (IN); Abdulhamid
KR20040086327A (ko) 간수로부터 저 나트륨 염의 회수를 위한 공정
MXPA06007414A (en) Process for recovery of sulphate of potash
MXPA06007416A (en) Simultaneous recovery of potassium chloride and kc1 enriched edible salt

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200380110930.2

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 548/DELNP/2004

Country of ref document: IN

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2003300719

Country of ref document: AU

Ref document number: 176482

Country of ref document: IL

WWE Wipo information: entry into national phase

Ref document number: PA/a/2006/007414

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2552104

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2005512762

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Ref document number: DE

WWE Wipo information: entry into national phase

Ref document number: 0614762.3

Country of ref document: GB

Ref document number: 0614762

Country of ref document: GB

ENP Entry into the national phase

Ref document number: PI0318666

Country of ref document: BR

122 Ep: pct application non-entry in european phase