MXPA97002648A - Joint production of potassium sulphate, sodium sulfate and so chloride - Google Patents
Joint production of potassium sulphate, sodium sulfate and so chlorideInfo
- Publication number
- MXPA97002648A MXPA97002648A MXPA/A/1997/002648A MX9702648A MXPA97002648A MX PA97002648 A MXPA97002648 A MX PA97002648A MX 9702648 A MX9702648 A MX 9702648A MX PA97002648 A MXPA97002648 A MX PA97002648A
- Authority
- MX
- Mexico
- Prior art keywords
- sulfate
- sodium sulfate
- sodium
- mother liquor
- water
- Prior art date
Links
- OTYBMLCTZGSZBG-UHFFFAOYSA-L Potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 title claims abstract description 52
- 229910052939 potassium sulfate Inorganic materials 0.000 title claims abstract description 30
- 235000011151 potassium sulphates Nutrition 0.000 title claims abstract description 29
- UOVHNSMBKKMHHP-UHFFFAOYSA-L potassium;sodium;sulfate Chemical compound [Na+].[K+].[O-]S([O-])(=O)=O UOVHNSMBKKMHHP-UHFFFAOYSA-L 0.000 title claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 title description 15
- 239000001120 potassium sulphate Substances 0.000 title description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L na2so4 Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 82
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 66
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 66
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 49
- 239000011780 sodium chloride Substances 0.000 claims abstract description 32
- 235000002639 sodium chloride Nutrition 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000012452 mother liquor Substances 0.000 claims abstract description 27
- 229940072033 potash Drugs 0.000 claims abstract description 23
- 235000015320 potassium carbonate Nutrition 0.000 claims abstract description 23
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000047 product Substances 0.000 claims abstract description 15
- 238000002425 crystallisation Methods 0.000 claims abstract description 14
- 230000005712 crystallization Effects 0.000 claims abstract description 14
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 10
- 239000012141 concentrate Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 159000000001 potassium salts Chemical class 0.000 claims abstract description 3
- 239000010446 mirabilite Substances 0.000 claims description 26
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical group O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 24
- 238000001704 evaporation Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000010309 melting process Methods 0.000 claims 1
- 150000003385 sodium Chemical group 0.000 claims 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 229910052700 potassium Inorganic materials 0.000 description 8
- 239000011591 potassium Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000012267 brine Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 239000001103 potassium chloride Substances 0.000 description 6
- 235000011164 potassium chloride Nutrition 0.000 description 6
- 238000011068 load Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001376 precipitating Effects 0.000 description 3
- 230000006399 behavior Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000002198 insoluble material Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010977 unit operation Methods 0.000 description 2
- 229910000792 Monel Inorganic materials 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M Sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 235000012970 cakes Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- RMOYURUHGCBZCX-UHFFFAOYSA-L dipotassium;sodium;sulfate Chemical compound [Na].[K+].[K+].[O-]S([O-])(=O)=O RMOYURUHGCBZCX-UHFFFAOYSA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Abstract
The present invention relates to a process for producing potassium sulfate, sodium sulfate and sodium chloride from potash and a source of sodium / water sulfate, comprising the steps of: a) treating the source of sodium sulfate / water to produce a suspension containing anhydrous sodium sulfate, b) concentrate the suspension to form a concentrate and a diluent, c) treat the diluent to precipitate anhydrous sodium sulfate, d) take a portion of the anhydrous sodium sulfate steps (b) and / or (c) as a co-product, leaving the remainder of the anhydrous sodium sulphate in steps (b) and / or (c), e) subjecting the rest of the anhydrous sodium sulfate from the steps (b) and / or (c) to the conversion with potash in an aqueous medium, to produce glaserite and a first mother liquor, f) to convert the glaserite with potash and water to produce a precipitate of potassium sulfate and a second mother liquor g) return the second mother liquor to step (e) h) introduce the first liquor madr directly to evaporative crystallization so that sodium chloride is precipitated in a third mother liquor, and i) return the third mother liquor for conversion into potassium salts
Description
JOINT PRODUCTION OF POTASSIUM SULPHATE. SODIUM SULFATE AND SODIUM CHLORIDE
FIELD AND BACKGROUND OF THE INVENTION The present invention relates to processes for producing potassium sulfate, and more particularly, to processes for producing sodium sulfate, potassium sulfate and sodium chloride from potash and a source of sodium sulfate.
Production of Sodium Sulphate Several processes are known for making sodium sulfate from hydrated sources of sodium sulfate. High-quality commercial grades of sodium sulfate have typically been produced from Glauber's salt (Na2SO4 * 10H2O). There are natural deposits of Glauber's salt ("mirabilita") in cold climates. Glauber's salt can also be obtained by cooling a natural brine, or a solution obtained from mining solutions or a process stream. Cooling is carried out in tanks or in crystallizers (surface-cooled or vacuum-cooled). The anhydrous sodium substrate is typically produced from the Glauber salts by crystallization by evaporation in a mechanical evaporator of
INT. MEX. 87/39 recompression of vapor or multiple effect (MVR), by dehydration in a rotary dryer or by melting followed either by evaporation or by saline displacement with sodium chloride. The melting of Glauber's salt to precipitate anhydrous sodium sulfate produces, in general, an unacceptable fine product. In addition, Glauber's salt usually contains insoluble material that is unacceptable in high-grade anhydrous sodium sulfate. Therefore, the operations of dissolution, filtration (and auxiliary separation methods such as de-loosening) and crystallization by evaporation are necessary to obtain material of adequate quality. In general, some of the mother liquor is purged in order to prevent impurities from precipitating with the product. Alternatively, the Glauber salts may be melted to produce a low grade "salt cake" sodium sulfate. The saturated mother liquor is filtered and subsequently evaporated to produce high-grade sodium sulfate.
Production of Potassium Sulphate In the production of potassium sulphate from potash and sodium sulfate, the economic thermodynamic restrictions require that potassium sulphate be produced in two stages. In conventional processes, these stages consist of:
INT. MEX. 87/39 1) production of glaserite (3Na (S04) 2) from sodium sulfate, potash and the mother liquor from Step 2;
2) production of potassium sulfate from potash, water and glaserite from Step 1; The mother liquor produced in Step 1 contains substantial amounts of dissolved sulphate and potassium which, in general, guarantee a recovery operation. The processes that are currently known differ mainly in the scheme used for the recovery of these values of sulphate and potassium. Several processes (hereinafter Type I processes) take advantage of the different solubility behaviors of potassium chloride, sodium chloride and sodium sulphate / Glauber's salt, at high and low temperatures. The effluent from Step 1, of composition "a" (at 25 ° C) (see Figure Ib) is cooled to approximately 0 ° C, precipitating Glauber's salt for reuse and, possibly, a certain amount of sodium chloride, depending on the water balance in the system. The potassium values are concentrated in the aqueous phase. After separation, the solution is evaporated at high temperature producing sodium chloride and also concentrating the potassium ions in the solution. Sodium chloride is removed as a byproduct of the process and a hot liquor is cooled, precipitating potassium as KCl and / or glaserite, which
INT. MEX. 87/39 essentially returns to the reaction stages. Alternatively, the hot brine is reacted with Glauber's salt recovered from the crystallization step in order to produce a suspension of glaserite., which is returned to Stage 1. Other cyclic processes (hereinafter "Type II" processes) take advantage of the behaviors of different solubility of potassium chloride and sodium chloride at high temperatures. The amount of water added to the reaction steps is adjusted so that the glaserite and solution "b" (at 25 ° C) are produced (Figure Ib). The glaserite is then reacted with potash and water to produce the potassium sulfate product and a liquor of composition "c" (at 25 ° C). The liquor is returned to Stage 1. The effluent liquor from Step 1 is evaporated at high temperatures (75-110 ° C), producing pure NaCl and the final liquor is returned to Stage 1. It should be emphasized that the sulphate production Potassium from potash and sodium sulfate is a process to which little value is added, even though the byproduct of sodium chloride can be marketed. The multi-stage processes described above require both a large amount of capital and a large amount of energy. Type I processes are particularly complex, and require a large number of operations
INT. MEX. 87/39 unit. These include 4 to 6 stages of filtration, not including filtration of washed potassium sulfate product. In addition, the crystallization by cooling is used to bring the temperature of the effluent from Step I to 0 ° C. The heat of crystallization of Glauber's salt, which is substantial (18.4 Kcal / m), must also be removed at low temperatures. The cooling and heating costs associated with this stage, together with expensive equipment (such as crystallizers, heat exchangers, refrigerant systems and the like), represent a serious disadvantage. Type II processes do not have cooling stages below environmental conditions. However, the recirculation current is much larger (~ 10 tons per ton of K2S04 produced), which increases the energy consumption. The low proportion of the evaporated water with respect to the performance in the crystallization stage by evaporation drastically reduces the density of the natural suspension, requiring large crystallizers and / or more sophisticated crystallization technology. Although Glauber's salt is a relatively cheap source of sodium sulfate, additional water from Glauber's salt decreases the conversion in the reaction stages and increases the sulphate composition
INT. MEX. 87/39 of effluent from Stage 1. Some cyclic processes can not work using Glauber's salt while others require additional unit operations (eg, evaporation). To date, there are no economically viable industrial processes to produce agricultural grade potassium sulfate from sodium sulfate or Glauber's salt. Therefore, it is widely recognized that a process is needed to produce potassium sulphate from sodium sulfate, which is much more efficient and cheaper than those known up to now, and which provides great advantages.
SUMMARY OF THE INVENTION According to the present invention there is provided a process for the production of potassium sulfate, sodium sulfate and sodium chloride from potash and a source of sodium / water sulfate, comprising the steps of: a) treating the sodium sulphate / water source to produce a slurry containing anhydrous sodium sulfate; (b) concentrating the suspension to form a concentrate and a diluent; (c) treating a diluent to precipitate the anhydrous sodium sulfate; (d) subjecting the anhydrous sodium sulfate from step (b) and / or (c) and / or from
INT. MEX. 87/39 any other source for the conversion with potash, in an aqueous medium, in order to give glaserite and a first mother liquor, where all the excess anhydrous sodium sulfate is taken as a by-product, - (e) convert glaserite with potash and water to produce a precipitate of potassium sulfate and a second mother liquor; (f) returning the second mother liquor to step (d); (g) subjecting the first mother liquor to crystallization by evaporation, so that the substantially pure sodium chloride is precipitated in a third mother liquor; and (h) return the third mother liquor for conversion into potassium salts. According to other features of the preferred embodiments of the invention described below, the aqueous sodium sulfate solution is treated by crystallization by evaporation or by saline displacement with sodium chloride. The present successfully focuses on solving the problems currently known, by providing a process for the integrated production of sodium sulfate and sodium chloride with sodium sulfate, from potash and Glauber's salt, which is a cheap and available source of sulfate. sodium. The use of Glauber's salt together with the coproduction of high-grade sodium sulphate reduces the costs of the raw material and raises the total value of the
INT. MEX. 87/39 product, so that the added value practically doubles. The present invention uses sodium sulfate salt cake grade, which has been produced in-situ, to obtain the potassium sulfate product. In addition to reducing the evaporation load, the integrated process allows a more efficient use of energy resources, including waste vapors. In addition, the purging of the mother liquor of sodium sulphate is eliminated or practically reduced.
BRIEF DESCRIPTION OF THE DRAWINGS The invention described herein, by way of example only, refers to the following accompanying drawings, wherein: Figures la, Ib and le are solution phase diagrams for the Na2S system? 4 / 2NaCl / K2S? 4 / 2KCl / H2? at 0 °, 25 ° and 100 ° C, respectively; Figure 2 is a block diagram schematically illustrating the processes according to the present invention.
DESCRIPTION OF THE PREFERRED MODALITIES The present invention is a process for the integrated production of potassium sulfate and
INT. MEX. 87/39 sodium with sodium sulfate, from potash and a source of sodium sulfate / water, where the source of sodium sulfate / water may be a low quality water containing sodium sulfate, for example salt of Glauber or sodiumhydrogen sulfate, that is to say a mixture of sodium sulphate and Glauber's salt or partially hydrated sodium sulphate. The principles and operation of a process according to the present invention may be better understood in relation to the drawings and the accompanying description. To illustrate the advantages and benefits of the proposed invention, it is worth considering two separate processes, wherein potassium sulphate is produced from potash and Glauber's salt and sodium sulfate from Glauber's salt. The use of Glauber's salt as the sole source of sodium sulfate in the production of potassium sulphate is problematic in the processes that are currently known. Some cyclic processes can not work using Glauber's salt or require additional unit operations (for example, evaporation). In the other processes, the use of Glauber's salt greatly increases the volume of internal currents and the amount of Glauber's salt that is recovered by high-cost crystallization by cooling.
INT. MEX. 87/39 In currently known processes, the evaporation load in the potassium recovery stage increases by ~ 3.0-3.5 tons per ton of potassium sulphate produced, all of which is evaporated at high temperatures in chloride-rich solutions and requires of expensive building materials, such as monel or titanium. In this way, known processes that can use Glauber salts still require higher capital and energy costs than processes that consume anhydrous sodium sulfate. Assuming that Glauber's salt is completely dissolved in order to produce high purity sodium sulphate with the required size distribution, the evaporation load is ~ 2.3 tons per ton of the produced anhydrous sodium sulfate. The combined evaporation load is ~ 5.5 tons per ton of each product produced in the separation processes, a block diagram of the proposed processes is provided in Figure 2, by way of example. The anhydrous sodium substrate produced in the melting device is of sufficient quality to produce the agricultural grade potassium sulphate, so that the evaporation load for the integrated process is only 4.6 to 4.8 tons per ton of sulfate. of potassium and sodium sulfate. In addition, the stages of crystallization by
INT. MEX. 87/39 evaporation can be linked, where the waste vapor from one stage is fed to another, which reduces the total amount of waste vapor in the system. Furthermore, in the melting stage, the heat requirements are practically doubled in relation to each individual process. In this way, in a process according to the present invention as described below, the available waste vapor and the low pressure vapor requirements are much more balanced, reducing the cost of water cooling, condensers and the like. Similarly, there are more fundamental energy optimization possibilities for the integrated process, including the joint generation of steam and electricity and / or the use of mechanical vapor recompression for at least one of the evaporation systems. In a process according to the present invention, the capital costs of services (such as steam, hot water, cooling water) and process control are reduced because only one system is needed instead of two. The drying, storage and transport of the sodium sulfate produced in the fusion device are eliminated. Purging of the sodium sulphate solutions is not necessary since in general the impurities are precipitated from the sodium sulphate produced in the melting apparatus. In this way, they increase the sulfate yield
INT. MEX. 87/39 sodium. In relation to Figure 2, the process according to the present invention is as follows: the conversion of potassium and sodium sulfate is carried out in two stages. In the first step 10, the reaction is carried out between about 15 ° to about 60 ° C, the preferred temperature varies between about 20 to about 40 ° C. Potash 12, sodium sulfate 14 and suspension 34 of the recovery stage, and brine 18 from the decomposition step of glaserite 20 are introduced. The sodium sulphate agent is mainly or exclusively anhydrous sodium sulfate, but some Glauber salts and / or aqueous sodium sulfate are added. In the following, each of the aforementioned materials, alone or in combination, will be dominated collectively or in singular form as "source of sodium / water sulphate". The term "potash" is used to indicate any potassium chloride containing included material, for example, silvinite. Sodium sulfate and potash dissolve, generating a supersaturation with respect to glaserite, so that the glaserite precipitates. The system can also be supersaturated with respect to sodium chloride and so that some of the sodium chloride is coprecipitated. The suspension is concentrated and supplied in 22 to the
INT. MEX. 87/39 glaserite decomposition step 20. The mother liquor 26 is saturated in relation to the glaserite and should approach saturation with sodium chloride and / or potassium chloride under ideal conditions. A typical composition of mother liquor has the following composition: potassium-6% by weight; sodium-8% by weight, - chloride-17% by weight; sulfate-1.5% by weight; and the rest is water. Substantial amounts of potassium and sulfate in the mother liquor are returned to the process in the recovery stage. The glaserite decomposition step 20 is carried out at a temperature between about 15-60 ° C, the preferred temperature range is between 20 and about 35 ° C, the water 24 is introduced together with the solids 22 obtained from the first stage 10, potash is introduced directly into 8 and / or by steam 22 introducing excess potash to stage 10. Potash and glaserite solids dissolve, generating a supersaturation only in relation to potassium sulfate, so that potassium sulfate is precipitated selectively. The maximum conversion is obtained when the composition of the mother liquor approaches the point without variation of KCl / K2S0 / glaserite / H20. The potassium sulfate solutions are separated, washed and dried to give a potassium sulfate product 27. The mother liquor 18 is removed from the reactor and returned to the production stage.
INT. MEX. 87/39 of glaserite 10. The spent washing water is used, however, in the decomposition of glaserite. Some or all of the portions of steps 10 and 20 may be carried out in a single countercurrent differential contact apparatus. The brine 26 produced in the production of glaserite 10 is evaporated in a crystallizer by evaporation 28, at about 70 and 130 ° C, the preferred range being between about 95 and 110 ° C. If necessary, the brine 26 can be filtered before evaporation to remove any insoluble material. The withdrawal of water '30 produces the supersaturation of the sodium chloride that precipitates from the solution. Care must be taken not to over-evaporate as undesirable co-precipitation of the glaze can be obtained. After the solid / liquid separation, the wet sodium chloride product 32 is removed from the system. The potassium rich brine 34 is cooled to 36 and returned to vessel 10. Sodium sulfate introduced into vessel 10 is produced in-situ, in a melter device 42, by melting the Glauber salt feed. Water 44 is added as needed. The suspension 41 of the product can be concentrated in the container 43. The concentrate 14 is fed to the container 10 and the diluent
INT. MEX. 87/39 45 is returned to the evaporator 48. The diluent may be filtered before it evaporates to remove water 50. The solids 52 are dried to produce anhydrous sodium sulfate products. While the invention has been described in relation to a limited number of embodiments, it will be appreciated that many variations, modifications and other applications of the invention may be made.
INT. MEX. 87/39
Claims (9)
- CLAIMS; 1. A process for producing potassium sulfate, sodium sulfate and sodium chloride from potash and a source of sodium / water sulfate, comprising the steps of: (a) treating the source of sodium / water sulfate for producing a suspension containing anhydrous sodium sulfate; (b) concentrating the suspension to form a concentrate and a diluent; (c) treating the diluent to precipitate the anhydrous sodium sulfate, - (d) subjecting the anhydrous sodium sulfate from steps (b) and / or (c) and / or from a different source to converting it with potash in a medium aqueous, in order to produce glaserite and a first mother liquor, and the excess anhydrous sodium sulfate is taken as a co-product, - (e) convert the glaserite with potash and water to produce a precipitate of potassium sulfate and a second mother liquor; (f) returning the second mother liquor to step (d); (g) subjecting the first mother liquor to crystallization by evaporation so as to precipitate substantially pure sodium chloride in a third liquor INT. MEX. 87/39 mother; and (h) return the third mother liquor for conversion into potassium salts.
- 2. The process according to claim 1, wherein the diluent is treated by crystallization by evaporation.
- 3. The process according to claim 1, wherein the diluent is treated by saline displacement with sodium chloride.
- 4. The process according to claim 1, wherein the sodium sulfate produced from the diluent is used as the raw material of step (b), and the excess solid sodium sulfate, produced in the melting process, is removed as product.
- The process according to claim 1, wherein the Glauber salt is added to the third mother liquor at or before step (d).
- 6. The process according to claim 1, wherein the sodium sulfate used in step (b) is a low-grade salt cake, so that all the high-grade sodium sulfate produced in steps (a) and (c) is withdrawn as a co-product.
- The process according to claim 1, wherein the source of sodium / water sulfate is Glauber's salt.
- 8. The process according to claim 7, in INT. MEX. 87/39 where the treatment includes fusion.
- 9. The process according to claim 1, wherein the source of sodium / water sulfate is sodium semianhydrous sulfate. INT. MEX. 87/39
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08348118 | 1994-11-28 | ||
| US08/348,118 US5552126A (en) | 1994-11-28 | 1994-11-28 | Co-production of potassium sulfate, sodium sulfate and sodium chloride |
| PCT/US1995/014961 WO1996016900A1 (en) | 1994-11-28 | 1995-11-13 | Co-production of potassium sulfate, sodium sulfate and sodium chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| MXPA97002648A true MXPA97002648A (en) | 1998-02-01 |
| MX9702648A MX9702648A (en) | 1998-02-28 |
Family
ID=23366720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| MX9702648A MX9702648A (en) | 1994-11-28 | 1995-11-13 | Co-production of potassium sulfate, sodium sulfate and sodium chloride. |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5552126A (en) |
| EP (1) | EP0796223B1 (en) |
| DE (1) | DE69520155T2 (en) |
| MX (1) | MX9702648A (en) |
| RU (1) | RU2157791C2 (en) |
| WO (1) | WO1996016900A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299663B1 (en) | 1996-04-19 | 2001-10-09 | Airborne Industrial Minerals Inc. | Granulation method and apparatus therefor |
| US6331193B1 (en) | 1998-04-17 | 2001-12-18 | Airborne Industrial Minerals Inc. | Wet granulation method generating sulfur granules |
| US6454979B1 (en) | 1998-04-17 | 2002-09-24 | Airborne Industrial Minerals Inc. | Wet granulation method for generating granules |
| US6132484A (en) * | 1998-04-17 | 2000-10-17 | Airborne Industrial Minerals Inc. | Wet granulation method for generating fertilizer granules |
| US6293985B1 (en) | 1998-04-17 | 2001-09-25 | Airborne Industrial Minerals | Fertilizer granulation method |
| US6315976B1 (en) | 1998-06-16 | 2001-11-13 | Aristos Capital Corporation | Method of producing potassium sulfate |
| US6143271A (en) * | 1998-09-14 | 2000-11-07 | Dead Sea Works | Process for producing potassium sulfate from potash and sodium sulfate |
| US6692716B1 (en) | 1998-10-13 | 2004-02-17 | Airborne Industrial Minerals, Inc. | Method of formulating alkali earth salts |
| US6106796A (en) * | 1998-10-13 | 2000-08-22 | Airborne Technologies Inc. | Method of ammonium sulfate purification |
| US6582637B1 (en) | 1999-05-05 | 2003-06-24 | Agronomic Growth Industries Ltd. | Compost granulation method |
| US6334990B1 (en) | 1999-10-21 | 2002-01-01 | Airborne Industrial Minerals Inc. | Formulation of potassium sulfate, sodium carbonate and sodium bicarbonate from potash brine |
| US6375824B1 (en) | 2001-01-16 | 2002-04-23 | Airborne Industrial Minerals Inc. | Process for producing potassium hydroxide and potassium sulfate from sodium sulfate |
| CA2414894C (en) * | 2001-12-19 | 2005-08-23 | Dirdal Rand Technologies | Method of producing potassium sulfate |
| FR2951383B1 (en) | 2009-10-20 | 2012-09-21 | Solvay | PROCESS FOR THE JOINT VALORIZATION OF SOLUBLE SALTS CONTAINED IN A RESIDUE OF AN INDUSTRIAL PROCESS |
| RU2502671C1 (en) * | 2012-07-13 | 2013-12-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Башкирский государственный университет" | Method of obtaining sodium sulfate |
| CN104628016B (en) * | 2015-01-29 | 2016-08-17 | 中盐金坛盐化有限责任公司 | A kind of high nitre mother liquor salt made from earth containing a comparatively high percentage of sodium chloride cogeneration facility and technique |
| CN104925835B (en) * | 2015-07-01 | 2016-08-24 | 化工部长沙设计研究院 | A kind of technique of mirabilite method preparing potassium sulfate |
| KR102378526B1 (en) * | 2017-06-13 | 2022-03-23 | 재단법인 포항산업과학연구원 | Method for preparing potassium sulfate |
| CN113896209B (en) * | 2021-12-09 | 2022-03-04 | 中国科学院过程工程研究所 | Method for preparing sodium carbonate and byproducts potassium sulfate, ammonium sulfate and ammonium chloride from waste salt |
| US11827599B1 (en) | 2022-11-09 | 2023-11-28 | Tetra Technologies, Inc. | Method of preparing ionic fluids |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB287511A (en) * | 1927-03-23 | 1928-05-10 | Goodyear Tire & Rubber | Improvements in or relating to twin detachable rim devices for vehicle wheels |
| US1936070A (en) * | 1931-03-11 | 1933-11-21 | American Potash & Chem Corp | Process for the manufacture of potassium sulphate |
| US1990896A (en) * | 1932-07-30 | 1935-02-12 | Pacific Coast Borax Co | Method of making potassium sulphate |
| GB410830A (en) * | 1932-11-25 | 1934-05-25 | John Arthur Lanyon | Improvements in or relating to the production of potassium sulphate |
| GB439287A (en) * | 1934-05-24 | 1935-11-25 | Ivor Laurance Clifford | Improvements in or relating to the production of potassium sulphate |
| GB460281A (en) * | 1935-07-25 | 1937-01-25 | Ivor Laurance Clifford | Improvements in or relating to the production of potassium sulphate |
| GB464040A (en) * | 1935-10-10 | 1937-04-12 | Ivor Laurance Clifford | Improvements in or relating to the manufacture of potassium sulphate |
| DE1467244B2 (en) * | 1963-10-31 | 1970-02-05 | Standard-Messo Duisburg, Gesellschaft f. Chemietechnik mbH & Co, 4100 Duisburg | Method and device for dewatering Glauber's salt |
| SU710945A1 (en) * | 1974-07-02 | 1980-01-25 | Всесоюзный Научно-Исследовательский И Проектный Институт Галургии (Внииг) | Method of potassium sulfate production |
| US4215100A (en) * | 1978-05-18 | 1980-07-29 | Antonova Nina V | Method of producing potassium sulfate |
| DE2904345A1 (en) * | 1979-02-06 | 1980-08-14 | Metallgesellschaft Ag | METHOD FOR PRODUCING WATER-FREE SODIUM SULFATE FROM GLAIN SALT |
| SU806606A1 (en) * | 1979-03-28 | 1981-02-23 | Всесоюзный Научно-Исследовательскийи Проектный Институт Галургии | Method of potassium sulfate production |
| DD244540A1 (en) * | 1985-12-20 | 1987-04-08 | Kali Veb K | PROCESS FOR PROCESSING GLASS SALT TO ALKALISULFATES |
| SU1557102A1 (en) * | 1988-05-25 | 1990-04-15 | Всесоюзный научно-исследовательский и проектный институт галургии | Method of obtaining potassium sulfate |
| DE4340105C1 (en) * | 1993-11-22 | 1995-01-26 | Mannesmann Ag | Process for the continuous preparation of potassium sulphate from sodium sulphate |
| DE4340806C1 (en) * | 1993-11-24 | 1994-11-17 | Mannesmann Ag | Process for the preparation of potassium sulphate |
-
1994
- 1994-11-28 US US08/348,118 patent/US5552126A/en not_active Expired - Lifetime
-
1995
- 1995-11-13 DE DE69520155T patent/DE69520155T2/en not_active Expired - Lifetime
- 1995-11-13 WO PCT/US1995/014961 patent/WO1996016900A1/en active IP Right Grant
- 1995-11-13 MX MX9702648A patent/MX9702648A/en unknown
- 1995-11-13 EP EP95943581A patent/EP0796223B1/en not_active Expired - Lifetime
- 1995-11-13 RU RU97112480/12A patent/RU2157791C2/en active
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