CN110283001B - Natural evaporation and staged mineralization process for magnesium sulfate subtype salt lake brine salt pan - Google Patents
Natural evaporation and staged mineralization process for magnesium sulfate subtype salt lake brine salt pan Download PDFInfo
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Abstract
The invention relates to a natural evaporation and segmentation mineralization process for magnesium sulfate subtype salt lake brine salt pan, which comprises the following steps: the method comprises the steps of introducing bittern adopted by a magnesium sulfate subtype salt lake well into a sodium salt pond by a pump, naturally evaporating to separate out sodium chloride, introducing into an adjusting pond when epsomite is close to saturation, and introducing into a potassium mixed salt pond when the bittern point reaches the state that the epsomite is close to saturation and is about to separate out; the brine obtained in the step is continuously subjected to natural evaporation in a potassium mixed salt pond, and when the brine is close to carnallite saturation and is going to be separated out, the brine is introduced into the carnallite pond, potassium mixed salt ores are separated out, and the potassium mixed salt ores enter a potassium magnesium sulfate fertilizer workshop to produce picromerite products; and thirdly, the brine obtained in the second step is continuously naturally evaporated in the carnallite pool, and when the brine reaches the old brine point, the brine is led into the old brine storage pool, carnallite is separated out, and the carnallite enters a potassium chloride workshop to produce potassium chloride products. The invention has simple process, low production cost and high sulfur-potassium ratio of the potassium mixed salt mine.
Description
Technical Field
The invention relates to the field of inorganic salt chemical industry, in particular to a natural evaporation and staged mineralization process for magnesium sulfate subtype salt lake brine in a salt pan.
Background
Salt lakes can be classified into 3 types of carbonate, sulfate and chloride according to the chemical composition of the salt lake brine. The most common in China is the sulphate type salt lake, which is also the most abundant. Chinese sulfate type salt lake resources are mainly concentrated in Qinghai and Xinjiang, wherein sulfate type magnesium subtype salt lake resources are mainly used, although the number of the sulfate type magnesium subtype salt lake resources is small, the area of the salt lake accounts for 1/2 of the total area, the resource reserves are large, and the sulfate type magnesium subtype salt lake resources are important brine raw materials for producing potassium sulfate.
The technical process for producing potassium sulfate by using sulfate type salt lake brine comprises the following steps: with K+、Na+、Mg2+//Cl-、SO4 2--H2The O quinary water-salt system is based on physical and chemical theory and is produced through natural evaporation in salt field by means of natural phase separation technologyThe process is realized. The salt field is an important facility for producing salt minerals by using brine as a raw material, the salt field phase separation technology is to store brine with a certain depth in the salt field, the brine is heated after absorbing solar radiation energy, water is evaporated to concentrate the brine, and when a certain salt reaches saturation or even supersaturation at the temperature, the salt is separated out in the form of solid salt (or hydrated salt or even water composite salt), so that the purpose of separating the certain salt from multi-component complex brine is achieved.
Chinese patent CN107352560A discloses a tedding process of high-magnesium low-potassium sulfate brine in a saltern, which comprises the steps of passing the brine through a sodium salt field, a epsomite field, a first-stage carnallite field, a second-stage carnallite field and an old brine field to obtain corresponding first-stage carnallite mixed salt ore and second-stage carnallite ore, crushing and decomposing the first-stage carnallite mixed salt ore to obtain a potassium-magnesium mixed salt ore, converting the potassium-magnesium mixed salt ore to obtain picromerite, decomposing the second-stage carnallite ore to obtain potassium chloride, and converting the picromerite and the potassium chloride to potassium sulfate. The process can meet the requirement of producing potassium sulfate from magnesium sulfate subtype brine, but has the problem of low efficiency. Because the epsomite field is arranged in the tedding evaporation process of the salt field, epsomite is separated out to reduce the sulfate radical content in brine, and the potassium-sulfur ratio of the sunned potassium mixed salt ore is not enough, so that the influence on the production of picromerite is great; in order to replenish sulfate, the epsomite which has to be separated off in the conversion process has to be added again into the soft potassium conversion section, which leads to an increase in production costs and is economically unreasonable.
Disclosure of Invention
The invention aims to solve the technical problem of providing a natural evaporation and segmentation mineralization process for a magnesium sulfate subtype salt lake brine salt pan, which has low production cost and high sulfur-potassium ratio of potassium mixed salt mine.
In order to solve the problems, the natural evaporation and segmentation mineralization process for the magnesium sulfate subtype salt lake brine salt pan comprises the following steps:
the method comprises the steps of introducing the magnesium sulfate subtype salt lake well brine into a sodium salt pond by a pump, naturally evaporating to separate out sodium chloride, introducing the sodium chloride into an adjusting pond when epsomite is nearly saturated, and when [ K ] is in the brine+]Greater than 23.0 g.L-1、[Mg2+]Between 55 and 80 g.L-1、[Cl-]Between 180 and 230 g.L-1、[SO4 2-]60 to 100 g.L-1Then the mixture is led into a potassium mixed salt pond;
naturally evaporating the brine obtained in the step in the potassium mixed salt pond, wherein the brine [ K ] is naturally evaporated+]Between 19.0 and 23.0 g.L-1、[Mg2+]Between 81 and 100 g.L-1、[Cl-]Between 240 and 280 g.L-1、[SO4 2-]Between 50 and 70 g.L-1Then leading the potassium mixed salt ore into a carnallite pool, separating out potassium mixed salt ore, and leading the potassium mixed salt ore into a potash magnesium sulphate fertilizer workshop to produce picromerite products;
the natural evaporation is continuously carried out on the brine obtained in the second step in the carnallite pool, and the brine [ K ] is naturally evaporated+]Between 1.0 and 5.0 g.L-1、[Mg2+]Between 101 and 125 g.L-1、[Cl-]Between 285 and 330 g.L-1、[SO4 2-]Between 30 and 50 g.L-1Namely, when the old brine point is reached, the old brine is led into an old brine storage pool, carnallite ore is separated out, and the carnallite ore enters a potassium chloride workshop to produce potassium chloride products.
The method comprises the step of [ K ] of brine mining of magnesium sulfate subtype salt lake wells+]Between 5 and 12 g.L-1，[Mg2+]Between 20 and 35 g.L-1，[Cl-]Between 170 and 200 g.L-1 ，[SO4 2-]Between 20 and 40 g.L-1And the content of trace ions is less than 0.5 percent of the total ion content.
The magnesium sulfate subtype salt lake well brine adopted in the step is brine with the following properties, namely the original point of the brine is at 25 ℃ K+、Na+、Mg2+//Cl-、SO4 2--H2An epsomite region in a metastable phase diagram of an O quinary water-salt system; in natural evaporation, when potassium ions are saturated to separate out potassium salt, the brine composition point is positioned on a section of the saturation line of epsomite and picromerite or the saturation line of epsomite and potassium chloride in the five-element phase diagram, and the section length is the section length of the epsomite and potassium chlorideMore than 50% of the total length of the saturation line.
The magnesium sulfate subtype salt lake well brine recovery system belongs to K+、Na+、Mg2+//Cl-、SO4 2--H2O quinary water-salt system, the phase diagram of the system uses the Jernike index to indicate the composition point of the brine, and the original brine composition point of the system at 25 ℃ meets the requirement that the Jernike index of potassium ions is more than 6.0 and less than J2KLess than 9.0, magnesium ion Jenke 67.0 < JMg< 76.5, sulfate ion Jernike index 16.0 < JSO4＜27.0。
The method comprises the steps of leading the brine into a potassium mixed salt pond [ K ]+]Greater than 24.0 g.L-1、[Mg2+]Between 60 and 75 g.L-1、[Cl-]Between 185 and 225 g.L-1、[SO4 2-]Between 70 and 95 g.L-1。
The method comprises the step of introducing the brine into the carnallite pool [ K ]+]Between 19.5 and 22.5 g.L-1、[Mg2+]Between 85 and 95 g.L-1、[Cl-]Between 245 and 270 g.L-1、[SO4 2-]Between 50 and 68 g.L-1。
The step three is that the brine is led into brine in the old brine storage tank (K)+]Between 1.5 and 3.5 g.L-1、[Mg2+]Between 105 and 125 g.L-1、[Cl-]Between 290 and 330 g.L-1、[SO4 2-]Between 35 and 50 g.L-1。
Compared with the prior art, the invention has the following advantages:
1. the invention takes magnesium sulfate subtype salt lake brine as a raw material, the ratio of potassium to sulfur in the sun-dried potassium mixed salt ore is often insufficient in the natural evaporation process of the brine in a salt pan, the epsomite section is completely collected into the potassium mixed salt section, the epsomite pan is cancelled, and K is used+、Na+、Mg2+//Cl-、SO4 2--H2Taking O quinary water-salt system metastable phase diagram as theoretical basis, determining natural evaporation route of brine salt pan according to evaporation and crystallization rules, wherein the brine sequentially flows through sodium salt pan-regulating tank-potassium mixed salt pan-carnallite pan in the natural evaporation process of the brine salt panAnd the old brine pan reduces the flow of the salt pan, reduces the brine loss and improves the mineralization efficiency.
2. The invention takes the magnesium sulfate subtype salt lake brine as the raw material, defines the positioning and operation process of each salt field, fully utilizes the sulfate radical in the brine, improves the sulfur-potassium ratio of the potassium mixed salt mine, simplifies the picromerite flotation process flow, reduces the production cost, is suitable for the advantages of large-scale salt field operation, and is particularly suitable for the salt field production of the magnesium sulfate subtype salt lake brine.
3. The invention takes magnesium sulfate subtype salt lake brine as a raw material, has simple natural evaporation process of a salt field, and can flexibly adjust the grade of the brine in the adjusting tank, so that the potassium-containing mineral produced in the salt field has controllable quality and stable quality. According to the ore type, a potassic fertilizer workshop can respectively produce three products of picromerite (a potash magnesium sulphate fertilizer), potassium chloride and potassium sulphate, and the potassic fertilizer production can be flexibly adjusted according to the market sales condition, so that the potassic fertilizer has strong market risk resistance.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a flow chart of the natural evaporation process of the salt pan of the present invention.
FIG. 2 shows a temperature of 25 ℃ K+、Na+、Mg2+∥Cl-、SO4 2--H2And (3) an evaporative crystallization route of a metastable phase diagram of an O quinary water salt system.
Detailed Description
As shown in fig. 1, a natural evaporation and staged mineralization process for magnesium sulfate subtype salt lake brine salt pan comprises the following steps:
the method comprises the steps of introducing the magnesium sulfate subtype salt lake well brine into a sodium salt pond by a pump, naturally evaporating to separate out sodium chloride, introducing the sodium chloride into an adjusting pond when epsomite is nearly saturated, and when [ K ] is in the brine+]Greater than 23.0 g.L-1、[Mg2+]Between 55 and 80 g.L-1、[Cl-]Between 180 and 230 g.L-1、[SO4 2-]60 to 100 g.L-1When brine is nearly saturated, the brine is introduced into a potassium salt-mixed pool and is about to be separated out. Introducing potassium mixtureThe preferable concentration of [ K ] in brine of the salt pond+]Greater than 24.0 g.L-1、[Mg2+]Between 60 and 75 g.L-1、[Cl-]Between 185 and 225 g.L-1、[SO4 2-]Between 70 and 95 g.L-1. Sodium chloride or a small amount of epsomite is precipitated from the regulating reservoir.
Wherein: the bittern mainly contains K+、Na+、Mg2+、Cl-、SO4 2-Plasma salt lake or underground brine [ K+]Between 5 and 12 g.L-1，[Mg2+]Between 20 and 35 g.L-1，[Cl-]Between 170 and 200 g.L-1 ，[SO4 2-]Between 20 and 40 g.L-1And the content of other trace ions such as boron, lithium and the like is less than 0.5 percent of the total ion content.
The well-mining brine of the magnesium sulfate subtype salt lake is brine with the following property that the original point of the brine is at K at 25 DEG C+、Na+、Mg2+//Cl-、SO4 2--H2The epsomite region in the O quinary water salt system metastable phase diagram (see FIG. 2); in natural evaporation, when potassium ions are saturated to separate out potassium salts, the brine composition point is located on a section of a saturation line of epsomite and picromerite or a section of the saturation line of the epsomite and potassium chloride in the five-element phase diagram, and the section length is more than 50% of the total length of the saturation line of the epsomite and potassium chloride.
A magnesium sulfate subtype salt lake well brine recovery system, belonging to K+、Na+、Mg2+//Cl-、SO4 2--H2O quinary water-salt system, the phase diagram of the system uses the Jernike index to indicate the composition point of the brine, and the original brine composition point of the system at 25 ℃ meets the requirement that the Jernike index of potassium ions is more than 6.0 and less than J2KLess than 9.0, magnesium ion Jenke 67.0 < JMg< 76.5, sulfate ion Jernike index 16.0 < JSO4＜27.0。
Naturally evaporating the brine obtained in the step in a potassium mixed salt pond, wherein the brine [ K ] is naturally evaporated+]Between 19.0 and 23.0 g.L-1、[Mg2+]Between 81 and 100 g.L-1、[Cl-]Between 240 and 280 g.L-1、[SO4 2-]Between 50 and 70 g.L-1When brine is saturated and is about to be separated out, the brine is led into a carnallite pool, and potassium mixed salt ore is separated out. Preferably [ K ] is selected from brine introduced into carnallite pool+]Between 19.5 and 22.5 g.L-1、[Mg2+]Between 85 and 95 g.L-1、[Cl-]Between 245 and 270 g.L-1、[SO4 2-]Between 50 and 68 g.L-1。
Wherein: the minerals separated out from the potassium mixed salt pond are mixed salt consisting of sodium chloride, epsomite, potassium chloride and kainite, and are called potassium mixed salt ores. The potassium mixed salt ore enters a potash magnesium sulphate fertilizer workshop, and is added with water for conversion, flotation and separation to obtain picromerite.
The brine obtained in the second step is naturally evaporated continuously in the carnallite pool, and the brine K is subjected to natural evaporation+]Between 1.0 and 5.0 g.L-1、[Mg2+]Between 101 and 125 g.L-1、[Cl-]Between 285 and 330 g.L-1、[SO4 2-]Between 30 and 50 g.L-1Namely, the crude product is led into the crude brine storage tank when the crude brine point is reached, and carnallite is separated out. Selecting [ K ] from brine led into old brine storage tank+]Between 1.5 and 3.5 g.L-1、[Mg2+]Between 105 and 125 g.L-1、[Cl-]Between 290 and 330 g.L-1、[SO4 2-]Between 35 and 50 g.L-1。
Wherein: the minerals separated out in the carnallite pool are mixed salts consisting of sodium chloride, epsomite and carnallite, and are called carnallite ore. The carnallite ore enters a potassium chloride workshop, and is added with water for decomposition, flotation and separation to obtain a potassium chloride product. And converting, crystallizing, separating and drying the picromerite and the potassium chloride to obtain a potassium sulfate product.
In view of the detailed technical description of the natural evaporation and staged mineralization process of the magnesium sulfate subtype salt lake brine pan, the embodiments of the present invention represent only a part of the description of the present invention, but not all embodiments, so that all embodiments obtained within the framework of the description of the present invention without invasive and innovative innovations belong to the protection scope of the present invention.
Example 1
The raw material is taken from a underground brine halogen extraction pump station which is mined from West Tai Ginell salt lake of Qinghai Chauda basin in 1 month of 2018, has the chemical composition shown in the table 1, and the chemical type of the water in a salt water system is analyzed from the composition to belong to the subtype of magnesium sulfate. Potassium ion Jernike J composed of the brine2K=8.0, magnesium ion Jernike JMg=68.81 sulfate ion Jenker JSO4=23.19, its bittern composition point is at 25 deg.C K+、Na+、Mg2+∥Cl-、SO4 2--H2O quinary water salt system is the epsomite region in the metastable phase diagram.
Table 1: chemical composition of well-mined brine in West platform Ginell salt lake 2018 in 1 month
The method comprises the steps of taking 213.86 liters of brine collected from a magnesium sulfate subtype salt lake well, naturally evaporating by using a plastic basin to separate out sodium chloride, and obtaining the sodium chloride in a [ K ]+]To 24.243 g.L-1，[Mg2+]Is 67.825 g.L-1，[Cl-]Is 194.580 g.L-1，[SO4 2-]Is 86.183 g.L-1Carrying out solid-liquid separation to obtain 39.351kg of sodium chloride solid;
the natural evaporation is continuously carried out to separate out the potassium-containing mixed salt mineral in the [ K ]+] = 20.510 g·L-1Then solid-liquid separation is carried out; at this time [ Mg2+]Is 90.068 g.L-1，[Cl-]Is 253.520 g.L-1，[SO4 2-]Is 55.346 g.L-1The obtained mineral is mixed salt consisting of sodium chloride, epsomite, potassium chloride and kainite, which is called potassium mixed salt ore, and 21.81 kg of the potassium mixed salt ore is separated out;
thirdly, natural evaporation is continuously carried out to separate out carnallite mixed salt minerals in the position of [ K ]+]To 1.515 g.L-1Solid-liquid separation; at this time [ Mg2+]Is 120.873 g.L-1，[Cl-]Is 328.637 g.L-1，[SO4 2-]Is 44.292 g.L-1The mineral obtained was a mixed salt of sodium chloride, epsomite and carnallite, called carnallite, from which 8.91 kg of carnallite was precipitated.
The composition of the resulting potassium mixed salt ore and carnallite ore are shown in Table 2.
Table 2: mineral composition obtained by natural evaporation of well-mined brine in 2018 and 1 month of West platform Ginell salt lake
Example 2
The raw material is taken from a well brine extraction halogen pump station for 2018 months of well extraction brine in West Tai Ginell salt lake of Qinghai Chaila, and has the chemical composition shown in the table 3, and the water chemical type of a brine system is analyzed from the composition to belong to magnesium sulfate subtype. Potassium ion Jernike J composed of the brine2K=7.07, magnesium ion Jernike JMg=74.12 sulfate ion Jenker JSO4=18.82, its bittern composition point is at 25 deg.C K+、Na+、Mg2+∥Cl-、SO4 2--H2O quinary water salt system is the epsomite region in the metastable phase diagram. Compared with the method provided in example 1, the main difference of this example is that the chemical compositions of the selected raw materials are different, and the adaptability of the method under different raw materials is mainly examined.
Table 3: chemical composition of well-mined brine in West platform Ginell salt lake 2018 in 4 months
Taking 46.2 kg of brine for magnesium sulfate subtype salt lake well, naturally evaporating by using a plastic basin to separate out sodium chloride, and obtaining the sodium chloride in the step (K)+]To 25.613 g.L-1，[Mg2+]Is 68.216 g.L-1，[Cl-]Is 203.901 g.L-1，[SO4 2-]Is 91.841 g.L-1Carrying out solid-liquid separation to obtain chlorine7.31 kg of sodium chloride solid;
the natural evaporation is continuously carried out to separate out the potassium-containing mixed salt mineral in the [ K ]+]To 19.542 g.L-1Then solid-liquid separation is carried out; the obtained mineral is mixed salt consisting of sodium chloride, epsomite, potassium chloride and kainite, which is called potassium mixed salt ore, and 2.53 kg of the potassium mixed salt ore is separated out; at this time [ Mg2+]Is 90.184 g.L-1，[Cl-]Is 247.798 g.L-1，[SO4 2-]Is 64.694 g.L-1；
Thirdly, natural evaporation is continuously carried out to separate out carnallite mixed salt minerals in the position of [ K ]+]To 1.520 g.L-1Solid-liquid separation; the obtained mineral is mixed salt consisting of sodium chloride, epsomite and carnallite, which is called carnallite ore, and the separated carnallite ore is 1.145 kg; at this time [ Mg2+]Is 115.668 g.L-1，[Cl-]Is 315.172 g.L-1，[SO4 2-]Is 43.542 g.L-1。
The composition of the resulting potassium mixed salt ore and carnallite ore are shown in Table 4.
Table 4: mineral composition obtained by natural evaporation of well-mined brine in 2018 and 4 months of West Ginell salt lake
Example 3
The raw material is taken from a brine extraction pump station for underground brine extraction in 10 months in 2018 of a well in the West Tai Gillel salt lake of the Qinghai Chailada basin, has the chemical composition shown in the table 5, and the chemical type of the water in a brine system is analyzed from the composition and belongs to the subtype of magnesium sulfate. Potassium ion Jernike J composed of the brine2K=7.68, magnesium ion Jernike JMg=76.26 sulfate ion Jernike JSO4=16.07, its bittern composition point is at 25 deg.C K+、Na+、Mg2+∥Cl-、SO4 2--H2O quinary water salt system is the epsomite region in the metastable phase diagram. Compared with the method provided in example 2, the main difference of this example is that the selected raw materials have different chemical compositions, and different raw materials are mainly consideredThe following is the flexibility of the method.
Table 5: chemical composition of well-mined brine in West platform Ginell salt lake 2018 in 10 months
Taking 51.5 kg of magnesium sulfate subtype salt lake well brine, naturally evaporating by using a plastic basin to separate out sodium chloride, and obtaining the sodium chloride in the step (K)+]To 26.251 g.L-1，[Mg2+]Is 69.488 g.L-1，[Cl-]Is 220.694 g.L-1，[SO4 2-]Is 71.711 g.L-1Carrying out solid-liquid separation to obtain 3.41 kg of sodium chloride solid;
the natural evaporation is continuously carried out to separate out the potassium-containing mixed salt mineral in the [ K ]+]To 22.067 g.L-1Then solid-liquid separation is carried out; the obtained mineral is mixed salt consisting of sodium chloride, epsomite, potassium chloride and kainite, which is called potassium mixed salt ore, and 1.6 kg of the potassium mixed salt ore is separated out; at this time [ Mg2+]Is 89.203 g.L-1，[Cl-]Is 253.365 g.L-1，[SO4 2-]Is 60.318 g.L-1；
Thirdly, natural evaporation is continuously carried out to separate out carnallite mixed salt minerals in the position of [ K ]+]To 1.881 g.L-1Solid-liquid separation; the obtained mineral is mixed salt consisting of sodium chloride, epsomite and carnallite, which is called carnallite ore, and 2.04 kg of carnallite ore is separated out; at this time [ Mg2+]Is 110.534 g.L-1，[Cl-]Is 305.372-g.L-1，[SO4 2-]Is 44.010 g.L-1；
The composition of the resulting potassium mixed salt ore and carnallite ore are shown in Table 6.
Table 6: mineral composition obtained by natural evaporation of well-mined brine in 2018 and 10 months of West Ginell salt lake
Example 4
The present example is different from examples 1 to 3, and aims to perform preparation verification of picromerite, potassium chloride and potassium sulfate by using the potassium mixed salt ore and the carnallite ore produced in examples 1 to 3, respectively. Wherein, the preparation of the picromerite adopts a conversion-alkyl sulfonate direct flotation method, the preparation of the potassium chloride adopts a cold decomposition-octadecylamine direct flotation method, the preparation of the potassium sulfate adopts a conversion method, and the following concrete processes are carried out.
Firstly, mixing, crushing and screening the potassium mixed salt ores obtained in the embodiment 1-3, adding water and conversion mother liquor, converting for 40 minutes at 25 ℃, adding a sodium dodecyl sulfate flotation agent, transferring the slurry into a flotation machine, setting the rotation speed to 2600 r/min, carrying out flotation for 10-15 minutes, adding the obtained roughing foam into the conversion mother liquor, mixing the obtained roughing foam into slurry to 30% of concentration, then carrying out concentration again, carrying out solid-liquid separation and drying to obtain a picromerite product. The experimental data are shown in Table 7:
table 7: soft potassium magnesium alum preparation experiment data table
As can be seen from table 7, the picromerite product prepared by the conversion-alkylsulfonate flotation method from the potassium mixed salt mine obtained in examples 1 to 3 meets the first-class standard of the potash magnesium sulphate fertilizer GB/T20937-2007.
Mixing, crushing and screening the carnallite ores obtained in the embodiment 1-3, adding water for decomposition for 30 minutes, adding octadecylamine hydrochloride flotation agent and pine oil, starting a flotation machine, setting the flotation rotation speed to 1900 r/min for flotation for 15 minutes, adding the obtained crude potassium foam into decomposition mother liquor for size mixing, refining again, washing, carrying out solid-liquid separation, and drying to obtain a potassium chloride product. The experimental data are shown in Table 8.
Table 8: potassium chloride preparation experiment data table
As can be seen from table 8, the potassium chloride product prepared by the cold decomposition — octadecylamine flotation method on the carnallite ore obtained in examples 1 to 3 meets the first-class ii agricultural standard of potassium chloride GB 6549-2011.
③ the wet products of schoenite and potassium chloride obtained in the steps of the first and the second embodiments are mixed according to the calculated proportion, fresh water is added quantitatively, the mixture is transformed for 1.5 hours at the temperature of 40 ℃, solid-liquid separation and drying are carried out to obtain solid potassium sulfate, and the experimental data are shown in Table 9.
Table 9: experimental data table for preparing potassium sulfate by converting schoenite and potassium chloride
As can be seen from Table 9, the potassium sulfate product prepared by converting the wet products of picromerite and potassium chloride obtained in the steps of (i) and (ii) in example 4 meets the standards of superior products in potassium sulfate GB/T20406-.
Claims (5)
1. A natural evaporation and segmentation mineralization process for magnesium sulfate subtype salt lake brine salt pan comprises the following steps:
the method comprises the steps of introducing bittern collected from a magnesium sulfate subtype salt lake well of a Qinghai Kazada wood basin Sitai Gillel salt lake into a sodium salt pond by a pump, naturally evaporating to separate out sodium chloride, introducing the sodium chloride into an adjusting pond when epsomite is nearly saturated, and introducing the sodium chloride into the adjusting pond when epsomite is nearly saturated+]Greater than 23.0 g.L-1、[Mg2+]Between 55 and 80 g.L-1、[Cl-]Between 180 and 230 g.L-1、[SO4 2-]60 to 100 g.L-1Then the mixture is led into a potassium mixed salt pond; the magnesium sulfate subtype salt lake well adopts the [ K ] of brine+]Between 5 and 12 g.L-1，[Mg2+]Between 20 and 35 g.L-1，[Cl-]Between 170 and 200 g.L-1 ，[SO4 2-]Between 20 and 40 g.L-1The content of trace ions is less than 0.5 percent of the total ion content; the magnesium sulfate subtype salt lake well mining brine is brine with the following properties that the original point of the brine is at K at 25 DEG C+、Na+、Mg2+//Cl-、SO4 2--H2An epsomite region in a metastable phase diagram of an O quinary water-salt system; in thatIn natural evaporation, when potassium ions are saturated to separate out potassium salts, the brine composition point is positioned on a section of a saturation line of epsomite and picromerite or a section of the saturation line of the epsomite and potassium chloride in the five-element phase diagram, and the section length is more than 50% of the total length of the saturation line of the epsomite and potassium chloride;
naturally evaporating the brine obtained in the step in the potassium mixed salt pond, wherein the brine [ K ] is naturally evaporated+]Between 19.0 and 23.0 g.L-1、[Mg2+]Between 81 and 100 g.L-1、[Cl-]Between 240 and 280 g.L-1、[SO4 2-]Between 50 and 70 g.L-1Then leading the potassium mixed salt ore into a carnallite pool, separating out potassium mixed salt ore, and leading the potassium mixed salt ore into a potash magnesium sulphate fertilizer workshop to produce picromerite products;
the natural evaporation is continuously carried out on the brine obtained in the second step in the carnallite pool, and the brine [ K ] is naturally evaporated+]Between 1.0 and 5.0 g.L-1、[Mg2+]Between 101 and 125 g.L-1、[Cl-]Between 285 and 330 g.L-1、[SO4 2-]Between 30 and 50 g.L-1Namely, when the old brine point is reached, the old brine is led into an old brine storage pool, carnallite ore is separated out, and the carnallite ore enters a potassium chloride workshop to produce potassium chloride products.
2. The natural evaporation and staged mineralization process of the magnesium sulfate subtype salt lake brine in the salt pan as claimed in claim 1, wherein: the magnesium sulfate subtype salt lake well brine recovery system belongs to K+、Na+、Mg2+//Cl-、SO4 2--H2O quinary water-salt system, the phase diagram of the system uses the Jernike index to indicate the composition point of the brine, and the original brine composition point of the system at 25 ℃ meets the requirement that the Jernike index of potassium ions is more than 6.0 and less than J2KLess than 9.0, magnesium ion Jenke 67.0 < JMg< 76.5, sulfate ion Jernike index 16.0 < JSO4＜27.0。
3. The natural evaporation and staged mineralization process of claim 1, wherein the natural evaporation and staged mineralization is carried out in a salt field of the magnesium sulfate subtype salt lake brine: the method comprises the steps of leading the brine into a potassium mixed salt pond [ K ]+]Greater than 24.0 g.L-1、[Mg2+]Between 60 and 75 g.L-1、[Cl-]Between 185 and 225 g.L-1、[SO4 2-]Between 70 and 95 g.L-1。
4. The natural evaporation and staged mineralization process of the magnesium sulfate subtype salt lake brine in the salt pan as claimed in claim 1, wherein: the method comprises the step of introducing the brine into the carnallite pool [ K ]+]Between 19.5 and 22.5 g.L-1、[Mg2+]Between 85 and 95 g.L-1、[Cl-]Between 245 and 270 g.L-1、[SO4 2-]Between 50 and 68 g.L-1。
5. The natural evaporation and staged mineralization process of the magnesium sulfate subtype salt lake brine in the salt pan as claimed in claim 1, wherein: the step three is that the brine is led into brine in the old brine storage tank (K)+]Between 1.5 and 3.5 g.L-1、[Mg2+]Between 105 and 125 g.L-1、[Cl-]Between 290 and 330 g.L-1、[SO4 2-]Between 35 and 50 g.L-1。
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