CN110713195A - Method for improving production efficiency of chloride type salt pan and chloride type salt pan product - Google Patents
Method for improving production efficiency of chloride type salt pan and chloride type salt pan product Download PDFInfo
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- CN110713195A CN110713195A CN201911186061.0A CN201911186061A CN110713195A CN 110713195 A CN110713195 A CN 110713195A CN 201911186061 A CN201911186061 A CN 201911186061A CN 110713195 A CN110713195 A CN 110713195A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
- C01D3/06—Preparation by working up brines; seawater or spent lyes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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Abstract
The application relates to the field of salt fields, in particular to a method for improving production efficiency of a chloride type salt field and a chloride type salt field product. The method comprises the steps of firstly adding a mirabilite solution into brine to combine magnesium ions in the brine with sulfate radicals in mirabilite, separating out the magnesium ions from the brine in the form of magnesium sulfate crystals, reducing the content of the magnesium ions in the brine, and then evaporating and solarizing the residual brine with the reduced content of the magnesium ions to obtain a salt field product. Because the method firstly reduces the magnesium ions in the brine, the magnesium salt does not need to spend time to sun-dry in the subsequent salt evaporation process, the salt forming time is greatly shortened, and the production efficiency of the salt pan is improved. After magnesium ions are reduced, the potash fertilizer production line is changed from a magnesium hydrohalite line to a more energy-saving and simple sylvite line, and the process difficulty is greatly reduced.
Description
Technical Field
The application relates to the field of salt fields, in particular to a method for improving production efficiency of a chloride type salt field and a chloride type salt field product.
Background
The Cherokee salt lake is one of the rare large inland salt lakes with industrial value in the world, and is a comprehensive ore deposit which mainly contains liquid potassium ore, coexists solid and liquid and is accompanied with useful elements such as boron, lithium, magnesium, bromine and the like. The total area of the Chaer sweat salt lake is 5856km2The Cherokee salt lake has abundant mineral resources of salts such as potassium chloride, magnesium chloride, sodium chloride and the like. Most of potassium chloride resources in China are concentrated in the Chaer sweat salt lake, so that the development of the Chaer sweat salt lake resources has very important significance for promoting the agricultural development in China.
The salt pan process for producing potash fertilizer with carnallite as raw material is to tedge, evaporate and concentrate raw bittern in salt pan, to make sodium chloride first reach saturation and separate out, then to concentrate potassium chloride, and to separate out part of potassium chloride in solid phase form, and to make magnesium chloride always exist in liquid phase form.
However, this evaporation process is slow and requires large amounts of salt pan to sun produce acceptable mineralised brine (1-2 years). The ore-forming brine not only contains potassium chloride and sodium chloride, but also contains a large amount of magnesium chloride, wherein part of the magnesium chloride, the potassium chloride and the sodium chloride form carnallite which is separated out in a solid form, and a large amount of magnesium chloride still exists in a liquid phase, and finally enters an old brine pool to be sun-cured into the bischofite. The magnesium chloride is easily soluble in water and high in viscosity, and can seriously interfere the precipitation speed and quality of sodium chloride and potassium chloride in the evaporation process of a salt pan, so that the production efficiency of the salt pan is low.
Disclosure of Invention
The embodiment of the application aims to provide a method for improving the production efficiency of a chloride type salt pan and a chloride type salt pan product, which aims to solve the problem of low production efficiency of the existing chloride type salt pan.
In a first aspect, the present application provides a technical solution:
a method for improving the production efficiency of chloride type salt pan comprises the following steps:
adding mirabilite into brine, separating out magnesium sulfate crystals, and then evaporating the residual brine to prepare potassium chloride and/or sodium chloride;
wherein, the brine comprises: potassium chloride, sodium chloride and magnesium chloride.
The method comprises the steps of firstly adding a mirabilite solution into brine to combine magnesium ions in the brine with sulfate radicals in mirabilite, separating out the magnesium ions from the brine in the form of magnesium sulfate crystals, reducing the content of the magnesium ions in the brine, and then evaporating and solarizing the residual brine with the reduced content of the magnesium ions to obtain a salt field product. The method firstly reduces magnesium ions in brine, does not need to spend time to sun-dry magnesium salts in the subsequent process of evaporating salt (potassium chloride and/or sodium chloride), and is equivalent to the step of extracting the magnesium salts in the conventional operation, so the salt forming time is greatly shortened, and the production efficiency of a salt field is improved. Furthermore, after magnesium ions are reduced, the production route of the potash fertilizer is changed from a magnesium hydrohalite route to a more energy-saving and simple sylvite route, and the process difficulty is greatly reduced.
In other embodiments of the present application, the step of adding the salt cake solution to the brine includes:
calculated according to the molar mass ratio, according to mirabilite: magnesium chloride equal to 1: 1-3: 1, adding the mirabilite solution into brine.
In other embodiments of the present application, the step of adding the salt cake solution to the brine includes:
calculated according to the molar mass ratio, according to mirabilite: magnesium chloride equal to 2: 1-3: 1, adding the mirabilite solution into brine.
In other embodiments of the present application, the brine is from the khaki salt lake, Qinghai, China.
In other embodiments of the present application, the salt cake is derived from salt lake by-products.
In other embodiments of the present application, the step of evaporating the remaining brine is performed at room temperature.
In other embodiments of the present application, the step of evaporating the remaining brine is performed under dry or forced air drying conditions.
In other embodiments of the present application, the step of evaporating the remaining brine is performed under sub-ambient conditions.
In other embodiments of the present application, the content of magnesium ions in the remaining brine is less than 10% by mass.
In a second aspect, the present application provides a technical solution:
a chloride type salt pan product is prepared by the above production method, and comprises potassium chloride, sodium chloride and magnesium sulfate.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The terms "first" and "second" are used merely to distinguish one description from another, and are not to be construed as indicating or implying relative importance.
Salt field ore drying refers to a product processing mode for extracting potassium ions, sodium ions and magnesium ions from potassium-containing brine of a salt lake. Generally, the production process of salt field solarized ore mainly includes two steps of solarization (sun irradiation) and evaporation (natural evaporation of water), and the processed material of salt field is carnallite (its main component is KCl. MGCl)2·6H2O) mainly, and when the salt pan is aired, the control of the content ratio of sodium chloride and impurity substances in the airing of the substances should be paid attention to.
At present, the general operation flow of salt pan ore solarization mainly comprises the following steps:
(1) raw brine is collected and enters a sodium salt pond, the brine firstly evaporates water and gradually separates out sodium chloride crystals under the action of illumination and wind power, the content of sodium chloride in the brine is gradually reduced, and the content of potassium chloride and magnesium chloride is gradually increased;
(2) guiding the brine with the content of sodium chloride reduced to below 3% (determined by the concrete production test) into an adjusting tank through a self-flowing or pump station to be continuously solarized;
(3) the brine with the sodium chloride content reduced to about 2 percent and the magnesium chloride content more than 25 percent (combined with a phase diagram, the point is slightly ahead) starts to guide water to the carnallite pool in a large scale;
(4) evaporating the brine led into the carnallite pool to crystallize long ores until the potassium chloride content in the brine is less than 0.3 percent, and discharging.
The inventor finds that the main reason of the slow production efficiency of the method is that the content of the magnesium and the potassium in the brine is greatly increased by reducing the content of the sodium chloride, and when the subsequent magnesium salt extracting step is carried out, the magnesium salt extracting time is very long, so that the whole ore forming time is prolonged, and the production efficiency is reduced. In addition, the production method strictly controls the content ratio of potassium chloride and sodium chloride in the brine according to a phase diagram, and the process is complex.
The embodiment of the application provides a method for improving production efficiency of a chloride type salt pan, which comprises the steps of firstly adding mirabilite (the mirabilite mainly comprises aqueous sodium sulfate (Na)2SO4·10H2O)), so that magnesium ions in the brine are combined with sulfate radicals in the mirabilite, thereby separating out the magnesium ions from the brine in the form of magnesium sulfate crystals, reducing the content of the magnesium ions in the brine, and then evaporating and solarizing the residual brine with the reduced content of the magnesium ions to obtain a salt field product.
The method firstly reduces magnesium ions in brine, does not need to spend time to sun-dry magnesium salts in the subsequent process of evaporating salt (potassium chloride and/or sodium chloride), and is equivalent to the step of extracting the magnesium salts in the conventional operation, so the salt forming time is greatly shortened, and the production efficiency of a salt field is improved. Furthermore, after magnesium ions are reduced, the production route of the potash fertilizer is changed from a magnesium hydrohalite route to a more energy-saving and simple sylvite route, and the process difficulty is greatly reduced.
In some embodiments of the present application, the method for increasing the production efficiency of a chloride-type salt pan comprises the steps of:
and step S1, adding mirabilite into the brine, and separating out magnesium sulfate crystals.
Further, the brine comes from the sweat salt lake of Chaoer, Qinghai, China.
The Cherokee salt lake contains abundant inorganic salts such as sodium chloride, potassium chloride, magnesium chloride and the like. The main components of the brine comprise potassium chloride, sodium chloride and magnesium chloride.
Further, mirabilite comes from salt lake by-products.
The salt lake of Chaer sweat produces a large amount of mirabilite as a by-product when producing the potash fertilizer, but the utilization rate of the mirabilite is extremely low.
The inventor creatively proposes that the salt lake by-product of mirabilite is combined with magnesium ions in brine to reduce the content of the magnesium ions in the brine, thereby not only effectively improving the salt lake salt forming efficiency, but also utilizing the by-product of the salt lake to the maximum extent and greatly improving the utilization rate of the salt lake.
Further, since the mirabilite mainly includes hydrous sodium sulfate (Na)2SO4·10H2O), thereby adding mirabilite to the brine, increasing SO in the brine4 2-Concentration of Mg in brine2+With magnesium sulfate MgSO4The form (4) crystallizes out. Removing Mg from brine2+And then, the evaporation rate is greatly improved, and the mineralization rate can be effectively improved.
Further, the step of adding a mirabilite solution to the brine comprises:
calculated according to the molar mass ratio, according to mirabilite: magnesium chloride equal to 1: 1-3: 1, adding the mirabilite solution into brine.
Illustratively, when the mirabilite solution is added into the brine, the molar mass ratio is calculated according to the following formula: magnesium chloride equal to 1:1, adding the mirabilite solution into brine.
Or when the mirabilite solution is added into the brine, the molar mass ratio is calculated according to the formula: magnesium chloride equal to 1.5: 1, adding the mirabilite solution into brine.
Or when the mirabilite solution is added into the brine, the molar mass ratio is calculated according to the formula: magnesium chloride equal to 2.0: 1, adding the mirabilite solution into brine.
Or when the mirabilite solution is added into the brine, the molar mass ratio is calculated according to the formula: magnesium chloride equal to 2.5: 1, adding the mirabilite solution into brine.
Or when the mirabilite solution is added into the brine, the molar mass ratio is calculated according to the formula: magnesium chloride equal to 3:1, adding the mirabilite solution into brine.
The salt pan production effect can be effectively improved by setting the content of the magnesium chloride in the mirabilite and the brine in the range.
In some embodiments, the production efficiency of the salt pan can be improved by 15% -50%, the cost is greatly reduced, the production efficiency is improved, and the industrial benefit is increased.
Further optionally, the step of adding a salt cake solution to the brine comprises:
calculated according to the molar mass ratio, according to mirabilite: magnesium chloride equal to 1.5: 1-3: 1, adding the mirabilite solution into brine.
Further optionally, the step of adding a salt cake solution to the brine comprises:
calculated according to the molar mass ratio, according to mirabilite: magnesium chloride equal to 2: 1-3: 1, adding the mirabilite solution into brine.
Further optionally, the step of adding a salt cake solution to the brine comprises:
calculated according to the molar mass ratio, according to mirabilite: magnesium chloride equal to 2.5: 1-3: 1, adding the mirabilite solution into brine.
And step S2, evaporating the residual brine to prepare potassium chloride and/or sodium chloride.
Because the content of magnesium ions is reduced in the step S1, when the residual brine is evaporated, the magnesium salt does not need to be exposed in the sun in time, which is equivalent to the step of extracting the magnesium salt in the conventional operation, so that the salt forming time is greatly shortened, and the production efficiency of the salt field is improved.
Further, the content of magnesium ions in the residual brine is less than 10% by mass percentage.
By removing the magnesium ion content in the residual brine to be lower than 10%, the evaporation efficiency of the whole salt field can be improved by 30-50%.
Further optionally, the content of magnesium ions in the remaining brine is less than 20% by mass.
By removing the magnesium ion content in the residual brine to be lower than 10%, the evaporation efficiency of the whole salt field can be improved by 20-30%.
Further optionally, the content of magnesium ions in the remaining brine is less than 30% by mass.
By removing the magnesium ion content in the residual brine to be lower than 10%, the evaporation efficiency of the whole salt field can be improved by 15-20%.
In some embodiments of the present application, the step of evaporating the remaining brine is performed at room temperature.
Under the condition of room temperature, the evaporation efficiency can be improved by 15.6-20.1%.
In some embodiments of the present application, the step of evaporating the remaining brine is performed under dry or forced air drying conditions.
Under the condition of room temperature, the evaporation efficiency can be improved by 6.4-17.3%.
In some embodiments of the present application, the step of evaporating the remaining brine is performed under sub-ambient conditions.
Under the condition of negative temperature, the evaporation efficiency can be improved by 19.2-23.5%.
Some embodiments of the present application also provide a chloride-type salt pan product produced by a method of high chloride-type salt pan production efficiency as described above.
Further, the salt pan product includes potassium chloride, sodium chloride, and magnesium sulfate.
The features and properties of the present application are described in further detail below with reference to examples:
examples 1-4 simulate brine with different components and possibly different environmental conditions in the production practice process of a Carlo salt lake, so as to test the condition of the method for improving the evaporation efficiency of the brine.
Example 1
In brine (concentration of 0.5g/L and 2.3g/L) containing only potassium chloride and sodium chloride, the evaporation efficiency of the brine is respectively 0.1017kg/(m2 h) and 0.010 under the conditions of room temperature, refrigerator (-18 ℃), forced air drying (35 ℃) and drying (35 ℃); kg/(m 2. h), 0.749kg/(m 2. h) and 0.05488kg/(m 2. h). The evaporation efficiency is much higher than that in brine containing potassium chloride + sodium chloride + magnesium chloride (concentration: 0.5g/L, 2.3g/L, 90g/L), potassium chloride + sodium chloride + half less magnesium chloride (concentration: 0.5g/L, 2.3g/L, 45g/L), potassium chloride + sodium chloride + half more magnesium chloride (concentration: 0.5g/L, 2.3g/L, 135 g/L). Therefore, the brine is treated under different experimental conditions, and the evaporation efficiency is improved.
Under the condition of room temperature, adding a mirabilite solution into potassium chloride, sodium chloride, magnesium chloride (with the concentration of 0.5g/L, 2.3g/L and 90g/L), potassium chloride, sodium chloride and less than half of magnesium chloride (with the concentration of 0.5g/L, 2.3g/L and 45g/L) and potassium chloride, sodium chloride and more than half of magnesium chloride brine (with the concentration of 0.5g/L, 2.3g/L and 135g/L), wherein the molar mass ratio of the mirabilite solution to the original brine is 1:1, 2:1 and 3:1 respectively. The evaporation efficiency improvement ratio is shown in table 1.
Table 1 example 1 evaporation results
Example 2
Under the condition of a refrigerator (at (-18 ℃), adding a mirabilite solution into potassium chloride + sodium chloride + magnesium chloride (with the concentration of 0.5g/L, 2.3g/L and 90g/L), potassium chloride + sodium chloride + less than half of magnesium chloride (with the concentration of 0.5g/L, 2.3g/L and 45g/L) and potassium chloride + sodium chloride + more than half of magnesium chloride brine (with the concentration of 0.5g/L, 2.3g/L and 135g/L), wherein the molar mass ratio of the mirabilite solution to the original brine is respectively 1:1, 2:1 and 3: 1. The evaporation efficiency improvement ratio is shown in table 2.
Table 2 example 2 evaporation results
Example 3
Under the conditions of drying and blowing (35 ℃), a mirabilite solution is added into potassium chloride, sodium chloride, magnesium chloride (with the concentration of 0.5g/L, 2.3g/L and 90g/L), potassium chloride, sodium chloride and half less of magnesium chloride (with the concentration of 0.5g/L, 2.3g/L and 45g/L) and potassium chloride, sodium chloride and half more of magnesium chloride brine (with the concentration of 0.5g/L, 2.3g/L and 135g/L), and the molar mass ratio of the mirabilite solution to the original brine is respectively 1:1, 2:1 and 3: 1. The evaporation efficiency improvement ratio is shown in table 3.
Table 3 example 3 evaporation results
Example 4
Under the condition of drying (35 ℃), adding a mirabilite solution into potassium chloride + sodium chloride + magnesium chloride (with the concentration of 0.5g/L, 2.3g/L and 90g/L), potassium chloride + sodium chloride + less than half of magnesium chloride (with the concentration of 0.5g/L, 2.3g/L and 45g/L) and potassium chloride + sodium chloride + more than half of magnesium chloride brine (with the concentration of 0.5g/L, 2.3g/L and 135g/L), wherein the molar mass ratio of the mirabilite solution to the original brine is 1:1, 2:1 and 3:1 respectively. The evaporation efficiency improvement ratio is shown in table 4.
Table 4 example 4 evaporation results
It can be seen from the above embodiments 1 to 4 that, by using the method provided by the present application, the evaporation efficiency can be effectively improved for brine with different components under room temperature conditions, drying conditions or forced air drying conditions or negative temperature conditions, thereby improving the production efficiency of the salt pan.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A method for improving the production efficiency of chloride type salt pan is characterized by comprising the following steps:
adding mirabilite into brine, separating out magnesium sulfate crystals, and then evaporating the residual brine to prepare potassium chloride and/or sodium chloride;
wherein the brine comprises: potassium chloride, sodium chloride and magnesium chloride.
2. The method for improving the production efficiency of chloride type salt pan according to claim 1,
the step of adding the mirabilite solution into the brine comprises the following steps:
calculated according to the molar mass ratio, according to the mirabilite: the magnesium chloride is equal to 1: 1-3: 1, adding the mirabilite solution into the brine.
3. The method for improving the production efficiency of chloride type salt pan according to claim 1 or 2,
the step of adding the mirabilite solution into the brine comprises the following steps:
calculated according to the molar mass ratio, according to the mirabilite: the magnesium chloride is equal to 2: 1-3: 1, adding the mirabilite solution into the brine.
4. The method for improving the production efficiency of chloride type salt pan according to claim 3,
the brine is from the salt lake of Chaoer sweat of Qinghai province of China.
5. The method for improving the production efficiency of chloride type salt pan according to claim 4,
the mirabilite is from salt lake by-product.
6. The method for improving the production efficiency of chloride type salt pan according to claim 1 or 2,
the step of evaporating the remaining brine is performed at room temperature.
7. The method for improving the production efficiency of chloride type salt pan according to claim 1 or 2,
the step of evaporating the remaining brine is performed under dry or forced air drying conditions.
8. The method for improving the production efficiency of chloride type salt pan according to claim 1 or 2,
the step of evaporating the remaining brine is performed at a sub-ambient temperature.
9. The method for improving the production efficiency of chloride type salt pan according to claim 1 or 2,
and the content of magnesium ions in the residual brine is less than 10 percent in percentage by mass.
10. A chloride-type salt pan product produced by the method of any one of claims 1 to 9, comprising potassium chloride, sodium chloride and magnesium sulfate.
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Application publication date: 20200121 |