CN114560480A - Multi-element extraction method of bittern after desulfurization by calcium method - Google Patents
Multi-element extraction method of bittern after desulfurization by calcium method Download PDFInfo
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- CN114560480A CN114560480A CN202210190571.0A CN202210190571A CN114560480A CN 114560480 A CN114560480 A CN 114560480A CN 202210190571 A CN202210190571 A CN 202210190571A CN 114560480 A CN114560480 A CN 114560480A
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- bittern
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- carnallite
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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
- C01F5/26—Magnesium halides
- C01F5/30—Chlorides
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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
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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Abstract
The invention discloses a multi-element extraction method of bittern after sulfur removal by a calcium method, which comprises the steps of adding solid calcium chloride dihydrate into the bittern, removing partial sulfate radicals in the bittern, then evaporating, carrying out heat preservation, settling, solid-liquid separation on the evaporated liquid after the evaporation is finished, obtaining high-temperature salt from a solid phase, cooling and crystallizing the liquid phase to obtain carnallite and thick bittern, decomposing and washing the carnallite to obtain potassium chloride, and evaporating the thick bittern to produce magnesium chloride. The invention carries out process innovation on the basis of the traditional process technology, develops a new way for comprehensively utilizing the salt-making waste liquid, removes sulfate radicals in bittern by adopting a method of adding solid calcium chloride, and simultaneously realizes the maximization of economic benefit on the basis of not influencing the product quality by controlling process parameters.
Description
Technical Field
The invention belongs to the technical field of potassium chloride production methods, and particularly relates to a multi-element extraction method of bittern after sulfur removal by a calcium method.
Background
The salt-making waste liquor (bittern) is the waste liquor produced by concentrating seawater to separate out raw salt, and the interior of said waste liquor contains rich Na+、K+、Mg2+、Cl-、SO4 2-Plasma components with specific gravity of 1.2 × 103Kg/m3In the above, if the bittern is not used, the bittern is directly discharged to the sea, which results in waste, and the offshore area is polluted, so that the bittern must be used to further extract different chemical substances.
For many years, coastal salinization enterprises adopt the traditional bittern chemical process, namely bittern is mixed with thick bittern and then enters a tank for evaporation, then high-temperature salt and clear liquid are separated out after heat preservation and sedimentation, the clear liquid is cooled and crystallized to separate out carnallite and thick bittern, and the carnallite is decomposed and washed to prepare potassium chloride.
The other process for producing potassium chloride by using bittern is that calcium chloride waste water is firstly used for removing sulfate radical in bittern, and then is evaporated to produce potassium chloride.
The two processes have the defects of high energy consumption, serious equipment corrosion, short tank brushing period and the like, so that the bittern chemical industry is in a loss state all the time for many years, the economic benefit is very unattractive, but the industry is also responsible for the environment-friendly function of treating the salt-making waste liquid and cannot discharge the salt-making waste liquid at will, and therefore, a process route for saving energy and reducing loss is urgently needed to be developed.
Disclosure of Invention
The invention is provided for overcoming the defects in the prior art, and aims to provide a method for extracting multiple elements of bittern after sulfur removal by a calcium method.
The invention is realized by the following technical scheme:
a method for extracting multiple elements of bittern after sulfur removal by a calcium method is characterized in that: the method comprises the following steps:
adding solid calcium chloride dihydrate into bittern, reacting at normal temperature for 15-20 min under the condition of uniform stirring, removing part of sulfate ions, and performing suction filtration to obtain a solid-phase calcium cake and a liquid-phase filtrate I;
(ii) mixing the filtrate I with the carnallite decomposed solution and the washing solution to form mixed halogen, directly evaporating and concentrating the mixed halogen, and stopping evaporation after the mixed halogen is evaporated to 128 ℃ to obtain evaporation finished solution;
(iii) carrying out heat preservation and sedimentation on the evaporated solution, then carrying out high-temperature solid-liquid separation, separating supernatant and solid-phase slurry after the solid phase is completely settled, carrying out suction filtration on the solid-phase slurry to obtain high-temperature salt, mixing the filtrate and the supernatant to obtain clear solution, cooling and crystallizing the clear solution, carrying out solid-liquid separation after crystallization to obtain solid-phase carnallite and liquid-phase thick brine;
(iv) decomposing and washing carnallite to obtain a potassium chloride product, a decomposition liquid and a washing liquid, and returning the decomposition liquid and the washing liquid to the step (ii) to form mixed halogen;
and (v) evaporating and concentrating the thick halogen to produce a magnesium chloride product.
In the technical scheme, the solid calcium chloride dihydrate is any one of granular, powdery or flaky.
In the technical scheme, the addition amount of the solid calcium chloride dihydrate is used for controlling MgSO (MgSO) in the mixed halogen4/MgCl2In a mass ratio of 0.04 to 0.07, Ca2+The concentration is less than or equal to 0.015mol/L as the reference.
In the above technical scheme, the calcium cake in the step (i) is washed by adding water to prepare calcium sulfate.
In the above technical scheme, during the first production, no carnallite decomposition liquid and washing liquid are produced, and the filtrate I in the step (ii) is directly evaporated and concentrated.
In the above-mentioned technologyIn scheme, MgSO in the concentrated halogen4/MgCl2The mass ratio of (A) is controlled to be 0.04-0.07.
In the above embodiment, the temperature for the high-temperature solid-liquid separation in the step (iii) is 110 ℃.
In the above technical scheme, solid-liquid separation is carried out when the temperature of the clear liquid in the step (iii) is reduced to 45 DEG C
In the above technical solution, the specific steps of decomposing and washing carnallite in step (iv) are as follows: adding water accounting for 45% of the mass of the carnallite into the carnallite for decomposition, and then filtering to obtain crude potassium and decomposition liquid, and adding water accounting for 75% of the mass of the crude potassium into the crude potassium for washing to obtain a potassium chloride product and washing liquid.
The invention has the beneficial effects that:
the invention provides a multi-element extraction method of bittern after calcium desulphurization, which carries out process innovation on the basis of the traditional process technology, develops a new way for comprehensively utilizing salt production waste liquid, removes sulfate radicals in the bittern by adopting a method of adding solid calcium chloride, and realizes the maximization of economic benefit on the basis of not influencing the product quality by controlling process parameters.
Drawings
FIG. 1 is a flow chart of the multi-element extraction method of bittern after the sulfur removal by calcium method of the present invention.
Detailed Description
In order to make the technical scheme of the invention better understood by those skilled in the art, the technical scheme of the multi-element extraction method of bittern after sulfur removal by calcium method of the invention is further described by the following specific implementation mode in combination with the attached drawings of the specification.
As shown in figure 1, a method for extracting multiple elements from bittern after sulfur removal by calcium method comprises the following steps:
adding solid calcium chloride dihydrate into bittern, reacting at normal temperature for 15-20 min under the condition of uniform stirring, removing part of sulfate ions, performing suction filtration to obtain solid-phase calcium cake and liquid-phase filtrate I, and washing the calcium cake with water to obtain calcium sulfate dihydrate.
The solid calcium chloride dihydrate is in any one of granular, powdery or flaky form.
The solid calcium chloride dihydrate is added in an amount to control MgSO in the mixed halogen4/MgCl2In a mass ratio of 0.04 to 0.07, Ca2+The concentration is less than or equal to 0.015mol/L as the reference.
(ii) mixing the filtrate I with the carnallite decomposed solution and the washing solution to form mixed halogen, directly evaporating and concentrating the mixed halogen, and stopping evaporation after the mixed halogen is evaporated to 128 ℃ to obtain evaporation finished solution;
during the first production, no decomposing liquid and washing liquid of the carnallite are produced, and the filtrate I in the step (ii) is directly evaporated and concentrated.
(iii) carrying out heat preservation and sedimentation on the evaporated solution, then carrying out high-temperature solid-liquid separation, separating supernatant and solid-phase slurry after the solid phase is completely settled, carrying out suction filtration on the solid-phase slurry to obtain high-temperature salt, mixing the filtrate and the supernatant to obtain clear solution, cooling and crystallizing the clear solution, carrying out solid-liquid separation after crystallization to obtain solid-phase carnallite and liquid-phase thick brine;
MgSO in the concentrated brine4/MgCl2The mass ratio of (A) is controlled to be 0.04-0.07.
The temperature of the high-temperature solid-liquid separation is 110 ℃.
Cooling the clear liquid to 45 ℃ and then carrying out solid-liquid separation
(iv) adding carnallite into water accounting for 45% of the weight of carnallite for decomposition and then filtering to obtain crude potassium and decomposition liquid, adding water accounting for 75% of the weight of crude potassium into crude potassium for washing to obtain a potassium chloride product and washing liquid, and returning the decomposition liquid and the washing liquid to the step (ii) to form mixed halogen;
and (v) evaporating and concentrating the thick halogen to produce a magnesium chloride product.
Example 1
(1) 500ml of bittern is taken, calcium chloride dihydrate is added according to 70 percent of the total weight of sulfate radical removal for reaction, and then calcium cake and filtrate I are obtained by suction filtration.
(2) And washing the calcium cake to obtain the calcium sulfate.
(3) Mixing the filtrate I with the decomposition liquid and the washing liquid to obtain mixed halogen. Evaporating the mixed brine to 128 ℃, stopping evaporation, carrying out heat preservation and sedimentation on the feed liquid, and then carrying out high-temperature solid-liquid separation (110 ℃) to obtain high-temperature salt and clear liquid.
(4) Cooling the clear liquid to 45 ℃, carrying out solid-liquid separation to obtain carnallite and thick halogen, and evaporating and concentrating the thick halogen again to obtain the magnesium chloride.
(5) Adding water (45% of the weight of the carnallite) into carnallite for decomposition, filtering to obtain crude potassium and decomposition liquid, and adding water (75% of the weight of the crude potassium) into the crude potassium for washing to obtain a potassium chloride product and washing liquid. The decomposition liquid and the washing liquid are returned to be evaporated.
The invention provides a multi-element extraction method of bittern after sulfur removal by using a calcium method, which has the advantages of simple process, easy operation, energy conservation and consumption reduction, can improve the market competitiveness of the same industry, and can reduce the energy consumption and prolong the tank brushing period by implementing the process method, thereby realizing energy conservation and loss reduction.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (9)
1. A multi-element extraction method of bittern after desulfurization by calcium method is characterized in that: the method comprises the following steps:
adding solid calcium chloride dihydrate into bittern, reacting at normal temperature for 15-20 min under the condition of uniform stirring, removing part of sulfate ions, and performing suction filtration to obtain a solid-phase calcium cake and a liquid-phase filtrate I;
(ii) mixing the filtrate I with the carnallite decomposed solution and the washing solution to form mixed halogen, directly evaporating and concentrating the mixed halogen, and stopping evaporation after the mixed halogen is evaporated to 128 ℃ to obtain evaporation finished solution;
(iii) carrying out heat preservation and sedimentation on the evaporated solution, then carrying out high-temperature solid-liquid separation, separating supernatant and solid-phase slurry after the solid phase is completely settled, carrying out suction filtration on the solid-phase slurry to obtain high-temperature salt, mixing the filtrate and the supernatant to obtain clear solution, cooling and crystallizing the clear solution, carrying out solid-liquid separation after crystallization to obtain solid-phase carnallite and liquid-phase thick brine;
(iv) decomposing and washing carnallite to obtain a potassium chloride product, a decomposition liquid and a washing liquid, and returning the decomposition liquid and the washing liquid to the step (ii) to form mixed halogen;
and (v) evaporating and concentrating the thick halogen to produce a magnesium chloride product.
2. The multi-element extraction method of bittern after calcium desulphurization according to claim 1, characterized in that: the solid calcium chloride dihydrate is in any one of granular shape, powder shape or flake shape.
3. The multi-element extraction method of bittern after calcium desulphurization according to claim 1, characterized in that: the solid calcium chloride dihydrate is added in an amount to control MgSO in the mixed halogen4/MgCl2In a mass ratio of 0.04 to 0.07, Ca2+The concentration is less than or equal to 0.015mol/L as the reference.
4. The multi-element extraction method of bittern after calcium desulphurization according to claim 1, characterized in that: and (3) washing the calcium cake in the step (i) by adding water to prepare calcium sulfate dihydrate.
5. The multi-element extraction method of bittern after calcium desulphurization according to claim 1, characterized in that: during the first production, no decomposing liquid and washing liquid of the carnallite are produced, and the filtrate I in the step (ii) is directly evaporated and concentrated.
6. The multi-element extraction method of bittern after calcium desulphurization according to claim 1, characterized in that: MgSO in the concentrated brine4/MgCl2The mass ratio of (A) is controlled to be 0.04-0.07.
7. The multi-element extraction method of bittern after calcium desulphurization according to claim 1, characterized in that: the temperature for the high-temperature solid-liquid separation in the step (iii) is 110 ℃.
8. The multi-element extraction method of bittern after calcium desulphurization according to claim 1, characterized in that: and (5) cooling the clear liquid in the step (iii) to 45 ℃ and carrying out solid-liquid separation.
9. The multi-element extraction method of bittern after calcium desulphurization according to claim 1, characterized in that: the specific steps of decomposing and washing the carnallite in the step (iv) are as follows: adding water accounting for 45% of the mass of the carnallite into the carnallite for decomposition, and then filtering to obtain crude potassium and decomposition liquid, and adding water accounting for 75% of the mass of the crude potassium into the crude potassium for washing to obtain a potassium chloride product and washing liquid.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS557505A (en) * | 1978-06-26 | 1980-01-19 | Mitsubishi Mining & Cement Co Ltd | Removing method for calcium chloride in bittern |
| CN1077434A (en) * | 1993-05-14 | 1993-10-20 | 中国石油天然气总公司工程技术研究所 | A kind of method of producing vitriolate of tartar with bittern and Repone K |
| CN1099008A (en) * | 1993-08-19 | 1995-02-22 | 天津长芦塘沽盐场 | Bittern prepares the new process of production of white magnesium chloride |
| WO2003035550A1 (en) * | 2001-10-22 | 2003-05-01 | Council Of Scientific And Industrial Research | Recovery of sodium chloride and other salts from brine |
| CN1429768A (en) * | 2001-12-31 | 2003-07-16 | 中盐制盐工程技术研究院 | Improved process of producing potassium chloride by halogen conversion method |
| CN1886339A (en) * | 2003-12-31 | 2006-12-27 | 科学与工业研究委员会 | Process for recovery of potassium sulphate |
| CN1903729A (en) * | 2006-08-08 | 2007-01-31 | 河北银山精制碘盐有限责任公司 | Comprehensive utilization method of sea salt bittern |
| CN102583446A (en) * | 2012-02-13 | 2012-07-18 | 河北工业大学 | Method for preparing potassium chloride through decomposing carnallite by concentrated brine |
| CN112174171A (en) * | 2020-11-02 | 2021-01-05 | 天津长芦海晶集团有限公司 | Method for producing carnallite by using salt production waste liquid |
-
2022
- 2022-03-01 CN CN202210190571.0A patent/CN114560480A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS557505A (en) * | 1978-06-26 | 1980-01-19 | Mitsubishi Mining & Cement Co Ltd | Removing method for calcium chloride in bittern |
| CN1077434A (en) * | 1993-05-14 | 1993-10-20 | 中国石油天然气总公司工程技术研究所 | A kind of method of producing vitriolate of tartar with bittern and Repone K |
| CN1099008A (en) * | 1993-08-19 | 1995-02-22 | 天津长芦塘沽盐场 | Bittern prepares the new process of production of white magnesium chloride |
| WO2003035550A1 (en) * | 2001-10-22 | 2003-05-01 | Council Of Scientific And Industrial Research | Recovery of sodium chloride and other salts from brine |
| CN1429768A (en) * | 2001-12-31 | 2003-07-16 | 中盐制盐工程技术研究院 | Improved process of producing potassium chloride by halogen conversion method |
| CN1886339A (en) * | 2003-12-31 | 2006-12-27 | 科学与工业研究委员会 | Process for recovery of potassium sulphate |
| CN1903729A (en) * | 2006-08-08 | 2007-01-31 | 河北银山精制碘盐有限责任公司 | Comprehensive utilization method of sea salt bittern |
| CN102583446A (en) * | 2012-02-13 | 2012-07-18 | 河北工业大学 | Method for preparing potassium chloride through decomposing carnallite by concentrated brine |
| CN112174171A (en) * | 2020-11-02 | 2021-01-05 | 天津长芦海晶集团有限公司 | Method for producing carnallite by using salt production waste liquid |
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