CN113813638A - Method for separating water and calcium chloride by eutectic freezing crystallization - Google Patents
Method for separating water and calcium chloride by eutectic freezing crystallization Download PDFInfo
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- CN113813638A CN113813638A CN202111286818.0A CN202111286818A CN113813638A CN 113813638 A CN113813638 A CN 113813638A CN 202111286818 A CN202111286818 A CN 202111286818A CN 113813638 A CN113813638 A CN 113813638A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D9/0004—Crystallisation cooling by heat exchange
- B01D9/0013—Crystallisation cooling by heat exchange by indirect heat exchange
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C01F11/20—Halides
- C01F11/24—Chlorides
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Abstract
The invention discloses a method for separating water and calcium chloride by eutectic freezing crystallization, which comprises the following steps: (a) precooling the calcium chloride solution in a heat exchanger; (b) pumping the pre-cooled calcium chloride solution into a crystallizer, and introducing CO into the crystallizer2Cooling the gas in the crystallizer by a refrigerant; (c) maintaining the pressure and the temperature in the crystallizer for a certain time, and forming a calcium chloride solid and a carbon dioxide inclusion compound in the crystallizer; (d) and discharging the calcium chloride solid through a discharge outlet at the bottom of the crystallizer, and performing solid-liquid separation through a centrifugal machine to obtain calcium chloride and calcium chloride mother liquor. The method for separating water and calcium chloride by eutectic freezing crystallization has the advantages of simple process operation, energy conservation, environmental protection, low operation cost, no secondary pollution, energy conservation and consumption reduction.
Description
Technical Field
The invention relates to the technical field of salt recovery, in particular to a method for separating water and calcium chloride by eutectic freezing crystallization.
Background
Chlorination ofCalcium is a chemical substance composed of chlorine element and calcium element, and has a chemical formula of CaCl2It is slightly bitter. It is typically an ionic halide that is white, hard, in small pieces or particles at room temperature. The use of calcium chloride includes the prevention of food spoilage, which is commonly used as a food preservative. It also helps to maintain food freshness. The pasteurized milk reduces a large amount of calcium during processing, while the addition of a small amount of calcium chloride can aid in coagulation. The calcium chloride solution can be applied to a refrigerator, and is an essential coolant. Because of its strong moisture absorption properties, it can be used to dry other organic liquids and is therefore sometimes used as a desiccant. The compound helps to lower the melting point of water, it melts ice faster than other chemicals, and therefore can be used to de-ice on roads and sidewalks under extreme cold conditions. Calcium chloride is also widely used as an additive in the paper industry and as a dye in the manufacturing industry. In addition, it is also frequently used as a dehydrating agent in the petrochemical industry because it has an effect of reducing the moisture of a compound. The use of calcium chloride also includes road dust reduction applications. It can be added into concrete to increase hardening speed. Unlike other compounds, it is not particularly hazardous. Calcium chloride can release heat, so when the liquid is added to remove moisture, a large amount of heat can be released, and the temperature can be raised to be more than 60 ℃. Therefore, the calcium chloride has wide application and huge demand in industrial production.
The conventional process flow for producing calcium chloride solid at present comprises the steps of heating a stock solution by a preheater, evaporating and concentrating the stock solution in a triple-effect evaporator to about 50% concentration, and discharging the concentrated stock solution. Filtering the concentrated solution by a filter to remove insoluble substances in the solution, continuously evaporating and concentrating the filtrate in an evaporator, and discharging the concentrated solution after concentration to 70% to obtain calcium chloride solid after drying. The calcium chloride solid obtained by the process method through evaporative crystallization has the defects of high energy consumption, complex process, high operation cost, high operation difficulty and the like. Therefore, there is a need to develop a new process for realizing a calcium chloride crystallization method with low energy consumption, simple process and low operation cost.
Disclosure of Invention
The invention aims to provide a method for separating water and calcium chloride by eutectic freezing crystallization, which has the advantages of simple process operation, energy conservation, environmental protection, low operation cost, no secondary pollution, energy conservation and consumption reduction.
In order to achieve the purpose, the invention provides a method for separating water and calcium chloride by eutectic freezing crystallization, which comprises the following steps: (a) precooling the calcium chloride solution in a heat exchanger;
(b) pumping the pre-cooled calcium chloride solution into a crystallizer, and introducing CO into the crystallizer2Cooling the gas in the crystallizer by a refrigerant;
(c) maintaining the pressure and the temperature in the crystallizer for a certain time, and forming a calcium chloride solid and a carbon dioxide inclusion compound in the crystallizer;
(d) discharging the calcium chloride solid through a discharge outlet at the bottom of the crystallizer, and performing solid-liquid separation through a centrifugal machine to obtain calcium chloride and calcium chloride mother liquor;
(e) the calcium chloride mother liquor obtained in the step d returns to the crystallizer for secondary circulating crystallization;
(f) discharging the carbon dioxide inclusion compound obtained in the step d through an upper liquid outlet of the crystallizer and washing;
(g) decomposing the carbon dioxide clathrate washed in the step f to obtain CO2Gas and pure water;
(h) said CO obtained in step g2And returning the gas to the crystallizer for recycling, wherein the pure water is a cooling medium in the heat exchanger.
Preferably, in step a), the calcium chloride solution contains 0-30% of calcium chloride.
Preferably, in the step a), the heat exchanger is a tube type heat exchanger, the refrigerant of the heat exchanger is ice water, and the precooling temperature of the heat exchanger is 5-10 ℃.
Preferably, in step b), the crystallizer is a disc tower crystallizer (CDCC) or a scraped wall cooling crystallizer (SCWC); the crystallizer can realize crystallization and gravity separation; the cooling medium of the crystallizer is glycol.
Preferably, in step c), the pressure is 1.0 to 1.5 MPa; the temperature is-20 to 30 ℃; the calcium chloride solids settle downward; the carbon dioxide inclusion compound floats upward.
Preferably, in step d), the centrifuge is a horizontal screw centrifuge or a bipolar pusher centrifuge.
Preferably, in the step e), the calcium chloride mother liquor is added from a feed inlet at the upper part of the crystallizer.
Preferably, in step f), the carbon dioxide inclusion compound is a mixture of dry ice and ice.
Preferably, in step f), the washing apparatus is a washing column.
Preferably, in step g), the carbon dioxide inclusion compound is prepared by decomposing dry ice by a method of reducing pressure.
The invention has the beneficial effects that:
(1) compared with the traditional evaporative crystallization process, the method for separating calcium chloride by using eutectic freezing crystallization has the advantage of low energy consumption;
(2) the carbon dioxide clathrate crystal is used for replacing common ice, so that the eutectic temperature can be increased, and the power consumption can be reduced by about 32% compared with the conventional eutectic freezing crystal;
(3) compared with the traditional high-temperature evaporation crystallization process, the corrosion resistance of the equipment can be greatly reduced;
(4) ice crystals generated in the freezing and crystallizing process can be repeatedly used as cooling water, so that energy reutilization is realized;
(5) the eutectic freezing crystallization method is simple and convenient to operate, simple in equipment, free of adding any chemical reagent, free of causing secondary pollution and low in energy consumption.
The technical solution of the present invention is further described in detail by the accompanying drawings and embodiments.
Drawings
FIG. 1 is a process flow diagram of a method for separating water and calcium chloride by eutectic freezing crystallization according to the present invention.
Detailed Description
The present invention will be further described with reference to examples, in which various chemicals and reagents are commercially available unless otherwise specified.
Example 1
Preparing 5L of aqueous solution with the calcium chloride content of 20%, precooling the 5L of calcium chloride solution to 5 ℃ by using ice water as a cold medium through a tube type heat exchanger, pumping the precooled calcium chloride solution into a crystallizer, stirring the crystallizer to 750rpm, introducing carbon dioxide from the bottom of the crystallizer until the interior of the crystallizer, stopping introducing carbon dioxide gas after the pressure shows to be 1.22Mpa, continuously cooling the calcium chloride solution by using a glycol refrigerant through a jacket of the crystallizer, stopping precooling when the interior temperature of the crystallizer is reduced to-29 ℃, and stopping CO at the moment2And the feeding valve is closed.
The pressure and temperature were maintained for 1.0 hour, and it was observed that the salt crystallized out first, a clathrate of carbon dioxide cage type was formed on the upper layer of the crystallizer, and CO was supplemented when the pressure was slightly lowered2Otherwise, some decomposition of the carbon dioxide clathrate may result. Discharging the salt crystals from a discharge hole at the bottom of the crystallizer, filtering the salt crystals by a centrifugal machine to obtain calcium chloride hexahydrate solid and calcium chloride mother liquor, and returning the calcium chloride mother liquor to the crystallizer for circulating cooling crystallization; discharging and washing the carbon dioxide inclusion compound from a discharge hole at the upper part of the crystallizer, decomposing the washed carbon dioxide inclusion compound under reduced pressure to obtain carbon dioxide gas and ice crystals, recycling the carbon dioxide gas back to the crystallizer, and returning the ice crystals to the tubular heat exchanger for precooling the calcium chloride solution.
The finally obtained calcium chloride solid is needle-shaped, and the mass of the calcium chloride solid is 788.6 g.
Example 2
Preparing 5L of aqueous solution with the calcium chloride content of 20%, precooling the 5L of calcium chloride solution to 5 ℃ by using ice water as a cold medium through a tube type heat exchanger, pumping the precooled calcium chloride solution into a crystallizer, stirring the crystallizer to 750rpm, introducing carbon dioxide from the bottom of the crystallizer until the interior of the crystallizer, stopping introducing carbon dioxide gas after the pressure shows to be 1.06Mpa, continuously cooling the calcium chloride solution by using an ethylene glycol refrigerant through a jacket of the crystallizer, stopping precooling when the interior temperature of the crystallizer is reduced to-33 ℃, and stopping CO at the moment2And the feeding valve is closed.
The pressure and temperature were maintained for 1.0 hour, and salt was observed to crystallize out first and the upper layer of the crystallizer was observed to formForming a clathrate of carbon dioxide cage type, and supplementing CO when the pressure is slightly reduced2Otherwise, some decomposition of the carbon dioxide clathrate may result. Discharging the salt crystals from a discharge hole at the bottom of the crystallizer, filtering the salt crystals by a centrifugal machine to obtain calcium chloride hexahydrate solid and calcium chloride mother liquor, and returning the calcium chloride mother liquor to the crystallizer for circulating cooling crystallization; discharging and washing the carbon dioxide inclusion compound from a discharge hole at the upper part of the crystallizer, decomposing the washed carbon dioxide inclusion compound under reduced pressure to obtain carbon dioxide gas and ice crystals, recycling the carbon dioxide gas back to the crystallizer, and returning the ice crystals to the tubular heat exchanger for precooling the calcium chloride solution.
The finally obtained calcium chloride solid is needle-shaped, and the mass of the calcium chloride solid is 746.3 g.
Example 3
Preparing 5L of aqueous solution with the calcium chloride content of 20%, precooling the 5L of calcium chloride solution to 5 ℃ by using ice water as a cold medium through a tube type heat exchanger, pumping the precooled calcium chloride solution into a crystallizer, stirring the crystallizer to 750rpm, introducing carbon dioxide from the bottom of the crystallizer until the interior of the crystallizer, stopping introducing carbon dioxide gas after the pressure shows to be 1.34Mpa, continuously cooling the calcium chloride solution by using a glycol refrigerant through a jacket of the crystallizer, stopping precooling when the interior temperature of the crystallizer is reduced to-25 ℃, and stopping CO at the moment2And the feeding valve is closed.
The pressure and temperature were maintained for an additional 1.0 hour. Salt is observed to crystallize out first, a carbon dioxide cage-type inclusion compound is formed at the upper layer of the crystallizer, and CO is supplemented when the pressure is slightly reduced2Otherwise, some decomposition of the carbon dioxide clathrate may result. Discharging the salt crystals from a discharge hole at the bottom of the crystallizer, filtering the salt crystals by a centrifugal machine to obtain calcium chloride hexahydrate solid and calcium chloride mother liquor, and returning the calcium chloride mother liquor to the crystallizer for circulating cooling crystallization; discharging and washing the carbon dioxide inclusion compound from a discharge hole at the upper part of the crystallizer, decomposing the washed carbon dioxide inclusion compound under reduced pressure to obtain carbon dioxide gas and ice crystals, recycling the carbon dioxide gas back to the crystallizer, and returning the ice crystals to the tubular heat exchanger for precooling the calcium chloride solution.
The finally obtained calcium chloride solid is needle-shaped, and the mass of the calcium chloride solid is 797.5 g.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that: modifications and equivalents may be made to the invention without departing from the spirit and scope of the invention.
Claims (10)
1. A method for separating water and calcium chloride by eutectic freezing crystallization is characterized by comprising the following steps: (a) precooling the calcium chloride solution in a heat exchanger;
(b) pumping the pre-cooled calcium chloride solution into a crystallizer, and introducing CO into the crystallizer2Cooling the gas in the crystallizer by a refrigerant;
(c) maintaining the pressure and the temperature in the crystallizer for a certain time, and forming a calcium chloride solid and a carbon dioxide inclusion compound in the crystallizer;
(d) discharging the calcium chloride solid through a discharge outlet at the bottom of the crystallizer, and performing solid-liquid separation through a centrifugal machine to obtain calcium chloride and calcium chloride mother liquor;
(e) the calcium chloride mother liquor obtained in the step d returns to the crystallizer for secondary circulating crystallization;
(f) discharging the carbon dioxide inclusion compound obtained in the step d through an upper liquid outlet of the crystallizer and washing;
(g) decomposing the carbon dioxide clathrate washed in the step f to obtain CO2Gas and pure water;
(h) said CO obtained in step g2And returning the gas to the crystallizer for recycling, wherein the pure water is a cooling medium in the heat exchanger.
2. The method for separating water and calcium chloride by eutectic freezing crystallization according to claim 1, wherein: in the step a), the content of calcium chloride in the calcium chloride solution is 0-30%.
3. The method for separating water and calcium chloride by eutectic freezing crystallization according to claim 1, wherein: in the step a), the heat exchanger is a tube type heat exchanger, the refrigerant of the heat exchanger is ice water, and the precooling temperature of the heat exchanger is 5-10 ℃.
4. The method for separating water and calcium chloride by eutectic freezing crystallization according to claim 1, wherein: in step b), the crystallizer is a disc tower crystallizer (CDCC) or a scraped wall cooling crystallizer (SCWC); the cooling medium of the crystallizer is glycol.
5. The method for separating water and calcium chloride by eutectic freezing crystallization according to claim 1, wherein: in step c), the pressure is 1.0-1.5 MPa; the temperature is-20 to 30 ℃; the calcium chloride solids settle downward; the carbon dioxide inclusion compound floats upward.
6. The method for separating water and calcium chloride by eutectic freezing crystallization according to claim 1, wherein: in step d), the centrifuge is a horizontal screw centrifuge or a bipolar pusher centrifuge.
7. The method for separating water and calcium chloride by eutectic freezing crystallization according to claim 1, wherein: in the step e), the calcium chloride mother liquor is added from a feed inlet at the upper part of the crystallizer.
8. The method for separating water and calcium chloride by eutectic freezing crystallization according to claim 1, wherein: in step f), the carbon dioxide inclusion compound is a mixture of dry ice and ice.
9. The method for separating water and calcium chloride by eutectic freezing crystallization according to claim 1, wherein: in step f), the washing device is a washing tower.
10. The method for separating water and calcium chloride by eutectic freezing crystallization according to claim 1, wherein: in the step g), the carbon dioxide inclusion compound decomposes the dry ice by a method of reducing pressure.
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| CN111041204A (en) * | 2018-10-11 | 2020-04-21 | 有研稀土新材料股份有限公司 | Comprehensive utilization method of magnesium and/or calcium-containing waste liquid in rare earth smelting separation process |
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2021
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| CN101151080A (en) * | 2005-03-30 | 2008-03-26 | 月岛机械株式会社 | Method and apparatus for crystallization of organic compound through adiabatic cooling |
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