Purifying medicament material, device and method for CaCl2 solution

Abstract

The invention belongs to the field of material application and resource recovery, and provides a purification medicament material, device and method for a CaCl2 solution. According to the method, low-value materials such as shells which take calcium-based materials as main components are used as main components of the crystallization inducing agent, natural organic matters such as wood flour and straws are used as carbon sources, and after mechanical activation and hydrothermal treatment, calcination is performed under nitrogen protection, so that the crystallization inducing agent can be obtained. The purification material can be applied to purification of various CaCl2 solutions. The crystallization inducer is mild in preparation condition, low in material cost and high in pertinence, and sulfate radicals and other impurities in the CaCl2 solution are efficiently removed at low cost.

Description

Technical Field

[0001] The invention belongs to the field of material application and resource recovery, and relates to a purification agent material, a device and a method for a CaCl2 solution. Background Art

[0002] The wastewater generated in the production process of titanium dioxide chloride is mainly chlorine-containing acidic wastewater, which is usually treated by neutralization reaction. This is the most common and direct and effective treatment method. The treatment process is as follows: lime milk is passed into the wastewater treatment tank, and then chlorine-containing acidic wastewater is passed to react with it. The direct product is iron hydroxide in the form of precipitate, which is then filtered and washed. The filtered solution is a mixed wastewater containing calcium chloride. Other impurities in the wastewater affect the purity of calcium chloride, and evaporation alone cannot achieve the purpose of purification. The main impurities include a certain concentration of sulfate, organic matter, etc.

[0003] In industry, high-salt (non-calcium chloride main component) wastewater is usually treated by adding calcium chloride to remove sulfate ions by precipitation. However, for calcium chloride high-salt wastewater, sulfate ions are difficult to remove due to the salt effect. Barium salt precipitation introduces barium ions, and barium is expensive and not suitable for industrial applications. Therefore, there is currently no reliable method reported for the directional removal of sulfate ions in high-concentration calcium chloride wastewater.

[0004] The present invention prepares an induced crystallization adsorbent, and designs a method and equipment matching the method in combination with the adsorbent. By adding the induced crystallization adsorbent in the present invention into the designed equipment and adopting a corresponding reaction method, sulfate ions in calcium chloride wastewater can be effectively removed, thereby achieving purification of the calcium chloride solution. Summary of the invention

[0005] The present invention provides a method and equipment for treating impurities such as sulfate in calcium chloride by using an inducing crystallization agent, so that low-cost raw materials can be used in specific equipment after being treated, and CaCl2 solution can be effectively treated to achieve product compliance.

[0006] The technical solution of the present invention:

[0007] A purification agent material for a CaCl2 solution comprises an oxidant, a deoxidant and an inducer, wherein the mass ratio of the inducer, the oxidant and the deoxidant is 1:0.2-1:0.2-1; by adding the purification agent material, organic matter in the CaCl2 solution is removed, dissolved oxygen is removed, and sulfate radical removal is induced.

[0008] The oxidant is an oxidant material such as calcium hypochlorite or hydrogen peroxide that does not add any new elements. Under the special environmental requirements of the reactor, the organic matter in the solution can be oxidized and removed to achieve decolorization of the solution.

[0009] The deoxidizer material includes, but is not limited to, iron powder and other reducing materials such as ethanol, etc. Its main function is to remove dissolved oxygen in water and reduce the corrosion of oxygen to heating equipment.

[0010] The inducer is made of natural calcium-containing substances as the main material, which is mixed with biomass materials and prepared under specific conditions to synthesize a calcium-based inducer of a specific crystal form.

[0011] The inducer material, natural calcium-containing substances include but are not limited to shells, animal bones, calcium carbonate minerals and other materials, the biomass material includes but is not limited to wood, leaves, peels and other natural plants, and the specific preparation conditions refer to mechanical ball milling, hydrothermal reaction at a temperature of 80-200°C for 1 to 3 hours, and then heating to 600-1000°C under nitrogen protection for 1 to 3 hours. The mass ratio of natural calcium-containing substances to biomass materials is 0.5:1 to 3:1.

[0012] The specific crystal form of the calcium-based inducing agent refers specifically to a calcium oxide material whose crystal has a dominant crystal face of 111. When the main crystal face peak in the XRD spectrum is at a 2θ angle of 33.7, the 111 crystal face should be the dominant crystal face of the crystal, that is, Figure 1 The main peak position is the same. And it is required that the oxide is closely combined with the carbon element, and its microscopic infrared spectrum should be as follows Figure 2 shown.

[0013] A purification device for CaCl2 solution, such as Figure 3 As shown, it is mainly composed of two parts: a calcium chloride impurity removal induced crystallization pool and a calcium chloride impurity removal induced crystallization precipitation pool;

[0014] The calcium chloride impurity removal induced crystallization pool is a circular reactor with a thick upper part and a thin lower part. The calcium chloride impurity removal induced crystallization pool is designed with a constant temperature protection device. A local heating device is arranged in the mixing zone of the thin tube area at the bottom of the calcium chloride impurity removal induced crystallization pool. The local heating device occupies 30% of the area of ​​the mixing zone of the thin tube area and is used in conjunction with an inducer to improve the induced crystallization efficiency. A stirring motor is arranged in the calcium chloride impurity removal induced crystallization pool, a water inlet is arranged in the mixing zone of the thin tube area at the bottom, and a pipeline connected to the outer ring of the calcium chloride impurity removal induced crystallization precipitation pool is opened in the thick tube area at the top;

[0015] The calcium chloride impurity removal induced crystallization precipitation tank is a cylindrical annular reactor with a coarse outer surface and a fine inner surface. The ratio of the inner diameter of the outer ring of the reactor to the inner diameter of the inner ring is 10:1, and the outer ring and the inner ring are connected at the bottom; the outer ring is connected to the calcium chloride impurity removal induced crystallization precipitation tank through a pipeline inlet, and a mud discharge port is provided at the bottom of the outer ring; the inner ring is provided with a water outlet, and multiple inclined surfaces are arranged between the outer ring and the inner ring, with or without holes on the inclined surface, and the angle between the inclined surface and the horizontal plane is 30-60 degrees, so as to facilitate the crystallization precipitation and separation of the inducer and impurities.

[0016] A purification treatment method for a CaCl2 solution comprises the following steps: introducing a calcium chloride solution (containing sulfate impurities) with a mass concentration of 20% to 35% and a temperature of 10 to 85 DEG C into a calcium chloride impurity removal induced crystallization pool through a pipeline, adding an inducer (protection) in an amount of 0.5 g / L to 10 g / L, starting a stirring motor and a local heating device in the calcium chloride impurity removal induced crystallization pool, raising the temperature of the liquid to above 65 DEG C, maintaining the solution temperature, and reacting continuously for 2 to 4 hours, discharging the liquid from the outlet of the calcium chloride impurity removal induced crystallization pool into a calcium chloride impurity removal induced crystallization precipitation pool, wherein the calcium chloride impurity removal induced crystallization precipitation pool has a residence time of 2 hours, and the effluent can achieve the removal of impurities such as sulfate.

[0017] The natural calcium-containing material is first washed and dried, then crushed, crushed with a crusher, and subjected to a mechanochemical reaction with the crushed biomass material, ball-milled in a ball mill for 40 minutes, and then calcined in a tubular furnace under nitrogen protection for 3 hours. After washing with deionized water, a powdered inducer is obtained.

[0018] The beneficial effects of the present invention are as follows: the present invention utilizes shells and other materials and waste biomass as main materials, adopts certain pretreatment and roasting processes, prepares calcium-based inducing crystallization agent materials of specific crystal form, and designs and invents a special locally hot calcium chloride impurity removal inducing crystallization pool and a calcium chloride impurity removal inducing crystallization precipitation pool according to the characteristics of the material for treating calcium chloride solution. The CaCl2 solution treated by the agent material and treatment method proposed by the present invention can effectively reduce the sulfate ion concentration in the solution, and a qualified calcium chloride product can be obtained through subsequent evaporation and pelletizing.

[0019] The induced crystallization agent and equipment prepared by the present invention can be used for the removal of organic matter such as sulfate in CaCl2 wastewater, achieving zero discharge of calcium chloride wastewater in various types of enterprises, and has broad market prospects.

[0020] The preparation process of the invention is simple, the process is environmentally friendly, the cost is low, and the treatment of CaCl2 solution wastewater has a positive effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 It is the XRD reference spectrum of the crystallization inducing agent of the present invention.

[0022] Figure 2 It is a microscopic infrared spectrum of the crystallization inducing agent of the present invention, wherein (a) is a microscopic image of the sample, (b) is a mass density distribution diagram of the sample in the microscopic image, and (c) is an infrared spectrum of 9 sample points corresponding to a and b.

[0023] Figure 3 It is a schematic diagram of a calcium chloride impurity removal induction crystallization tank and a precipitation tank of the present invention.

[0024] Figure 4 It is a cross-sectional schematic diagram of a calcium chloride impurity removal induced crystallization precipitation tank of the present invention.

[0025] In the figure: 1 stirring motor, 2 induced crystallization zone, 3 induced crystallization pool water inlet, 4 heating zone, 5 sedimentation pool water inlet, 6 sedimentation pool inner pipe, 7 sedimentation pool drain, 8 inclined surface (inclined plate) between inner and outer rings, 9 mud discharge port. DETAILED DESCRIPTION

[0026] The specific implementation of the present invention is further described below in conjunction with the accompanying drawings and technical solutions.

[0027] Embodiment 1:

[0028] Wash and crush the shells, take 5g, add 3g of wood powder and put it into a ball mill, ball mill at 400r / min for 40 minutes to activate, then put the powder into a tube furnace, heat it to 850℃ under nitrogen protection, keep it warm for 2h, and cool it down to obtain crystallization inducer 1-1. Take 1L of calcium chloride wastewater from a certain enterprise, containing 30% calcium chloride and 0.7% sulfate, control the room temperature at about 25℃, add 1g of crystallization inducer 1-1, stir for 2h, add 3mg of polyaluminium chloride, coagulate for 25min, precipitate for 1h, take the supernatant and test the sulfate content, which is about 0.07%.

[0029] Embodiment 2:

[0030] Take 1L of calcium chloride wastewater from a certain enterprise, containing 30% calcium chloride and 0.7% sulfate. Control the reaction temperature to 85°C, add 1g of crystallization inducer 1-1, stir for 2h, add 3mg of polyaluminium chloride, coagulate for 25min, precipitate for 1h, and take the supernatant to test the sulfate content, which is about 0.06%.

[0031] Embodiment 3:

[0032] Take 3L of calcium chloride wastewater from a certain enterprise, containing 30% calcium chloride and 0.7% sulfate, put it into a local temperature rising reactor, heat it locally regularly, control the solution temperature in the reactor to be greater than 65°C, add 1g of crystallization inducer 1-1, stir for 2h, add 3mg of polyaluminium chloride, coagulate for 25min, precipitate for 1h (do not heat up during precipitation), take the supernatant to test the sulfate content, which is about 0.04%.

Claims

1. A purification agent material for CaCl2 solution, characterized in that: The purification agent material of the CaCl2 solution comprises an oxidant, a deoxidant and an inducer, wherein the mass ratio of the inducer, the oxidant and the deoxidant is 1:0.2-1:0.2-1; by adding the purification agent material, the removal of organic matter and dissolved oxygen in the CaCl2 solution is completed, and the removal of sulfate radicals is induced.

2. The CaCl2 solution purification agent material according to claim 1, characterized in that: The oxidant is calcium hypochlorite or hydrogen peroxide.

3. The CaCl2 solution purification agent material according to claim 1, characterized in that: The deoxidizer includes but is not limited to iron powder or ethanol.

4. The CaCl2 solution purification agent material according to claim 1, characterized in that: The inducer is prepared by taking natural calcium-containing substances as main materials and mixing them with biomass materials.

5. The CaCl2 solution purification agent material according to claim 4, characterized in that: The natural calcium-containing substances include shells, animal bones, and calcium carbonate minerals, and the biomass materials include wood, leaves, and fruit peels. The preparation conditions refer to mechanical ball milling, hydrothermal reaction at a temperature of 80-200°C for 1 to 3 hours, and then heating to 600-1000°C under nitrogen protection and keeping warm for 1 to 3 hours; wherein the mass ratio of natural calcium-containing substances to biomass materials is 0.5:1 to 3:

1.

6. A purification device for CaCl2 solution, characterized in that: It is mainly composed of two parts: calcium chloride impurity removal induced crystallization pool and calcium chloride impurity removal induced crystallization precipitation pool; The calcium chloride impurity removal induced crystallization pool is a circular reactor with a thick upper part and a thin lower part. The calcium chloride impurity removal induced crystallization pool is designed with a constant temperature protection device. A local heating device is arranged in the mixing zone of the thin tube area at the bottom of the calcium chloride impurity removal induced crystallization pool, and is used in conjunction with an inducer to improve the induced crystallization efficiency. A stirring motor is arranged in the calcium chloride impurity removal induced crystallization pool, a water inlet is arranged in the mixing zone of the thin tube area at the bottom, and a pipeline connected to the outer ring of the calcium chloride impurity removal induced crystallization precipitation pool is opened in the thick tube area at the top; The calcium chloride impurity removal induced crystallization precipitation tank is a cylindrical annular reactor with a coarse outer surface and a fine inner surface. The outer ring is connected to the inner ring at the bottom. The outer ring is connected to the calcium chloride impurity removal induced crystallization precipitation tank through a pipeline inlet, and a mud discharge port is provided at the bottom of the outer ring. The inner ring is provided with a water outlet, and multiple inclined surfaces are arranged between the outer ring and the inner ring to facilitate the crystallization precipitation and separation of the inducer and impurities.

7. The purification device according to claim 6, characterized in that: The inclined surface may be perforated or not, and the angle between the inclined surface and the horizontal plane is 30-60 degrees.

8. The purification device according to claim 6, characterized in that: The local heating device occupies 30% of the mixing area of ​​the thin tube region.

9. The purification device according to claim 6, characterized in that: The ratio of the inner diameter of the outer ring to the inner diameter of the inner ring of the reactor is 10:

1.

10. A method for purifying a CaCl2 solution, characterized in that: A calcium chloride solution with a mass concentration of 20% to 35% and a temperature of 10 to 85°C is introduced into a calcium chloride impurity removal induced crystallization pool through a pipeline, and the amount of inducer added is 0.5 g / L to 10 g / L. The stirring motor and local heating device in the calcium chloride impurity removal induced crystallization pool are started to raise the liquid temperature to above 65°C, and the solution temperature is maintained. The reaction is continued for 2 to 4 hours, and the liquid is discharged from the outlet of the calcium chloride impurity removal induced crystallization pool to the calcium chloride impurity removal induced crystallization precipitation pool. The residence time in the calcium chloride impurity removal induced crystallization precipitation pool is 2 hours, and sulfate radicals are removed from the effluent.

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