CN111689517B - Method for preparing potassium fluozirconate and co-producing polyaluminium chloride - Google Patents
Method for preparing potassium fluozirconate and co-producing polyaluminium chloride Download PDFInfo
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- CN111689517B CN111689517B CN202010473133.6A CN202010473133A CN111689517B CN 111689517 B CN111689517 B CN 111689517B CN 202010473133 A CN202010473133 A CN 202010473133A CN 111689517 B CN111689517 B CN 111689517B
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- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
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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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Abstract
The invention provides a method for preparing potassium fluozirconate and co-producing polyaluminium chloride, which can realize the preparation of the potassium fluozirconate and the production of the polyaluminium chloride by using hydrofluoric acid with lower concentration. Meanwhile, the acidolysis reaction is carried out at the temperature of 70-95 ℃, so that the volatilization loss of hydrogen fluoride is greatly reduced, the resources are saved, the environment is protected, the reaction process is more stable and controllable, and the operating environment is obviously improved. The filtrate produced in the preparation process can be used for preparing qualified polyaluminium chloride products, thereby avoiding the adverse effect on the environment caused by hydrochloric acid produced in the production process, realizing the comprehensive utilization of resources and having remarkable economic and social benefits.
Description
Technical Field
The invention belongs to the technical field of preparation of potassium fluozirconate, and particularly relates to a method for preparing potassium fluozirconate and co-producing polyaluminium chloride.
Background
The potassium fluozirconate is white needle crystal with a melting point of 840 ℃. Insoluble in water and insoluble in ammonia. Stable in air, does not absorb moisture and has hard crystal. The potassium fluozirconate has wide application, is mainly used for producing metal zirconium and other zirconium compounds, and can also be used for the atomic energy industry, the production of magnesium-zirconium alloy, aluminum-zirconium alloy, glass, ceramics and the like.
The most traditional preparation process of potassium fluozirconate is a potassium fluosilicate-zirconite sintering method, and because the process needs to sinter potassium fluosilicate and zirconite at high temperature for a long time, the process has high energy consumption, long production period, low productivity and poor operating environment, and is rarely adopted nowadays.
CN102874868B discloses a method for preparing potassium fluozirconate by using fluosilicic acid, which comprises the steps of firstly adding fluosilicic acid solution into a leaching tank, heating, then adding zirconium oxychloride with theoretical amount into the fluosilicic acid solution, filtering the fluosilicic acid solution obtained by leaching after heat preservation, washing and drying filter residue to obtain a white carbon black product, then adding sodium chloride with theoretical amount into a mixture of filtrate and first washing water to obtain sodium fluosilicate slurry, then filtering, washing and drying the obtained slurry to obtain sodium fluosilicate, then adding the filtrate obtained in the previous step into the potassium chloride solution with theoretical amount, reacting and filtering to obtain ointment, washing and drying the ointment to obtain the finished product. Although the raw materials used in the method are easy to obtain, the steps are complex, the product quality is poor, and the production efficiency is low.
CN110092417A discloses a method for preparing potassium fluozirconate, which takes zirconium dioxide, hydrofluoric acid and potassium hydroxide as raw materials to prepare the potassium fluozirconate. The byproduct obtained after the reaction is only water, and the target product of potassium fluozirconate is not dissolved in water, so that the potassium fluozirconate can be easily separated from the water.
One of the existing production processes of potassium fluozirconate is a hydrofluoric acid-zirconium oxychloride method, and as the production process of zirconium oxychloride which is a main raw material is complex and a large amount of hydrochloric acid is consumed in the production process, the product price is high and the adverse effect on the environment is generated. Therefore, a new process for preparing potassium fluorozirconate is still required to be developed.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a method for preparing potassium fluozirconate and co-producing polyaluminium chloride.
The invention provides a method for preparing potassium fluozirconate and co-producing polyaluminium chloride, which comprises the following steps:
s1: carrying out acidolysis reaction on hydrofluoric acid and zirconium oxide to obtain a fluorozirconic acid solution;
s2: adding potassium chloride into the fluozirconate solution obtained in the step S1 for reaction, filtering to obtain filtrate and filter cake, and washing and drying the filter cake to obtain potassium fluozirconate;
s3: and (4) adding lime into the filtrate obtained in the step (S2) for reaction, adding clay ore for neutralization, and obtaining the polyaluminum chloride after solid-liquid separation, evaporative concentration, alkalinity adjustment, polymerization and slaking.
According to some embodiments of the invention, in the step S1, the concentration of the hydrofluoric acid is 28-48%.
According to some embodiments of the present invention, in the step S1, the temperature of the acidolysis reaction is 70 to 95 ℃.
According to some embodiments of the invention, in step S1, the acidolysis reaction time is 6-8 h.
In step S1, performing an acidolysis reaction between hydrofluoric acid and zirconia to obtain a fluorozirconic acid solution, wherein the reaction formula is as follows:
ZrO 2 +6HF→H 2 F 6 Zr+2H 2 O。
according to some embodiments of the present invention, in step S2, the amount of potassium chloride added is 1.2 to 1.5 times the mass of zirconia.
According to some embodiments of the invention, the temperature of the reaction in step S2 is 30 to 50 ℃.
According to some embodiments of the invention, in step S2, the reaction time is 1-2 h.
In step S2, potassium chloride is added to the fluorozirconic acid solution to react, and the reaction formula is:
H 2 F 6 Zr+2KCl→K2ZrF 6 +2HCl。
according to some embodiments of the invention, in the step S3, the lime is added in an amount of 3-5% by mass of the filtrate.
According to some embodiments of the invention, in the step S3, the clay mineral is added in an amount of 0.2 to 0.25 times the mass of the filtrate.
In the step S3, in the step S,
adding lime into the filtrate obtained in the step S2 for reaction, wherein the reaction formula is as follows:
Ca(OH) 2 +2HF→CaF 2 +2H 2 O
adding clay ore for neutralization, wherein the reaction formula is as follows:
6HCl+Al 2 O 3 →2AlCl 3 +3H 2 O。
in step S3, the solid-liquid separation means that the material is subjected to filter pressing to obtain an aluminum chloride solution. The aluminum chloride solution is evaporated and concentrated until the concentration of alumina in the solution is higher than 10%. And adding the concentrated aluminum chloride solution into a reaction kettle, adding a sodium carbonate solution under strong stirring to adjust the alkalinity, and adjusting the pH value to 3.5-5.
The temperature of polymerization curing is 35-55 ℃, and the time is 1-2 h.
The method for preparing the potassium fluozirconate and co-producing the polyaluminium chloride according to the embodiment of the invention has at least the following technical effects:
in the prior art, the concentration of the used hydrofluoric acid is usually 55%, but the method provided by the invention can realize the preparation of the potassium fluozirconate and the production of the polyaluminium chloride by using the hydrofluoric acid with lower concentration, greatly reduces the dangerousness in the transportation, storage and use processes of the raw materials due to the reduction of the concentration of the hydrofluoric acid, and is beneficial to ensuring the safety of the production.
The method provided by the invention has the advantages that the acidolysis reaction is carried out at the temperature of 70-95 ℃, the volatilization loss of hydrogen fluoride is greatly reduced, the resources are saved, the environment is protected, the reaction process is more stable and controllable, and the operation environment is obviously improved.
The filtrate can be used for preparing qualified polyaluminium chloride products by pretreating the filtrate, thereby avoiding adverse effects on the environment due to hydrochloric acid generated in the production process, realizing comprehensive utilization of resources and having remarkable economic and social benefits.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention will be further described with reference to the examples, but the present invention is not limited to the examples.
Example 1
The potassium fluorozirconate and the polyaluminium chloride are prepared by the embodiment in a co-production way, and the specific steps are as follows:
s1: 1667kg of hydrofluoric acid with the concentration of 30 percent is added into the reactor, 500kg of zirconia is added under stirring, the temperature is heated to 70 ℃, and the reaction is carried out for 8 hours under heat preservation, thus obtaining fluozirconate solution;
s2: cooling the fluozirconic acid, adding 2410kg of 25 percent potassium chloride solution while stirring, controlling the reaction temperature at 30 ℃, continuing stirring for reaction for 1 hour after the addition is finished, and filtering, washing and drying the materials to obtain a potassium fluozirconate product;
s3: adding 3000kg of the filtrate after liquid-solid separation into a reactor, adding 90kg of lime into the reactor while stirring, continuing to stir for 0.5 hour, adding clay ore into the reactor, continuing to stir and react for 1 hour after the addition is finished, and then performing filter pressing on the materials to obtain an aluminum chloride solution.
Adding the aluminum chloride solution into an evaporator, evaporating and concentrating until the concentration of aluminum oxide in the solution reaches more than 10%, adding the concentrated aluminum chloride solution into a reaction kettle, adding a sodium carbonate solution under strong stirring to adjust the alkalinity, and continuing to perform heat preservation, curing and polymerization for 2 hours after the addition is finished to obtain a polyaluminum chloride product.
Example 2
The potassium fluorozirconate and the polyaluminium chloride are prepared by the embodiment in a co-production way, and the specific steps are as follows:
s1: 1250kg of hydrofluoric acid with the concentration of 40 percent is added into the reactor, 500kg of zirconia is added under stirring, the temperature is heated to 80 ℃, and the reaction is carried out for 7 hours under heat preservation, thus obtaining fluozirconate solution;
s2: cooling the fluozirconic acid, adding 2650kg of 25% potassium chloride solution while stirring, controlling the reaction temperature at 40 ℃, continuing stirring to react for 1.5 hours after the addition is finished, and filtering, washing and drying the materials to obtain a potassium fluozirconate product;
s3: adding 2000kg of the filtrate after the liquid-solid separation into a reactor, adding 80kg of lime into the reactor while stirring, continuing to stir for 0.5 hour, adding clay ore into the reactor, continuing to stir and react for 1 hour after the addition is finished, and then performing filter pressing on the materials to obtain an aluminum chloride solution.
Adding the aluminum chloride solution into an evaporator, evaporating and concentrating until the concentration of aluminum oxide in the solution reaches more than 10%, adding the concentrated aluminum chloride solution into a reaction kettle, adding a sodium carbonate solution under strong stirring to adjust the alkalinity, and continuing to perform heat preservation, curing and polymerization for 1.5 hours after the addition is finished to obtain the polyaluminum chloride product.
Example 3
The potassium fluorozirconate and the polyaluminium chloride are prepared by the embodiment in a co-production way, and the specific steps are as follows:
s1: 1050kg of hydrofluoric acid with the concentration of 48% is added into a reactor, 500kg of zirconia is added under stirring, the temperature is heated to 90 ℃, and the reaction is carried out for 6 hours under heat preservation, so as to obtain fluozirconate solution;
s2: cooling the fluozirconic acid, adding 2960kg of 25% potassium chloride solution while stirring, controlling the reaction temperature at 50 ℃, continuing stirring for reaction for 2 hours after the addition is finished, and filtering, washing and drying the materials to obtain a potassium fluozirconate product;
s3: adding 2000kg of the filtrate after the liquid-solid separation into a reactor, adding 100kg of lime into the reactor while stirring, continuing to stir for 0.5 hour, adding clay ore into the reactor, continuing to stir and react for 1 hour after the addition is finished, and then performing filter pressing on the materials to obtain an aluminum chloride solution.
Adding the aluminum chloride solution into an evaporator, evaporating and concentrating until the concentration of aluminum oxide in the solution reaches more than 10%, adding the concentrated aluminum chloride solution into a reaction kettle, adding a sodium carbonate solution under strong stirring to adjust the alkalinity, and continuing to perform heat preservation, curing and polymerization for 2 hours after the addition is finished to obtain a polyaluminum chloride product.
Example of detection
In this example, the product quality of the potassium fluorozirconate obtained in examples 1 to 3 was measured, and the results are shown in Table 1.
TABLE 1 Potassium fluorozirconate product quality
| Item (%) | Industrial grade | Example 1 | Example 2 | Example 3 |
| K 2 ZrF 6 | ≥98 | 98.6 | 98.8 | 98.7 |
| Si | ≤0.15 | 0.06 | 0.08 | 0.07 |
| Fe | ≤0.1 | 0.04 | 0.03 | 0.03 |
| Cl | ≤0.15 | 0.08 | 0.09 | 0.07 |
| H 2 O | ≤0.5 | 0.11 | 0.12 | 0.11 |
In this example, the quality of the polyaluminum chloride products prepared in examples 1 to 3 was also measured, and the results are shown in Table 2.
TABLE 2 polyaluminium chloride product quality
| Item | Industrial grade | Example 1 | Example 2 | Example 3 |
| Density (g/cm) 3 ) | ≥1.16 | 1.18 | 1.19 | 1.19 |
| Al 2 O 3 (％) | ≥10 | 10.5 | 10.8 | 10.7 |
| Degree of basicity (%) | 20-90 | 56 | 54 | 63 |
| Water-insoluble substance (%) | ≤0.2 | 0.12 | 0.15 | 0.11 |
| pH value | 3.5～5.0 | 3.9 | 4.3 | 4.1 |
| SO 4 (％) | ≤0.005 | 0.003 | 0.002 | 0.003 |
| Fe(％) | ≤0.005 | 0.002 | 0.003 | 0.003 |
Claims (7)
1. A method for preparing potassium fluozirconate and co-producing polyaluminium chloride is characterized by comprising the following steps:
s1: carrying out acidolysis reaction on hydrofluoric acid and zirconium oxide to obtain a fluorozirconic acid solution;
in the step S1, the concentration of the hydrofluoric acid is 28% -48%;
in the step S1, the temperature of the acidolysis reaction is 70-95 ℃;
s2: adding potassium chloride into the fluozirconate solution obtained in the step S1 for reaction, filtering to obtain filtrate and filter cake, and washing and drying the filter cake to obtain potassium fluozirconate;
s3: adding lime into the filtrate obtained in the step S2 for reaction, adding clay ore into the solution for neutralization, and obtaining polyaluminium chloride after solid-liquid separation, evaporative concentration, alkalinity adjustment and polymerization slaking;
in step S3, the evaporation concentration and the alkalinity adjustment specifically refer to: evaporating and concentrating the filtrate obtained after solid-liquid separation until the concentration of alumina in the solution is higher than 10%, adding the concentrated aluminum chloride solution into a reaction kettle, adding a sodium carbonate solution under strong stirring to adjust the alkalinity, and adjusting the pH to 3.5-5;
in step S3, the polymerization curing temperature is 35-55 ℃ and the time is 1-2 h.
2. The method as claimed in claim 1, wherein the acidolysis reaction is performed for 6 to 8 hours in step S1.
3. The method according to claim 1, wherein in step S2, the amount of potassium chloride added is 1.2 to 1.5 times the mass of zirconia.
4. The method of claim 1, wherein the temperature of the reaction in step S2 is 30 ℃ to 50 ℃.
5. The method of claim 4, wherein in step S2, the reaction time is 1-2 h.
6. The method according to claim 1, wherein in step S3, the lime is added in an amount of 3% to 5% by mass of the filtrate.
7. The method according to claim 1, wherein in step S3, the clay mineral is added in an amount of 0.2 to 0.25 times the mass of the filtrate.
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| CA2950328C (en) * | 2014-06-13 | 2022-12-06 | Geo Specialty Chemicals, Inc. | Method for making sulfated polyaluminum chloride (pacs) or polyaluminum chloride (pac) and pacs or pac made by same |
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