CN114604885B - Preparation method for preparing calcium chloride by using waste hydrochloric acid - Google Patents
Preparation method for preparing calcium chloride by using waste hydrochloric acid Download PDFInfo
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- CN114604885B CN114604885B CN202210411200.0A CN202210411200A CN114604885B CN 114604885 B CN114604885 B CN 114604885B CN 202210411200 A CN202210411200 A CN 202210411200A CN 114604885 B CN114604885 B CN 114604885B
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- calcium chloride
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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
- C01F11/20—Halides
- C01F11/24—Chlorides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a preparation method for preparing calcium chloride by using waste hydrochloric acid, which comprises the following steps: s1, mixing waste hydrochloric acid with the mass concentration of 20% and lime milk according to the mass ratio of 3-5: 3, adding the calcium chloride into an acid-soluble reaction tank, and reacting to produce liquid calcium chloride; s2, adding lime milk into the liquid calcium chloride obtained in the step S1 to neutralize and regulate the pH value to 8.5-9.5, adding 20-50 g/L of active magnetic powder according to the liquid calcium chloride during the neutralization, and then rapidly stirring for 30-50 min to precipitate impurities contained in the calcium chloride solution; and S3, performing pressure filtration on the product obtained in the step S2 by using a pressure filter, putting ion exchange resin into the obtained filtrate according to 40-70 g/L for treatment for 10-30 min, and then concentrating the treated filtrate by an evaporation system to obtain a liquid calcium chloride product. The invention can effectively improve the quality of the liquid calcium chloride product by improving the preparation process, thereby improving the resource utilization efficiency of the waste hydrochloric acid.
Description
Technical Field
The invention relates to the technical field of resource recycling, in particular to a preparation method for preparing calcium chloride by using waste hydrochloric acid.
Background
The construction of the project of the metal product waste acid liquid recycling centralized treatment is under comprehensive planning and implementation, and as for the situation of the project of the metal product waste acid liquid recycling centralized treatment at the present stage, because of the lack of a proprietary mature technology and related experience, the number of demonstration projects for reference is very small; also, the treatment of the metal product acid pickle is insufficient for professional teams and has limited experience.
Because the metal product waste acid liquor has wide sources and various types, not only has different properties, but also has different phase states, forms and components, the process method adopted by each metal product waste acid liquor treatment has certain difference, and if one process can only treat one metal product waste acid liquor, the operation cannot be carried out, and the process is not economical.
The preparation of calcium chloride by using waste hydrochloric acid is a preparation process for effectively utilizing waste hydrochloric acid, but the waste hydrochloric acid is often mixed with various other elements such as fluoride ions, and in the process of preparing calcium chloride from waste hydrochloric acid, ferric ions and fluoride ions are complexed to synthesize relatively stable hexafluoroferrate radicals which are easily carried into calcium chloride mother liquor in the production process, so that the quality of a liquid calcium chloride product is influenced.
Therefore, a preparation method capable of solving the above technical problems to improve the effect of preparing calcium chloride from waste hydrochloric acid is needed, so as to optimize the resource utilization of the waste hydrochloric acid.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method for preparing calcium chloride by using waste hydrochloric acid.
The technical scheme of the invention is as follows: a preparation method for preparing calcium chloride by using waste hydrochloric acid comprises the following steps:
s1, acid dissolution
Waste hydrochloric acid with the mass concentration of 20% and lime milk are mixed according to the mass ratio of 3-5: 3 adding the calcium chloride into an acid-soluble reaction tank, and reacting to produce liquid calcium chloride;
s2, neutralizing
Adding lime milk into the liquid calcium chloride obtained in the step S1 for neutralization to adjust the pH value to 8.5-9.5, adding 20-50 g/L of active magnetic powder according to the liquid calcium chloride in the period, and then rapidly stirring for 30-50 min to precipitate impurities contained in the calcium chloride solution;
s3, filter pressing
Performing filter pressing on the product obtained in the step S2 by using a filter press, putting ion exchange resin into the obtained filtrate according to 40-70 g/L for treatment for 10-30 min, and then concentrating the treated filtrate by using an evaporation system to obtain a liquid calcium chloride product;
because various other elements such as fluoride ions are often mixed in the waste hydrochloric acid, in the process of preparing calcium chloride from the waste hydrochloric acid, ferric ions and fluoride ions are complexed to form a relatively stable hexafluoroferrite acid radical, and the hexafluoroferrite acid radical is not converted into an iron hydroxide precipitate after neutralization reaction treatment and is then subjected to pressure filtration, so that the hexafluoroferrite acid radical is carried into a filtrate, and the hexafluoroferrite acid radical is gradually converted into the iron hydroxide precipitate under an alkaline condition, so that the quality of the obtained liquid calcium chloride is poor, in order to obtain high-quality liquid calcium chloride, the active magnetic powder is added in the neutralization stage of the step S2 to promote the removal of the iron ions in the calcium chloride solution, and meanwhile, a certain amount of ion exchange resin is added in the step S3, so that the high-quality liquid calcium chloride is obtained to the maximum extent while the production cost is controlled, and the resource utilization of the waste hydrochloric acid is promoted; by adopting the method for preparing calcium chloride by using the waste hydrochloric acid, high-quality liquid calcium chloride can be efficiently obtained, and the problems that the mother liquor of a calcium chloride product prepared by using the waste hydrochloric acid in the traditional process is yellow and the like can be effectively solved.
Further, the stirring speed of the rapid stirring in the step S2 is 150-200 r/min; the stirring speed range is adopted to enhance the mass transfer effect in the neutralization reaction, thereby improving the effect of removing the sediment of other impurities contained in the calcium chloride solution.
Further, the concentration in the step S3 is carried out by an evaporation system to a concentration of 25% + -3%.
Further, the preparation method of the active magnetic powder comprises the following steps:
1) Mixing magnet powder with a ferric iron solution, and then adjusting the pH value of a mixed system to 2.1-2.3;
2) Continuously stirring and slowly dropwise adding alkali liquor into the mixed system in the step 1) until the pH value of the mixed system is 4.6-4.8, and then carrying out microwave irradiation reaction for 5-30 min, wherein the microwave energy is 10-20W/kg, and the microwave frequency is 600-1100 MHz;
3) Filtering the mixed system obtained in the step 2) through a filter screen, and taking oversize products to obtain active magnetic powder;
the active magnetic powder prepared by the method promotes the generation of iron precipitates in the liquid calcium chloride through the active ferric hydroxide coated outside, so that the content of iron ions in the liquid calcium chloride is obviously reduced, and the problem of yellowing of the prepared liquid calcium chloride product is avoided; meanwhile, the active magnetic powder prepared by the method can quickly obtain the active magnetic powder with excellent use effect, and the active ferric hydroxide generated in a mixed system is promoted to be combined with the iron powder through microwave irradiation reaction, so that the high-quality active magnetic powder is obtained.
Further, the slowly dropping alkali liquor in the step 2) specifically comprises: slowly dripping alkali liquor into the mixed system in the step 1) at the speed of 1-3 s/drop, and by adopting the dripping speed, the condition that active iron hydroxide coated outside the prepared active magnetic powder is accumulated in a large amount due to over-speed addition, and the like, which influences the use effect of the active magnetic powder can be avoided.
Furthermore, the ion exchange resin is anion exchange resin, and the selected commercially available anion exchange resin can effectively adsorb residual iron ions in the liquid calcium chloride, so that the quality of the prepared liquid calcium chloride product is ensured.
Further, the ion exchange resin is subjected to a pretreatment comprising the steps of:
1) Adding the ion exchange resin into a potassium chloride solution with the mass concentration of 30% to soak for 8-14 h;
2) Washing the ion exchange resin obtained in the step 1) for 2-3 times by using 80% ethanol, and then adding the washed ion exchange resin into 70% ethanol at 50-60 ℃ for soaking for 2-4 h at constant temperature;
3) Adding deionized water with the temperature 5-10 ℃ lower than the temperature of the current mixing system into the mixing system in the step 2) until the mass concentration of ethanol in the mixing system is reduced from 70% to 40-50%, and after the temperature in the mixing system is reduced from 50-60 ℃ to 30-35 ℃, soaking the mixture in the current mixing system environment for 1-2 hours at constant temperature;
4) Repeating the step 3) for a plurality of times until the mass concentration of the ethanol in the mixed system is reduced to below 25 percent and the temperature is reduced to below 20 ℃;
5) Washing the ion exchange resin obtained in the step 2) with deionized water for several times, and then filtering to obtain pretreated ion exchange resin;
by pretreating the anion exchange resin by the method, the adsorption capacity of the anion exchange resin to iron ions can be improved under the same addition amount, and the multiple service life of the anion exchange resin is prolonged, so that the input cost of the anion exchange resin is reduced, and the production cost of preparing calcium chloride from waste hydrochloric acid is reasonably controlled.
Furthermore, the constant temperature soaking in the step 2) and the step 3) adopts a water bath temperature control mode to keep the temperature of the current mixed system environment, the water bath temperature control mode is accurate in temperature control, the condition of overlarge temperature fluctuation is avoided, the temperature control mode is not limited to the temperature control mode, and other temperature control modes can be selected.
The invention has the beneficial effects that:
(1) The preparation method for preparing calcium chloride by using the waste hydrochloric acid can effectively utilize the waste hydrochloric acid as a resource, improve the additional value of the waste hydrochloric acid and achieve the aims of energy conservation and environmental protection.
(2) According to the preparation method for preparing the calcium chloride by using the waste hydrochloric acid, the preparation method is improved, so that the problem that the liquid calcium chloride product cannot be normally sold due to yellowing of the liquid calcium chloride in the concentration process can be effectively solved, the quality of the liquid calcium chloride product can be effectively improved through the improvement of the preparation process, and the recycling efficiency of the waste hydrochloric acid is improved.
(3) According to the preparation method for preparing calcium chloride by using waste hydrochloric acid, the anion exchange resin is pretreated, so that the adsorption capacity of the anion exchange resin to iron ions can be improved under the condition of the same addition amount, the multiple service lives of the anion exchange resin are prolonged, the input cost of the anion exchange resin is reduced, and the production cost for preparing calcium chloride by using waste hydrochloric acid is reasonably controlled.
Drawings
FIG. 1 is a flow chart of the preparation method of calcium chloride from waste hydrochloric acid according to the present invention, wherein G-waste gas, W-waste water, N-noise and S-solid waste are used.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments thereof for better understanding the advantages of the invention.
Example 1
As shown in figure 1, the preparation method for preparing calcium chloride by using waste hydrochloric acid comprises the following steps:
s1, acid dissolution
Waste hydrochloric acid with the mass concentration of 20% and lime milk are mixed according to the mass ratio of 4:3, adding the calcium chloride into an acid-soluble reaction tank, and reacting to produce liquid calcium chloride; wherein, a small amount of hydrogen chloride tail gas is generated in the acid dissolution reaction process, the hydrogen chloride tail gas enters a spray absorption tower after being collected, liquid alkali is used for spray absorption, and the residual tail gas reaches the standard and is discharged;
s2, neutralizing
Adding lime milk into the liquid calcium chloride of step S1 for neutralization to adjust pH to 9.2, adding 40g/L active magnetic powder based on the liquid calcium chloride, and rapidly stirring at stirring rate of 180r/min for 40min to precipitate impurities contained in the calcium chloride solution, such as Fe 3+ 、Al 3+ Etc. form insoluble Fe (OH) 3 、Al(OH) 3 Precipitating;
the preparation method of the active magnetic powder comprises the following steps:
1) Mixing magnet powder with a ferric iron solution, and then adjusting the pH of the mixed system to 2.2;
2) Continuously stirring and slowly dripping alkali liquor into the mixed system in the step 1) at the speed of 2 s/drop until the pH value of the mixed system is 4.7, and then carrying out microwave irradiation reaction for 18min, wherein the microwave energy is 15W/kg, and the microwave frequency is 900MHz;
3) Filtering the mixed system obtained in the step 2) through a filter screen, and taking oversize products to obtain active magnetic powder;
s3, filter pressing
Performing filter pressing on the product obtained in the step S2 by using a filter press, performing magnetic separation on filter residues to recover active magnetic powder, putting the rest filter residues into solid waste, adding ion exchange resin into the obtained filtrate according to the proportion of 60g/L for treatment for 20min, and then concentrating the treated filtrate to the concentration of 25% by using an evaporation system (MVR evaporator) to obtain a liquid calcium chloride product;
wherein the ion exchange resin is a commercially available anion exchange resin, and the ion exchange resin is pretreated, wherein the pretreatment comprises the following steps:
1) Adding the ion exchange resin into a potassium chloride solution with the mass concentration of 30% to soak for 12h;
2) Washing the ion exchange resin obtained in the step 1) for 2 times by using ethanol with the mass concentration of 80%, then adding ethanol with the mass concentration of 70% at 55 ℃ for soaking for 3 hours at constant temperature, and keeping the temperature of the current mixed system environment by adopting a water bath temperature control mode;
3) Adding deionized water with the temperature 8 ℃ lower than the temperature of the current mixing system into the mixing system in the step 2) until the mass concentration of ethanol in the mixing system is reduced from 70% to 45%, reducing the temperature in the mixing system from 55 ℃ to 32 ℃, soaking for 1.5h in the environment of the current mixing system at constant temperature, maintaining the temperature of the environment of the current mixing system in a water bath temperature control mode, and adjusting the temperature of the water bath in a follow-up manner according to the temperature in the mixing system;
4) Repeating the step 3) for a plurality of times until the mass concentration of the ethanol in the mixed system is reduced to below 25 percent and the temperature is reduced to below 20 ℃;
5) Washing the ion exchange resin obtained in the step 2) with deionized water for 3 times, and then filtering to obtain the pretreated ion exchange resin.
Example 2
This example is substantially the same as example 1, except that in step S1, waste hydrochloric acid having a mass concentration of 20% and lime milk are mixed in a mass ratio of 1:1 is added into an acid-soluble reaction tank.
Example 3
This example is substantially the same as example 1, except that in step S1, waste hydrochloric acid having a mass concentration of 20% and lime milk are mixed in a mass ratio of 5:3, adding the mixture into an acid-soluble reaction tank.
Example 4
This example is substantially the same as example 1 except that in step S2, lime milk is added to the liquid calcium chloride in step S1 to adjust the pH to 8.5 by neutralization.
Example 5
This example is substantially the same as example 1 except that in step S2, lime milk is added to the liquid calcium chloride in step S1 to adjust the pH to 9.5 by neutralization.
Example 6
This example is substantially the same as example 1 except that in step S2, 20g/L of activated magnetic powder was added in terms of liquid calcium chloride.
Example 7
This example is substantially the same as example 1 except that 50g/L of activated magnetic powder was added in terms of liquid calcium chloride during step S2.
Example 8
This example is substantially the same as example 1 except that, in step S2, rapid stirring treatment was subsequently carried out at a stirring rate of 150r/min for 40min.
Example 9
This example is substantially the same as example 1 except that, in step S2, rapid stirring treatment was subsequently carried out at a stirring rate of 200r/min for 40min.
Example 10
This example is substantially the same as example 1, except that in the method for preparing the activated magnetic powder, 2) stirring is continuously carried out and alkali liquor is slowly added dropwise into the mixed system in the step 1) at a rate of 1 s/drop.
Example 11
This example is substantially the same as example 1, except that in step 2) of the method for preparing the activated magnetic powder, alkali solution was slowly added dropwise to the mixed system of step 1) at a rate of 3 s/drop with continuous stirring.
Example 12
This example is substantially the same as example 1 except that in step 2) of the method for preparing the reactive magnetic powder, a microwave irradiation reaction is performed for 5min, wherein the microwave energy is 10W/kg and the microwave frequency is 600MHz.
Example 13
This example is substantially the same as example 1 except that in step 2) of the method for preparing the activated magnetic powder, the reaction is performed for 30min by irradiation with a microwave having a microwave energy of 20W/kg and a microwave frequency of 1100MHz.
Example 14
This example is substantially the same as example 1 except that in step S3, 40g/L of the filtrate was treated with an ion exchange resin for 10min.
Example 15
This example is substantially the same as example 1 except that in step S3, 70g/L of the filtrate was treated with an ion exchange resin for 30min.
Example 16
This example is substantially the same as example 1, except that in step 1) of the pretreatment of the ion exchange resin, the ion exchange resin was immersed in a 30% by mass potassium chloride solution for 8 hours.
Example 17
This example is substantially the same as example 1, except that in step 1) of the pretreatment of the ion exchange resin, the ion exchange resin was immersed for 14 hours in a potassium chloride solution having a mass concentration of 30%.
Example 18
This example is substantially the same as example 1 except that, in steps 2) and 3) of the pretreatment of the ion exchange resin,
2) Washing the ion exchange resin obtained in the step 1) for 3 times by using ethanol with the mass concentration of 80%, then adding ethanol with the mass concentration of 70% to soak for 2 hours at the constant temperature of 50 ℃, and keeping the temperature of the current mixed system environment by adopting a water bath temperature control mode;
3) Adding deionized water with the temperature 5 ℃ lower than that of the current mixing system into the mixing system in the step 2) until the mass concentration of ethanol in the mixing system is reduced from 70% to 40%, and soaking the mixture in the environment of the current mixing system for 1h at constant temperature after the temperature in the mixing system is reduced from 50 ℃ to 30 ℃.
Example 19
This example is substantially the same as example 1 except that, in steps 2) and 3) of the pretreatment of the ion exchange resin,
2) Washing the ion exchange resin obtained in the step 1) for 3 times by using ethanol with the mass concentration of 80%, then adding ethanol with the mass concentration of 70% at 60 ℃ for soaking for 4 hours at constant temperature, and maintaining the temperature of the current mixed system environment by adopting a water bath temperature control mode;
3) Adding deionized water with the temperature of 10 ℃ lower than that of the current mixing system into the mixing system in the step 2) until the mass concentration of ethanol in the mixing system is reduced from 70% to 50%, and soaking the mixture in the environment of the current mixing system for 2 hours at constant temperature after the temperature in the mixing system is reduced from 60 ℃ to 35 ℃.
Examples of the experiments
Now, the liquid calcium chloride products prepared by the preparation methods of examples 1 to 21 were subjected to iron content measurement, and the influence of each parameter on the quality of the liquid calcium chloride products was investigated as follows:
explore the influence of the mixing quality ratio of different waste hydrochloric acid and lime cream on the iron content of the liquid calcium chloride product
Taking examples 1, 2 and 3 as examples, the iron content of the prepared liquid calcium chloride product was measured, and the results are shown in table 1 below:
table 1 iron content in liquid calcium chloride products of examples 1, 2, 3
As can be seen from the above Table 1, the mixing quality ratio of different waste hydrochloric acids and lime milk has no obvious influence on the quality of the prepared liquid calcium chloride product, and the addition of the lime milk is mainly determined according to the content of hydrochloric acid in the waste hydrochloric acid.
The influence of two different pH values on the iron content of the liquid calcium chloride product is researched
Taking examples 1, 4 and 5 as examples, the iron content of the prepared liquid calcium chloride product was measured, and the results are shown in the following table 2:
table 2 iron content in liquid calcium chloride products of examples 1, 4, 5
| Group of | Color of the product | Iron content |
| Example 1 | Colorless and colorless | 0.83×10 -6 |
| Example 4 | Colorless and colorless | 1.02×10 -6 |
| Example 5 | Colorless and colorless | 0.81×10 -6 |
As can be seen from table 2, different pH values for neutralization have certain influence on the quality of the prepared liquid calcium chloride product, and example 1 and example 5 are better in consideration of errors such as detection and environment, and it can be seen that the iron content in the liquid calcium chloride product is reduced to some extent by increasing the pH value for neutralization, but the pH value of example 5 is higher by comparing examples 1 and 5, but the iron content reduction of comparative example 1 has a tendency to be slowed down, so that example 1 is more suitable for the process production in consideration of economic factors and the like.
The influence of the addition amount of three different active magnetic powders on the iron content of the liquid calcium chloride product is researched
The iron content of the prepared liquid calcium chloride products was measured by taking examples 1, 6 and 7 as examples, and the results of comparative example 1, in which no active magnetic powder was added in step S2, were as shown in table 3 below, using example 1 as an example:
table 3 iron content in liquid calcium chloride products of examples 1, 6, 7
| Group of | Product color | Iron content |
| Example 1 | Colorless and colorless | 0.83×10 -6 |
| Example 6 | Colorless and colorless | 1.02×10 -6 |
| Example 7 | Colorless and colorless | 0.81×10 -6 |
| Comparative example 1 | Light yellow | 7.5×10 -6 |
As can be seen from table 3, different amounts of the added active magnetic powder have certain influence on the quality of the prepared liquid calcium chloride product, wherein example 7 is the best, but by comparing example 7 with example 1, example 7 adds more active magnetic powder but the iron content is not significantly reduced, so that example 1 is better in consideration of production cost, recovery of the active magnetic powder and other factors;
meanwhile, as can be seen from comparison of examples 1, 6 and 7 with comparative example 1, the liquid calcium chloride product prepared in comparative example 1 without the addition of the active magnetic powder is yellow, and the iron content is significantly increased, so that the production quality of the liquid calcium chloride product can be well controlled by adding the active magnetic powder, and the active magnetic powder can be subjected to magnetic separation and recycling after subsequent pressure filtration, and the production cost is controllable.
Explore the influence of four different rapid stirring treatment parameters on the iron content of the liquid calcium chloride product
The iron content of the prepared liquid calcium chloride products was measured by taking examples 1, 8 and 9 as examples, and the results are shown in the following table 4:
table 4 iron content in liquid calcium chloride products of examples 1, 8, 9
| Group of | Product color | Iron content |
| Example 1 | Colorless and colorless | 0.83×10 -6 |
| Example 8 | Colorless and colorless | 0.97×10 -6 |
| Example 9 | Colorless and colorless | 0.80×10 -6 |
As can be seen from table 4, different rapid stirring treatment parameters have certain influence on the prepared liquid calcium chloride product, wherein the liquid calcium chloride product prepared in example 9 is optimal, but the iron content difference between example 1 and example 9 is not large in consideration of actual production, and the liquid calcium chloride product is selected as required according to cost factors such as production power consumption.
Researches the influence of five different alkali liquor dropping rates on the using effect of the prepared active magnetic powder on the quality of the prepared liquid calcium chloride product,
taking examples 1, 10 and 11 as examples, the iron content of the prepared liquid calcium chloride product was measured, and the results are shown in the following table 5:
table 5 iron content in liquid calcium chloride products of examples 1, 10, 11
| Group of | Product color | Iron content |
| Example 1 | Colorless and colorless | 0.83×10 -6 |
| Example 6 | Colorless and colorless | 1.44×10 -6 |
| Example 7 | Colorless and colorless | 1.25×10 -6 |
It can be seen from table 5 above that different alkali liquor dropping rates have excellent and obvious effects on the use effect of the prepared active magnetic powder, wherein the use effect of the active magnetic powder prepared in example 1 is optimal.
The influence of six different microwave irradiation reactions on the using effect of the prepared active magnetic powder is explored
Taking examples 1, 12 and 13 as examples, the iron content of the prepared liquid calcium chloride product was measured, and meanwhile, based on the preparation method of the activated magnetic powder in example 1, the microwave irradiation treatment was removed, and the rest steps and parameters were unchanged, and set as comparative example 2, and the results are shown in table 6 below:
table 6 iron content in liquid calcium chloride products of examples 1, 12, 13
| Group of | Product color | Iron content |
| Example 1 | Colorless and colorless | 0.83×10 -6 |
| Example 12 | Colorless and colorless | 1.12×10 -6 |
| Example 13 | Colorless and colorless | 1.23×10 -6 |
| Comparative example 2 | Colorless and colorless | 2.07×10 -6 |
As can be seen from the above Table 6, different microwave irradiation reaction parameters have certain influence on the use effect of the prepared active magnetic powder, wherein the use effect of the active magnetic powder prepared in example 1 is optimal,
meanwhile, as can be seen from comparison of examples 1, 12 and 13 with comparative example 2, the use effect of the active magnetic powder is significantly reduced without microwave irradiation treatment, so that the active iron hydroxide generated in the mixed system can be effectively promoted to be combined with the iron powder through the microwave irradiation reaction under appropriate parameters, thereby obtaining high-quality active magnetic powder.
Researches the influence of the addition of seven different ion exchange resins on the iron content of the liquid calcium chloride product
The iron content of the prepared liquid calcium chloride products was measured by taking examples 1, 14 and 15 as examples, and the results are shown in the following table 7:
table 7 iron content in liquid calcium chloride products of examples 1, 14, 15
| Group of | Product color | Iron content |
| Example 1 | Colorless and colorless | 0.83×10 -6 |
| Example 14 | Colorless and colorless | 1.44×10 -6 |
| Example 15 | Colorless and colorless | 0.79×10 -6 |
As can be seen from the above Table 7, different amounts of the ion exchange resin added have certain influence on the prepared liquid calcium chloride product, wherein the treatment effect is optimal with the amount of the ion exchange resin added in example 15, but in consideration of the problems of actual production cost and the like, the amount of the ion exchange resin added in example 1 is less than 10g per liter compared with the ion exchange resin added in example 15, so that the ion exchange resin is selected as required according to the quality requirements of the liquid calcium chloride product to be processed in actual production.
The influence of eight different pretreatment parameters on the using effect of the prepared pretreated ion exchange resin is researched
Taking examples 1, 16 and 17 as examples, the prepared liquid calcium chloride product was measured for iron content, and based on the ion exchange resin pretreatment method of example 1, step 1) was removed, and the remaining parameters were unchanged, and recorded as comparative example 3, and the results are shown in table 8 below:
table 8 iron content in liquid calcium chloride products of examples 1, 16, 17
| Group of | Product color | Iron content |
| Example 1 | Colorless and colorless | 0.83×10 -6 |
| Example 16 | Colorless and colorless | 0.92×10 -6 |
| Example 17 | Colorless and colorless | 0.82×10 -6 |
| Comparative example 3 | Colorless and colorless | 1.10×10 -6 |
As can be seen from table 8, different soaking times of the potassium chloride solution have a certain effect on the prepared liquid calcium chloride product, and as the soaking time increases, the iron content reduction effect on the prepared liquid calcium chloride product is smaller, and the embodiment 1 is relatively more excellent in terms of the pretreatment time cost;
meanwhile, as can be seen from comparing examples 1, 16 and 17 with comparative example 3, the potassium chloride solution soaking of the ion exchange resin is not performed, and the iron ion adsorption effect of the ion exchange resin is significantly reduced, so that the potassium chloride solution soaking of the ion exchange resin can improve the iron ion adsorption effect of the ion exchange resin to a certain extent.
The influence of nine different pretreatment parameters on the using effect of the prepared pretreated ion exchange resin is researched
Taking examples 1, 18 and 19 as examples, the iron content of the prepared liquid calcium chloride product is respectively measured,
meanwhile, based on the ion exchange resin pretreatment method of example 1, steps 2) and 3) are removed, and the obtained product is recorded as comparative example 4 without changing parameters; based on the ion exchange resin pretreatment method of example 1, the steps 2) and 3) were replaced with ethanol of 55 ℃ at a concentration of 70% by mass, and the soaking time was the same, and it was recorded as comparative example 5,
the results are shown in table 9 below:
table 9 iron content in liquid calcium chloride products of examples 1, 18, 19
As can be seen from table 9, different ethanol cascade treatment methods have certain influence on the prepared liquid calcium chloride product, wherein the method is relatively optimal in example 19, but the total treatment time of example 1 is obviously shortened compared with example 19, the pretreatment time cost is comprehensively considered, and the method can be correspondingly selected according to the actual production condition;
meanwhile, as can be seen from comparing examples 1, 18 and 19 with comparative example 4, the iron ion adsorption effect is significantly reduced without performing the ethanol step treatment on the ion exchange resin, so that the iron ion adsorption effect of the ion exchange resin can be improved to a certain extent by performing the ethanol step treatment on the ion exchange resin;
it can be seen by comparing examples 1, 18, and 19 with comparative example 5 that iron ion adsorption effect is significantly reduced when ion exchange resin is not treated by the ethanol step treatment method of the present invention, so that iron ion adsorption effect of ion exchange resin can be effectively improved by the ethanol step treatment of the present invention compared with common ethanol soaking treatment.
Claims (7)
1. A preparation method for preparing calcium chloride by using waste hydrochloric acid is characterized by comprising the following steps:
s1, acid dissolution
Waste hydrochloric acid with the mass concentration of 20% and lime milk are mixed according to the mass ratio of 3-5: 3, adding the calcium chloride into an acid-soluble reaction tank, and reacting to produce liquid calcium chloride;
s2, neutralizing
Adding lime milk into the liquid calcium chloride obtained in the step S1 for neutralization to adjust the pH value to 8.5-9.5, adding 20-50 g/L of active magnetic powder according to the liquid calcium chloride in the period, and then rapidly stirring for 30-50 min to precipitate impurities contained in the calcium chloride solution;
the preparation method of the active magnetic powder comprises the following steps:
1) Mixing magnet powder with a ferric iron solution, and then adjusting the pH of a mixed system to 2.1-2.3;
2) Continuously stirring and slowly dripping alkali liquor into the mixed system in the step 1) until the pH value of the mixed system is 4.6-4.8, and then irradiating and reacting for 5-30 min by using microwave, wherein the microwave energy is 10-20W/kg, and the microwave frequency is 600-1100 MHz;
3) Filtering the mixed system obtained in the step 2) through a filter screen, and taking oversize products to obtain active magnetic powder;
s3, filter pressing
Performing filter pressing on the product obtained in the step S2 by using a filter press, putting ion exchange resin into the obtained filtrate according to 40-70 g/L for treatment for 10-30 min, and then concentrating the treated filtrate by using an evaporation system to obtain a liquid calcium chloride product;
wherein the ion exchange resin is subjected to a pretreatment comprising the steps of:
1) Adding the ion exchange resin into a potassium chloride solution with the mass concentration of 30% to soak for 8-14 h;
2) Washing the ion exchange resin obtained in the step 1) for 2-3 times by using 80% ethanol, and then adding the washed ion exchange resin into 70% ethanol at 50-60 ℃ for soaking for 2-4 h at constant temperature;
3) Adding deionized water with the temperature 5-10 ℃ lower than the temperature of the current mixing system into the mixing system in the step 2) until the mass concentration of ethanol in the mixing system is reduced from 70% to 40-50%, and soaking in the environment of the current mixing system for 1-2 hours after the temperature in the mixing system is reduced from 50-60 ℃ to 30-35 ℃;
4) Repeating the step 3) for a plurality of times until the mass concentration of the ethanol in the mixed system is reduced to below 25 percent and the temperature is reduced to below 20 ℃;
5) Washing the ion exchange resin obtained in the step 2) with deionized water for several times, and then filtering to obtain the pretreated ion exchange resin.
2. The method for preparing calcium chloride from waste hydrochloric acid as claimed in claim 1, wherein the stirring speed of the rapid stirring in step S2 is 150-200 r/min.
3. The method for preparing calcium chloride from waste hydrochloric acid as claimed in claim 1, wherein the concentration in step S3 is 25% ± 3% concentration by evaporation system.
4. The method for preparing calcium chloride from waste hydrochloric acid as claimed in claim 1, wherein the slow dropwise addition of alkali solution in step 2) of the method for preparing active magnetic powder is specifically: slowly dripping alkali liquor into the mixed system in the step 1) at the speed of 1-3 s/drop.
5. The method for preparing calcium chloride from waste hydrochloric acid as claimed in claim 1, wherein the liquid calcium chloride product is obtained by concentrating the treated filtrate to a concentration of 25% ± 3% by evaporation system.
6. The method for preparing calcium chloride from waste hydrochloric acid as claimed in claim 1, wherein the ion exchange resin is an anion exchange resin.
7. The method for preparing calcium chloride from waste hydrochloric acid as claimed in claim 1, wherein the constant temperature soaking in step 2) and step 3) of pretreating the ion exchange resin maintains the temperature of the current mixed system environment by means of water bath temperature control.
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