CN115652114B - Recycling process of thallium in thallium-containing solution - Google Patents
Recycling process of thallium in thallium-containing solution Download PDFInfo
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Abstract
Disclosure of the inventionA resource recovery process of thallium in a thallium-containing solution is provided, which comprises the following steps: and (3) adsorbing the thallium-containing solution by adopting mercaptan resin to remove thallium, cleaning the thallium adsorption resin adsorbed with thallium, eluting thallium in the resin, performing precipitation, impurity removal and reduction treatment on the eluted solution, and cleaning sponge thallium, melting and casting ingots to obtain metal thallium ingots. The resource recovery process of the invention takes the mercaptan resin as the thallium adsorption resin, and can adsorb the Tl in the solution with high selectivity + And Tl 3+ And the thallium in the solution is thoroughly separated, and other impurities can be avoided from being brought in, so that the thallium-containing eluted solution with high concentration and high purity can be obtained, and the thallium-containing eluent can be prepared into a metal thallium product with the purity of 99.99% through one-time impurity removal and reduction.
Description
Technical Field
The invention belongs to the field of thallium-containing wastewater treatment and metal recycling, and relates to a recycling process of thallium in a thallium-containing solution.
Background
Thallium is one of rare dispersion elements with the highest toxicity and harm at present and has bioaccumulation. Thallium and the compound thereof have mutagenicity, carcinogenicity and teratogenicity to organisms, and the toxicity to human beings is far greater than other heavy metal elements such As Hg, cd, pb, as, sb and the like. Thallium can enter human body through digestive tract, respiratory system and skin contact, and participate in human metabolism, causing continuous damage to human nervous system and central system. Thallium is widely distributed in the earth crust and is low in content, but can coexist with a plurality of elements in a plurality of ores, and when the ores are utilized, thallium enters the environment together with other elements. The thallium-involved industry mainly focuses on the industries of lead and zinc smelting, steel smelting, chemical production, pigment manufacturing and the like. Along with human activities, thallium environmental migration is accelerated, so that some soil environments and natural flow domains are polluted by thallium and thallium compounds.
Based on the characteristics of thallium, the thallium treatment technology is mainly classified into an electrochemical method, a chemical precipitation method, an ion exchange method, an adsorption method, a membrane method, a biochemical method and the like.
An electrochemical method: mainly adopts an electrocoagulation process and an electrocatalytic oxidation process, wherein the electrocoagulation process is characterized in that the cerium is adsorbed and coagulated by using high-activity polymeric metal hydroxide and polymers thereof generated by electrolysis, and the electrocatalytic oxidation process is to carry out Tl + I.e. oxidized to TI 3+ The removal is carried out, however, the process flow is long and a complicated pretreatment process is required.
Chemical precipitation method: with oxidative precipitation, adsorptive precipitation and sulfidic precipitation, using Tl (OH) 3 And Tl 2 S and the like have small solubility, oxidation neutralization or sulfuration precipitation is carried out, however, a large amount of medicament needs to be added, the effluent can only be stabilized at about 0.05mg/L generally, and when the thallium removal rate needs to be improved, the maximum medicament dosage is doubled, and in addition, the thallium is difficult to be stably reduced to below 0.005 mg/L.
Ion exchange method: cationic exchange resin can be used for Tl + Adsorption removal is carried out, but the thallium is difficult to be completely separated from other metals by the conventional resin under the influence of other metal ions such as Ca and Mg in water. Anion exchange resin can also be used for TlCl 4 - And Tl (SO) 4 ) 2 - The anionic complex of the trivalent thallium is removed by adsorption, but the ionic complex can only be used for the anionic complex of specific thallium, and the pretreatment condition is complexAnd the thallium removal rate is not high, and the purity of the obtained thallium chloride product is not high. In addition, the macroporous chelate resin containing sulfydryl in the prior art has poor absorption effect on thallium ions in wastewater, and thallium ions (Tl) cannot be absorbed 3+ ) Is completely separated from the waste water, and the macroporous chelating resin containing sulfydryl can also adsorb other metal ions to thallium ions (Tl) + ) The selectivity is poor, so that the thallium product with high purity is not obtained, and the resource utilization of thallium in the wastewater is also greatly limited.
An adsorption method: adsorption removal is performed by using an adsorbing material such as activated carbon or metal oxide, for example, thallium can be reduced to 0.02mg/L by using a nanoscale manganese ferrite adsorbent, but raw water needs to be oxidized first.
Membrane method: a nanofiltration membrane or a reverse osmosis membrane is mainly adopted, so that various salts such as thallium and the like, colloids, microorganisms, organic matters and the like can be intercepted, but the investment and operation cost is high, particularly when the salt content of raw water is high.
The biochemical method comprises the following steps: the microorganism metabolism is utilized to carry out indirect or direct oxidation-reduction reaction with pollutants, but the treatment effect is general and the impact resistance is poor.
In particular, the above-mentioned drawbacks make it difficult to achieve efficient recycling of thallium in the thallium-containing solution. Therefore, the recycling process of thallium in the thallium-containing solution, which is simple in process, convenient to operate, low in treatment cost and high in benefit, is obtained, and has important significance for thoroughly solving the thallium pollution problem and improving the thallium recycling utilization rate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a recycling process for thallium in a thallium-containing solution, which has the advantages of simple process, convenient operation, low treatment cost and high benefit.
In order to solve the technical problems, the invention adopts the technical scheme that:
a recycling technology of thallium in a thallium-containing solution comprises the following steps:
s1, adsorbing a thallium-containing solution by using thallium adsorption resin to remove thallium to obtain a thallium-removed solution; the thallium adsorption resin is mercaptan resin;
s2, carrying out first cleaning on the thallium-adsorbed resin by adopting a first cleaning solution to obtain first cleaning wastewater;
s3, eluting the thallium-adsorbed thallium adsorption resin by using an eluent to obtain an unloaded thallium adsorption resin and a thallium-containing eluent;
s4, adjusting the oxidation-reduction potential of the thallium-containing eluent to 0-200 mV, keeping the redox potential for more than 0.5h, adding a precipitator to carry out precipitation and impurity removal, and filtering to obtain waste residues and impurity-removed liquid;
s5, adding a reducing agent into the impurity-removed solution to perform a reduction reaction, and filtering to obtain sponge thallium and a reduced solution;
and S6, cleaning the sponge thallium, and melting the cast ingot to obtain a metal thallium ingot.
In the resource recycling process, in the step S1, the thallium adsorption resin is filled in an adsorption column, and a plurality of the adsorption columns are connected in series for adsorption; the flow speed of the thallium-containing solution through the adsorption column is 1 BV/h-40 BV/h; the thiol resin is a methyl thiol resin.
In the recycling process, the initial concentration of thallium in the thallium-containing solution in S1 is 0.005 mg/L-100 mg/L; the pH of the thallium containing solution is greater than 1; the thallium-containing solution further includes the following treatments before the adsorption: filtering the thallium-containing solution by using a filtering membrane with the aperture of 1 mu m to remove suspended matters in the solution; and discharging the liquid after the thallium is removed after the liquid reaches the standard.
In the resource recycling process, in S2, the first cleaning solution includes at least one of water, a sodium hydroxide solution with a mass concentration of 0.1% to 20%, a hydrochloric acid solution with a mass concentration of 0.1% to 3%, and a sulfuric acid solution with a mass concentration of 0.1% to 3%; the dosage of the first cleaning fluid is 1 BV-5 BV; the speed of the first cleaning solution is 1 BV/h-10 BV/h; the first cleaning wastewater is returned to the thallium-containing solution in step S1.
In the resource recycling process, in S3, the eluent includes at least one of a hydrochloric acid solution with a mass concentration of 1% to 36%, a sulfuric acid solution with a mass concentration of 1% to 50%, and a mixed solution of hydrochloric acid and chlorine salt; the mass concentration of the hydrochloric acid in the mixed solution of the hydrochloric acid/the chlorine salt is 0.1-5%, and the mass concentration of the chlorine salt is 10-30%; the chlorine salt is at least one of sodium chloride, potassium chloride, calcium chloride and magnesium chloride; the dosage of the eluent is 3 BV-10 BV; the speed of the eluent is 1 BV/h-10 BV/h.
In the above recycling process, in a further improvement, in S3, the unloaded thallium adsorbing resin further includes the following steps: cleaning the no-load thallium adsorption resin by using a second cleaning solution to obtain regenerated thallium adsorption resin and second cleaning wastewater; the second cleaning solution comprises at least one of water, a sodium hydroxide solution with the mass concentration of 0.1-5%, a hydrochloric acid solution with the mass concentration of 0.1-3% and a sulfuric acid solution with the mass concentration of 0.1-3%; the dosage of the second cleaning solution is 1 BV-5 BV; the speed of the second cleaning fluid is 1 BV/h-10 BV/h; the regenerated thallium adsorption resin returns to the step S1 and is used for adsorbing and removing thallium from the thallium-containing solution; the second cleaning wastewater is used as a solvent for preparing an eluent.
In the above recycling process, further improvement is made, in S4, an ORP regulator is used to regulate the oxidation-reduction potential of the thallium-containing eluent; the ORP regulator is at least one of sodium hydroxide, sodium carbonate, formic acid, hydrazine hydrate, ferrous sulfate, sodium sulfite and hydrogen peroxide.
In the above recycling process, a further improvement is that in S4, the precipitant is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and potassium carbonate; and in the precipitation and impurity removal treatment process, the pH value of the system is adjusted to be 8-12.
In the recycling process, the addition amount of the reducing agent in S5 is 1 to 1.5 times of the theoretical amount of reduced thallium; the reducing agent is at least one of formic acid, hydrazine hydrate, ferrous sulfate, sodium sulfite, zinc powder and aluminum powder; controlling the temperature to be 40-90 ℃ in the reduction reaction process; the time of the reduction reaction is 0.5 to 4 hours; the solution after reduction is returned to the thallium-containing solution in step S1.
In the recycling process, the sponge thallium is further improved by adopting water to clean the sponge thallium in the step S6; and covering AR-grade flake caustic soda on the surface of the sponge thallium in the process of melting and ingot casting, and controlling the temperature to be 350-500 ℃.
Compared with the prior art, the invention has the advantages that:
aiming at the defects of complex process, difficult operation, high treatment cost, difficult obtainment of high-purity thallium products and the like in the existing ion exchange method, the invention creatively provides a resource recovery process of thallium in a thallium-containing solution, uses mercaptan resin as thallium adsorption resin, and has the following advantages: (a) The method has good selectivity on thallium, is not influenced by elements such as calcium, magnesium and the like, has wide applicability, can thoroughly separate thallium from other impurity elements in the solution, has good adaptability to natural water bodies and industrial sewage with high salinity and low thallium concentration, and can also thoroughly separate thallium from thallium-containing water bodies with high salinity and low concentration; (b) The thallium adsorption removal rate is high and can reach more than 99.99 percent, and the thallium concentration in effluent (thallium-removed liquid) can be reduced to below 0.0001mg/L and is far lower than the discharge standard; (c) The regeneration is convenient, after the thallium adsorption resin is adsorbed and saturated, the regeneration can be realized only by using a small amount of acid and alkali with low concentration, the resin can be recycled, the treatment cost is favorably reduced, and the thallium-containing eluent obtained after elution has high concentration and high purity, so that a high-purity thallium product is favorably obtained; (d) Independent of thallium ion morphology for Tl + And Tl 3+ Can be directly adsorbed and removed, so that the pretreatment of the thallium-containing solution is hardly needed, and the process is simpler; (f) The adsorption capacity is large, the saturation time is long, so the treatment cost is low, and the treatment cost per ton is less than 0.5 yuan. On the basis, the thallium-containing eluent can be prepared into a metal thallium product with the purity of 99.99% only by once impurity removal and reduction, and compared with the existing thallium repeated precipitation and dissolution metallurgy process, the method greatly simplifies the recovery process, is more favorable for realizing thallium resource utilization, and obtains higher benefits. The resource recovery process of thallium in the thallium-containing solution comprises the following stepsThe method has the advantages of simple process, convenience in operation, low treatment cost, high benefit and the like, can recover thallium in different solutions, is convenient for realizing the resource utilization of thallium, and has high use value and good application prospect.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a flow chart of a recycling process of thallium in a thallium-containing solution in example 3 of the invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
In the following examples, materials and instruments used are commercially available unless otherwise specified. The adopted process is a conventional process, the adopted equipment is conventional equipment, and the obtained data are average values of more than three repeated experiments.
Example 1
Investigating the adsorption effect of different resins on different thallium-containing solutions
Firstly, thallium-containing solution is waste acid neutralization wastewater of a certain zinc smelting plant, the pH value is 6.8, and the solution is filtered by 1um for standby. Respectively taking 2g of thallium adsorption resin, mercapto resin, aminophosphonic acid resin, iminodiacetic acid resin, cation resin and anion resin, and respectively adding 100mL of thallium-containing solution. And (5) after shaking for adsorption for 6 hours, taking the liquid after thallium removal for analysis.
Wherein the thallium adsorbent resin is mercaptan resin, specifically methyl mercaptan resin (R-CH) 2 SH, wherein R is a polystyrene polymer); the sulfhydryl resin is macroporous chelating resin containing sulfhydryl.
The results obtained are shown in Table 1 below.
TABLE 1 adsorption Effect of different resins on thallium in thallium-containing solutions
Secondly, thallium-containing solution is waste acid neutralization wastewater of a certain smelting plant, the pH value is 7.1, and the thallium-containing solution is filtered by 1um for standby.
0.5g of thallium adsorption resin and 0.5g of mercapto resin are respectively added into 100mL of thallium-containing solution. And (5) after shaking for adsorption for 6 hours, taking the liquid after thallium removal for analysis.
The results obtained are shown in Table 2 below.
TABLE 2 adsorption Effect of thallium-adsorbing resin and mercapto resin on thallium in thallium-containing solution
Thirdly, thallium-containing solution is sewage acid neutralization wastewater of a certain smeltery, the pH is 7.1, and the solution is filtered by 1um for standby. Adding a reducing agent into the stock solution, stirring, reducing, and filtering for later use. 0.5g of thallium adsorption resin and mercapto resin are respectively added into 100mL of thallium-containing solution. And (5) after shaking for adsorption for 6 hours, taking the liquid after thallium removal for analysis.
The results obtained are shown in Table 3 below.
TABLE 3 adsorption Effect of thallium adsorbent resin and mercapto resin on thallium in the reduced thallium-containing solution
As can be seen from tables 1-3, the thallium adsorption resin (methyl mercaptan resin) adopted in the invention has a thallium adsorption rate as high as 99.99%, weak adsorption capacity for other ions, and good selectivity, and the thallium ion concentration in the effluent solution can be reduced to below 0.0001mg/L after the thallium adsorption resin (methyl mercaptan resin) is treated. In addition, the waste acid neutralizes thallium element in the wastewater to Tl + Mainly contains a small amount of Tl 3+ . Aminophosphonic acid resin, iminodiacetic acid resin and cation resin have certain adsorption capacity to thallium, but also have strong adsorption capacity to metal ions such as Ca, mg and the like. Although mercapto resin (macroporous chelate resin containing mercapto group) has thallium (Tl) pair + ) Has good adsorption effect, but also adsorbs zinc, has very small adsorption capacity of the sulfhydryl resin, has good adsorption effect only on low-concentration solution, and can not adsorb thallium ions (Tl) 3+ ). In addition, the adsorption capacity of the anion resin to thallium is weak.
Example 2:
investigating the adsorption effect of the thallium adsorption resin on different thallium-containing solutions
Firstly, thallium-containing solution is waste acid neutralized wastewater of a certain zinc smelting plant, the pH value is 6.7, the conductivity is 31700us/cm, and the thallium-containing solution is filtered by 1um for later use.
Adsorption at the 1 st stage: 50g of thallium adsorption resin is newly filled in the resin column, and the height of the filling layer is 27cm. The filtered thallium containing solution was then pumped continuously at a rate of 20BV/h and then sampled every 500mL for analysis.
The results obtained in stage 1 adsorption are shown in table 4 below.
TABLE 4 adsorption Effect of thallium adsorbent resin on different elements in thallium-containing solution
The average concentration of thallium in the obtained grade 1 thallium-removed solution is 0.00021mg/L, and the thallium adsorption rate is 99.992%.
Stage 2 adsorption: and (3) filling 50g of thallium adsorption resin into the resin column, pumping the grade-1 thallium-removed solution into the resin column to obtain a grade-2 thallium-removed solution, and sampling and analyzing.
The results obtained in stage 2 adsorption are shown in table 5 below.
TABLE 5 absorption effect of thallium adsorption resin in series on thallium-containing solution
Secondly, the thallium-containing solution is high-salinity wastewater of a certain zinc-germanium smelting plant, the pH value is 7.1, the potassium chloride content is about 200g/L, the sodium chloride content is about 100g/L, and the fluorine content is about 10g/L, and the thallium-containing solution is filtered by 1um for later use.
Stage 1 adsorption: and (3) filling 50g of thallium adsorption resin into the resin column, pumping the filtered thallium-containing solution into the resin column to obtain a grade-1 thallium-removed solution, and sampling and analyzing.
And (3) adsorption of the 2 nd stage: and (3) filling 50g of thallium adsorption resin into the resin column, pumping the 1-grade thallium-removed liquid into the resin column to obtain a 2-grade thallium-removed liquid, and sampling and analyzing.
The results obtained are shown in Table 6 below.
TABLE 6 adsorption Effect of thallium adsorbent resins on thallium-containing solutions after cascading
Thirdly, the thallium-containing solution is zinc sulfate solution of a certain zinc sulfate smelting plant, the pH value is 5.0, the zinc content is about 67.3g/L, and the thallium-containing solution is filtered by 1um for standby.
Adsorption at the 1 st stage: and (3) filling 50g of thallium adsorption resin into the resin column, pumping the filtered thallium-containing solution into the resin column to obtain a grade-1 thallium-removed solution, and sampling and analyzing.
And (3) adsorption of the 2 nd stage: and (3) filling 50g of thallium adsorption resin into the resin column, pumping the grade-1 thallium-removed solution into the resin column to obtain a grade-2 thallium-removed solution, and sampling and analyzing.
The results obtained are shown in Table 7 below.
TABLE 7 adsorption Effect of thallium adsorbent resins on thallium-containing solutions after cascading
Fourthly, the thallium-containing solution is desulfurization wastewater of a certain cold steel plant, is filtered by 1um, is pumped into a resin column filled with 25g of thallium adsorption resin, and continuously takes 4 liquid samples with thallium removed every 200mL for analysis.
The results obtained are shown in Table 8 below.
TABLE 8 adsorption Effect of thallium adsorbing resin on thallium in thallium containing solution
Fifthly, the thallium-containing solution is a natural water body, is filtered by 1um, is pumped into a resin column filled with 25g of thallium adsorption resin, and is continuously extracted every 200mL for 5 thallium-removed liquid samples to be analyzed.
The results obtained are shown in Table 9 below.
TABLE 9 adsorption Effect of thallium adsorbing resin on thallium in thallium containing solution
Example 3:
a resource recovery process of thallium in a thallium-containing solution, as shown in figure 1, comprises the following steps:
(1) The thallium-containing solution is waste acid neutralized wastewater of a certain zinc smelting plant, the pH value is 6-10, the thallium-containing solution is conveyed to a filter by a pump, and filtering treatment (precise filtering) is carried out by utilizing a filtering membrane with the aperture of 1 mu m to remove suspended matters in the solution.
(2) At a speed of 10BV/h, 70m 3 Continuously pumping the thallium-containing solution after filtration treatment into two adsorption columns (each adsorption column is filled with 25L of adsorption resin) which are connected in series and are filled with thallium adsorption resin (methyl mercaptan resin), and adsorbing Tl in the solution by using the thallium adsorption resin connected in series + And Tl 3+ And obtaining the thallium adsorption resin adsorbed with thallium and the thallium removal liquid. The crude liquid and the liquid sample after thallium removal were analyzed, and the results are shown in Table 10. As can be seen from Table 10, after the treatment with the thallium adsorbent resin, the adsorption removal rate of thallium in the thallium-containing solution is 99.991%, and the concentration of thallium in the solution after thallium removal is 0.00015mg/L, which meets the relevant discharge requirements and can be directly discharged.
TABLE 10 comparison of the contents of each component in the thallium-containing solution before and after adsorption
(3) After the resin adsorption is finished, respectively and continuously pumping 50L of sodium hydroxide solution with the mass concentration of 3% and 50L of clear water (namely taking the sodium hydroxide solution and the clear water as cleaning solution 1) into an adsorption column filled with the thallium adsorption resin at the speed of 5BV/h, cleaning the thallium adsorption resin with thallium adsorption (first cleaning) to obtain first cleaning wastewater (cleaning wastewater 1), returning the first cleaning wastewater to the thallium-containing solution in the step (1), and continuously adsorbing and removing thallium by using the thallium adsorption resin.
(4) 200L of sulfuric acid solution (eluent and eluant) with the mass concentration of 5% is continuously pumped into an adsorption column filled with the thallium adsorption resin at the flow rate of 3BV/h, and the thallium adsorption resin after the first cleaning is eluted to obtain no-load thallium adsorption resin and thallium-containing eluent, wherein the content of each component in the thallium-containing eluent is shown in Table 11. In the step, the obtained no-load thallium adsorption resin further comprises the following treatment: and continuously pumping the second cleaning solution into an adsorption column filled with the no-load thallium adsorbent resin at the speed of 5BV/h, and cleaning the no-load thallium adsorbent resin (second cleaning) to obtain regenerated thallium adsorbent resin and second cleaning wastewater, wherein the second cleaning solution is water and the using amount is 3BV. In the step, the regenerated thallium adsorption resin returns to the step (1) and is continuously used for adsorbing and removing thallium from the thallium-containing solution, and the second cleaning wastewater (cleaning wastewater 2) is continuously used for preparing eluent.
TABLE 11 concentration of each component in thallium-containing eluate
(5) Adjusting the oxidation-reduction potential (ORP) of the thallium-containing eluent to 189mV by adopting formic acid, keeping the ORP for more than 0.5h, adding sodium carbonate, adjusting the pH value to 10.1, precipitating, removing impurities, and filtering to obtain waste residues and impurity-removed liquid. And performing subsequent safe disposal on the waste residue.
(6) Slowly and dropwise adding hydrazine hydrate into the solution after impurity removal for carrying out reduction reaction according to the addition amount of 1.2 times of the theoretical amount of the reduced thallium, controlling the temperature of the solution after impurity removal in the reduction reaction process to be 85 ℃ and the time to be 2 hours, and filtering to obtain the sponge thallium and the solution after reduction. In this step, the solution after reduction is returned to the thallium-containing solution in step (1), and the treatment is repeated.
(7) Covering AR grade flake alkali on the surface of the sponge thallium, heating to 350-500 ℃ to melt and cast ingot to obtain a thallium ingot with the purity of 99.99%, wherein the product meets the requirements of YS/T224-2016 standard.
From the above results, it is understood that the thiol resin used as the thallium adsorbent resin in the present invention has the following advantages: (a) The method has good selectivity on thallium, is not influenced by elements such as calcium, magnesium and the like, has wide applicability, can thoroughly separate thallium from other impurity elements in the solution, has good adaptability to natural water bodies and industrial sewage with high salinity and low thallium concentration, and can also thoroughly separate thallium from thallium-containing water bodies with high salinity and low concentration; (b) The thallium adsorption removal rate is high and can reach more than 99.99 percent, and the thallium concentration in effluent (thallium-removed liquid) can be reduced to below 0.0001mg/L and is far lower than the discharge standard; (c) The regeneration is convenient, after the thallium adsorption resin is adsorbed and saturated, the regeneration can be realized only by using a small amount of acid and alkali with low concentration, the resin can be recycled, the treatment cost is favorably reduced, and the thallium-containing eluent obtained after elution has high concentration and high purity, so that a high-purity thallium product is favorably obtained; (d) Independent of thallium ion morphology for Tl + And Tl 3+ Can be directly adsorbed and removed, so that the pretreatment of the thallium-containing solution is hardly needed, and the process is simpler; (f) The adsorption capacity is large, the saturation time is long, so the treatment cost is low, and the treatment cost per ton is less than 0.5 yuan. On the basis, the thallium-containing eluent can be prepared into a metal thallium product with the purity of 99.99% only by once impurity removal and reduction, and compared with the existing thallium repeated precipitation and dissolution metallurgy process, the method greatly simplifies the recovery process, is more favorable for realizing thallium resource utilization, and obtains higher benefits. Therefore, the thallium-containing solution thallium recycling process has the advantages of simple process, convenience in operation, low treatment cost, high benefit and the like, thallium in different solutions can be recycled, thallium recycling is facilitated, the use value is high, and the application prospect is good.
The foregoing is merely a preferred embodiment of the invention, which is not to be construed as limiting the invention. Many possible variations and modifications of the present invention may be made by one of ordinary skill in the art using the above disclosure. Therefore, any simple modifications to the above embodiments according to the technical essence of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (10)
1. A resource recovery process of thallium in a thallium-containing solution is characterized by comprising the following steps:
s1, adsorbing a thallium-containing solution by using thallium adsorption resin to remove thallium to obtain a thallium-removed solution; the thallium adsorption resin is mercaptan resin; the thallium adsorption resin is filled in adsorption columns, and more than two adsorption columns are used for adsorption in a serial connection mode until the thallium adsorption removal rate reaches more than 99.99%; the thiol resin is methyl thiol resin;
s2, carrying out first cleaning on the thallium-adsorbed resin by adopting a first cleaning solution to obtain first cleaning wastewater;
s3, eluting the thallium-adsorbed thallium adsorption resin by using an eluent to obtain an unloaded thallium adsorption resin and a thallium-containing eluent;
s4, adjusting the oxidation-reduction potential of the thallium-containing eluent to 0-200 mV, keeping the oxidation-reduction potential for more than 0.5h, adding a precipitator to carry out precipitation and impurity removal, and filtering to obtain waste residues and impurity-removed liquid;
s5, adding a reducing agent into the impurity-removed solution to perform a reduction reaction, and filtering to obtain sponge thallium and a reduced solution; the addition amount of the reducing agent is 1 to 1.5 times of the theoretical amount of the reduced thallium;
and S6, cleaning the sponge thallium, and melting the cast ingot to obtain a metal thallium ingot.
2. The resource recovery process according to claim 1, wherein in the S1, the flow speed of the thallium-containing solution through the adsorption column is 1BV/h to 40BV/h.
3. The resource recovery process according to claim 2, wherein in the S1, the initial concentration of thallium in the thallium-containing solution is 0.005 mg/L-100 mg/L; the pH of the thallium containing solution is > 1; the thallium-containing solution further includes the following treatments before the adsorption: filtering the thallium-containing solution by using a filtering membrane with the aperture of 1 mu m to remove suspended matters in the solution; and discharging the liquid after the thallium is removed after the liquid reaches the standard.
4. A resource recovery process according to any one of claims 1 to 3, wherein in S2, the first washing liquid includes at least one of water, a sodium hydroxide solution having a mass concentration of 0.1% to 20%, a hydrochloric acid solution having a mass concentration of 0.1% to 3%, and a sulfuric acid solution having a mass concentration of 0.1% to 3%; the dosage of the first cleaning solution is 1 BV-5 BV; the speed of the first cleaning solution is 1 BV/h-10 BV/h; the first cleaning wastewater is returned to the thallium-containing solution in step S1.
5. A resource recovery process according to any one of claims 1 to 3, wherein in S3, the eluent comprises at least one of a hydrochloric acid solution having a mass concentration of 1% to 36%, a sulfuric acid solution having a mass concentration of 1% to 50%, and a mixed solution of hydrochloric acid/chlorine salt; the mass concentration of the hydrochloric acid in the mixed solution of the hydrochloric acid/the chlorine salt is 0.1-5%, and the mass concentration of the chlorine salt is 10-30%; the chlorine salt is at least one of sodium chloride, potassium chloride, calcium chloride and magnesium chloride; the dosage of the eluent is 3 BV-10 BV; the speed of the eluent is 1 BV/h-10 BV/h.
6. The resource recovery process according to claim 5, wherein in the S3, the no-load thallium adsorption resin further comprises: cleaning the no-load thallium adsorption resin by using a second cleaning solution to obtain regenerated thallium adsorption resin and second cleaning wastewater; the second cleaning solution comprises at least one of water, a sodium hydroxide solution with the mass concentration of 0.1-5%, a hydrochloric acid solution with the mass concentration of 0.1-3% and a sulfuric acid solution with the mass concentration of 0.1-3%; the dosage of the second cleaning solution is 1 BV-5 BV; the speed of the second cleaning solution is 1 BV/h-10 BV/h; the regenerated thallium adsorption resin returns to the step S1 and is used for adsorbing and removing thallium from the thallium-containing solution; the second cleaning wastewater is used as a solvent for preparing an eluent.
7. The resource recovery process according to any one of claims 1 to 3, wherein in S4, an ORP regulator is used to regulate the oxidation-reduction potential of the thallium-containing eluate; the ORP regulator is at least one of sodium hydroxide, sodium carbonate, formic acid, hydrazine hydrate, ferrous sulfate, sodium sulfite and hydrogen peroxide.
8. A resource recovery process according to any one of claims 1 to 3, wherein in S4, the precipitant is at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and potassium carbonate; and in the precipitation and impurity removal treatment process, the pH value of the system is adjusted to be 8-12.
9. A resource recovery process according to any one of claims 1 to 3, wherein in S5, the reducing agent is at least one of formic acid, hydrazine hydrate, ferrous sulfate, sodium sulfite, zinc powder, and aluminum powder; controlling the temperature to be 40-90 ℃ in the reduction reaction process; the time of the reduction reaction is 0.5 to 4 hours; the post-reduction solution is returned to the thallium-containing solution in step S1.
10. The resource recovery process according to any one of claims 1 to 3, wherein in S6, sponge thallium is washed with water; covering AR-level flake caustic soda on the surface of the sponge thallium in the melting and ingot casting process, and controlling the temperature to be 350-500 ℃.
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| FR2657863B1 (en) * | 1990-02-05 | 1992-08-28 | Metaleurop Sa | THALLIUM EXTRACTION PROCESS. |
| JP3901572B2 (en) * | 2002-04-25 | 2007-04-04 | 株式会社タクマ | Thallium-containing liquid treatment system |
| AR054096A1 (en) * | 2004-11-12 | 2007-06-06 | Monsanto Technology Llc | RECOVERY OF NOBLE METALS OF WATER PROCESS CURRENTS AND PREPARATION PROCESS OF N- (PHOSPHONOMETIL) -GLYCINE |
| WO2012143394A1 (en) * | 2011-04-20 | 2012-10-26 | Solvay Sa | Method for recovery of thallium from an aqueous solution |
| JP6450681B2 (en) * | 2013-08-23 | 2019-01-09 | 株式会社Adeka | One-part curable resin composition |
| EP3214137B1 (en) * | 2014-10-29 | 2019-10-23 | Kaneka Corporation | Resin-modifying particles and vinyl chloride resin composition containing same |
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