CN111910082A - Method for recovering noble metal from strong acid waste liquid - Google Patents
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- CN111910082A CN111910082A CN202010894353.6A CN202010894353A CN111910082A CN 111910082 A CN111910082 A CN 111910082A CN 202010894353 A CN202010894353 A CN 202010894353A CN 111910082 A CN111910082 A CN 111910082A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B11/00—Obtaining noble metals
- C22B11/04—Obtaining noble metals by wet processes
- C22B11/042—Recovery of noble metals from waste materials
- C22B11/048—Recovery of noble metals from waste materials from spent catalysts
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Abstract
The invention provides a method for recovering noble metals from strong acid waste liquid, which adopts metal ion adsorbent to carry out staged chelating and settling treatment on filtrate of the strong acid waste liquid, wherein the chelating pH values of different stages are 1-3, 3-5 and 5-7 respectively, different complexing agents are adopted to carry out matched settling treatment in different stages, and the mixture with high noble metal content is obtained by carrying out high-temperature ashing after collecting sediments, collecting ashed components, dissolving and removing impurities by using acid liquor and then carrying out reduction. The recovery method is simple, does not need to consume a large amount of energy, does not produce secondary pollution to the waste liquid, and has good application prospect.
Description
Technical Field
The invention relates to the technical field of waste liquid treatment, in particular to a method for recovering noble metals from strong acid waste liquid.
Background
Along with the application and popularization of the flue gas denitration technology in China, the importance of the SCR catalyst is gradually known, under the conditions of the prior art, the SCR technology is stable in operation, good in denitration performance, low in ammonia escape and the like, and is widely applied, because the SCR catalyst works in a high-temperature, high-dust and high-pollution environment for a long time, after the SCR catalyst is operated for a long time, the surface of the SCR catalyst is covered by flue gas and dust, the catalytic effect of the SCR catalyst is influenced, meanwhile, a large amount of toxic and harmful components in the flue gas can be enriched on the surface of the catalyst, the catalyst is poisoned, and the SCR catalyst needs to be activated and regenerated regularly.
The conventional means for activating and regenerating is to soak the SCR catalyst in an acid solution for acid washing and stirring, so that on one hand, the covering on the surface of the SCR catalyst can be removed, and on the other hand, the active ingredients in the SCR catalyst can be activated again under acidic conditions.
However, the active ingredients in the SCR catalyst contain precious metals, such as silver, platinum and palladium, and during the activation process, trace amounts of precious metals are dissolved in the acid solution, but because the amount of the dissolved precious metals is too small, the yield and the return are not in proportion by directly using the conventional precious metal recovery process. Therefore, a method for recovering trace precious metals from waste liquid is needed.
Disclosure of Invention
In view of the above, the present invention provides a method for recovering precious metals from a strongly acidic waste liquid after activation of an SCR catalyst.
The technical scheme of the invention is realized as follows: the invention provides a method for recovering noble metals from strong acid waste liquid, in particular to a method for recovering noble metals from strong acid waste liquid containing trace noble metals, which comprises the following steps:
step one, carrying out primary filtration on the strong acid waste liquid, and taking a first filtrate;
step two, adding a metal ion adsorbent into the first filtrate obtained in the step one, adjusting the pH value to 1-3, adding a first complexing agent, stirring at normal temperature, stirring for reaction for 0.5-1.5h, and filtering to obtain first filter residue and second filtrate;
step three, adding a metal ion adsorbent into the second filtrate obtained in the step two, adjusting the pH value to 3-5, adding a second complexing agent, stirring at normal temperature, stirring for reaction for 0.5-1.5h, and filtering to obtain second filter residue and third filtrate;
step four, adding a metal ion adsorbent into the third filtrate obtained in the step three, adjusting the pH value to 5-7, adding a third complexing agent, stirring at normal temperature, stirring for reaction for 0.5-1.5h, and filtering to obtain third filter residue and fourth filtrate;
step five, combining the first filter residue, the second filter residue and the third filter residue, then ashing, dissolving the ashed components with dilute hydrochloric acid, and then filtering to obtain a fourth filter residue;
and step six, keeping the fourth filter residue at the temperature of 350-400 ℃ in a hydrogen atmosphere, and reacting for 0.5-1.5h to obtain a noble metal mixture.
In the technical scheme, the ashing operation can effectively remove organic components and retain metal components and inorganic salts, and dilute hydrochloric acid can dissolve active base metals and inorganic salts so as to retain precious metal components.
On the basis of the technical scheme, preferably, the method further comprises a seventh step of washing the precious metal mixture obtained in the sixth step with a sodium hydroxide solution, filtering, washing the filter residue with water to be neutral to obtain a fifth filter residue, and washing with sodium hydroxide to remove impurities, such as silicate, which cannot be removed by partial acid washing, so as to further improve the purity of the precious metal mixture.
On the basis of the technical scheme, preferably, the metal ion adsorbent is chitosan-modified magnesium-aluminum hydrotalcite nano powder, and the preparation method comprises the following steps: respectively mixing chitosan and magnesium-aluminum hydrotalcite, adding the mixture into 5 wt% oxalic acid solution, mixing, stirring and dissolving, heating to 70-80 ℃, adding toluene diisocyanate, keeping the temperature, stirring and reacting for 0.5-1h, cooling to 20-30 ℃ after the reaction is finished, filtering, taking the obtained filter cake as a product, drying the filter cake at 50-60 ℃, and mechanically ball-milling the dried product to obtain chitosan-modified magnesium-aluminum hydrotalcite nano powder, wherein the chitosan: aluminum magnesium hydrotalcite: oxalic acid: the mass ratio of the toluene diisocyanate is 1: (2-3): (0.5-1): (10-15).
The obtained metal ion adsorbent in the technical scheme can chelate metal ions in waste liquid, and simultaneously has different chelating effects on different metal ions under different pH values, so that all the metal ions can be chelated and adsorbed as far as possible by adjusting the pH value.
On the basis of the technical scheme, preferably, the chitosan is sodium dodecyl sulfate graft modified chitosan, and the preparation method comprises the following steps: dissolving chitosan in 2 wt% acetic acid to obtain a chitosan acetic acid solution, dissolving sodium dodecyl sulfate in water, heating to 50-60 ℃, stirring until the solution is dissolved to obtain a sodium dodecyl sulfate solution with the weight percentage of 3-5%, dropwise adding the chitosan acetic acid solution into the sodium dodecyl sulfate solution, stirring and reacting for 2-3h at the temperature of 50-60 ℃, cooling to 20-30 ℃ to obtain a mixed solution, adjusting the pH value of the mixed solution to 6.5-7.5, filtering, washing and drying to obtain the sodium dodecyl sulfate graft modified chitosan.
The modified chitosan is adopted to ensure that the chitosan still has good stability under the strong acid condition, and the grafted sodium dodecyl sulfate can have stronger chelating effect on cations.
On the basis of the technical scheme, preferably, the chitosan: acetic acid: the mass ratio of the sodium dodecyl sulfate is 1: (1-2): (1-2).
On the basis of the above technical solution, preferably, in the second step, the first complexing agent is EDTA or DPTA.
On the basis of the above technical solution, preferably, in step three, the second complexing agent is STPP or HEDP.
On the basis of the above technical solution, preferably, in step four, the third complexing agent is citric acid or tartaric acid.
On the basis of the above technical scheme, preferably, in the second step, 0.4-0.8g of metal ion adsorbent is added to every 1L of the first filtrate, and 0.3-0.5g of first complexing agent is added to every 1L of the first filtrate.
On the basis of the technical scheme, preferably, in the third step, 0.3-0.7g of metal ion adsorbent is added into every 1L of second filtrate, and 0.2-0.4g of second complexing agent is added into every 1L of second filtrate.
On the basis of the above technical scheme, preferably, in the fourth step, 0.2-0.6g of metal ion adsorbent is added to every 1L of third filtrate, and 0.1-0.3g of second complexing agent is added to every 1L of third filtrate.
On the basis of the above technical scheme, preferably, in the fifth step, the ashing temperature is 400-.
On the basis of the technical scheme, preferably, the strong acid waste liquid is generated after the precious metal SCR catalyst is subjected to acid washing and activation.
On the basis of the above technical scheme, preferably, the first filter residue obtained in the step two can be used as the metal ion adsorbent in the step two of the process step for recovering the noble metal for the second time after being dried, and the metal ion adsorbent in the step two can be reused for 3 times at most.
On the basis of the above technical scheme, preferably, the second filter residue obtained in the third step can be dried and then used as the metal ion adsorbent in the third step of the process step of recovering the precious metal for the second time, and the metal ion adsorbent in the third step can be reused for at most 2 times.
Compared with the prior art, the method for recovering the noble metal from the strongly acidic waste liquid has the following beneficial effects:
(1) the invention provides a method for recovering noble metals from strongly acidic waste liquid, which comprises the steps of carrying out chelation and sedimentation on noble metal ions in the waste liquid by using a specific metal ion adsorbent, carrying out chelation and sedimentation on the corresponding metal ion adsorbent and different complexing agents under different pH conditions, and chelating most of noble metals in the waste liquid as much as possible;
(2) according to the preparation method, the Mg-Al hydrotalcite nano powder modified by chitosan is used as a metal ion adsorbent, the Mg-Al hydrotalcite nano powder has a good chelating effect under a strong acid condition, and meanwhile, in order to overcome the problem that the grafted chitosan is poor in stability under the strong acid condition, the grafted chitosan is subjected to grafting modification, so that the grafted chitosan still has good stability under the acid condition, and meanwhile, the grafted chitosan has a better adsorption effect on cations, and the chelating and settling effects on noble metal ions are further improved.
(3) The recovery method is simple, and the mixture with high noble metal content can be obtained by carrying out staged chelating adsorption and sedimentation on the waste liquid, collecting sediments and then carrying out simple ashing, impurity dissolution and reduction treatment.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The strongly acidic waste liquid treated in the following examples is a pickling waste liquid of a precious metal SCR catalyst, the catalyst system comprises Pt, Pd and Ag, and a part of alkaline earth metal, and the pH of the corresponding waste liquid is 1.2.
Example 1
Preparing a metal ion adsorbent:
weighing 100g of chitosan and 200g of magnesium-aluminum hydrotalcite, weighing 50g of oxalic acid to prepare 1kg of 5 wt% oxalic acid solution, mixing the chitosan, the magnesium-aluminum hydrotalcite and the oxalic acid solution, stirring until the mixture is dissolved, heating to 70 ℃, weighing 1kg of toluene diisocyanate, slowly adding the toluene diisocyanate into the system, keeping the temperature, stirring and reacting for 30min, cooling to 20 ℃ after the reaction is finished, filtering to obtain a target product, drying a filter cake at 50 ℃, and performing mechanical ball milling on the dried product to obtain chitosan modified magnesium-aluminum hydrotalcite nano powder serving as a metal ion adsorbent.
And (3) recovering precious metals:
taking 100L of strong acid waste liquid, filtering off ash residues on the surface of a catalyst in the acid washing process, collecting filtrate, weighing 80g of metal ion adsorbent, adding the metal ion adsorbent, mixing and stirring uniformly at normal temperature, adding hydrochloric acid and a sodium hydroxide solution, adjusting the pH value to 1.0, adding 50g of EDTA, stirring and reacting for 0.5h at normal temperature, filtering to obtain a first filter residue and a second filtrate, adding 70g of metal ion adsorbent into the second filtrate, mixing and stirring uniformly at normal temperature after adding, adjusting the pH value to 3.0 by adding hydrochloric acid and a sodium hydroxide solution, adding 40g of STPP, stirring and reacting for 0.5h at normal temperature, filtering to obtain a second filter residue and a third filtrate, adding 60g of metal ion adsorbent into the third filtrate, mixing and stirring uniformly at normal temperature after adding, adjusting the pH value to 5.0 by adding hydrochloric acid and a sodium hydroxide solution, adding 30g of citric acid, stirring and reacting for 0.5h at normal temperature, filtering to obtain a third filter residue and a fourth filter liquid, combining the first filter residue, the second filter residue and the third filter residue, carrying out ashing for 3 hours at 400-: and (3) after ashing, filtering to obtain filter residue, and reducing the filter residue for 30min at 350 ℃ in a hydrogen atmosphere to obtain a noble metal mixture.
Example 2
Preparing a metal ion adsorbent:
preparing lauryl sodium sulfate graft modified chitosan: weighing 100g of chitosan, dissolving the chitosan in 5L of acetic acid with the mass concentration of 2%, stirring and dissolving to obtain a chitosan acetic acid solution, dissolving 100g of lauryl sodium sulfate in 3200ml of water, heating to 50 ℃, stirring and dissolving to obtain a lauryl sodium sulfate solution, dropwise adding the chitosan acetic acid solution into the lauryl sodium sulfate solution, keeping the temperature at 50 ℃, stirring and reacting for 2 hours, after the reaction is finished, cooling to 20 ℃, dropwise adding a sodium hydroxide solution, adjusting the pH value to 6.5, filtering to obtain filter residues, washing the filter residues with 100ml of water for three times, drying the filter residues, crushing and sieving by a 100-mesh sieve to obtain the lauryl sodium sulfate graft-modified chitosan.
Weighing 100g of sodium dodecyl sulfate graft-modified chitosan and 230g of magnesium aluminum hydrotalcite, weighing 60g of oxalic acid to prepare 1.2kg of 5 wt% oxalic acid solution, mixing the sodium dodecyl sulfate graft-modified chitosan, the magnesium aluminum hydrotalcite and the oxalic acid solution, stirring until the mixture is dissolved, heating to 72 ℃, weighing 1.1kg of toluene diisocyanate, slowly adding the toluene diisocyanate into the system, keeping the temperature and stirring for reaction for 40min, cooling to 22 ℃ after the reaction is finished, filtering to obtain a target product, drying a filter cake at 53 ℃, performing mechanical ball milling on the dried product to obtain chitosan-modified magnesium aluminum hydrotalcite nano powder serving as a metal ion adsorbent.
And (3) recovering precious metals:
taking 100L of strong acid waste liquid, filtering off ash residues on the surface of a catalyst in the acid washing process, collecting filtrate, weighing 70g of metal ion adsorbent, adding the metal ion adsorbent, mixing and stirring uniformly at normal temperature, adding hydrochloric acid and sodium hydroxide solution, adjusting the pH to 2.0, adding 40g of DPTA, stirring and reacting for 1h at normal temperature, filtering to obtain a first filter residue and a second filtrate, adding 60g of metal ion adsorbent into the second filtrate, mixing and stirring uniformly at normal temperature after adding, adjusting the pH to 4.0 by adding hydrochloric acid and sodium hydroxide solution, adding 30g of HEDP, stirring and reacting for 1h at normal temperature, filtering to obtain a second filter residue and a third filtrate, adding 50g of metal ion adsorbent into the third filtrate, mixing and stirring uniformly at normal temperature, adjusting the pH to 6.0 by adding hydrochloric acid and sodium hydroxide solution, adding 20g of tartaric acid, stirring and reacting for 1h at normal temperature, filtering to obtain a third filter residue and a fourth filter liquid, combining the first filter residue, the second filter residue and the third filter residue, carrying out ashing for 2 hours at 400-: and (3) after ashing, filtering to obtain filter residue, and reducing the filter residue at 360 ℃ for 40min in a hydrogen atmosphere to obtain a noble metal mixture.
Example 3
Preparing a metal ion adsorbent:
preparing lauryl sodium sulfate graft modified chitosan: weighing 100g of chitosan, dissolving the chitosan in 10L of acetic acid with the mass concentration of 2%, stirring and dissolving to obtain a chitosan acetic acid solution, dissolving 200g of lauryl sodium sulfate in 3800ml of water, heating to 60 ℃, stirring and dissolving to obtain a lauryl sodium sulfate solution, dropwise adding the chitosan acetic acid solution into the lauryl sodium sulfate solution, keeping the temperature at 60 ℃, stirring and reacting for 3 hours, cooling to 30 ℃ after the reaction is finished, dropwise adding a sodium hydroxide solution, adjusting the pH value to 7.5, filtering to obtain filter residue, washing the filter residue with 100ml of water for three times, drying the filter residue, crushing and sieving by a 100-mesh sieve to obtain the lauryl sodium sulfate graft-modified chitosan.
Weighing 100g of sodium dodecyl sulfate graft-modified chitosan and 240g of magnesium aluminum hydrotalcite, weighing 80g of oxalic acid to prepare 1.6kg of 5 wt% oxalic acid solution, mixing the sodium dodecyl sulfate graft-modified chitosan, the magnesium aluminum hydrotalcite and the oxalic acid solution, stirring until the mixture is dissolved, heating to 76 ℃, weighing 1.3kg of toluene diisocyanate, slowly adding the toluene diisocyanate into the system, carrying out heat preservation and stirring reaction for 50min, cooling to 25 ℃ after the reaction is finished, filtering to obtain a target product, drying a filter cake at 55 ℃, carrying out mechanical ball milling on the dried product to obtain chitosan-modified magnesium aluminum hydrotalcite nano powder serving as a metal ion adsorbent.
And (3) recovering precious metals:
taking 100L of strong acid waste liquid, filtering off ash residues on the surface of a catalyst in the acid washing process, collecting filtrate, weighing 60g of metal ion adsorbent, adding the metal ion adsorbent, mixing and stirring uniformly at normal temperature, adding hydrochloric acid and a sodium hydroxide solution, adjusting the pH value to 3.0, adding 30g of EDTA, stirring and reacting for 1.5h at normal temperature, filtering to obtain first filter residue and second filtrate, adding 50g of metal ion adsorbent into the second filtrate, mixing and stirring uniformly at normal temperature after adding, adjusting the pH value to 5.0 by adding hydrochloric acid and a sodium hydroxide solution, adding 20g of STPP, stirring and reacting for 1.5h at normal temperature, filtering to obtain second filter residue and third filtrate, adding 40g of metal ion adsorbent into the third filtrate, mixing and stirring uniformly at normal temperature after adding, adjusting the pH value to 7.0 by adding hydrochloric acid and a sodium hydroxide solution, adding 10g of citric acid, stirring and reacting for 1.5h at normal temperature, filtering to obtain a third filter residue and a fourth filter liquid, combining the first filter residue, the second filter residue and the third filter residue, ashing for 1h at 400-: and (3) after ashing, filtering to obtain filter residue, and reducing the filter residue for 50min at 380 ℃ in a hydrogen atmosphere to obtain a noble metal mixture.
Example 4
Preparing a metal ion adsorbent:
preparing lauryl sodium sulfate graft modified chitosan: weighing 100g of chitosan, dissolving the chitosan in 8L of acetic acid with the mass concentration of 2%, stirring and dissolving to obtain a chitosan acetic acid solution, dissolving 150g of lauryl sodium sulfate in 3500ml of water, heating to 55 ℃, stirring and dissolving to obtain a lauryl sodium sulfate solution, dropwise adding the chitosan acetic acid solution into the lauryl sodium sulfate solution, keeping the temperature at 55 ℃, stirring and reacting for 2.5 hours, cooling to 25 ℃ after the reaction is finished, dropwise adding a sodium hydroxide solution, adjusting the pH value to 7.0, filtering to obtain filter residue, washing the filter residue with 100ml of water for three times, drying the filter residue, crushing and sieving by a 100-mesh sieve to obtain the lauryl sodium sulfate graft-modified chitosan.
Weighing 100g of sodium dodecyl sulfate graft-modified chitosan and 300g of magnesium aluminum hydrotalcite, weighing 100g of oxalic acid to prepare 2kg of 5 wt% oxalic acid solution, mixing the sodium dodecyl sulfate graft-modified chitosan, the magnesium aluminum hydrotalcite and the oxalic acid solution, stirring until the mixture is dissolved, heating to 80 ℃, weighing 1.5kg of toluene diisocyanate, slowly adding the toluene diisocyanate into the system, keeping the temperature, stirring and reacting for 60min, cooling to 30 ℃ after the reaction is finished, filtering to obtain a target product, drying a filter cake at 60 ℃, performing mechanical ball milling on the dried product to obtain chitosan-modified magnesium aluminum hydrotalcite nano powder serving as a metal ion adsorbent.
And (3) recovering precious metals:
taking 100L of strong acid waste liquid, filtering off ash residues on the surface of a catalyst in the acid washing process, collecting filtrate, weighing 40g of metal ion adsorbent, adding the metal ion adsorbent, mixing and stirring uniformly at normal temperature, adding hydrochloric acid and a sodium hydroxide solution, adjusting the pH to 2.5, adding 40g of EDTA, stirring and reacting for 1h at normal temperature, filtering to obtain a first filter residue and a second filtrate, adding 30g of metal ion adsorbent into the second filtrate, mixing and stirring uniformly at normal temperature after adding, adjusting the pH to 4.5 by adding hydrochloric acid and a sodium hydroxide solution, adding 30g of STPP, stirring and reacting for 1h at normal temperature, filtering to obtain a second filter residue and a third filtrate, adding 20g of metal ion adsorbent into the third filtrate, mixing and stirring uniformly at normal temperature after adding, adjusting the pH to 6.5 by adding hydrochloric acid and a sodium hydroxide solution, adding 20g of citric acid, stirring and reacting for 1h at normal temperature, filtering to obtain a third filter residue and a fourth filter liquid, combining the first filter residue, the second filter residue and the third filter residue, carrying out ashing for 3 hours at 400-: and (3) after ashing, filtering to obtain filter residue, and reducing the filter residue for 60min at 400 ℃ in a hydrogen atmosphere to obtain a noble metal mixture.
The untreated strongly acidic waste liquid and the fourth filtrate of examples 1 to 4 were subjected to precious metal detection, and the precious metal mixtures of examples 1 to 4 were weighed and subjected to content detection, respectively, and the obtained data are shown in the following table:
the data show that the recovery method can be used for recovering the noble metal from the strongly acidic waste liquid with extremely low noble metal content, and has the advantages of good recovery effect, high recovery rate, simple recovery process and difficult generation of other pollution.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for recovering noble metals from strongly acidic waste liquid is characterized by comprising the following steps:
step one, carrying out primary filtration on the strong acid waste liquid, and taking a first filtrate;
step two, adding a metal ion adsorbent into the first filtrate obtained in the step one, adjusting the pH value to 1-3, adding a first complexing agent, stirring at normal temperature, stirring for reaction for 0.5-1.5h, and filtering to obtain first filter residue and second filtrate;
step three, adding a metal ion adsorbent into the second filtrate obtained in the step two, adjusting the pH value to 3-5, adding a second complexing agent, stirring at normal temperature, stirring for reaction for 0.5-1.5h, and filtering to obtain second filter residue and third filtrate;
step four, adding a metal ion adsorbent into the third filtrate obtained in the step three, adjusting the pH value to 5-7, adding a third complexing agent, stirring at normal temperature, stirring for reaction for 0.5-1.5h, and filtering to obtain third filter residue and fourth filtrate;
step five, combining the first filter residue, the second filter residue and the third filter residue, then ashing, dissolving the ashed components with dilute hydrochloric acid, and then filtering to obtain a fourth filter residue;
and step six, keeping the fourth filter residue at the temperature of 350-400 ℃ in a hydrogen atmosphere, and reacting for 0.5-1.5h to obtain a noble metal mixture.
2. The method for recovering noble metals from strongly acidic waste liquid according to claim 1, wherein the metal ion adsorbent is chitosan-modified magnesium-aluminum hydrotalcite nanopowder, and the preparation method comprises: respectively mixing chitosan and magnesium-aluminum hydrotalcite, adding the mixture into 5 wt% oxalic acid solution, mixing, stirring and dissolving, heating to 70-80 ℃, adding toluene diisocyanate, keeping the temperature, stirring and reacting for 0.5-1h, cooling to 20-30 ℃ after the reaction is finished, filtering, taking the obtained filter cake as a product, drying the filter cake at 50-60 ℃, and mechanically ball-milling the dried product to obtain chitosan-modified magnesium-aluminum hydrotalcite nano powder, wherein the chitosan: aluminum magnesium hydrotalcite: oxalic acid: the mass ratio of the toluene diisocyanate is 1: (2-3): (0.5-1): (10-15).
3. The method for recovering noble metals from strongly acidic waste liquid according to claim 2, wherein the chitosan is a chitosan graft-modified with sodium dodecyl sulfate, and the preparation method comprises: dissolving chitosan in 2 wt% acetic acid to obtain a chitosan acetic acid solution, dissolving sodium dodecyl sulfate in water, heating to 50-60 ℃, stirring until the solution is dissolved to obtain a sodium dodecyl sulfate solution with the weight percentage of 3-5%, dropwise adding the chitosan acetic acid solution into the sodium dodecyl sulfate solution, stirring and reacting for 2-3h at the temperature of 50-60 ℃, cooling to 20-30 ℃ to obtain a mixed solution, adjusting the pH value of the mixed solution to 6.5-7.5, filtering, washing and drying to obtain the sodium dodecyl sulfate graft modified chitosan.
4. The method for recovering a noble metal from a strongly acidic waste liquid according to claim 3, wherein the ratio of chitosan: acetic acid: the mass ratio of the sodium dodecyl sulfate is 1: (1-2): (1-2).
5. The method according to claim 1, wherein in the second step, the first complexing agent is EDTA or DPTA.
6. The method according to claim 1, wherein the second complexing agent is STPP or HEDP in step three.
7. The method according to claim 1, wherein in the fourth step, the third complexing agent is citric acid or tartaric acid.
8. The method according to claim 1, wherein in the second step, 0.4 to 0.8g of the metal ion adsorbent is added to 1L of the first filtrate, and 0.3 to 0.5g of the first complexing agent is added to 1L of the first filtrate.
9. The method according to claim 1, wherein the metal ion adsorbent is added in an amount of 0.3 to 0.7g per 1L of the second filtrate, and the second complexing agent is added in an amount of 0.2 to 0.4g per 1L of the second filtrate.
10. The method according to claim 1, wherein in the fourth step, 0.2 to 0.6g of the metal ion adsorbent is added to 1L of the third filtrate, and 0.1 to 0.3g of the second complexing agent is added to 1L of the third filtrate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113233569A (en) * | 2021-04-17 | 2021-08-10 | 北京化工大学 | Method for quickly removing manganese ions in wastewater and application of manganese-containing product in precious metal recovery |
| CN117305612A (en) * | 2023-09-11 | 2023-12-29 | 广东金正龙科技有限公司 | Method for recovering noble metal from noble metal waste liquid |
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| CN117305612B (en) * | 2023-09-11 | 2024-02-23 | 广东金正龙科技有限公司 | Method for recovering noble metal from noble metal waste liquid |
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