CN1872418A - Method for recovering ruthenium catalyst carried by active carbon - Google Patents
Method for recovering ruthenium catalyst carried by active carbon Download PDFInfo
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- Y02P20/584—Recycling of catalysts
Abstract
A recovering process for the activated carbon carried Ru catalyst not containing the compound of alkali metal or alkali-earth metal includes such steps as calcining at 600-1000 deg.C for 2-20 hr to obtain gray mixture, mixing it with KOH and KNO3, holding the temp at 300-950 deg.C for 105 hr, cooling, dissolving in hot water at 50-90 deg.C to obtain K2RuO4 solution, adding sodium hypochlorite and concentrated sulfuric acid, distilling to generate RuO4 gas, absorbing it by strong acid solution, and distilling to obtain Ru salt.
Description
(I) technical field
The invention relates to the field of precious metal catalyst recovery, in particular to the recovery of an active carbon-supported ruthenium catalyst.
(II) background of the invention
Ruthenium-based ammonia synthesis catalysts have been intensively studied and developed domestically and abroad since the successful ruthenium-based ammonia synthesis catalysts were developed by british BP corporation and Kellogg corporation in the united states in 1992. Compared with iron-based catalysts, ruthenium-based ammonia synthesis catalysts have the main advantages of high activity and capability of catalyzing ammonia synthesis reaction under the conditions of lower temperature, pressure and the like. Ruthenium-based ammonia synthesis catalysts are therefore considered to be the second generation ammonia synthesis catalysts following iron-based ammonia synthesis catalysts. The active carbon loaded ruthenium catalyst also has wide application in catalytic hydrogenation in the fields of petrochemical industry, fine chemicals and the like.
The ruthenium-based ammonia synthesis catalyst takes active carbon as a carrier and ruthenium (Ru) as an active component. Ruthenium is an extremely expensive rare noble metal, the output of China is extremely low, most of ruthenium used for preparing ruthenium catalysts depends on import, and the price is high, so that the preparation cost of the active carbon supported ruthenium catalyst is very high. For example, the cost per cubic meter of activated carbon supported KAAP ruthenium based ammonia synthesis catalysts developed jointly by BP and Kellogg is 20 ten thousand dollars. Therefore, whether the ruthenium in the ruthenium catalyst can be recycled becomes the key of whether the ruthenium-based ammonia synthesis catalyst can realize industrial production and can be popularized and applied. Particularly, under the conditions of resource shortage and import dependence in China, the recycling of the noble metals is very important. The recovery of ruthenium and other noble metals has important industrial value, economic significance and ecologicalbenefit.
At present, no method for recovering ruthenium-based ammonia synthesis catalyst loaded by active carbon exists at home and abroad, and the invention fills the gap. The realization of the invention not only reduces the production cost of the catalyst and the pollution of heavy metal to the environment, but also greatly improves the economic benefit and the ecological benefit and is beneficial to the sustainable utilization of resources.
Disclosure of the invention
The invention aims to provide a method for recovering an activated carbon-supported ruthenium catalyst so as to recover noble metal ruthenium. Because some catalysts also contain an auxiliary agent, usually alkali metal and/or alkaline earth metal compounds, such as alkali metal salts, alkaline earth metal salts, alkali metal oxides or hydroxides, and alkaline earth metal oxides or hydroxides, wherein the alkali metal is one or more of sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), and the alkaline earth metal is one or more of calcium (Ca), magnesium (Mg), strontium (Sr) and barium (Ba), the invention can recover not only the noble metal ruthenium but also the alkali metal and the alkaline earth metal.
The technical scheme adopted by the invention is as follows:
a method for recovering an activated carbon-supported ruthenium catalyst, comprising the steps of:
(1) metallizing non-alkali or alkaline earth metalsRoasting the compound assistant or the activated carbon-loaded ruthenium catalyst without the alkali metal or alkaline earth metal compound assistant for 2-20 hours at 600-1000 ℃ to completely burn out the activated carbon to obtain a gray-black mixture which is RuO2And a small amount of Ru.
(2) Mixing the gray black mixtureobtained in the step (1) with KOH and KNO3Mixture of (KOH and KNO)31: 1) in a mass ratio of 1: 1.5-2 at 300-950 DEG CKeeping the temperature for 1-5 hours, carrying out alkali fusion, and cooling to obtain an alkali fusion; the reactions that occur are:
(3) dissolving the alkali melt obtained in the step (2) in hot water at 50-90 ℃ to obtain K2RuO4Solution of at K2RuO4Adding sodium hypochlorite and concentrated sulfuric acid into the solution, and oxidizing and distilling for 2-4 hours at 50-90 ℃ under normal pressure or reduced pressure to generate RuO4A gas; the specific reaction formula is as follows:
(4) absorbing the RuO obtained in the step (3) by using strong acid solution4And distilling the gas at normal pressure or reduced pressure to obtain corresponding ruthenium salt.
If metallic ruthenium is to be obtained, the recovery method further comprises the step (5): and (4) reducing the ruthenium salt obtained in the step (4) by using hydrogen at the temperature of 150-500 ℃ to obtain metal ruthenium.
The alkali metal or alkaline earth metal compound is one of the following or a mixture of the following in any proportion: alkali metal salts, alkaline earth metal salts, alkali metal oxides or hydroxides, alkaline earth metal oxides or hydroxides.
Since most of the active carbon-supported ruthenium catalysts are ruthenium catalysts containing an alkali metal or alkaline earth metal compound promoter, the recovery method further comprises: step a of removing the alkali metal or alkaline earth metal compound assistant: and (3) impregnating the activated carbon-supported ruthenium catalyst with strong acid, and separating and removing the alkali metal or alkaline earth metal compound to obtain the activated carbon-supported ruthenium catalyst after removing the alkali metal or alkaline earth metal compound auxiliary agent. If the catalyst does not contain the alkali metal or alkaline earth metal compound promoter, step (1) may be carried out directly.
Specifically, the step a is as follows: dipping the activated carbon-supported ruthenium catalyst containing the alkali metal or alkaline earth metal compound auxiliary agent for 2-20 hours by using strong acid, then washing to be neutral, and filtering to obtain filtrate and filter residue, wherein the filter residue is the activated carbon-supported ruthenium catalyst without the alkali metal or alkaline earth metal compound auxiliary agent, and the strong acid can be hydrochloric acid with the mass percentage concentration of 5-36%; the remaining filtrate is a solution of an alkali metal and/or an alkaline earth metal compound, and barium and potassium can be recovered by the following method, taking the case where the alkaline earth metal is barium and the active carbon-supported ruthenium catalyst contains potassium as an example: and adding dilute sulfuric acid into the filtrate to precipitate barium ions in the filtrate, filtering, wherein the filter residue is barium sulfate, and evaporating the filtrate after removing the barium ions to dryness to obtain potassium chloride.
Further, an operation is carried out before the step (3), namely the alkali melt obtained in the step (2) is washed by cold water to be neutral and then filtered to obtain filter residue; and (4) taking filter residues and then carrying out the operation of the step (3). Dissolving the filter residue in hot water at 50-90 ℃ to obtain K2RuO4Solution of at K2RuO4Adding NaClO into the solution, oxidizing the solution at the constant temperature of 50-70 ℃ under vacuum or normal pressure for 0.5-1 h, dropwise adding a part of concentrated sulfuric acid, and then carrying out reduced pressure distillation to obtain RuO with golden yellow color4Producing, stopping dripping and adding concentrated H2SO4Dropwise adding NaClO, reacting for 0.5-1H, and dropwise adding concentrated H2SO4This process was repeated until no golden yellow gas was produced.
The strong acid solution in the step (4) is recommended to be hydrochloric acid with the mass percentage concentration of 36% or nitric acid with the mass percentage concentration of 66%.
Namely RuO escaped from step (3)4With hydrochloric acid (HCl) solution or nitric acid (HNO)3) Solution absorption at 50 ℃Reduced to RuCl under heating at 95 DEG C3Or Ru (NO)3)3：
RuCl3Or Ru (NO)3)3Distilling the solution under reduced pressure to obtain RuCl3·xH2O or Ru (NO)3)3. If metallic ruthenium is to be obtained, RuCl is added3Or Ru (NO)3)3Then using H at 150-2Reducing for 1-5 hours to obtain the metallic ruthenium.
Specifically, the recovery method of the activated carbon-supported ruthenium catalyst comprises the following steps:
1) soaking the activated carbon-supported ruthenium catalyst for 2-20 hours by hydrochloric acid with the mass concentration of 10%, washing and filtering to obtain filter residue, namely the activated carbon-supported ruthenium catalyst after removing the alkali metal or alkaline earth metal compound auxiliary agent;
2) roasting the activated carbon-supported ruthenium catalyst obtained in the step 1) after removing the alkali metal or alkaline earth metal compound auxiliary agent at 800-900 ℃ for 8-15 hours to obtain a gray-black mixture;
3) washing the gray black mixture obtained in the step 2) to be neutral, drying the mixture, and then mixing the mixture with KOH and KNO3Mixing, heating for 1-3 hours at 500-700 ℃ in a muffle furnace, carrying out alkali fusion, and cooling to room temperature to obtain an alkali fusion; washing the alkali melt with cold water to neutrality, and filtering to obtain filter residue;
4) dissolving the filter residue obtained in the step 3) in hot water at the temperature of 80-90 ℃ to obtain K2RuO4Solution of at K2RuO4Adding NaClO into the solution, oxidizing the solution at the constant temperature of 50-70 ℃ for 0.5-1 h in vacuum, dropwise adding a part of concentrated sulfuric acid, and then carrying out reduced pressure distillation to obtain RuO with golden yellow4Producing, stopping dripping and adding concentrated H2SO4Dropwise adding NaClO, reacting for 0.5-1H, and dropwise adding concentrated H2SO4Repeating the process until no golden yellow gas is generated;
5) absorbing and reducing RuO obtained in step 4) by using hydrochloric acid with the concentration of 36% or nitric acid solution with the concentration of 66%4Gas is distilled under reduced pressure to obtain corresponding ruthenium salt RuCl3·xH2O or Ru (NO)3)3；
6) If the metallic ruthenium is obtained, RuCl is added3·xH2O or Ru (NO)3)3At 200-400 DEG CAnd reducing with hydrogen under the condition to obtain the metallic ruthenium.
The invention has the advantages of recovering the noble metal ruthenium, reducing the manufacturing cost of the catalyst, reducing the consumption of heavy metal resources and the pollution to the environment, greatly improving the economic benefit and the ecological benefit, being beneficial to the sustainable utilization of the resources, simultaneously recovering the alkali metal and the alkaline earth metal auxiliary agent in the catalyst, and respectively preparing the recovered products into RuCl according to different requirements3·xH2O、Ru(NO3)3Or metallic ruthenium. The method has the advantages of reliable technology, simple operation, low cost and high product recovery rate.
(IV) specific embodiment:
the technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
24.0g of the ruthenium spent catalyst (containing Ba and K auxiliaries) loaded on the activated carbon is soaked for 12 hours in a hydrochloric acid solution with the mass percentage concentration of 10%, and filtrate and filter residue are obtained through filtration. Adding a proper amount of dilute sulfuric acid into the filtrate to ensure that BaSO is generated4Precipitating completely, filtering, and oven drying to obtain BaSO42.1423g, Ba recovery rate is 87.8%; the remaining filtrate was evaporated to dryness to give 4.8485g of KCl, with a K recovery of 77.7%.
And (3) ruthenium recovery: the filter residue was calcined in a muffle furnace at 800 ℃ for 10 hours to obtain 0.9882g of a gray-black mixture. Mixing the gray black mixture with 2g of KOH and KNO in a mass ratio of 1: 13The solid mixture was mixed in a crucible and placed in a muffle furnace for 1 hour at 650 ℃. Cooling the alkali melt after coolingWashing with water to neutrality, filtering to obtain filter residue, and dissolving the filter residue with 80 deg.C hot water to obtain K2RuO4Adding a little NaClO into the solution, vacuumizing, and maintaining the temperature at 60 ℃ under oxygenDissolving for 30 minutes, slowly adding a small amount of concentrated sulfuric acid dropwise, and distilling under reduced pressure to obtain a large amount of golden yellow RuO4Producing, stopping dripping and adding concentrated H2SO4Adding NaClO dropwise, reacting for 30 min, and adding concentrated H dropwise2SO4The dropping is repeated until no golden yellow gas is generated.
Distilled RuO4Absorbing the gas with 36% hydrochloric acid solution, and reducing to RuCl under heating3The hydrochloric acid solution was distilled under reduced pressure to obtain 1.5565g of black crystals. The black crystal is RuCl by XRD inspection3·xH2And O, wherein x is 1.5-2.5 by thermogravimetric analysis. Adding RuCl3·xH2The O was reduced with hydrogen at 200 ℃ and the ruthenium recovery was 94.6%.
Example 2
20g of ruthenium catalyst (containing Ba additive) loaded on activated carbon is soaked in a dilute hydrochloric acid solution with the mass percentage concentration of 10% for 16 hours, and filtrate and filter residue are obtained through filtration. Adding a proper amount of dilute sulfuric acid into the filtrate to ensure that BaSO is generated4Precipitating completely, filtering, and oven drying to obtain BaSO42.1737g, the Ba recovery was 89.8%. The procedure of example 1 was otherwise the same as the ruthenium recovery procedure. The ruthenium recovery was 93.05%.
Example 3
20g of ruthenium catalyst (containing K additive) loaded on activated carbon is soaked for 6 hours in a dilute hydrochloric acid solution with the mass percentage concentration of 10%, and filtrate and filter residue are obtained through filtration. The filtrate was dried to give KCl4.5737g, with a K recovery of 81.8%. The procedure of example 1 was otherwise the same as the ruthenium recovery procedure. The ruthenium recovery was 95.55%.
Example 4
20g of active carbon-supported ruthenium catalyst (without auxiliary agent) is directly placed in a muffle furnace to be roasted for 12 hours at 700 ℃ so that the active carbon is completely burnt out, and a gray-black mixture is obtained. The other steps were the same as the method of treating the gray-black mixture in the ruthenium recovering step in example 1. The ruthenium recovery was 97.61%.
Example 5
The procedure of example 1 is repeated, the escaped RuO being recovered in the ruthenium recovery step4Gas with 66% nitric acid (HNO)3) The solution replaces 36 percent hydrochloric acid solution for absorption, and the obtained product is Ru (NO)3)3. The ruthenium recovery was 92.61%.
Example 6
The procedure of example 1 was repeated, and in the ruthenium recovery step, the alkali fusion temperature was changed to 550 ℃ and the ruthenium recovery was 89.02%.
Example 7
The procedure of example 1was repeated, with RuCl obtained in the ruthenium recovery step3With H at 200 deg.C2The reaction solution was reduced for 2 hours to obtain 0.6018g of metallic ruthenium (Ru). The recovery of metallic ruthenium was 85.02%.
Example 8
The procedure of example 1 was repeated to recover Ru (NO) obtained in the step of recovering ruthenium3)3At 300 ℃ with H2Reduction was carried out for 3 hours to obtain 0.5875g of metallic ruthenium (Ru). The ruthenium recovery was 83.00%.
Claims (10)
1. A method for recovering an activated carbon-supported ruthenium catalyst, characterized in that the method for recovering comprises the steps of:
(1) roasting the activated carbon-supported ruthenium catalyst which does not contain the alkali metal or alkaline earth metal compound auxiliary agent or is removed of the alkali metal or alkaline earth metal compound auxiliary agent for 2-20 hours at 600-1000 ℃ to obtain a gray-black mixture;
(2) mixing the gray black mixture obtained in the step (1) with KOH and KNO3Mixing, keeping the temperature at 300-950 ℃ for 1-5 hours, carrying out alkali fusion, and cooling to obtain an alkali fusion;
(3) the alkali melt obtained in the step (2) is heated to 50 ℃Dissolving in hot water at 90 deg.C to obtain K2RuO4Solution of at K2RuO4Adding sodium hypochlorite and concentrated sulfuric acid into the solution, and distilling at 50-90 ℃ under normal pressure or reduced pressure for 2-4 hours to generate RuO4A gas;
(4) absorbing the RuO obtained in the step (3) by using strong acid solution4And distilling the gas at normal pressure or reduced pressure to obtain corresponding ruthenium salt.
2. The method for recovering an activated carbon-supported ruthenium catalyst according to claim 1, wherein the activated carbon-supported ruthenium catalyst is a ruthenium catalyst containing an alkali metal or alkaline earth metal compound promoter, and the method for recovering further comprises: step a of removing the alkali metal or alkaline earth metal compound assistant: impregnating the activated carbon-supported ruthenium catalyst with strong acid, and separating and removing the alkali metal or alkaline earth metal compound to obtain the activated carbon-supported ruthenium catalyst without the alkali metal or alkaline earth metal compound auxiliary agent, wherein the alkali metal or alkaline earth metal compound is one of the following compounds or a mixture of the following compounds in any proportion: alkali metal salts, alkaline earth metal salts, alkali metal oxides or hydroxides, alkaline earth metal oxides or hydroxides.
3. The method for recovering an activated carbon-supported ruthenium catalyst according to claim 2, wherein the step A is: dipping the activated carbon-supported ruthenium catalyst containing the alkali metal or alkaline earth metal compound auxiliary agent for 2-20 hours by using strong acid, then washing to be neutral, and filtering to obtain filtrate and filter residue, wherein the filter residue is the activated carbon-supported ruthenium catalyst from which the alkali metal or alkaline earth metal compound auxiliary agent is removed.
4. The method for recovering an activated carbon-supported ruthenium catalyst according to claim 2, wherein the strong acid is hydrochloric acid and has a concentration of 5 to 36% by mass.
5. The method for recovering an activated carbon-supported ruthenium catalyst according to claim 3, wherein the auxiliary contains barium ions and an alkali metal compound, and the method for recovering barium ions and an alkali metal compound comprises: and adding dilute sulfuric acid into the filtrate to precipitate barium ions in the filtrate, filtering, wherein the filter residue is barium sulfate, and evaporating the filtrate to dryness to obtain the alkali metal compound.
6. The method for recovering an activated carbon-supported ruthenium catalyst according to any one of claims 1 to 5, wherein the recovery method further comprises the step (5): and (4) reducing the ruthenium salt in the step (4) by using hydrogen at the temperature of 150-500 ℃ to obtain the metal ruthenium.
7. The method for recovering an activated carbon-supported ruthenium catalyst according to claim 1 or 2, wherein the step (3) is preceded by washing the alkali melt obtained in the step (2) with cold water to neutrality, and then filtering to obtain a filter residue; and (4) taking filter residues and then carrying out the operation of the step (3).
8. The method for recovering an activated carbon-supported ruthenium catalyst according to claim 1, wherein the step (3) is specifically: at K2RuO4Adding NaClO into the solution, oxidizing the solution at the constant temperature of 50-70 ℃ for 0.5-1 h in vacuum, dropwise adding a part of concentrated sulfuric acid, and then carrying out reduced pressure distillation to obtain RuO with golden yellow4Producing, stopping dripping and adding concentrated H2SO4Dropwise adding NaClO, reacting for 0.5-1H, and dropwise adding concentrated H2SO4This process was repeated until no golden yellow gas was produced.
9. The method for recovering an activated carbon-supported ruthenium catalyst according to claim 1, wherein the strong acid solution in the step (4) is a hydrochloric acid solution having a mass concentration of 36% or a nitric acid solution having a mass concentration of 66%.
10. The method for recovering an activated carbon-supported ruthenium catalyst according to claim 2, wherein the recovery method comprises the steps of:
1) adding hydrochloric acid with the mass concentration of 10% into the activated carbon-supported ruthenium catalyst, soaking for 2-20 hours, washing and filtering to obtain filter residue, namely the activated carbon-supported ruthenium catalyst after removing the alkali metal or alkaline earth metal compound auxiliary agent;
2) roasting the activated carbon-supported ruthenium catalyst obtained in the step 1) after removing the alkali metal or alkaline earth metal compound auxiliary agent at 800-900 ℃ for 8-15 hours to obtain a gray-black mixture;
3) mixing the gray black mixture obtained in the step 2) with KOH and KNO3Mixing, heating at 500-700 ℃ for 1-3 hours, carrying out alkali fusion, and cooling to obtain an alkali fusion; washing the alkali melt with cold water to neutrality, and filtering to obtain filter residue;
4) dissolving the filter residue obtained in the step 3) in hot water at the temperature of 80-90 ℃ to obtain K2RuO4Solution of at K2RuO4Adding NaClO into the solution, oxidizing the solution at the constant temperature of 50-70 ℃ for 0.5-1 h in vacuum, dropwise adding a part of concentrated sulfuric acid, and then carrying out reduced pressure distillation to obtain RuO with golden yellow4Producing, stopping dripping and adding concentrated H2SO4Dropwise adding NaClO, reacting for 0.5-1H, and dropwise adding concentrated H2SO4Repeating the process until no golden yellow gas is generated;
5) absorbing and reducing RuO obtained in step 4) by using hydrochloric acid with the concentration of 36% or nitric acid solution with the concentration of 66%4And carrying out reduced pressure distillation on the gas to obtain corresponding ruthenium salt.
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| EP2090669A3 (en) * | 2008-01-30 | 2009-11-04 | W.C. Heraeus GmbH | Method for generating ruthenium from materials or noble metal ore concentrates containing ruthenium or ruthenium oxide |
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| JP2020105632A (en) * | 2018-12-27 | 2020-07-09 | 国立大学法人福井大学 | Pre-treatment method, extracting method of platinum group metal, and extracting system of platinum group metal |
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| CN109433197B (en) * | 2018-12-31 | 2021-06-08 | 浙江工业大学 | Preparation of supported ruthenium-based hydrogenation catalyst and application of supported ruthenium-based hydrogenation catalyst in catalytic hydrogenation reaction of aldehyde-containing compound |
| CN109433196A (en) * | 2018-12-31 | 2019-03-08 | 浙江工业大学 | The preparation and the application in anhydride maleique catalytic hydrogenation reaction of supported ruthenium base hydrogenation catalyst |
| CN110499427A (en) * | 2019-08-30 | 2019-11-26 | 云南省环境科学研究院(中国昆明高原湖泊国际研究中心) | A method of recycling noble metal from the wire mesh integral catalyzer of waste and old carried noble metal |
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| DE102022111440B3 (en) | 2022-05-09 | 2022-08-25 | Technische Universität Bergakademie Freiberg, Körperschaft des öffentlichen Rechts | Process for recovering ruthenium from a ruthenium-containing material |
| WO2023217568A1 (en) | 2022-05-09 | 2023-11-16 | Technische Universität Bergakademie Freiberg | Method for recovering ruthenium from a ruthenium-containing material |
| CN115874060A (en) * | 2022-12-19 | 2023-03-31 | 本源精化环保科技有限公司 | Method for extracting precious metal from waste supported composite catalyst |
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