CN102373335A - Method for recovering rhodium from inactivated rhodium-phosphine complex catalyst - Google Patents
Method for recovering rhodium from inactivated rhodium-phosphine complex catalyst Download PDFInfo
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Abstract
The invention provides an easy and effective organic one-phase method. The method comprises dissolving, oxidizing, adding alkaline substances and filtering. Rhodium is recovered from the inactivated rhodium-phosphine complex catalyst by separating. An obtained rhodium-containing solid can be directly used for synthesizing the rhodium-phosphine complex catalyst, and is not required to be reduced into simple substance rhodium, so that the conventional process flow is simplified. The method has the advantages of wide application range, mild process condition, simple needed requirement, no need of burning or high-temperature treatment, small pollution, and easiness for operating.
Description
Technical field
The present invention relates to a kind of Rare Metals method, be specifically related to from the rhodium phosphine complex catalyst of inactivation, reclaim the method for rhodium.
Background technology
As catalyzer, making alkene and hydrogen and reaction of carbon monoxide generate the hydroformylation process of aldehyde product with rhodium-uncle's organophosphorus complex compound, is well-known technically.Prevailing example is with RhH (CO) (TPP)
3Be catalyzer, prepare butyraldehyde by propylene and hydrogen and carbon monoxide.In long-continued Industrial processes, normal because produce in the reaction process various high boiling point by-products produced of rhodium phosphine complex catalyst and impurity that raw material is carried secretly and inactivation.Even do not carry impurity in the raw material basically secretly, catalyzer also can generate under the comprehensive action of the processing condition such as mol ratio of temperature of reaction, reactant partial pressure, part and rhodium does not have active rhodium bunch complex compound and inactivation gradually.When catalyst activity reduction when the unacceptable level, in order to keep productivity, just must stopped reaction, catalyzer is drawn off, and the cleaning reaction device, add live catalyst then and restart, decaying catalyst is through handling to reclaim rhodium.Such operation was carried out once conventional operation in per approximately 2 years.Because the rhodium resource-constrained, cost an arm and a leg, and rhodium in the international market price go up day by day, so the high efficiente callback of rhodium has great importance for the development in oxo process field in the decaying catalyst.
The recovery method of existing inactivation rhodium phosphine complex catalyst can be divided into combustion method and hydrometallurgic recovery two big classes.
It is the method that generally adopts in the present industrial production that combustion method reclaims rhodium.The method that patent CN1414125A invented is for adding the carbonate of basic metal or earth alkali metal in the spent rhodium catalyst of carbongl group synthesis reaction; Under 650～700 ℃, burn; Residual residue again with molten state under basic metal bisulphate reactant salt; Generate the rhodium salt of solubility, adopt electrolysis tech that rhodium is separated then.Patent CN1151443A discloses a kind of method that reclaims rhodium; To contain the spent rhodium catalyst solution of organophosphorus ligand and the basic cpd of I A or II A family element mixes; Ash content is burnt in control under 600～950 ℃ high temperature; And, after removing foreign metal, separation obtains metal rhodium with reductive agents such as methyl alcohol, hydrazine or Peng Qinghuana processing ash content.In combustion method reclaims the process of rhodium, can produce great amount of wastewater, waste gas, and rhodium possibly generate volatile components and cause damage, so the problem that combustion method reclaims rhodium is seriously polluted, also higher to the requirement of equipment simultaneously.
It is former thereby be difficult to industrial application that the many because complex process of hydrometallurgic recovery, yield are lower etc.Patent CN101177306 uses the mixing solutions of mineral acid and oxygenant that spent catalyst is cleared up; Clear up the solution that obtains with the alkali neutralization again, prepare aqua oxidation rhodium deposition, obtain rhodium chloride solution with the dissolving with hydrochloric acid deposition; Behind removal of impurities and recrystallizing and refining, obtain the hydration rhodium chloride.The method of patent JP-A-51-63388 invention does; Distillation residue with mineral acid and hydrogen peroxide treatment hydroformylation reaction; Contained rhodium or iridium are extracted into aqueous phase; In the presence of tertiary phosphine and haloid acid or alkali metal halide, handle then, filter the deposition that generates at last with carbon monoxide.Owing to used halogenide in this method, so device must use the halogen resistant material, this is unfavorable for the industrial production application.
Patent US4340570 has invented the free liberation method of a kind of amination.Earlier, be preferably methanol treatment oxonation resistates, evaporate volatile constituent under certain condition, Tri N-Propyl Amine is added in the residue resistates make rhodium dissociate out, repeatedly extract with hydrochloric acid with methylene dichloride then and separate and obtain rhodium with alcohol.The method of introducing among the clear 56-2994 of Japanese Patent is that to use carbonatoms be 5～15 alkane and acetonitrile, vinyl cyanide isopolarity organic solvent and handles spent catalyst as extraction agent and water or strong acid; Rhodium complex concentrates in polar organic solvent; Remove organic solvent with the distillatory mode again, make rhodium complex be able to Separation and Recovery.These two kinds of methods have higher requirement owing to use acid to equipment, and process step is more, complicated operation.
Also have some other method, mix the back with N, haloid acid and triphenyl phosphorus like the catalyst waste solution of patent US4363764 after and reflux, obtain the deposition of rhodium-containing oxide treatment; Patent US4446074 concentrates the back with catalyst waste solution and handles with tertbutanol peroxide and Glacial acetic acid min. 99.5, and reflux obtains the compound of rhodium-containing under synthetic gas atmosphere.
The above-described art methods that from catalyst waste solution, reclaims rhodium all has its useful separately aspect, but still needs a kind of method, and it can not need complex processing or procedure of processing to make rhodium be able to high efficiente callback under simple gentle condition
Summary of the invention
The technical problem that the present invention will solve:
To reclaim complex process, problem such as seriously polluted in the art methods in order overcoming, to the invention provides an a kind of organic phase method that simply and efficiently from the rhodium phosphine complex catalyst of inactivation, reclaims rhodium.
The method that the present invention introduced is applicable to the rhodium in the rhodium-uncle's organophosphorus complex catalyst that is recovered in inactivation in the hydroformylation of olefin.In existing industrial production, when catalyst activity reduction to 30% when following of live catalyst, then must unload to reclaim.The catalyst waste solution composition of this inactivation is very complicated, contains rhodium, butyraldehyde polymer, high boiling point organic by-products, triphenylphosphine, triphenylphosphine oxide and other the little metal impurity of hundreds of to several thousand ppm usually.Structure to the inactivation rhodium phosphine complex also is not clear especially at present, but relatively is recognized that to have formed do not have the multinuclear of catalytic activity rhodium cluster compound.
Raw material used in the present invention is above-mentioned rhodium-containing catalyst waste liquid.For the industrial installation that itself has the catalyst activation regenerating unit, the concentration of rhodium is higher in its catalyst waste solution, is generally 1,000 more than the ppm.If there is not the activating and regenerating device, then the content of rhodium is merely a hundreds of ppm in its decaying catalyst waste liquid, and the content of light constituent (being mostly aldehydes), triphenyl phosphorus, triphenylphosphinc oxide is higher relatively.For the lower waste liquid of rhodium content, when reclaiming, preferably waste liquid is concentrated, to remove light constituent.When the concentration of rhodium in the raw material waste liquid is 1000～10000ppm, treatment process used in the present invention all is fit to.When rhodium concentration was lower than this scope, too much light constituent can generate in subsequent processes and be unfavorable for by product of the present invention in the waste liquid, causes the rhodium yield to descend.When rhodium concentration was too high, then the extent of polymerization of rhodium cluster compound increased rapidly in the waste liquid, was unfavorable for the recovery of rhodium, and can cause the flowability of waste liquid extremely low, had increased the difficulty of operation.Usually use the method for underpressure distillation that catalyst waste solution is concentrated, employed condition and method have more detailed introduction when concentrating in patent US4374278.But because the source of raw material waste liquid is different, also difference to some extent of the kind of contained each material and content wherein, so do not have a most preferred condition and be applicable to the waste liquid that unloads from various process units.
Technical scheme of the present invention is:
The first step, dissolving is dissolved in catalyst waste solution in the polar solvent, stirs to make it to mix.This polar solvent is meant the alcohols that contains 1～4 carbon atom, like methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol etc.The difference that the consumption of solvent is formed with catalyst waste solution changes, and too little solvent then causes the rhodium yield to reduce, and then is a kind of waste too much.The concentration of dissolving back rhodium in solvent is 0.1g/L～2.0g/L.
In second step, above-mentioned mixing solutions is handled with oxygenant.Oxygenant is oxidized to its oxide compound (triphenylphosphinc oxide) with part (triphenyl phosphorus) in oxidising process, has weakened its coordination ability, thereby makes rhodium bunch be easy to broken.Oxygenant can be gaseous oxidant or superoxide.
Gaseous oxidant is oxygen or oxygenous gas, and like the gas mixture of air, oxygen and nitrogen etc., wherein the volumn concentration of oxygen is 5%～100%.Can or under certain pressure, carry out oxidation at normal pressure, pressure is 0.1MPa～1.0MPa.Gas must be at the reaction container bottom bubbling through above-mentioned mixing solutions, so that oxygen and waste liquid are fully reacted, flow is 20ml/min～200ml/min.Then mixing solutions slowly is heated to 50～110 ℃ under agitation condition, oxide treatment 5～48h.
Superoxide can be inorganic peroxide, and like hydrogen peroxide, sodiumperoxide, or organo-peroxide are like tertbutanol peroxide etc.Consumption is the superoxide that every gram rhodium needs 10～100g.It slowly is added in the mixing solutions, under agitation condition, is heated to 50～80 ℃ then, oxide treatment 5～48h.
The 3rd step added alkaline matter in the mixing solutions after above-mentioned oxide treatment, and continued heating, stirring, precipitated.Bunch generated insolubles by the rhodium broken, be able to from mixing solutions separated with alkali reaction.This alkaline matter can be the oxyhydroxide of basic metal or earth alkali metal, like sodium hydroxide, and Pottasium Hydroxide, Marinco H, calcium hydroxide etc.This alkaline matter can add with form of powder, can be dissolved in also that the form with solution adds behind the ethanol.The consumption of this alkaline matter must be big excessive, with the mass ratio of rhodium be 50～500, must guarantee that the pH value of mixing solutions after adding alkali is perhaps higher greater than 10.The temperature of precipitation process can be 20～90 ℃, and the time is 30min～10h.
The 4th step, the last rhodium-containing insolubles-alcohol mixed solution that obtains of step is filtered, to the deposition that obtains wash, drying.
The aftertreatment in the 4th step is a conventional steps, and is similar with washing, drying in the general organism synthesis technique.The deposition of using any known or not known step that the 4th step was obtained is separated, and all is equal to the present invention.
For example: can the insolubles that obtain in the 3rd step be filtered, then the gained deposition used zero(ppm) water, washing with alcohol respectively, and, promptly obtain the rhodium-containing solid 50 ℃ of vacuum-dryings.
As preferably:
In the first step, described alcohol is ethanol or Virahol;
In second step, described gaseous oxidant is an air, under normal pressure, handles, and flow is 80～150ml/min; Treatment temperature is 70～90 ℃, and the time is 15～24h;
In second step, said superoxide is hydrogen peroxide or tertbutanol peroxide;
In second step, the consumption of said superoxide is the superoxide that every gram rhodium needs 30～60g, and treatment temp is 60～70 ℃, and the time is 15～24h;
In the 3rd step, described alkaline matter is sodium hydroxide or Pottasium Hydroxide, with the mass ratio of rhodium be 50～250;
In the 3rd step, the temperature of precipitation process is 50～70 ℃, and the time is 2～5h.
The invention provides an a kind of simple and effective organic phase method; Can rhodium be separated from the rhodium phosphine complex catalyst of inactivation and be able to reclaim; Resulting rhodium-containing solid can directly be used for synthetic rhodium phosphine complex catalyst, need not be reduced into the simple substance rhodium, has simplified the existing processes flow process.Applied widely, the rhodium of inactivation in the various technologies of preparing aldehyde by hydro formylating defin-uncle's organophosphorus complex catalyst can reclaim rhodium with the method among the present invention.Processing condition are gentle, and required equipment is simple, need not burn or pyroprocessing, pollute little, easy handling.
Embodiment
Embodiment 1
The catalyst system therefor waste liquid is the catalyzer of inactivation in the technology of propylene and carbon monoxide and hydrogen generation hydroformylation reaction producing butyladehyde, and its activity is reduced to below 30% of live catalyst.
Catalyst waste solution is concentrated on the scraper plate thin film evaporation unit.The concentration of rhodium is 1700ppm in the gained concentrating spent liquor, contains triphenylphosphine 6.5wt%, triphenylphosphine oxide 11.1%, and all the other are butyraldehyde trimer and polymer, high boiling point organic by-products, and other little metal impurity.
Take by weighing above-mentioned catalyst concentration waste liquid 24.97g and join in the 500ml there-necked flask, and then add the 200ml absolute ethyl alcohol, stirring makes it to mix.Mixing solutions bubbling air in flask makes air pass through from the liquid bottom bubbling through an immersion tube, oxygen is fully contacted with catalyst waste solution and reacts, and the flow of air is 100ml/min.Stir also and slowly be warming up to 70 ℃, stop bubbling air behind the reaction 20h.Triphenylphosphine all is oxidized to triphenylphosphine oxide basically in this process.The NaOH ethanolic soln that in flask, adds 50ml 20% then after continuing reaction 5h under the same temperature, is reduced to room temperature.Filter, remove and desolvate, use zero(ppm) water and washing with alcohol respectively, 50 ℃ of vacuum-dryings obtain yellowish brown solid 0.26g.Results of elemental analyses shows, is 81% by the rhodium atom calculated yield.
Embodiment 2
Take by weighing with the catalyst concentration waste liquid 26.79g among the embodiment 1 and join in the 500ml there-necked flask, and then add the 200ml absolute ethyl alcohol, stir and make it to mix.Liquid bubbling air in flask makes air pass through from the liquid bottom bubbling through an immersion tube, oxygen is fully contacted with catalyst waste solution and reacts, and the flow of air is 100ml/min.Stir also and slowly be warming up to 90 ℃, stop bubbling air behind the reaction 24h.Triphenylphosphine all is oxidized to triphenylphosphine oxide basically in this process.Then reactive system is cooled to 70 ℃, in flask, adds the NaOH ethanolic soln of 50ml 20%, behind 70 ℃ of continuation reaction 5h, reduce to room temperature.Filter, remove and desolvate, use zero(ppm) water and washing with alcohol respectively, 50 ℃ of vacuum-dryings obtain yellowish brown solid 0.31g.Results of elemental analyses shows, is 74% by the rhodium atom calculated yield.
Embodiment 3
Take by weighing with the catalyst concentration waste liquid 25.54g among the embodiment 1 and join in the 500ml there-necked flask, add the 100ml absolute ethyl alcohol then, stir and make it to mix.In flask, add the 2ml t-butyl hydroperoxide, slowly be heated to 60 ℃, reaction 15h.Add the 5.06gNaOH powder then, be heated to 70 ℃, after continuing to react 3h, reduce to room temperature.Filter, remove and desolvate, use zero(ppm) water and washing with alcohol respectively, 50 ℃ of vacuum-dryings obtain yellowish brown solid 0.28g.Results of elemental analyses shows, is 65% by the rhodium atom calculated yield.
Embodiment 4
Take by weighing with the catalyst concentration waste liquid 25.08g among the embodiment 1 and join in the there-necked flask, add the 100ml Virahol then, stir and make it to mix.In flask, add the 2ml hydrogen peroxide, slowly be heated to 60 ℃, reaction 15h.Add 5.03g NaOH powder then, be heated to 70 ℃, after continuing to react 3h, reduce to room temperature.Filter, remove and desolvate, use zero(ppm) water and washing with alcohol respectively, 50 ℃ of vacuum-dryings obtain yellowish brown solid 0.30g.Results of elemental analyses shows, is 70% by the rhodium atom calculated yield.
Embodiment 5
Catalyst waste solution is carried out twice concentrate on the scraper plate thin film evaporation unit, the concentration of rhodium is 4900ppm in the gained concentrating spent liquor.
Take by weighing this catalyst concentration waste liquid 8.81g and join in the there-necked flask, add the 50ml absolute ethyl alcohol then, stirring makes it to mix.In flask, add the 2ml hydrogen peroxide, slowly be heated to 60 ℃, reaction 15h.Add 10.0g NaOH and 100ml absolute ethyl alcohol then, be heated to 70 ℃, after continuing to react 3h, reduce to room temperature.Filter, remove and desolvate, use zero(ppm) water and washing with alcohol respectively, 50 ℃ of vacuum-dryings obtain yellowish brown solid 0.34g.Results of elemental analyses shows, is 92% by the rhodium atom calculated yield.
Embodiment 6
The catalyst concentration waste liquid 8.52g that takes by weighing with embodiment 5 joins in the there-necked flask, adds the 50ml absolute ethyl alcohol then, stirs to make it to mix.In flask, add the 2ml tertbutanol peroxide, slowly be heated to 60 ℃, reaction 15h.Add 10.0g NaOH and 100ml absolute ethyl alcohol then, be heated to 70 ℃, after continuing to react 3h, reduce to room temperature.Filter, remove and desolvate, use zero(ppm) water and washing with alcohol respectively, 50 ℃ of vacuum-dryings obtain yellowish brown solid 0.44g.Results of elemental analyses shows, is 83% by the rhodium atom calculated yield.
Claims (11)
1. method that from the rhodium phosphine complex catalyst of inactivation, reclaims rhodium in turn includes the following steps:
The first step, dissolving is dissolved in catalyst waste solution in the polar solvent, stirs to make it to mix, and this polar solvent is meant the alcohols that contains 1～4 carbon atom, and the concentration of dissolving back rhodium in solvent is 0.1g/L～2.0g/L;
Second step, above-mentioned mixing solutions to be handled with oxygenant, oxygenant can be gaseous oxidant or superoxide;
The 3rd step added alkaline matter in the mixing solutions after above-mentioned oxide treatment, and continued heating, stirring; Precipitate; The consumption of this alkaline matter is big excessive, with the mass ratio of rhodium be 50～500, the pH value of mixing solutions is perhaps higher greater than 10 after adding alkali;
In the 4th step, the rhodium-containing insolubles-alcohol mixed solution that a last step is obtained filters, to the deposition that obtains wash, drying.
2. method according to claim 1, in the first step, described alcohol is ethanol or Virahol.
3. method according to claim 1; In second step; Described gaseous oxidant is oxygen or oxygenous gas, and through above-mentioned mixing solutions, flow is 20ml/min～200ml/min to gas at the reaction container bottom bubbling; Then mixing solutions slowly is heated to 50～110 ℃ under agitation condition, oxide treatment 5～48h.
4. method according to claim 1; In second step; Described superoxide is inorganic peroxide or organo-peroxide, and consumption is the superoxide of every gram rhodium 10～100g, slowly is added to it in mixing solutions; Under agitation condition, be heated to 50～80 ℃ then, oxide treatment 5～48h.
5. method according to claim 3, described gaseous oxidant are air, under normal pressure, handle, and flow is 80～150ml/min; Treatment temperature is 70～90 ℃, and the time is 15～24h.
6. method according to claim 4, said superoxide are hydrogen peroxide or tertbutanol peroxide; The consumption of said superoxide is the superoxide of every gram rhodium 30～60g, and treatment temp is 60～70 ℃, and the time is 15～24h.
7. method according to claim 1, in the 3rd step, described alkaline matter is the oxyhydroxide of basic metal or earth alkali metal.
8. method according to claim 7, described alkaline matter are sodium hydroxide or Pottasium Hydroxide, with the mass ratio of rhodium be 50～250.
9. method according to claim 1, in the 3rd step, the temperature of precipitation process is 20～90 ℃, the time is 30min～10h.
10. method according to claim 9, the temperature of precipitation process are 50～70 ℃, and the time is 2～5h.
11. according to the described method of above arbitrary claim, the rhodium phosphine complex catalyst of said inactivation is meant rhodium-uncle's organophosphorus complex catalyst of inactivation in hydroformylation of olefin.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102925699A (en) * | 2012-11-05 | 2013-02-13 | 中国海洋石油总公司 | Method for recovering rhodium from dead catalysts containing rhodium of hydroformylation reaction through treatment of hydrogen peroxide |
| CN103014322A (en) * | 2013-01-07 | 2013-04-03 | 郴州高鑫铂业有限公司 | Method for efficiently separating and purifying rhodium and ruthenium |
| CN103506167A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Treatment method of inactivated rhodium-phosphine catalyst |
| CN103509061A (en) * | 2012-06-19 | 2014-01-15 | 中国石油化工股份有限公司 | Recovery method for rhodium from deactivated catalyst used in formylation of propenyl hydrogen |
| CN103769225A (en) * | 2012-10-22 | 2014-05-07 | 中国石油化工股份有限公司 | Regeneration method of rhodium-phosphine catalyst losing all or part of carbonylation catalytic activity |
| CN104248994A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Method for recovering activity of carbonylation Rh-P catalyst |
| CN105503959A (en) * | 2014-09-26 | 2016-04-20 | 中国石油化工股份有限公司 | Method for preparing acetylacetonatocarbonyltriphenylp hosphinerhodium(I) |
| CN109922882A (en) * | 2016-11-08 | 2019-06-21 | 陶氏技术投资有限责任公司 | Make the hydroformylation catalyst solution regeneration method of inactivation |
| CN109963649A (en) * | 2016-11-08 | 2019-07-02 | 陶氏技术投资有限责任公司 | Make the hydroformylation catalysts solution regeneration method of inactivation |
| WO2020263462A1 (en) | 2019-06-27 | 2020-12-30 | Dow Technology Investments Llc | Process to prepare solution from hydroformylation process for precious metal recovery |
| US11033890B2 (en) | 2017-11-13 | 2021-06-15 | Dow Technology Investments Llc | Processes for recovery of rhodium from a hydroformylation process |
| CN114471736A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Activation method of rhodium cluster compound and application of rhodium cluster compound in catalyst regeneration |
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| CN103506167A (en) * | 2012-06-27 | 2014-01-15 | 中国石油化工股份有限公司 | Treatment method of inactivated rhodium-phosphine catalyst |
| CN103506167B (en) * | 2012-06-27 | 2015-08-19 | 中国石油化工股份有限公司 | A kind of processing method of inactivation Rhodium Phosphine catalyst |
| CN103769225B (en) * | 2012-10-22 | 2016-03-02 | 中国石油化工股份有限公司 | The renovation process of carbonylation inactivation or part inactivation Rhodium Phosphine catalyst |
| CN103769225A (en) * | 2012-10-22 | 2014-05-07 | 中国石油化工股份有限公司 | Regeneration method of rhodium-phosphine catalyst losing all or part of carbonylation catalytic activity |
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| CN105503959A (en) * | 2014-09-26 | 2016-04-20 | 中国石油化工股份有限公司 | Method for preparing acetylacetonatocarbonyltriphenylp hosphinerhodium(I) |
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| WO2020263462A1 (en) | 2019-06-27 | 2020-12-30 | Dow Technology Investments Llc | Process to prepare solution from hydroformylation process for precious metal recovery |
| CN114471736A (en) * | 2020-10-28 | 2022-05-13 | 中国石油化工股份有限公司 | Activation method of rhodium cluster compound and application of rhodium cluster compound in catalyst regeneration |
| CN114471736B (en) * | 2020-10-28 | 2023-12-05 | 中国石油化工股份有限公司 | Activation method of rhodium cluster compound and application of rhodium cluster compound in regenerating catalyst |
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