CN113735910B - Method for treating waste rhodium acetylacetonate triphenylphosphine carbonyl agent and rhodium acetylacetonate triphenylphosphine carbonyl catalyst - Google Patents
Method for treating waste rhodium acetylacetonate triphenylphosphine carbonyl agent and rhodium acetylacetonate triphenylphosphine carbonyl catalyst Download PDFInfo
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- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
- B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
- B01J31/4046—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals containing rhodium
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
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- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/68—Liquid treating or treating in liquid phase, e.g. dissolved or suspended including substantial dissolution or chemical precipitation of a catalyst component in the ultimate reconstitution of the catalyst
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- C01G55/00—Compounds of ruthenium, rhodium, palladium, osmium, iridium, or platinum
- C01G55/005—Halides
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5022—Aromatic phosphines (P-C aromatic linkage)
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0258—Flexible ligands, e.g. mainly sp3-carbon framework as exemplified by the "tedicyp" ligand, i.e. cis-cis-cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to the technical field of catalysts, and discloses a method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent. The method comprises the following steps: mixing aldehyde, a first inorganic acid and an acetylacetone triphenylphosphine rhodium carbonyl waste agent, and separating to obtain a first water phase and a first oil phase; adjusting the pH value of the first water phase to be more than 6, and carrying out solid-liquid separation to obtain triphenylphosphine; the first oil phase is reacted with an oxidant in the presence of a second inorganic acid, the reaction product is mixed with a water-soluble rhodium extractant and a third inorganic acid, and the second aqueous phase and the second oil phase are separated. The invention can recover triphenylphosphine and rhodium simultaneously, and the recovery effect of the triphenylphosphine and rhodium is good.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a treatment method of an acetylacetonate triphenylphosphine carbonyl rhodium waste agent and an acetylacetonate triphenylphosphine carbonyl rhodium catalyst prepared by using triphenylphosphine and/or rhodium obtained by the treatment method as raw materials.
Background
Rhodium acetylacetonate triphenylphosphine carbonyl is a catalyst for hydroformylation, formylation and hydroxylation, which is expensive and results in high production costs. Therefore, in recent years, recovery and reuse of rhodium acetylacetonate triphenylphosphine carbonyl have become a research hotspot in the industry.
US3968134a discloses a process for recovering rhodium and triphenylphosphine: a mixture containing rhodium and triphenylphosphine in the form of soluble complexes is treated with an aqueous solution containing formaldehyde and hydrochloric acid. Boiling, filtering to obtainSolid Rh (CO) Cl (PPh 3 ) 2 . The aqueous layer and the organic layer were separated and sodium carbonate was added to the aqueous solution until it became alkaline. Then the solid triphenylphosphine containing trace rhodium compounds is obtained through precipitation, filtration separation, water washing and vacuum drying. The recovery rate of rhodium and triphenylphosphine is low.
He Yulian et al, "extraction-solvent recrystallization method for recovering triphenylphosphine from carbonyl catalyst waste liquid" ("Industrial catalyst", volume 12, pages 389-390, J.2014) discloses a method for recovering triphenylphosphine from carbonyl catalyst waste liquid, which comprises adding triphenylphosphine waste liquid, hydrochloric acid and formaldehyde in a certain proportion into a reactor equipped with a thermometer and a reflux condenser, stirring and refluxing for a certain period of time, standing for separation, and separating aqueous phase extract by Na 2 CO 3 Neutralizing, filtering, and drying the filter cake to obtain a crude TPP product. Weighing a certain amount of crude TPP, methanol and water, adding into a crystallizer, and heating to dissolve the TPP completely. After refluxing for a certain time, cooling, stopping stirring, filtering, washing with a small amount of methanol for crystallization, and drying the filter cake to obtain the refined TPP product. By adopting the method, only triphenylphosphine can be recovered, and rhodium cannot be recovered at the same time.
Disclosure of Invention
The invention aims to solve the problem that the high-efficiency recovery of the waste rhodium acetylacetonate triphenylphosphine carbonyl agent is difficult in the prior art, and provides a treatment method of the waste rhodium acetylacetonate triphenylphosphine carbonyl agent, by using the method, triphenylphosphine and rhodium can be recovered simultaneously, and the recovery effect is good.
In order to achieve the above object, the present invention provides in one aspect a method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent, comprising the steps of:
1) Mixing the acetylacetonate triphenylphosphine rhodium carbonyl waste agent with aldehyde and a first inorganic acid, and separating to obtain a first water phase and a first oil phase;
2) Adjusting the pH value of the first water phase to be more than 6, and carrying out solid-liquid separation to obtain triphenylphosphine;
3) After the first oil phase is reacted with an oxidant in the presence of a second inorganic acid, the oxidation product is mixed with a water-soluble rhodium extractant and a third inorganic acid, and the second aqueous phase and the second oil phase are separated.
Wherein the water-soluble rhodium extractant is selected from one or more compounds with a structure shown in a formula (I):
in the formula (I), R 1 And R is 2 Selected from hydrogen, hydroxy or hydroxy substituted C1-C3 alkyl, respectively.
Preferably, the method further comprises: and reducing the second aqueous phase with a first reducing agent to obtain a first rhodium solution.
Preferably, the method further comprises incinerating the second oil phase to obtain ash, reducing the ash with a second reducing agent, and then dissolving the ash with a fourth mineral acid to obtain a second rhodium solution.
Preferably, the first rhodium solution and/or the second rhodium solution is purified and concentrated to obtain rhodium trichloride.
Preferably, in formula (I), R 1 And R is 2 Respectively selected from hydrogen, hydroxy, hydroxymethyl, hydroxyethyl or hydroxypropyl.
Preferably, the water-soluble rhodium extractant is thiourea and/or ethylene thiourea.
Preferably, the water-soluble rhodium extractant is thiourea.
Preferably, the concentration of rhodium in the acetylacetonate triphenylphosphine rhodium carbonyl waste agent is 100-2000ppm, preferably 100-1000ppm.
Preferably, the rhodium acetylacetonate waste triphenylphosphine carbonyl agent is derived from the rhodium acetylacetonate waste agent produced during oxo alcohol (mainly butyl/octyl alcohol).
Preferably, the aldehyde in step (1) is one or more of formaldehyde, acetaldehyde and glutaraldehyde, preferably formaldehyde and/or acetaldehyde, more preferably formaldehyde.
Preferably, the first inorganic acid is one or more of hydrochloric acid, nitric acid and sulfuric acid, preferably hydrochloric acid and/or nitric acid, more preferably hydrochloric acid.
Preferably, the mass ratio of the acetylacetonate triphenylphosphine rhodium carbonyl waste agent to aldehyde is above 1:0.2, preferably above 1:0.8, more preferably between 1:0.8 and 1.2.
Preferably, the first mineral acid is used in an amount such that the pH of the extraction system is 2-6, preferably 2-5, more preferably 3-4.
Preferably, in step 2), the pH of the first aqueous phase is adjusted to 7-12, more preferably the pH of the first aqueous phase is adjusted to 7-9.
Preferably, in step 3), the second inorganic acid is one or more of hydrochloric acid, nitric acid and sulfuric acid, preferably hydrochloric acid and/or nitric acid, more preferably hydrochloric acid.
Preferably, the second mineral acid is used in an amount such that the pH of the oxidizing system is in the range of 2 to 6, preferably 2 to 5, more preferably 3 to 4.
Preferably, the oxidant is one or more of hydrogen peroxide, sodium peroxide, potassium permanganate, sodium chlorate and ammonium persulfate; preferably one or more of potassium permanganate, sodium peroxide and sodium chlorate; more preferably sodium chlorate.
Preferably, the mass ratio of the oxidant to the first oil phase is from 0.2 to 1:1, preferably from 0.3 to 1:1, more preferably from 0.3 to 0.8:1.
Preferably, in step 3), the mass ratio of the water-soluble rhodium extractant to the first oil phase is 0.1 or more, preferably 0.3 or more, 1, more preferably 0.3 to 0.5:1.
Preferably, in step 3), the third inorganic acid is one or more of hydrochloric acid, nitric acid and sulfuric acid, preferably hydrochloric acid and/or nitric acid, more preferably hydrochloric acid.
Preferably, the mass ratio of the third inorganic acid to the first oil phase is 1-5:1, preferably 1-4:1, more preferably 2-3:1.
Preferably, in step 3), the reaction temperature of the first oil phase and the oxidant is 70-130 ℃, the reaction time is 4-10 hours, more preferably, the reaction temperature is 80-120 ℃, and the reaction time is 4-8 hours; further preferably, the reaction temperature is 85-100deg.C and the reaction time is 4-6h.
Preferably, the first reducing agent and the second reducing agent are one or more of zinc powder, iron powder, magnesium powder and aluminum powder, respectively, and more preferably, the first reducing agent and the second reducing agent are zinc powder, respectively.
Preferably, the fourth inorganic acid solution is one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid.
Preferably, the acids in the fourth mineral acid solution are hydrochloric acid and nitric acid.
Preferably, the concentration of the acid in the fourth mineral acid solution is 5-15 wt%.
The second aspect of the invention provides an acetylacetone triphenylphosphine carbonyl rhodium catalyst prepared by using triphenylphosphine and/or rhodium trichloride obtained by the method as raw materials.
According to the technical scheme, the invention can provide the treatment method of the waste catalyst of the triphenylphosphine carbonyl rhodium acetylacetonate catalyst, the triphenylphosphine and rhodium can be recovered simultaneously by using the method, the recovery rate is high, and the recovered triphenylphosphine and rhodium can be used as raw materials to prepare the triphenylphosphine carbonyl rhodium acetylacetonate catalyst again, so that the recovery and cyclic utilization of resources are realized, and the production cost is reduced.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In one aspect, the invention provides a method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent, comprising the following steps:
1) Mixing the acetylacetonate triphenylphosphine rhodium carbonyl waste agent with aldehyde and a first inorganic acid, and separating to obtain a first water phase and a first oil phase;
2) Adjusting the pH value of the first water phase to be more than 6, and carrying out solid-liquid separation to obtain triphenylphosphine;
3) The first oil phase reacts with oxidant in the presence of second inorganic acid, the oxidation product is mixed with water-soluble rhodium extractant and third inorganic acid, the second water phase and the second oil phase are obtained by separation,
wherein the water-soluble rhodium extractant is selected from one or more compounds with a structure shown in a formula (I):
in the formula (I), R 1 And R is 2 Selected from hydrogen, hydroxy or hydroxy substituted C1-C3 alkyl, respectively.
According to the present invention, the rhodium acetylacetonate waste triphenylphosphine carbonyl agent may be one derived from the process of synthesizing alcohol (mainly butyl/octyl alcohol) from carbonyl. The concentration of rhodium in the acetylacetonate triphenylphosphine carbonyl rhodium spent reagent can vary over a wide range, preferably the concentration of rhodium in the acetylacetonate triphenylphosphine carbonyl rhodium spent reagent is 100-2000ppm; more preferably, the concentration of rhodium in the acetylacetonate triphenylphosphine carbonyl rhodium spent reagent is in the range of 100 to 1000ppm.
According to the present invention, when the concentration of rhodium in the waste rhodium acetylacetonate produced during the above-mentioned oxo-alcohol (mainly butyl/octyl alcohol) process is not within the above-mentioned range, concentration can be carried out to obtain the waste rhodium acetylacetonate waste triphenylphosphine carbonyl having the concentration of rhodium within the above-mentioned range.
The concentration may be carried out by atmospheric distillation or vacuum distillation, and preferably by vacuum distillation.
When the reduced pressure distillation mode is adopted, the temperature of the reduced pressure distillation can be 80-160 ℃; preferably, the temperature of the reduced pressure distillation is 100-150 ℃; more preferably, the temperature of the reduced pressure distillation is 100 to 130 ℃. The pressure of reduced pressure distillation can be-0.05 to-0.15 MPa; preferably, the pressure of reduced pressure distillation is-0.07 to-0.12 MPa; more preferably, the pressure of the reduced pressure distillation is-0.07 to-0.10 MPa. In addition, the distillation under reduced pressure may be carried out for a period of 2 to 8 hours; preferably, the distillation under reduced pressure is carried out for 3-7 hours; more preferably, the distillation under reduced pressure is carried out for a period of 4 to 6 hours. By carrying out distillation under the conditions, the light component solvent can be well evaporated, and the distillation bottom can not become solid, thereby being beneficial to subsequent extraction and rhodium recovery.
According to the invention, in step (1), the aldehyde may be one or more of formaldehyde, acetaldehyde and glutaraldehyde, preferably formaldehyde and/or acetaldehyde, more preferably formaldehyde. The aldehyde can achieve good extraction effect and save cost.
According to the present invention, the amount of the aldehyde may be determined according to the amount of the rhodium acetylacetonate waste agent, and preferably, the weight ratio of the rhodium acetylacetonate waste agent to the aldehyde may be 1:0.2, may be 1:0.4, may be 1:0.6, may be 1:0.8, and may be 1:1.
Preferably, the mass ratio of the acetylacetonate triphenylphosphine rhodium carbonyl waste agent to aldehyde is above 1:0.2, preferably above 1:0.8, more preferably between 1:0.8 and 1.2. When the amount of aldehyde is less than this range, insufficient extraction may result, and when the amount of aldehyde is more than this range, waste may be caused, increasing costs.
According to the present invention, in the step (1), the first inorganic acid is preferably one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, more preferably one or more of hydrochloric acid, nitric acid, and sulfuric acid, further preferably hydrochloric acid and/or nitric acid, and particularly preferably hydrochloric acid.
According to the present invention, preferably, the first inorganic acid is used in the form of a solution, and more preferably, the concentration of the first inorganic acid solution is 5 to 15 wt%.
According to the invention, the pH of the extraction system is adjusted by adding the first mineral acid. Preferably, in step 1), the first mineral acid is used in an amount such that the pH of the extraction system is between 2 and 6; more preferably, the first mineral acid is used in an amount such that the pH of the extraction system is between 2 and 5; further preferably, the first mineral acid is used in an amount such that the pH of the extraction system is 3-4. By performing the extraction in the above pH range, it is ensured that the extraction can be performed stably.
According to the invention, the extraction temperature of the mixed solution of aldehyde, first inorganic acid and the acetylacetonate triphenylphosphine rhodium carbonyl waste agent is 80-150 ℃ and the time is 0.5-3h; preferably, the extraction temperature is 100-150 ℃ and the extraction time is 1-3h; more preferably, the extraction temperature is 100-120℃and the time is 1-1.5h.
According to the invention, in step 1), after the extraction is completed, a first aqueous phase and a first oily phase are obtained by separation. The separation method is not particularly limited, and may be any of various means commonly used in the art for liquid-liquid separation in extraction, for example, the separation may be performed by taking out an oil phase of an upper layer.
According to the invention, in step 2), the pH of the first aqueous phase is preferably adjusted to a value of 6 to 14; more preferably, the pH of the first aqueous phase is adjusted to 7-12; further preferably, the pH of the first aqueous phase is adjusted to 7-9. By adjusting the pH of the first aqueous phase to the above range, the triphenylphosphine salt in the aqueous phase can be better precipitated as triphenylphosphine, thereby improving the recovery rate of triphenylphosphine.
The substance for adjusting the pH of the first aqueous phase may be various inorganic alkaline substances, for example, may be one or more of sodium hydroxide, sodium carbonate, calcium carbonate, potassium hydroxide and aqueous ammonia; preferably, the alkaline substance is sodium carbonate and/or calcium carbonate; more preferably, the alkaline substance is sodium carbonate. By adjusting the pH value by using the alkaline substance, triphenylphosphine can be better separated out, and the recovery rate of triphenylphosphine can be improved.
The method of solid-liquid separation in step 2) is not particularly limited, and may be any of various means commonly used in the art for separating solids from liquids, for example, filtration or centrifugation.
According to the invention. The triphenylphosphine obtained by solid-liquid separation can be further crystallized and purified.
The method of crystallizing triphenylphosphine is not particularly limited, and various methods generally used in the art for crystallization may be employed. Preferably, the crystallization is performed according to the following method: and mixing an acidic solution with the triphenylphosphine before crystallization, adjusting the pH of the mixed solution to be neutral, separating the triphenylphosphine in the mixed solution, washing with deionized water, drying, and then crystallizing. The acid in the acidic solution is preferably an inorganic acid, more preferably one or more of hydrochloric acid, sulfuric acid, nitric acid, and the like, and further preferably hydrochloric acid. By the addition of the acid, the excess alkaline substances in the triphenylphosphine can be neutralized, and a large amount of salts in the triphenylphosphine can be removed by washing, whereby the purity of the triphenylphosphine can be improved.
According to the present invention, the solvent for the crystallization treatment may be selected from one or more of methanol, ethanol, isopropanol, toluene, diethyl ether; preferably, the solvent for crystallization is selected from methanol and/or ethanol; more preferably, the solvent for crystallization is methanol. The recovery rate and purity of triphenylphosphine can be improved by using the above-mentioned solvent as a crystallization treatment solvent.
According to the invention, the mass ratio of the crystallization solvent to the triphenylphosphine may be 1.0-3.2:1; preferably 1.0-2.4:1; more preferably 1.5-2.4:1. The crystallization temperature is 80-120 ℃, preferably the reflux temperature.
The crystallization time may be 30 to 90min, preferably 30 to 40min. Thus, the purity of the triphenylphosphine can be ensured, and the yield of the triphenylphosphine can be improved.
The inventors of the present invention found that, in the crystallization treatment, when the mass ratio of the crystallization solvent to the triphenylphosphine is in the range, the purity of the obtained product is high, and this is probably due to the fact that in this range, the concentration of the solution is high, the concentration of impurities in the mother liquor is also high, the crystallization engineering growth rate is slow, and the impurities are not easily encapsulated, so that the purity of the obtained product is high.
According to the present invention, in step 3), the second inorganic acid is preferably one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, preferably one or more of hydrochloric acid, nitric acid and sulfuric acid, more preferably hydrochloric acid and/or nitric acid, and even more preferably hydrochloric acid.
According to the present invention, preferably, the second inorganic acid is used in the form of a solution, and more preferably, the concentration of the second inorganic acid solution is 5 to 15 wt%.
According to the invention, the second mineral acid is preferably used in an amount such that the pH of the oxidizing system is between 2 and 6, preferably between 2 and 5, more preferably between 3 and 4;
according to the invention, the oxidizing agent is one or more of hydrogen peroxide, sodium peroxide, potassium permanganate, sodium chlorate and ammonium persulfate, preferably one or more of potassium permanganate, sodium peroxide and sodium chlorate, more preferably sodium chlorate. The inventor of the present invention found that the oxidation reaction using the above-mentioned oxidizing agent is more advantageous for the subsequent recovery of rhodium.
According to the present invention, the amount of the oxidizing agent may be determined according to the amount of the first oil phase, and the mass ratio of the oxidizing agent to the first oil phase is 0.2 to 1:1, preferably 0.3 to 1:1, and more preferably 0.3 to 0.8:1. Thus, rhodium can be better led into a second water phase obtained by subsequent separation, and the consumption of an oxidant can be saved.
According to the invention, the oxidizing agent may be added dropwise to the first oil phase in the form of a solution, the content of the oxidizing agent in the solution may be 10 to 50% by weight, preferably 20 to 40% by weight, more preferably 30 to 40% by weight. In this way, the progress of the oxidation reaction can be promoted.
According to the invention, in step 3), the reaction temperature of the first oil phase and the oxidant is 70-130 ℃ and the reaction time is 4-10h; preferably, the reaction temperature is 80-120 ℃ and the reaction time is 4-8h; more preferably, the reaction temperature is 85-100deg.C and the reaction time is 4-6h. Too high a reaction temperature may cause the inorganic acid in the reaction system to be converted into a gaseous state to corrode the reaction equipment, and too low a reaction temperature may cause too low a reaction rate. By adopting the reaction conditions in the range, the rate of the oxidation reaction can be ensured, more rhodium can enter a second water phase obtained by subsequent separation, and the recovery rate of rhodium is improved.
According to the inventionAfter the oxidation reaction, the oxidation product is mixed with a water-soluble rhodium extractant and a third inorganic acid for extraction. Wherein in formula (I), R 1 And R is 2 Respectively selected from hydrogen, hydroxy, hydroxymethyl, hydroxyethyl or hydroxypropyl.
For example, the water-soluble rhodium extractant may be R 1 Is hydrogen, R 2 Compounds which are hydrogen can be R 1 Is hydroxy, R 2 A compound which is hydroxypropyl, and can also be R 1 Is hydroxymethyl, R 2 A compound which is hydroxyethyl. Preferably, the water-soluble rhodium extractant is thiourea and/or ethylene thiourea; more preferably, the water-soluble rhodium extractant is thiourea.
According to the present invention, the third inorganic acid is preferably one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, preferably one or more of hydrochloric acid, nitric acid, and sulfuric acid, more preferably hydrochloric acid and/or nitric acid, and even more preferably hydrochloric acid.
According to the present invention, it is preferable that the third inorganic acid is used in the form of a solution, and more preferably, the concentration of the third inorganic acid solution is 5 to 15 wt%.
According to the present invention, in step 3), the oxidation product is obtained by reacting the first oil phase with the oxidizing agent, and then the obtained oxidation product is directly extracted with the third inorganic acid and the water-soluble rhodium extractant, so that the water-soluble rhodium extractant may be determined according to the amount of the first oil phase, and preferably, the weight ratio of the water-soluble rhodium extractant to the first oil phase may be 0.1:1, may be 0.2:1, may be 0.3:1, may be 0.4:1, and may be 0.5:1.
Preferably, the mass ratio of the water-soluble rhodium extractant to the first oil phase is 0.1 or more, preferably 0.3 or more, 1, more preferably 0.3 to 0.5:1.
According to the present invention, the amount of the third inorganic acid may also be determined according to the amount of the first oil phase, preferably, the weight ratio of the third inorganic acid to the first oil phase is 1-5:1, preferably 1-4:1, more preferably 2-3:1.
When the amounts of the water-soluble rhodium extractant and the third inorganic acid are in the above-mentioned ranges, a better extraction effect can be achieved, thereby improving the recovery rate of rhodium.
According to the invention, the treatment method of the acetylacetonate triphenylphosphine carbonyl rhodium waste agent further comprises the following steps: and reducing the second aqueous phase with a first reducing agent to obtain a first rhodium solution. Preferably, the method further comprises incinerating the second oil phase to obtain ash, reducing the ash with a second reducing agent, and then dissolving the ash with a fourth mineral acid to obtain a second rhodium solution. Preferably, the first rhodium solution and/or the second rhodium solution is purified and concentrated to obtain rhodium trichloride.
According to the invention, the first reducing agent and the second reducing agent are respectively one or more of zinc powder, iron powder, aluminum powder and magnesium powder. Preferably, the first reducing agent and the second reducing agent are zinc powders. The inventor of the present invention found that when the first reducing agent and the second reducing agent are both zinc powders, the reaction speed is moderate and the reaction activity is controllable.
According to the present invention, the inorganic acid in the fourth inorganic acid solution is one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid. Preferably, the concentration of the acid in the fourth mineral acid solution is 5-15 wt%. The acid in the fourth inorganic acid solution may be hydrochloric acid and nitric acid, and preferably, the concentration of the hydrochloric acid is 10 wt% and the concentration of the nitric acid is 10 wt%. The volume ratio of hydrochloric acid to nitric acid may be 1-5:1, preferably 2-4:1. Thus, the ash can be fully dissolved, and the recovery rate of rhodium is improved.
In the present invention, when the second aqueous phase is reduced with the first reducing agent, the amount of the first reducing agent may be determined according to the amount of the second aqueous phase, and preferably, the mass ratio of the first reducing agent to the second aqueous phase is 0.3 to 0.5:1; more preferably, the mass ratio of the first reducing agent to the second aqueous phase is 0.3-0.4:1; further preferably, the mass ratio of the first reducing agent to the second aqueous phase is 0.32-0.35:1.
According to the invention, when the first reducing agent reduces the second aqueous phase, the reduction reaction temperature is 20-80 ℃ and the reaction time is 1-6h; preferably, the reaction temperature is 30-70 ℃ and the reaction time is 2-5h; more preferably, the reaction temperature is 40-60℃and the reaction time is 3-4 hours.
In the invention, the second oil phase is burnt and then added with a second reducing agent for reduction, the dosage of the second reducing agent can be determined according to the quantity of ash, and preferably, the mass ratio of the second reducing agent to the ash is 0.1-0.5:1; more preferably, the mass ratio of the second reducing agent to ash is 0.1-0.4:1; further preferably, the mass ratio of the second reducing agent to the ash is 0.2-0.35:1.
The reaction temperature of the ash reduction by the second reducing agent is 20-80 ℃ and the reaction time is 1-6h; preferably, the reaction temperature is 30-70 ℃ and the reaction time is 2-5h; more preferably, the reaction temperature is 40-60℃and the reaction time is 3-4 hours.
According to the invention, the ash is dissolved by a fourth inorganic acid solution after reduction, the dosage of the fourth inorganic acid solution can be determined according to the amount of ash, and preferably, the mass ratio of the fourth inorganic acid solution to the ash is 1-6:1; more preferably, the mass ratio of the fourth mineral acid solution to the ash is 2-5:1; further preferably, the mass ratio of the fourth mineral acid solution to the ash is 3-4:1. And dissolving to obtain a second rhodium solution.
According to the invention, the removal of impurities from the first rhodium solution and/or the second rhodium solution may be carried out by using a column, may be carried out by methods commonly used in the art, for example, by using a cation exchange column, for example, a strongly acidic styrene-based cation exchange resin, and the space velocity may be from 0.2 to 2.0 hours -1 。
According to the present invention, the first rhodium solution and/or the second rhodium solution may be further concentrated to increase the concentration of the solution after removing impurities, and the concentration may be performed by a concentration method commonly used in the art, which is not described herein.
The invention also provides an acetylacetone triphenylphosphine carbonyl rhodium catalyst which is prepared by taking triphenylphosphine and/or rhodium trichloride obtained by the method as raw materials.
The preparation of the rhodium acetylacetonate triphenylphosphine carbonyl can be carried out by carrying out a first reaction on the recovered rhodium trichloride and acetylacetone in the presence of a first solvent to obtain dihydroxyrhodium acetylacetonate; and carrying out a second reaction on the dihydroxyrhodium acetylacetonate and the recovered triphenylphosphine in the presence of a second solvent to obtain triphenylphosphine rhodium carbonyl acetylacetonate crystals.
According to the present invention, in the first reaction, the recovered rhodium trichloride may be dissolved in a first solvent, then mixed with acetylacetone, heated for reaction, and cooled to precipitate dihydroxyrhodium acetylacetonate crystals. The first solvent may be selected from N, N-dimethylformamide and/or N, N-dimethylacetamide, preferably N, N-dimethylformamide. The volume to mass ratio of the first solvent to rhodium trichloride is 30-100:1mL/g, preferably 30-60:1mL/g, more preferably 30-40:1mL/g. The dissolution temperature is 80-140 ℃, preferably 100-140 ℃, more preferably 120-140 ℃. Thus, not only can the rhodium chloride be fully dissolved, but also the consumption of the solvent can be saved. The volume mass ratio of the acetylacetone to the rhodium trichloride is 6-12:1mL/g, preferably 6-10:1mL/g, more preferably 6-8:1mL/g. Thus, not only can higher yield be achieved, but also the consumption of raw materials can be saved. The temperature of the first reaction may be 100-135 ℃; preferably, the reaction temperature is 110-135 ℃; more preferably, the reaction temperature is 120-135 ℃. The reaction time can be 1-5h; preferably, the reaction time is 2 to 4 hours; more preferably, the reaction time is 2 to 3 hours. Thus, the yield of the product can be improved, and the reaction rate can be improved.
According to the invention, in the second reaction, the second solvent may be selected from one or more of n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, cycloheptane, cyclooctane; preferably, the second solvent is selected from one or more of n-hexane, n-heptane, n-octane and n-nonane; more preferably, the second solvent is n-hexane. The temperature of the reaction of the dihydroxyrhodium acetylacetonate and triphenylphosphine can be 50-90 ℃; preferably, the reaction temperature is 60-90 ℃; more preferably, the reaction temperature is 80-90 ℃. The mass ratio of triphenylphosphine to acetylacetone dihydroxyrhodium is 0.4-1:1; preferably, the mass ratio of triphenylphosphine to acetylacetone dihydroxyrhodium is 0.5-1:1; more preferably, the mass ratio of triphenylphosphine to dihydroxyrhodium acetylacetonate is in the range of 0.5 to 0.7:1. Thus, the consumption of raw materials can be saved, and the reaction yield can be increased. The volume mass ratio of the solvent B to the dihydroxyrhodium acetylacetonate can be 30-80:1mL/g; preferably 30-60:1mL/g; more preferably 30-40:1mL/g.
The inventor of the present invention found that the rhodium acetylacetonate triphenylphosphine carbonyl prepared by the method can be subjected to ultrasonic cavitation, so that the purity of the rhodium acetylacetonate triphenylphosphine carbonyl can be improved. The reason for this is probably that ultrasonic cavitation increases intermolecular collision, accelerates crystal nucleus formation, promotes rapid crystal growth, and reduces the phenomenon of excessive encapsulation of triphenylphosphine, thereby increasing the purity of the rhodium acetylacetonate triphenylphosphine carbonyl crystals.
In the present invention, the ultrasonic cavitation conditions may be: ultrasonic frequency is 10-100kHz, ultrasonic cavitation time is 10-100min, and ultrasonic temperature is 20-30 ℃.
The present invention will be described in detail with reference to examples, but the present invention is not limited to the examples. In the following examples, the reagents used were commercially available unless otherwise specified.
Example 1
1) 1000g of the rhodium acetylacetonate triphenylphosphine carbonyl waste agent from the oxo alcohol (mainly butyl/octyl alcohol) production was distilled under reduced pressure at 120℃under-0.09 MPa for 4 hours to obtain 644g of the rhodium acetylacetonate triphenylphosphine carbonyl waste agent, wherein the rhodium concentration was 300ppm. Adding formaldehyde with the mass ratio of 1:1 to the waste agent of the triphenylphosphine rhodium carbonyl acetylacetonate, and adding hydrochloric acid solution with the concentration of 10 weight percent to adjust the pH value of the formaldehyde and the waste agent of the triphenylphosphine rhodium carbonyl acetylacetonate to 3. Extracting the mixture at 120 ℃ for 1h, and separating to obtain a first water phase and a first oil phase;
2) The pH of the aqueous phase a was adjusted to 9 with sodium carbonate and filtered to give triphenylphosphine. Hydrochloric acid solution with the concentration of 10 weight percent is added into triphenylphosphine until the mixture is neutral, the triphenylphosphine is obtained by filtering, and then the triphenylphosphine is washed by deionized water with the volume of 3 times, and then the triphenylphosphine is dried under reduced pressure at low temperature. And (3) after drying, crystallizing by taking methanol as a solvent, wherein the mass ratio of the methanol to the triphenylphosphine is 1.6:1, refluxing at the reflux temperature of 85 ℃ for 30min, and cooling to 63 ℃ to obtain the triphenylphosphine. Wherein, the recovery rate of triphenylphosphine is 98.5%. The quality parameters of the triphenylphosphine recovered are shown in Table 1.
3) Adding hydrochloric acid solution with the concentration of 10 weight percent into the first oil phase, adjusting the pH value of the catalytic system to 3, then dropwise adding sodium chlorate solution (with the concentration of 10 weight percent) into the first oil phase, wherein the mass ratio of the sodium chlorate solution to the first oil phase calculated by sodium chlorate is 0.35:1, and carrying out oxidation reaction at the reaction temperature of 85 ℃ for 4 hours. Mixing the oxidation product with thiourea and 10 wt% hydrochloric acid solution, wherein the mass ratio of the thiourea to the first oil phase is 0.3:1, the mass ratio of the hydrochloric acid solution to the first oil phase is 2:1, stirring for 1h, and separating to obtain a second water phase and a second oil phase.
4) Mixing zinc powder with the mass ratio of 0.3:1 with the second water phase, and reducing for 3 hours at 60 ℃ after mixing to obtain a first rhodium solution. Incinerating the second oil phase to obtain ash, mixing zinc powder with the mass ratio of 0.3:1 with the ash, reducing for 3 hours at 60 ℃, and dissolving with a mixed solution of 10 weight percent hydrochloric acid and 10 weight percent nitric acid with the volume ratio of 3:1 (the using amount ratio of the ash to the mixed acid is 1:3) to obtain a second rhodium solution; the first rhodium solution and the second rhodium solution were purified by passing through a strongly acidic styrene-based cation exchange resin (Amberlite IR-120, jiaxing Chemie Co., ltd.) at a space velocity of 0.5h -1 Concentrating to obtain rhodium chloride. Wherein the total recovery of rhodium was 99.6%.
5) The recovered rhodium trichloride is dissolved in N, N-dimethylformamide (the volume-mass ratio of the N, N-dimethylformamide to the rhodium trichloride is 30:1 mL/g), then the mixture is mixed with acetylacetone (the volume-mass ratio of the acetylacetone to the rhodium trichloride is 8:1 mL/g), the reaction temperature is 135 ℃, the reaction time is 2 hours, the cooling is carried out, the dihydroxyrhodium acetylacetonate crystal is separated out, and the dihydroxyrhodium acetylacetonate crystal yield is 97%. And (3) reacting the prepared acetylacetonate dihydroxyrhodium crystal with the recycled triphenylphosphine (the mass ratio of triphenylphosphine to acetylacetonate dihydroxyrhodium is 1:2) under the condition that normal hexane is used as a solvent (the volume mass ratio of normal hexane to acetylacetonate dihydroxyrhodium is 30:1 mL/g), the reaction temperature is 85 ℃, the reaction time is 2 hours, cooling to separate out the acetylacetonate triphenylphosphine carbonyl rhodium crystal, and then carrying out ultrasonic cavitation for 30 minutes under the condition of 25kHz at the temperature of 25 ℃ to obtain the acetylacetonate triphenylphosphine carbonyl rhodium crystal. Wherein, the yield of the triphenylphosphine rhodium carbonyl acetylacetonate crystal is 98.2%.
TABLE 1
| Detecting content | Analysis results |
| Appearance of | White crystals |
| Content (%) | 99.16 |
| Loss on drying (%) | 0.1 |
| Melting point (. Degree. C.) | 80.7～81.2 |
| Iron content (mg/kg) | 9 |
| Chlorine content (mg/kg) | 11 |
| Solubility of | Colorless and transparent |
| Triphenylphosphine oxide content (%) | 0.11 |
| Sulfur content (mg/kg) | 4 |
Example 2
The procedure of example 1 was followed, except that the mass ratio of formaldehyde to the rhodium acetylacetonate triphenylphosphine carbonyl waste agent added in step 1) was 0.8:1; the mass ratio of the methanol to the triphenylphosphine in the step 2) is 2:1; in the step 3), the mass ratio of thiourea to the first oil phase is 0.4:1. As a result, the recovery rate of the obtained triphenylphosphine was 98.5%, the total recovery rate of rhodium was 99.5%, and the yield of the acetylacetonate triphenylphosphine rhodium carbonyl crystals was 98.1%.
Example 3
The procedure of example 1 was followed, except that the mass ratio of formaldehyde to the rhodium acetylacetonate triphenylphosphine carbonyl waste agent added in step 1) was 0.9:1; the mass ratio of the methanol to the triphenylphosphine in the step 2) is 2.4:1; in the step 3), the mass ratio of thiourea to the first oil phase is 0.35:1. As a result, the recovery rate of the obtained triphenylphosphine was 98.5%, the total recovery rate of rhodium was 99.6%, and the yield of the acetylacetonate triphenylphosphine rhodium carbonyl crystals was 98.3%.
Example 4
The procedure of example 1 was followed except that thiourea was replaced with the same weight of ethylene thiourea to extract the oxidation reaction product. As a result, the total recovery of rhodium obtained was 98.5%.
Examples 5 to 9
The procedure of example 1 was followed except that the mass ratio of formaldehyde to the rhodium acetylacetonate triphenylphosphine carbonyl waste agent in step 1) was varied, and the amounts thereof and the extraction rates of the corresponding triphenylphosphine were as shown in Table 2.
TABLE 2
| Examples | Formaldehyde and acetylacetonate triphenylphosphine rhodium carbonyl waste agent mass ratio | Extraction yield (%) |
| 1 | 1:1 | 97.8 |
| 5 | 0.2:1 | 74.5 |
| 6 | 0.4:1 | 86.7 |
| 7 | 0.6:1 | 92.3 |
| 8 | 0.8:1 | 97.8 |
| 9 | 1.2:1 | 97.8 |
Experiments show that the extraction rate of triphenylphosphine can be increased by increasing the dosage of formaldehyde, and when the dosage of formaldehyde reaches a certain degree, the extraction rate of triphenylphosphine is not increased continuously.
Examples 10 to 14
The procedure of example 1 was followed, except that the mass ratio of the oxidizing agent to the first oil phase in step 3) was varied, and the amounts and the corresponding proportions of rhodium introduced into the aqueous phase were as shown in Table 3.
TABLE 3 Table 3
| Examples | Mass ratio of sodium chlorate solution to first oil phase | Proportion of rhodium into aqueous phase (%) |
| 10 | 0.2:1 | 65.5 |
| 11 | 0.3:1 | 77.7 |
| 12 | 0.4:1 | 78.3 |
| 13 | 0.5:1 | 78.28 |
| 14 | 0.8:1 | 78.51 |
The proportion of rhodium entering the aqueous phase tends to increase with increasing amount of sodium chlorate added, but the proportion of rhodium entering the aqueous phase increases to a small extent when the amount of sodium chlorate increases to some extent.
Examples 15 to 19
The procedure of example 1 was followed except that the conditions for the oxidation reaction in step 3) were different, and the conditions and results are shown in Table 4.
TABLE 4 Table 4
| Examples | 15 | 16 | 17 | 18 | 19 |
| Reaction temperature (. Degree. C.) | 25 | 65 | 85 | 105 | 120 |
| Reaction time (h) | 2 | 2 | 2 | 2 | 2 |
| Proportion of rhodium into aqueous phase (%) | 2.63 | 25.97 | 55.32 | 55.67 | 58.64 |
| Reaction time (h) | 4 | 4 | 4 | 4 | 4 |
| Proportion of rhodium into aqueous phase (%) | 3.51 | 32.61 | 68.31 | 69.21 | 71.06 |
| Reaction time (h) | 6 | 6 | 6 | 6 | 6 |
| Proportion of rhodium into aqueous phase (%) | 6.32 | 44.31 | 66.38 | 67.52 | 70.58 |
The proportion of rhodium entering the water phase increases with the increase of the reaction temperature, but in actual operation, when the temperature rises too high, a large amount of yellow gas is generated on the inner wall of the return pipe, and the corrosion to the reaction equipment is serious.
It can also be seen from the above data that the proportion of rhodium entering the aqueous phase increases gradually as the reaction time increases, but the rhodium content in the aqueous phase increases little more as the reaction time reaches a certain level.
Examples 20 to 23
The procedure of example 1 was followed, except that the mass ratio of the water-soluble rhodium extractant to the first oil phase in step 3) was varied, and the amounts used and the recovery rates of rhodium were as shown in Table 5.
TABLE 5
| Examples | Mass ratio of thiourea to first oil phase | Rhodium recovery (%) |
| 1 | 0.3:1 | 99.6 |
| 20 | 0.1:1 | 89.3 |
| 21 | 0.2:1 | 96.8 |
| 22 | 0.4:1 | 99.6 |
| 23 | 0.5:1 | 99.6 |
From the above experimental results, it can be seen that rhodium recovery increased with the increase of thiourea, but the amount of thiourea increased to a certain extent, and recovery was not increased any more.
Comparative example 1
The procedure of example 1 was followed except that the water-soluble rhodium extractant in step 3) was replaced with the same weight of bis-thiourea, and as a result, the total recovery of rhodium was 98.6%.
As is evident from a comparison of example 1 with comparative example 1, the recovery of rhodium can be significantly improved by using the water-soluble rhodium extractant of the present invention.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (23)
1. A method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent is characterized by comprising the following steps:
1) Mixing the acetylacetonate triphenylphosphine rhodium carbonyl waste agent with aldehyde and a first inorganic acid, and separating to obtain a first water phase and a first oil phase;
2) Adjusting the pH value of the first water phase to be more than 6, and carrying out solid-liquid separation to obtain triphenylphosphine;
3) The first oil phase reacts with oxidant in the presence of second inorganic acid, the oxidation product is mixed with water-soluble rhodium extractant and third inorganic acid, the second water phase and the second oil phase are obtained by separation,
wherein the water-soluble rhodium extractant is selected from one or more compounds with a structure shown in a formula (I):
formula (I)
In the formula (I), R 1 And R is 2 Respectively selected from hydrogen, hydroxy or hydroxy substituted C1-C3 alkyl,
the method further comprises the steps of:
reducing the second aqueous phase with a first reducing agent to obtain a first rhodium solution;
incinerating the second oil phase to obtain ash, reducing the ash by using a second reducing agent, and then dissolving the ash by using a fourth inorganic acid to obtain a second rhodium solution;
and removing impurities from the first rhodium solution and/or the second rhodium solution, and concentrating to obtain rhodium trichloride.
2. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to claim 1, wherein in the formula (I), R 1 And R is 2 Respectively selected from hydrogen, hydroxy, hydroxymethyl, hydroxyethyl or hydroxypropyl.
3. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to claim 1, wherein said water-soluble rhodium extractant is thiourea.
4. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to any one of claims 1 to 3, wherein the concentration of rhodium in the rhodium acetylacetonate triphenylphosphine carbonyl waste agent is 100 to 2000ppm;
the rhodium acetylacetonate triphenylphosphine carbonyl waste agent is derived from the rhodium acetylacetonate triphenylphosphine carbonyl waste agent generated in the process of synthesizing alcohol by carbonyl.
5. The method for treating a rhodium acetylacetonate waste material according to claim 4, wherein the concentration of rhodium in the rhodium acetylacetonate waste material is 100-1000ppm.
6. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to any one of claims 1 to 3, wherein in step 1), the aldehyde is one or more of formaldehyde, acetaldehyde and glutaraldehyde;
the first inorganic acid is one or more of hydrochloric acid, nitric acid and sulfuric acid;
the mass ratio of the acetylacetonate triphenylphosphine rhodium carbonyl waste agent to aldehyde is more than 1:0.2;
the first inorganic acid is used in an amount such that the pH of the extraction system is 2-6.
7. The method for treating a rhodium acetylacetonate carbonyl waste agent as defined in claim 6, wherein in the step 1), the aldehyde is formaldehyde and/or acetaldehyde;
the first inorganic acid is hydrochloric acid and/or nitric acid;
the mass ratio of the acetylacetonate triphenylphosphine rhodium carbonyl waste agent to aldehyde is more than 1:0.8;
the first mineral acid is used in an amount such that the pH of the extraction system is between 2 and 5.
8. The method for treating a rhodium acetylacetonate carbonyl waste agent as defined in claim 7, wherein in the step 1), the aldehyde is formaldehyde;
the first inorganic acid is hydrochloric acid;
the mass ratio of the acetylacetonate triphenylphosphine rhodium carbonyl waste agent to aldehyde is 1:0.8-1.2;
the first mineral acid is used in an amount such that the pH of the extraction system is 3-4.
9. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to any one of claims 1 to 3, wherein in step 2), the pH of the first aqueous phase is adjusted to 7 to 12.
10. The method for treating a rhodium acetylacetonate carbonyl waste agent as defined in claim 9, wherein the pH of the first aqueous phase is adjusted to 7-9.
11. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to any one of claims 1 to 3, wherein in step 3), the second inorganic acid is one or more of hydrochloric acid, nitric acid and sulfuric acid;
the second inorganic acid is used in an amount such that the pH value of the oxidation system is 2-6;
the oxidant is one or more of hydrogen peroxide, sodium peroxide, potassium permanganate, sodium chlorate and ammonium persulfate;
the mass ratio of the oxidant to the first oil phase is 0.2-1:1.
12. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to any one of claims 1 to 3, wherein in step 3), the second inorganic acid is hydrochloric acid and/or nitric acid;
the second inorganic acid is used in an amount such that the pH value of the oxidation system is 2-5;
the oxidant is one or more of potassium permanganate, sodium peroxide and sodium chlorate;
the mass ratio of the oxidant to the first oil phase is 0.3-1:1.
13. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to claim 12, wherein in step 3), the second inorganic acid is hydrochloric acid;
the second inorganic acid is used in an amount such that the pH value of the oxidation system is 3-4;
the oxidant is sodium chlorate;
the mass ratio of the oxidant to the first oil phase is 0.3-0.8:1.
14. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to any one of claims 1 to 3, wherein in step 3), a mass ratio of the water-soluble rhodium extractant to the first oil phase is 0.1 or more and 1.
15. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to claim 14, wherein in step 3), a mass ratio of the water-soluble rhodium extractant to the first oil phase is 0.3-0.5:1.
16. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to any one of claims 1 to 3, wherein in step 3), the third inorganic acid is one or more of hydrochloric acid, nitric acid and sulfuric acid;
the mass ratio of the third inorganic acid to the first oil phase is 1-5:1.
17. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to claim 16, wherein in step 3), the third inorganic acid is hydrochloric acid and/or nitric acid;
the mass ratio of the third inorganic acid to the first oil phase is 1-4:1.
18. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to claim 17, wherein in step 3), the third inorganic acid is hydrochloric acid;
the mass ratio of the third inorganic acid to the first oil phase is 2-3:1.
19. The process for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to any one of claims 1 to 3, wherein in step 3), the reaction temperature of the first oil phase and the oxidizing agent is 70 to 130 ℃ and the reaction time is 4 to 10 hours.
20. The method for treating a rhodium acetylacetonate carbonyl waste agent as defined in claim 19, wherein in the step 3), the reaction temperature of the first oil phase and the oxidizing agent is 85-100 ℃ and the reaction time is 4-6 hours.
21. The method for treating a rhodium acetylacetonate carbonyl waste agent as defined in claim 1, wherein the first reducing agent and the second reducing agent are one or more of zinc powder, iron powder, magnesium powder and aluminum powder, respectively.
22. The method for treating a rhodium acetylacetonate carbonyl waste agent of triphenylphosphine according to claim 21, wherein said first reducing agent and said second reducing agent are zinc powders.
23. The method for treating a rhodium acetylacetonate triphenylphosphine carbonyl waste agent according to any one of claims 1, 21-22, wherein the acid in the fourth inorganic acid solution is hydrochloric acid and nitric acid;
the concentration of the acid in the fourth inorganic acid solution is 5-15 wt%.
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| 含铑废料的回收、提纯技术工艺现状;姜东 等;《中国资源综合利用》;第37卷(第12期);第79-82页 * |
| 羰基合成废铑催化剂的回收及合成工艺研究;肖占敏;《中国优秀博硕士学位论文全文数据库 (硕士)工程科技Ⅰ辑》(第3期);第B016-53页 * |
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