Process for the preparation of acetylacetone dicarbonyl rhodium, rhodium chloride hydrate, rhodium sulfate

Abstract

The application discloses a preparation method of acetylacetone dicarbonyl rhodium, hydrated rhodium chloride and rhodium sulfate. The preparation method of acetylacetone dicarbonyl rhodium comprises the following steps: under the condition of an inert atmosphere, complexing reaction is carried out between hydrated rhodium trichloride and a mixed solution A to obtain acetylacetone dicarbonyl rhodium; the mixed solution A comprises N,N-dimethylformamide, acetylacetone and a complexing promoter; the complexing promoter comprises one or more of sodium acetylacetone, sodium benzoate, phenol, benzyl dimethylamine, triethylamine, triethylenetetramine, triethanolamine and pyridine. The method has the advantages of mild reaction condition, environmental friendliness, high yield, low heat energy consumption and significant reduction of the generation amount of waste water.

Description

Technical Field

[0001] This invention relates to methods for preparing rhodium dicarbonyl acetylacetone, rhodium chloride hydrate, and rhodium sulfate. Background Technology

[0002] Currently, most large-scale petrochemical companies both domestically and internationally employ low-pressure propylene hydroformylation processes in their carbonyl synthesis of aldehydes or alcohols (mainly butanol / octanol). The core of this process is the use of rhodium acetylacetone triphenylphosphine carbonyl (ROPAC) as a catalyst. The precursor of ROPAC is rhodium acetylacetone dicarbonyl (CARAC). The yield and quality of CARAC directly determine the synthesis yield and quality of ROPAC, and CARAC itself can also serve as a catalyst in the butanol / octanol reaction system. Rhodium-containing catalysts have wide applications in catalytic hydrogenation, methanol carbonylation to acetic acid, and olefin hydroformylation. Furthermore, rhodium metal is an indispensable raw material in fuel cells, automotive exhaust purification, and electroplating.

[0003] Commercially available rhodium products include rhodium powder (GB / T1421-2004) and hydrated rhodium trichloride (GB / T23519-2009), which can be used to prepare CARAC, but the cost is relatively high. According to incomplete statistics, domestic enterprises need approximately 10,000 kilograms of CARAC annually for just one carbonyl synthesis process, most of which needs to be imported from abroad.

[0004] Therefore, it is necessary to fully recover and utilize rhodium as a secondary resource. Currently, typical methods for rhodium recovery in this field generally involve high-temperature incineration or direct oxidation digestion, extraction, and precipitation. However, the volatilization of flue gas during high-temperature incineration causes rhodium loss, which not only reduces the rhodium yield in subsequent processes but also causes serious pollution problems.

[0005] In summary, in order to further improve the yield of rhodium and reduce its environmental pollution, it is urgent to develop a high-yield method for preparing rhodium sulfate, hydrated rhodium chloride, and rhodium dicarbonyl acetylacetone. Summary of the Invention

[0006] The technical problem this invention aims to solve is to overcome the shortcomings of existing methods for preparing rhodium-containing compounds, such as significant environmental pollution, harsh conditions, high risk, and difficulty in industrial production. This invention provides a method for preparing rhodium dicarbonyl acetylacetone, rhodium chloride hydrate, and rhodium sulfate. The method of this invention has the advantages of mild reaction conditions, environmental friendliness, and high yield, while also having low heat energy consumption and significantly reducing wastewater generation.

[0007] To achieve the above objectives, the present invention provides the following technical solution:

[0008] This invention also provides a method for preparing rhodium carbonyl acetylacetone, comprising the following steps:

[0009] Under an inert atmosphere, hydrated rhodium trichloride was subjected to a complexation reaction with mixture A to prepare acetylacetone carbonyl rhodium.

[0010] The mixture A comprises N,N-dimethylformamide, acetylacetone, and a complexing agent;

[0011] The complexing agent is one or more of sodium acetylacetonate, sodium benzoate, phenol, benzyl dimethylamine, triethylamine, triethylenetetramine, triethanolamine and pyridine.

[0012] In this invention, those skilled in the art should know that N,N-dimethylformamide serves as both a solvent and a reactant in the complexation reaction.

[0013] In some embodiments, the mass ratio of the hydrated rhodium trichloride to the acetylacetone is 1:(1-10), preferably 1:(2-9).

[0014] In some embodiments, the mass ratio of the hydrated rhodium trichloride to the N,N-dimethylformamide is 1:(10-100), preferably 1:(20-70).

[0015] In some embodiments, the mass ratio of the hydrated rhodium trichloride to the complexing agent is 1:(0.01-1), preferably 1:(0.05-0.5).

[0016] In a specific embodiment, the mass ratio of the hydrated rhodium trichloride, the acetylacetone, the N,N-dimethylformamide, and the complexing agent is 1:(1-10):(10-100):(0.01-1). Controlling the amount of reagents involved in the complexation reaction can reduce costs and help reduce the volume of the post-treatment solution.

[0017] In some embodiments, the complexing agent is one or more of triethylenetetramine, sodium acetylacetonate, triethanolamine, triethylamine, and pyridine, preferably triethylenetetramine, triethanolamine, or triethylamine.

[0018] In some embodiments, the inert atmosphere includes a nitrogen atmosphere. An inert atmosphere can effectively prevent the raw materials for the complexation reaction from being oxidized at higher temperatures, thereby reducing the rhodium yield.

[0019] In some embodiments, the temperature of the complexation reaction is 125-200°C, preferably 130-200°C, for example 130°C, 145°C or 150°C.

[0020] In some embodiments, the complexation reaction takes 1-7 hours, preferably 1-5 hours.

[0021] In some embodiments, the complexation reaction is followed by a purification step; preferably, the purification step includes extraction, washing, and concentration in sequence.

[0022] In a specific embodiment, the extraction reagent is one or more of toluene, cyclohexane, n-hexane, ethyl acetate, methyl tert-butyl ether, tetrahydrofuran, dichloromethane, and chlorobenzene, preferably one or more of toluene, cyclohexane, ethyl acetate, and methyl tert-butyl ether, such as ethyl acetate, cyclohexane, or toluene.

[0023] In a specific embodiment, the mass ratio of N,N-dimethylformamide to the extraction reagent is 1:(1-10), preferably 1:(2-8).

[0024] In the method for preparing rhodium carbonyl acetylacetone of the present invention, by adding a complexing agent and under an inert atmosphere, the rhodium-containing compound can be fully complexed, which greatly improves the reaction yield.

[0025] In this invention, the preparation method of acetylacetone carbonyl rhodium does not require rhodium powder as a raw material, and the raw material does not need to undergo multiple purification steps. The catalyst acetylacetone dicarbonyl rhodium is directly synthesized using hydrated rhodium trichloride, and there are no excess impurity ions in the system.

[0026] In this invention, preferably, the method for preparing rhodium carbonyl acetylacetone further includes: The hydrated trichloride Preparation methods of rhodium It includes the following steps:

[0027] Under conditions of 30-90℃ and in the presence of a flocculant, the pH of rhodium sulfate is controlled to be less than or equal to 9.0 for a precipitation reaction of 1.5-10 hours. After acid treatment, hydrated rhodium trichloride is obtained. The mass ratio of rhodium sulfate to flocculant is (100-1000):1.

[0028] The settling agent is one or more of polyacrylamide, aluminum chloride, polyferric sulfate, polyferric aluminum sulfate, and alum.

[0029] In some implementations, the pH value is in the range of 5.0-9.0, such as 5.0-5.5, 6.0-6.5, 7.0-7.5, 8.0-8.5, or 8.5-9.0.

[0030] In some embodiments, the precipitation reaction is carried out at a temperature of 40-80°C, for example, 40°C, 60°C or 80°C.

[0031] In some embodiments, the precipitation reaction takes 2-10 hours, for example, 2 hours.

[0032] In some embodiments, the settling agent is one or more of polyacrylamide, aluminum chloride, polyferric sulfate, and alum, such as polyacrylamide, aluminum chloride, polyferric sulfate, or alum.

[0033] In some embodiments, the mass ratio of rhodium sulfate to the flocculant is (200-1000):1, for example 800:1 or 200:1.

[0034] In some embodiments, the pH of the rhodium sulfate solution is adjusted using an alkaline solution; preferably, the alkaline solution is a solution containing one or more solutes selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, and calcium hydroxide, and more preferably, a solution containing one or more solutes selected from sodium hydroxide, sodium carbonate, potassium carbonate, and ammonia, such as a sodium hydroxide solution or an ammonia solution.

[0035] In some embodiments, the temperature is lowered to 20-30°C after the precipitation reaction. By controlling the reduced temperature, it is to prevent inorganic salts (such as NaCl or sodium sulfate) from precipitating simultaneously with rhodium hydroxide and thus coating the rhodium hydroxide, resulting in the filtered rhodium hydroxide containing excessive inorganic salts.

[0036] In some embodiments, the acid solution in the acid treatment of the method for preparing hydrated rhodium trichloride includes hydrochloric acid; preferably, the concentration of the hydrochloric acid is 6 mol / L.

[0037] In some embodiments, the preparation method of hydrated rhodium trichloride further includes a concentration step after acid treatment.

[0038] In this invention, by adjusting the pH value and adding a flocculant, rhodium sulfate undergoes a precipitation reaction, causing rhodium hydroxide, which was originally a colloidal substance, to precipitate completely in solid form in one step. This method can greatly improve the yield of rhodium.

[0039] In this invention, preferably, the method for preparing rhodium carbonyl acetylacetone further includes: The preparation of rhodium sulfate Preparation method It includes the following steps:

[0040] S1. In an atmosphere with an oxygen content of 0-30% but not 0, a mixture of rhodium-containing waste liquid and a mixing reagent is incinerated to obtain rhodium ash; the mixing reagent is one or more of alkali metal compounds, alkaline earth metal compounds, carbon materials and silicon dioxide; the mass ratio of the rhodium-containing waste liquid to the mixing reagent is 100:(1-20).

[0041] S2. The rhodium ash is mixed with a molten reagent and subjected to a molten reaction, followed by acid treatment to obtain a rhodium sulfate solution; the molten reagent includes one or more of potassium pyrosulfate, sodium pyrosulfate, potassium sulfate, sodium bisulfate, and potassium bisulfate.

[0042] In some embodiments, in step S1, the rhodium-containing waste liquid includes rhodium-containing waste liquid after hydroformylation; the rhodium-containing waste liquid after hydroformylation generally includes organic high-boiling-point impurities, phosphine ligands, deactivated rhodium catalysts, and base metals; preferably, the rhodium-containing waste liquid contains one or more of Rh, Fe, Mg, Ca, Al, Cr, and Ni; more preferably, the content of Rh in the rhodium-containing waste liquid is 10-100 ppm, and the content of Fe, Mg, Ca, Al, Cr, and Ni in the rhodium-containing waste liquid is 10-500 ppm.

[0043] In some embodiments, in step S1, the alkali metal compound is one or more of sodium carbonate, sodium bicarbonate, sodium hydroxide, potassium carbonate, sodium chloride, potassium bicarbonate, and potassium hydroxide.

[0044] In some embodiments, in step S1, the alkaline earth metal compound is one or more of calcium carbonate, calcium chloride, and calcium hydroxide.

[0045] In some embodiments, in step S1, the carbon material includes wood chips and / or activated carbon.

[0046] In a specific implementation, in step S1, the mixing reagent is sodium carbonate, sodium chloride, calcium chloride, silicon dioxide, sodium hydroxide, activated carbon, or calcium hydroxide.

[0047] In step S1 of the present invention, the mixing reagent not only prevents splashing of the rhodium-containing waste liquid during incineration, but also prevents the rhodium element from being carried away from the system by the flue gas, and protects the rhodium from sintering into an inert substance, which is beneficial to the subsequent melting step and thus improves the yield.

[0048] In some embodiments, in step S1, the mass ratio of the rhodium-containing waste liquid to the mixing reagent is 100:(2-10), for example, 100:2.5 or 100:5. Using the reaction conditions of this application, the amount of mixing reagent used to mix with the rhodium-containing waste liquid can be reduced.

[0049] In some embodiments, in step S1, the incineration temperature is 100-800°C, preferably 150-750°C, for example 450°C, 650°C or 750°C.

[0050] In some embodiments, in step S1, the incineration is carried out in a muffle furnace.

[0051] In some embodiments, in step S1, the incineration process employs a programmed temperature rise method; preferably, the programmed temperature rise method includes: a first stage - raising the temperature from room temperature to 200°C and holding for 1 hour; a second stage - raising the temperature to 250°C and holding for 2 hours; a third stage - raising the temperature to 300°C and holding for 3 hours; a fourth stage - raising the temperature to 350°C and holding for 30 minutes; a fifth stage - raising the temperature to 400°C and holding for 30 minutes; and a sixth stage - raising the temperature to 450°C and holding for 8-12 hours.

[0052] In some embodiments, the atmosphere in step S1 further includes nitrogen.

[0053] In some embodiments, in step S1, the oxygen content of the atmosphere is 1%-20%, preferably 1%-10%, for example 1%-5%. The incineration is carried out under these oxygen-deficient conditions, yielding rhodium oxide and more elemental rhodium, which is more beneficial for subsequent steps.

[0054] In some embodiments, in step S2, the molten reagent is potassium bisulfate, sodium bisulfate, potassium pyrosulfate, or potassium sulfate.

[0055] In some embodiments, in step S2, the mass ratio of the rhodium ash to the molten reagent is 1:(1-10), preferably 1:(2-8), for example 1:3 or 1:5.

[0056] In some embodiments, in step S2, the temperature of the melting reaction is 200-800°C, preferably 300-800°C, for example 550°C or 750°C.

[0057] In some embodiments, the melting reaction time in step S2 is 1-10 hours, preferably 2-8 hours.

[0058] In some embodiments, in step S2, the acid treatment temperature of the rhodium sulfate preparation method is 10-100°C, preferably 20-90°C.

[0059] In some embodiments, in step S2, the acid in the acid treatment of the method for preparing rhodium sulfate includes hydrochloric acid; preferably, the concentration of the hydrochloric acid is 2 mol / L; preferably, the mass ratio of the hydrochloric acid to the rhodium ash is 40:1.

[0060] The present invention also provides a method for preparing hydrated rhodium trichloride, which includes the following steps: under the conditions of temperature of 30-90℃ and presence of a precipitant, the pH value of rhodium sulfate is controlled to be less than or equal to 9.0 for precipitation reaction for 1.5-10 hours, and after acid treatment, hydrated rhodium trichloride is obtained; wherein, the mass ratio of rhodium sulfate to precipitant is (100-1000):1.

[0061] The settling agent is one or more of polyacrylamide, aluminum chloride, polyferric sulfate, polyferric aluminum sulfate, and alum.

[0062] In this invention, preferably, the reaction conditions of the method for preparing hydrated rhodium trichloride are as described above.

[0063] In this invention, preferably, the method for preparing rhodium acetylacetone carbonyl further includes the method for preparing rhodium sulfate as described above.

[0064] This invention also provides a method for preparing rhodium sulfate, comprising the following steps:

[0065] S1. In an atmosphere with an oxygen content of 0-30%, but not 0%, a mixture of rhodium-containing waste liquid and a mixing reagent is incinerated to obtain rhodium ash; the mixing reagent is one or more of alkali metal compounds, alkaline earth metal compounds, carbon materials, and silicon dioxide; the mass ratio of the rhodium-containing waste liquid to the mixing reagent is 100:(1-20); % refers to the percentage of oxygen in the total volume of the atmosphere.

[0066] S2. The rhodium ash is mixed with a molten reagent and subjected to a molten reaction, followed by acid treatment to obtain a rhodium sulfate solution; the molten reagent includes one or more of potassium pyrosulfate, sodium pyrosulfate, potassium sulfate, sodium bisulfate, and potassium bisulfate.

[0067] In this invention, preferably, the reaction conditions of the method for preparing rhodium sulfate are as described above.

[0068] Based on common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain various preferred embodiments of the present invention.

[0069] The reagents and raw materials used in this invention are all commercially available.

[0070] The positive and progressive effects of this invention are as follows:

[0071] (1) In the preparation method of acetylacetone carbonyl rhodium of the present invention, crude rhodium trichloride hydrate can be used as raw material, which reduces the loss of raw materials. Moreover, the post-processing does not require a large amount of water to wash the obtained catalyst solid. Instead, the crude catalyst is directly extracted by solvent extraction, which effectively avoids the residue of chloride ions in the crude catalyst. The preparation method also has a high yield of rhodium.

[0072] (2) The method for preparing rhodium hydroxide in this invention is simple and has a high yield of rhodium;

[0073] (3) In the method for preparing rhodium sulfate of the present invention, rhodium-containing waste liquid is used as raw material, which has the advantages of low cost and equipment requirements, simple operation, mild conditions and high rhodium aqueous phase recovery rate; preferably, the rhodium recovery rate is increased to 99% or more.

[0074] (4) In each preparation method of the present invention, the heat energy consumption is low, and the amount of wastewater generated can be significantly reduced, which fundamentally reduces the pollution to the environment, has broad application prospects, and is conducive to industrialization. Detailed Implementation

[0075] The present invention is further illustrated below by way of embodiments, but the invention is not limited to the scope of the embodiments described herein. Experimental methods in the following embodiments that do not specify specific conditions were performed according to conventional methods and conditions, or as selected according to the product instructions.

[0076] The raw materials, solvents, catalysts, etc. used in the following examples were all obtained commercially;

[0077] The yields in the following examples and comparative examples refer to the molar yield calculated as actual yield / theoretical yield × 100%.

[0078] Example 1

[0079] (1) Preparation method of rhodium sulfate

[0080] S1. 400g of the distilled rhodium-containing waste liquid after hydroformylation is added to a 2L ceramic crucible, followed by 10g of sodium carbonate as a mixing agent. The mixture is then placed in a muffle furnace and incinerated using a programmed temperature rise method. By adjusting the ratio of air to nitrogen, the material is burned in an oxygen-deficient atmosphere (oxygen content between 1% and 5%). The programmed temperature rise method is as follows: Stage 1 – from room temperature to 200℃ and held at 200℃ for 1 hour; Stage 2 – to 250℃ and held for 2 hours; Stage 3 – to 300℃ and held for 3 hours; Stage 4 – to 350℃ and held for 30 minutes; Stage 5 – to 400℃ and held for 30 minutes; Stage 6 – to 450℃ and held for 8-12 hours, yielding rhodium ash. The rhodium-containing waste liquid includes organic high-boiling-point impurities, phosphine ligands, deactivated rhodium catalysts, and base metals such as Fe, Mg, Ca, Al, Cr, and Ni. (The rhodium content in the rhodium-containing wastewater is 10-100 ppm, and the base metal content is 10-500 ppm.)

[0081] S2. Add potassium hydrogen sulfate (50g) to rhodium ash (10g) as a melting reagent, stir well, place in a muffle furnace, and heat to 550℃ for 1 hour to carry out the melting reaction. Stop heating, cool to room temperature, remove, and then add 2mol / L hydrochloric acid (400g), heat to 80℃, stir to dissolve and perform acid treatment; then filter through a Buchner funnel, and the filtrate is the rhodium sulfate solution.

[0082] ICP (PerkinElmer, optical emission spectrometer, Avio200) was used for detection. The rhodium yield calculation formula ① is:

[0083] Rhodium yield y1 = Rhodium content in rhodium sulfate solution / Rhodium content in rhodium-containing distillation residue × 100%;

[0084] The calculated yield of rhodium transferred from the organic phase to the aqueous phase in this step is 98%.

[0085] (2) Preparation method of hydrated rhodium trichloride

[0086] Add 400g of rhodium sulfate solution prepared by the above method to a 500mL reaction flask, and heat to 80℃ for reaction. Then, add 30% sodium hydroxide solution dropwise to adjust the pH to 8.0-8.5, and add polyacrylamide (0.5g) as a precipitant. After the addition is complete, keep the mixture warm and stir for 2 hours to carry out the precipitation reaction. After the precipitation reaction is complete, slowly cool to 20-30℃ and filter to obtain a dark brown solid. Dissolve the dark brown solid in 6mol / L hydrochloric acid solution, heat to 80-85℃ and stir for 1 hour, cool to room temperature, and concentrate directly to dryness to obtain 2.5g of reddish-brown solid, which is rhodium trichloride hydrate.

[0087] ICP (PerkinElmer, optical emission spectrometer, Avio200) was used for detection. The rhodium yield calculation formula ② is as follows:

[0088] Rhodium yield y2 = Rhodium content in hydrated rhodium trichloride / Rhodium content in rhodium sulfate solution × 100%;

[0089] The calculated yield of rhodium in this step, converted from rhodium sulfate to hydrated rhodium trichloride, is 99%.

[0090] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0091] Transfer 2.5 g of hydrated rhodium trichloride to a 250 ml three-necked flask, then add 50 g of N,N-dimethylformamide, 17 g of acetylacetone, and 0.5 g of triethylenetetramine as a complexing agent. Purge the mixture three times with nitrogen and react at 145 °C for 1-1.5 h under nitrogen protection.

[0092] Cool to room temperature, pour the reaction solution into deionized water, stir to precipitate crystals, filter, add ethyl acetate (100g) to the filter cake for dissolution and extraction, and wash the extracted organic phase twice with saturated brine (50g). Allow to stand and separate into layers, then concentrate the upper organic phase at low temperature to obtain rhodium acetylacetone dicarbonyl (1.2g).

[0093] ICP (PerkinElmer, optical emission spectrometer, Avio200) was used for detection. The rhodium yield calculation formula ③ is as follows:

[0094] Rhodium yield y3 = Rhodium content in rhodium acetylacetone / Rhodium content in rhodium trichloride × 100%;

[0095] The calculated yield of rhodium in this step is 99%.

[0096] The formula for calculating the total yield of rhodium after steps (1), (2), and (3) is ④:

[0097] Rhodium yield y 总 =y1×y2×y3

[0098] The calculated total rhodium yield in this embodiment is 96%.

[0099] Example 2

[0100] (1) Preparation method of rhodium sulfate

[0101] In step S2, sodium bisulfate is used as the melting agent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0102] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 97.5%.

[0103] (2) Preparation method of hydrated rhodium trichloride

[0104] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0105] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0106] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0107] The total rhodium yield in this embodiment was calculated to be 95.5%.

[0108] Example 3

[0109] (1) Preparation method of rhodium sulfate

[0110] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0111] (2) Preparation method of hydrated rhodium trichloride

[0112] Aluminum chloride was used as a settling agent; otherwise, all other conditions were the same as step (2) in Example 1.

[0113] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 98%.

[0114] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0115] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0116] The calculated total rhodium yield in this embodiment is 95.1%.

[0117] Example 4

[0118] (1) Preparation method of rhodium sulfate

[0119] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0120] (2) Preparation method of hydrated rhodium trichloride

[0121] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0122] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0123] Triethanolamine was used as the complexing agent; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 98%.

[0124] The calculated total rhodium yield in this embodiment is 95%.

[0125] Example 5

[0126] (1) Preparation method of rhodium sulfate

[0127] In step S1, sodium chloride is used as the mixing reagent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0128] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 97%.

[0129] (2) Preparation method of hydrated rhodium trichloride

[0130] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0131] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0132] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0133] The calculated total rhodium yield in this embodiment is 95%.

[0134] Example 6

[0135] (1) Preparation method of rhodium sulfate

[0136] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0137] (2) Preparation method of hydrated rhodium trichloride

[0138] Adjust the pH value to 6.0-6.5; otherwise, all other conditions are the same as step (2) in Example 1.

[0139] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 97.5%.

[0140] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0141] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0142] The calculated total rhodium yield in this embodiment is 94.6%.

[0143] Example 7

[0144] (1) Preparation method of rhodium sulfate

[0145] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0146] (2) Preparation method of hydrated rhodium trichloride

[0147] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0148] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0149] The complexation reaction was carried out at a temperature of 150°C; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 97%.

[0150] The total rhodium yield in this embodiment was calculated to be 94.1%.

[0151] Example 8

[0152] (1) Preparation method of rhodium sulfate

[0153] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0154] (2) Preparation method of hydrated rhodium trichloride

[0155] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0156] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0157] The complexation reaction was carried out at a temperature of 130°C; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 96.5%.

[0158] The calculated total rhodium yield in this embodiment is 93.6%.

[0159] Example 9

[0160] (1) Preparation method of rhodium sulfate

[0161] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0162] (2) Preparation method of hydrated rhodium trichloride

[0163] Polyferric sulfate was used as a settling agent; otherwise, all other conditions were the same as step (2) in Example 1.

[0164] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride was 94.8%.

[0165] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0166] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0167] The calculated total rhodium yield in this embodiment is 92%.

[0168] Example 10

[0169] (1) Preparation method of rhodium sulfate

[0170] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0171] (2) Preparation method of hydrated rhodium trichloride

[0172] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0173] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0174] The complexation reaction time was extended to 3-4 hours; otherwise, all other conditions were the same as step (3) in Example 1; the yield of rhodium in this step was 93.2%.

[0175] The total rhodium yield in this embodiment is calculated to be 90.4%.

[0176] Example 11

[0177] (1) Preparation method of rhodium sulfate

[0178] In step S2, the melting temperature is 750°C; otherwise, all other conditions are the same as in step (1) of Example 1.

[0179] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 95%.

[0180] (2) Preparation method of hydrated rhodium trichloride

[0181] Adjust the pH value to 8.5-9.0; otherwise, all other conditions are the same as step (2) in Example 1.

[0182] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride was 95.7%.

[0183] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0184] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0185] The calculated total rhodium yield in this embodiment is 90%.

[0186] Example 12

[0187] (1) Preparation method of rhodium sulfate

[0188] In step S1, calcium chloride is used as the mixing reagent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0189] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 93%.

[0190] (2) Preparation method of hydrated rhodium trichloride

[0191] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0192] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0193] Triethylamine was used as the complexing agent; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 96%.

[0194] The total rhodium yield in this embodiment was calculated to be 88.4%.

[0195] Example 13

[0196] (1) Preparation method of rhodium sulfate

[0197] In step S1, silica is used as the mixing reagent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0198] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 93%.

[0199] (2) Preparation method of hydrated rhodium trichloride

[0200] Adjust the pH value to 5.0-5.5; otherwise, all other conditions are the same as step (2) in Example 1.

[0201] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride was 95.3%.

[0202] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0203] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0204] The total rhodium yield in this embodiment is calculated to be 87.7%.

[0205] Example 14

[0206] (1) Preparation method of rhodium sulfate

[0207] In step S1, sodium hydroxide is used as the mixing reagent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0208] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 90%.

[0209] (2) Preparation method of hydrated rhodium trichloride

[0210] The precipitation reaction was carried out at a temperature of 60°C; otherwise, all other conditions were the same as step (2) in Example 1.

[0211] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 98%.

[0212] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0213] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0214] The calculated total rhodium yield in this embodiment is 87.3%.

[0215] Example 15

[0216] (1) Preparation method of rhodium sulfate

[0217] In step S1, activated carbon is used as the mixing reagent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0218] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 93.7%.

[0219] (2) Preparation method of hydrated rhodium trichloride

[0220] The precipitation reaction was carried out at a temperature of 40°C; otherwise, all other conditions were the same as step (2) in Example 1.

[0221] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 94%.

[0222] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0223] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0224] The calculated total rhodium yield in this embodiment is 87.2%.

[0225] Example 16

[0226] (1) Preparation method of rhodium sulfate

[0227] In step S1, calcium hydroxide is used as the mixing reagent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0228] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 91.7%.

[0229] (2) Preparation method of hydrated rhodium trichloride

[0230] Alum was used as a settling agent; otherwise, all other conditions were the same as step (2) in Example 1.

[0231] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride was 96.3%.

[0232] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0233] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0234] The total rhodium yield in this embodiment is calculated to be 87.4%.

[0235] Example 17

[0236] (1) Preparation method of rhodium sulfate

[0237] In step S2, potassium pyrosulfate is used as the molten reagent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0238] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 94%.

[0239] (2) Preparation method of hydrated rhodium trichloride

[0240] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0241] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0242] Cyclohexane was used as the extraction reagent; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 94.3%.

[0243] The total rhodium yield in this embodiment was calculated to be 87.8%.

[0244] Example 18

[0245] (1) Preparation method of rhodium sulfate

[0246] In step S2, potassium sulfate is used as the melting agent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0247] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 93%.

[0248] (2) Preparation method of hydrated rhodium trichloride

[0249] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0250] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0251] Toluene was used as the extraction reagent; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 94.2%.

[0252] The total rhodium yield in this embodiment was calculated to be 86.7%.

[0253] Example 19

[0254] (1) Preparation method of rhodium sulfate

[0255] In step S1, the temperature of the sixth stage of incineration is 750°C; otherwise, all other conditions are the same as step (1) in Example 1.

[0256] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 94.3%.

[0257] (2) Preparation method of hydrated rhodium trichloride

[0258] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0259] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0260] The amount of N,N-dimethylformamide added was 25g; otherwise, all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 92%.

[0261] The total rhodium yield in this embodiment was calculated to be 85.9%.

[0262] Example 20

[0263] (1) Preparation method of rhodium sulfate

[0264] In step S1, the amount of sodium carbonate added is 20g; otherwise, all other conditions are the same as in step (1) of Example 1.

[0265] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 93.2%.

[0266] (2) Preparation method of hydrated rhodium trichloride

[0267] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0268] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0269] The amount of acetylacetone added was 8.5g; otherwise, all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 93%.

[0270] The total rhodium yield in this embodiment was calculated to be 85.8%.

[0271] Example 21

[0272] (1) Preparation method of rhodium sulfate

[0273] In step S2, the amount of potassium bisulfate used is 30g; otherwise, all other conditions are the same as in step (1) of Example 1.

[0274] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 92%.

[0275] (2) Preparation method of hydrated rhodium trichloride

[0276] Adjust the pH value with 25-28% ammonia; otherwise, all other conditions are the same as step (2) in Example 1.

[0277] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 94%.

[0278] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0279] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0280] The calculated total rhodium yield in this embodiment is 85.6%.

[0281] Example 22

[0282] (1) Preparation method of rhodium sulfate

[0283] In step S1, incineration is carried out in an atmosphere with an oxygen content between 5% and 10%; otherwise, all other conditions are the same as in step (1) of Example 1.

[0284] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 95%.

[0285] (2) Preparation method of hydrated rhodium trichloride

[0286] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0287] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0288] Methyl tert-butyl ether was used as the extraction reagent; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 92%.

[0289] The total rhodium yield in this embodiment was calculated to be 86.5%.

[0290] Example 23

[0291] (1) Preparation method of rhodium sulfate

[0292] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0293] (2) Preparation method of hydrated rhodium trichloride

[0294] Polyacrylamide (2g) was added as a settling agent; otherwise, all other conditions were the same as in step (2) of Example 1.

[0295] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride was 94.8%.

[0296] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0297] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0298] The calculated total rhodium yield in this embodiment is 92%.

[0299] Example 24

[0300] (1) Preparation method of rhodium sulfate

[0301] In step S1, incineration is carried out in an atmosphere with an oxygen content between 15% and 20%; otherwise, all other conditions are the same as in step (1) of Example 1.

[0302] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 93%.

[0303] (2) Preparation method of hydrated rhodium trichloride

[0304] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0305] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0306] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0307] The calculated total rhodium yield in this embodiment is 91%.

[0308] Example 25

[0309] (1) Preparation method of rhodium sulfate

[0310] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0311] (2) Preparation method of hydrated rhodium trichloride

[0312] The precipitation reaction was kept at a constant temperature for 8 hours; all other conditions were the same as step (2) in Example 1.

[0313] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 92%.

[0314] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0315] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0316] The calculated total rhodium yield in this embodiment is 89.3%.

[0317] Comparative Example 1

[0318] (1) Preparation method of rhodium sulfate

[0319] In step S1, the temperature of the sixth stage of incineration is 850°C; otherwise, all other conditions are the same as in step (1) of Example 1.

[0320] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 85%.

[0321] (2) Preparation method of hydrated rhodium trichloride

[0322] Adjust the pH value to 9.0-9.5, excluding 9.0; otherwise, all other conditions are the same as step (2) in Example 1.

[0323] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 82%.

[0324] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0325] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0326] The calculated total rhodium yield in this embodiment is 69%.

[0327] Comparative Example 2

[0328] (1) Preparation method of rhodium sulfate

[0329] In step S2, the melting temperature is 850°C; otherwise, all other conditions are the same as in step (1) of Example 1.

[0330] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 88%.

[0331] (2) Preparation method of hydrated rhodium trichloride

[0332] The precipitation reaction was carried out at a temperature of 20°C; otherwise, all other conditions were the same as step (2) in Example 1.

[0333] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 82%.

[0334] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0335] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0336] The total rhodium yield in this embodiment was calculated to be 71.4%.

[0337] Comparative Example 3

[0338] (1) Preparation method of rhodium sulfate

[0339] In step S1, flour is used as the mixing reagent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0340] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 78.8%.

[0341] (2) Preparation method of hydrated rhodium trichloride

[0342] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0343] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0344] The complexation reaction was carried out at a temperature of 120°C; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 86.2%.

[0345] The total rhodium yield in this embodiment was calculated to be 67.2%.

[0346] Comparative Example 4

[0347] (1) Preparation method of rhodium sulfate

[0348] In step S2, sodium sulfate is used as the melting agent; otherwise, all other conditions are the same as in step (1) of Example 1.

[0349] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 80.3%.

[0350] (2) Preparation method of hydrated rhodium trichloride

[0351] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0352] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0353] The complexation reaction took 8-8.5 hours; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 83.4%.

[0354] The total rhodium yield in this embodiment was calculated to be 66.3%.

[0355] Comparative Example 5

[0356] (1) Preparation method of rhodium sulfate

[0357] In step S1, no mixing reagent is added during incineration; otherwise, all other conditions are the same as step (1) in Example 1.

[0358] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 71%.

[0359] (2) Preparation method of hydrated rhodium trichloride

[0360] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0361] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0362] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0363] The total rhodium yield in this embodiment was calculated to be 69.6%.

[0364] Comparative Example 6

[0365] (1) Preparation method of rhodium sulfate

[0366] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0367] (2) Preparation method of hydrated rhodium trichloride

[0368] The pH was adjusted with 30% sodium hydroxide solution without adding a settling agent; all other conditions were the same as in step (2) of Example 1; the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride in this step was 81%.

[0369] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0370] The complexation reaction time was extended to 4-5 hours; otherwise, this step was the same as step (3) in Example 1; the yield of rhodium in this step was 92.7%.

[0371] The total rhodium yield in this embodiment was calculated to be 73.6%.

[0372] Comparative Example 7

[0373] (1) Preparation method of rhodium sulfate

[0374] In step S1, the temperature of the sixth stage of incineration is 650°C; otherwise, all other conditions are the same as step (1) in Example 1.

[0375] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 96%.

[0376] (2) Preparation method of hydrated rhodium trichloride

[0377] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0378] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0379] The solvent did not contain a complexing agent; all other conditions were the same as in step (3) of Example 1; the yield of rhodium in this step was 83%.

[0380] The total rhodium yield in this embodiment was calculated to be 78.9%.

[0381] Comparative Example 8

[0382] (1) Preparation method of rhodium sulfate

[0383] In step S1, the amount of mixing reagent added is 2g, and the mass ratio of rhodium-containing waste liquid to mixing reagent is 100:0.5; otherwise, all other conditions are the same as step (1) in Example 1.

[0384] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 89.5%.

[0385] (2) Preparation method of hydrated rhodium trichloride

[0386] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0387] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0388] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0389] The total rhodium yield in this embodiment is calculated to be 87.7%.

[0390] Comparative Example 9

[0391] (1) Preparation method of rhodium sulfate

[0392] In step S1, the amount of mixing reagent added is 80g, and the mass ratio of rhodium-containing waste liquid to mixing reagent is 100:20; otherwise, all other conditions are the same as step (1) in Example 1.

[0393] In this step, the yield of rhodium transferred from the organic phase to the aqueous phase was 88.3%.

[0394] (2) Preparation method of hydrated rhodium trichloride

[0395] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0396] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0397] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0398] The total rhodium yield in this embodiment is calculated to be 86.5%.

[0399] Comparative Example 10

[0400] (1) Preparation method of rhodium sulfate

[0401] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0402] (2) Preparation method of hydrated rhodium trichloride

[0403] The precipitation reaction was kept at a constant temperature for 1 hour; all other conditions were the same as step (2) in Example 1.

[0404] In this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride was 84.7%.

[0405] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0406] This step is the same as step (3) in Example 1; the rhodium yield in this step is 99%.

[0407] The calculated total rhodium yield in this embodiment is 82.2%.

[0408] Comparative Example 11

[0409] (1) Preparation method of rhodium sulfate

[0410] This step is the same as step (1) in Example 1; in this step, the yield of rhodium transferred from the organic phase to the aqueous phase is 98%.

[0411] (2) Preparation method of hydrated rhodium trichloride

[0412] This step is the same as step (2) in Example 1; in this step, the yield of rhodium converted from rhodium sulfate to hydrated rhodium trichloride is 99%.

[0413] (3) Preparation method of rhodium dicarbonyl acetylacetone

[0414] The complexation reaction was not carried out under an inert atmosphere. Apart from this, all other conditions are the same as step (3) in Example 1; the yield of rhodium in this step is 89%.

[0415] The calculated total rhodium yield in this embodiment is [percentage missing]. 86.3%.

[0416] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing rhodium carbonyl acetylacetone, characterized in that, It includes the following steps: Rhodium trichloride hydrate was subjected to a complexation reaction with mixture A under an inert atmosphere to prepare rhodium carbonyl acetylacetone; the temperature of the complexation reaction was 125-200℃; and the time of the complexation reaction was 1-7 h. The mixture A comprises N,N-dimethylformamide, acetylacetone, and a complexing agent; The complexing agent is one or more of triethylamine, triethylenetetramine, and triethanolamine.

2. The method for preparing rhodium carbonyl acetylacetone as described in claim 1, characterized in that, The mass ratio of the hydrated rhodium trichloride to the acetylacetone is 1:(1-10); And / or, the mass ratio of the hydrated rhodium trichloride to the N,N-dimethylformamide is 1:(10-100); And / or, the mass ratio of the hydrated rhodium trichloride to the complexing agent is 1:(0.01-1); And / or, the inert atmosphere includes a nitrogen atmosphere; And / or, the complexation reaction may be followed by a purification step.

3. The method for preparing rhodium carbonyl acetylacetone as described in claim 2, characterized in that, The complexation reaction is followed by a purification step, which includes extraction, washing, and concentration in sequence.

4. The method for preparing rhodium carbonyl acetylacetone as described in claim 3, characterized in that, The mass ratio of the hydrated rhodium trichloride, the acetylacetone, the N,N-dimethylformamide and the complexing agent is 1:(1-10):(10-100):(0.01-1); And / or, the mass ratio of the hydrated rhodium trichloride to the acetylacetone is 1:(2-9); And / or, the mass ratio of the hydrated rhodium trichloride to the N,N-dimethylformamide is 1:(20-70); And / or, the mass ratio of the hydrated rhodium trichloride to the complexing agent is 1:(0.05-0.5); And / or, the temperature of the complexation reaction is 130-200°C; And / or, the complexation reaction takes 1-5 hours; And / or, the extraction reagent is one or more of toluene, cyclohexane, n-hexane, ethyl acetate, methyl tert-butyl ether, tetrahydrofuran, dichloromethane, and chlorobenzene; And / or, the mass ratio of the N,N-dimethylformamide to the extraction reagent is 1:(1-10).

5. The method for preparing rhodium carbonyl acetylacetone as described in claim 4, characterized in that, The temperature of the complexation reaction is 130°C, 145°C, or 150°C. And / or, the extraction reagent is one or more of toluene, cyclohexane, ethyl acetate and methyl tert-butyl ether; And / or, the mass ratio of the N,N-dimethylformamide to the extraction reagent is 1:(2-8).

6. The method for preparing rhodium carbonyl acetylacetone as described in claim 5, characterized in that, The extraction reagent is ethyl acetate, cyclohexane, or toluene.

7. The method for preparing rhodium carbonyl acetylacetone according to claim 1, characterized in that, The method for preparing acetylacetone carbonyl rhodium further includes a method for preparing hydrated rhodium trichloride, which includes the following steps: Under conditions of 30-90℃ and in the presence of a flocculant, the pH of rhodium sulfate is controlled to be less than or equal to 9.0 for a precipitation reaction of 1.5-10 hours. After acid treatment, hydrated rhodium trichloride is obtained. The mass ratio of rhodium sulfate to flocculant is (100-1000):

1. The settling agent is one or more of polyacrylamide, aluminum chloride, polyferric sulfate, polyferric aluminum sulfate, and alum.

8. The method for preparing rhodium carbonyl acetylacetone as described in claim 7, characterized in that, The pH value range is 5.0-9.0; And / or, the precipitation reaction is carried out at a temperature of 40-80°C; And / or, the precipitation reaction takes 2-10 hours; And / or, the settling agent is one or more of polyacrylamide, aluminum chloride, polyferric sulfate and alum; And / or, the mass ratio of the rhodium sulfate to the precipitant is (200-1000):1; And / or, the pH value of the rhodium sulfate is adjusted using an alkaline solution; And / or, the precipitation reaction is followed by cooling to 20-30°C; And / or, in the acid treatment of the method for preparing hydrated rhodium trichloride, the acid solution includes hydrochloric acid; And / or, the method for preparing hydrated rhodium trichloride further includes a concentration step after acid treatment.

9. The method for preparing rhodium carbonyl acetylacetone as described in claim 8, characterized in that, The pH value range is 5.0-5.5, 6.0-6.5, 7.0-7.5, 8.0-8.5, or 8.5-9.0; And / or, the precipitation reaction is carried out at a temperature of 40°C, 60°C, or 80°C; And / or, the precipitation reaction takes 2 hours; And / or, the settling agent is polyacrylamide, aluminum chloride, polyferric sulfate or alum; And / or, the mass ratio of the rhodium sulfate to the precipitant is 800:1 or 200:1; And / or, the pH value of the rhodium sulfate is adjusted using an alkaline solution; the alkaline solution is a solution containing one or more solutes selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, and calcium hydroxide. And / or, in the acid treatment of the method for preparing hydrated rhodium trichloride, the acid solution includes hydrochloric acid; the concentration of the hydrochloric acid is 6 mol / L.

10. The method for preparing rhodium carbonyl acetylacetone as described in claim 9, characterized in that, The pH value of the rhodium sulfate is adjusted using an alkaline solution; the alkaline solution is a solution containing one or more solutes, such as sodium hydroxide, sodium carbonate, potassium carbonate, and ammonia.

11. The method for preparing rhodium carbonyl acetylacetone according to claim 10, characterized in that, The pH value of the rhodium sulfate is adjusted using an alkaline solution; the alkaline solution is a sodium hydroxide solution or an ammonia solution.

12. The method for preparing rhodium carbonyl acetylacetone as described in claim 7, characterized in that, The method for preparing rhodium carbonyl acetylacetone further includes a method for preparing rhodium sulfate, which includes the following steps: S1. In an atmosphere with an oxygen content of 0-30%, but not 0%, incinerate a mixture of rhodium-containing waste liquid and a mixing reagent to obtain rhodium ash; the mass ratio of the rhodium-containing waste liquid to the mixing reagent is 100:(1-20); % refers to the percentage of oxygen in the total volume of the atmosphere; the incineration temperature is 100-800℃; the mixing reagent is sodium carbonate, sodium chloride, calcium chloride, silicon dioxide, sodium hydroxide, activated carbon, or calcium hydroxide; S2. The rhodium ash is mixed with a molten reagent and subjected to a molten reaction, followed by acid treatment to obtain a rhodium sulfate solution; the molten reagent includes one or more of potassium pyrosulfate, sodium pyrosulfate, potassium sulfate, sodium bisulfate, and potassium bisulfate; the temperature of the molten reaction is 200-800℃.

13. The method for preparing rhodium carbonyl acetylacetone according to claim 12, characterized in that, In step S1, the rhodium-containing waste liquid includes the rhodium-containing waste liquid after hydroformylation reaction; And / or, the mass ratio of the rhodium-containing waste liquid to the mixing reagent is 100:(2-10); And / or, the incineration temperature is 150-750°C; And / or, the incineration is carried out in a muffle furnace; And / or, the incineration process employs a programmed temperature rise method; And / or, in step S1, the atmosphere further includes nitrogen; And / or, in step S1, the oxygen content of the atmosphere is 1%-20%.

14. The method for preparing rhodium carbonyl acetylacetone as described in claim 13, characterized in that, In step S1, the rhodium-containing waste liquid includes the rhodium-containing waste liquid after hydroformylation reaction; the rhodium-containing waste liquid contains one or more of Rh, Fe, Mg, Ca, Al, Cr and Ni; And / or, the mass ratio of the rhodium-containing waste liquid to the mixing reagent is 100:2.5 or 100:5; And / or, the incineration temperature is 450°C, 650°C or 750°C; And / or, the incineration process employs a programmed temperature rise method; The programmed temperature rise method includes: the first stage - raising the temperature from room temperature to 200°C and holding for 1 hour; the second stage - raising the temperature to 250°C and holding for 2 hours; the third stage - raising the temperature to 300°C and holding for 3 hours; the fourth stage - raising the temperature to 350°C and holding for 30 minutes; the fifth stage - raising the temperature to 400°C and holding for 30 minutes; and the sixth stage - raising the temperature to 450°C and holding for 8-12 hours. And / or, in step S1, the oxygen content of the atmosphere is 1%-10%.

15. The method for preparing rhodium carbonyl acetylacetone as described in claim 14, characterized in that, In step S1, the rhodium-containing waste liquid includes rhodium-containing waste liquid after hydroformylation reaction; the rhodium-containing waste liquid contains one or more of Rh, Fe, Mg, Ca, Al, Cr and Ni; the content of Rh in the rhodium-containing waste liquid is 10-100 ppm, and the content of Fe, Mg, Ca, Al, Cr and Ni in the rhodium-containing waste liquid is 10-500 ppm; And / or, in step S1, the oxygen content of the atmosphere is 1%-5%.

16. The method for preparing rhodium carbonyl acetylacetone according to claim 12, characterized in that, In step S2, the molten reagent is potassium bisulfate, sodium bisulfate, potassium pyrosulfate, or potassium sulfate; And / or, the mass ratio of the rhodium ash to the molten reagent is 1:(1-10); And / or, the temperature of the melting reaction is 300-800°C; And / or, the melting reaction takes 1-10 hours; And / or, the acid treatment temperature in the method for preparing rhodium sulfate is 10-100℃; And / or, in the acid treatment of the method for preparing rhodium sulfate, the acid includes hydrochloric acid.

17. The method for preparing rhodium carbonyl acetylacetone as described in claim 16, characterized in that, The mass ratio of the rhodium ash to the molten reagent is 1:(2-8); And / or, the temperature of the melting reaction is 550°C or 750°C; And / or, the melting reaction takes 2-8 hours; And / or, the acid treatment temperature in the method for preparing rhodium sulfate is 20-90°C; And / or, in the acid treatment of the method for preparing rhodium sulfate, the acid includes hydrochloric acid; the concentration of the hydrochloric acid is 2 mol / L; and / or, the mass ratio of the hydrochloric acid to the rhodium ash is 40:

1.

18. The method for preparing rhodium carbonyl acetylacetone as described in claim 16, characterized in that, The mass ratio of the rhodium ash to the molten reagent is 1:3 or 1:5.