CN110607448B - Method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid - Google Patents
Method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid Download PDFInfo
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Abstract
The invention discloses a method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid, which comprises the following steps: firstly, adsorbing rhodium in rhodium-containing organic waste liquid generated in the production process of a rhodium homogeneous catalyst on an adsorbent in a dynamic adsorption mode by adopting a high-molecular adsorbent; secondly, placing the rhodium-containing adsorbent in an acid solvent, adding a certain amount of stannous chloride, refluxing and stirring, transferring rhodium from the solid adsorbent to a solution, and filtering to obtain a rhodium-containing aqueous phase solution; thirdly, purifying; fourthly, rhodium trichloride is obtained through evaporation and concentration. The method is suitable for rhodium-containing organic waste liquid generated in the production process of a homogeneous catalyst, solves the problem of recovering rhodium from an organic phase, is simple and convenient to operate, does not generate secondary waste gas and waste water, is green and environment-friendly, and can achieve a recovery rate of the rhodium of more than 95%.
Description
Technical Field
The invention belongs to the technical field of precious metal recovery, and particularly relates to a method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid.
Background
The rhodium-containing homogeneous catalyst plays an important role in chemical synthesis, and is widely applied to the processes of catalytic hydrogenation of olefin, carbonylation of methanol to synthesize acetic acid, hydrogenation of propylene to synthesize aldehyde and the like. The main rhodium-containing homogeneous catalysts are: triphenylphosphine rhodium chloride, rhodium octanoate, triphenylphosphine rhodium carbonyl acetylacetonate (rhodium park), and the like. The yield of the catalyst can not reach 100% during preparation, and rhodium-containing organic waste liquid is inevitably generated. Since rhodium is expensive and scarce in resources, the recovery of rhodium from waste organic liquids is of great importance, since the rhodium content in these waste liquids is already high relative to that in mines.
At present, the main methods for recovering rhodium from organic waste liquid include a concentration incineration method, a precipitation method and the like.
The incineration method generally comprises the steps of mixing an organic waste catalyst solution and an alkaline compound (such as sodium carbonate), then placing the mixture into an incinerator, incinerating the mixture at a high temperature to enrich rhodium in incineration slag as much as possible, and then treating the incineration slag containing rhodium through reduction, activation dissolution, separation, purification and the like to finally obtain metal rhodium. The incineration method is simple to operate, and can completely remove organic impurities, but in the incineration process, rhodium volatilizes along with flue gas, the loss is more, and due to the addition of alkaline substances, the rhodium ash content is large, the impurities are high, and the subsequent purification process is complicated.
The precipitation method generally comprises the steps of adding sodium sulfide into an organic waste rhodium solution to precipitate rhodium, then dissolving the rhodium by aqua regia, and carrying out chemical precipitation and purification to obtain qualified rhodium powder.
Liugui Hua and the like (noble metals, 32 volumes in 2011) successfully recover rhodium in waste liquid by adopting a fire-humidity combined process aiming at organic rhodium-containing waste liquid generated in the synthesis process of triphenylphosphine rhodium chloride. The main process comprises the steps of distilling and recovering ethanol and removing moisture, incinerating and incinerating, chloridizing, purifying and hydrogen reducing to finally obtain rhodium powder. The burning process may generate dioxin to pollute the environment. Li Qiang et al (Kunming noble metal Shuichi article) aiming at acetylacetone rhodium waste liquid, which is a typical low-concentration rhodium-containing organic waste liquid, is used as a raw material, and rhodium is recovered by adopting the sodium sulfide precipitation-aqua regia dissolution-sodium nitrite complexation method for preparing crude rhodium, a medium-temperature chlorination method and a calcination reduction process, and the recovery rate is about 90 percent. There will be a large amount of H in the precipitation step2S gas is generated and can cause harm to the environment and human body. And the process is long and the efficiency is low. CN108165758A reports a method for recovering rhodium from rhodium octoate spent catalyst by using supercritical oxidation method, and does not specifically suggest the recovery rate of rhodium, and industrial application of the supercritical method is difficult.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid aiming at the defects of the prior art. The method is simple and convenient to operate, does not generate secondary waste gas and waste water, is green and environment-friendly, is suitable for the rhodium-containing organic waste liquid generated in the production process of the homogeneous catalyst, solves the problem of recovering rhodium from the organic phase, and can achieve the recovery rate of the rhodium of more than 95%.
In order to solve the technical problems, the invention adopts the technical scheme that: a method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid is characterized by comprising the following steps:
step one, adsorption: adsorbing rhodium in rhodium-containing organic waste liquid generated in the production process of a rhodium homogeneous catalyst to a high-molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the mass content of rhodium in the rhodium-containing organic waste liquid is 10 ppm-1000 ppm; the rhodium-containing organic waste liquid is produced in the process of producing homogeneous catalysts of rhodium park, rhodium acetylacetonate carbonyl, rhodium octanoate or Wilkinson;
step two, desorption: drying the rhodium-containing adsorbent in the step one, then placing the rhodium-containing adsorbent in an acid solution, then adding stannous chloride, refluxing and stirring for 4-8 h at the temperature of 80-120 ℃, and filtering to obtain a rhodium-containing aqueous phase solution; the acid solution is hydrochloric acid or aqua regia, and the mass of the acid solution is 5-10 times of that of the dried rhodium-containing adsorbent;
step three, purification: adding alkali liquor into the rhodium-containing aqueous phase solution in the second step until the pH value is 7.5-9 to generate a precipitate, and filtering and washing the precipitate; then dissolving the precipitate with hydrochloric acid solution, adjusting the pH value to 1.0-1.5, and filtering to remove insoluble substances; purifying the solution after filtering and removing insoluble substances by adopting cation exchange resin;
step four, concentration: and (4) putting the solution purified in the third step into a rotary evaporator for evaporation and concentration to obtain the rhodium trichloride.
The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid is characterized in that in the step one, the macromolecular adsorbent is a macromolecular adsorbent containing sulfydryl and imino groups, or a macromolecular adsorbent containing sulfoxide groups and imino groups.
The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid is characterized in that the macromolecular adsorbent is a macromolecular polymer bonded with dialkyl sulfide or dialkyl sulfoxide, and the macromolecular polymer is a polymer of N, N-methylene bisacrylamide and vinyl imidazole or a polymer of ethylene glycol dimethacrylate and acrylic acid.
The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid is characterized in that the mass ratio of the polymeric adsorbent to rhodium in the rhodium-containing organic waste liquid in the step one is 50 (1-5).
The method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid is characterized in that the adsorption temperature in the first step is 25-60 ℃.
The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid is characterized in that the flow rate of the rhodium-containing organic waste liquid in the adsorption process in the step one is 1 mL/min-30 mL/min.
The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid is characterized in that the mass concentration of hydrochloric acid in the step two is 36-38%.
The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid is characterized in that the molar ratio of stannous chloride in the step two to rhodium in the rhodium-containing organic waste liquid in the step one is 0.05 (1-5).
The method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid is characterized in that the alkali liquor in the third step is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or sodium carbonate aqueous solution, and the mass concentration of the alkali liquor is 5-20%; the mass concentration of the hydrochloric acid solution in the third step is 1-2%; in the third step, the cation exchange resin is formed by that sulfonic acid groups (-SO) are carried on a styrene-divinyl copolymer with 7 percent of crosslinking3H) Per hour of the cation exchange resin of (4)The flow rate of the solution is 1-4 times of the volume of the cation exchange resin, wherein the unit of the flow rate is mL/h, and the unit of the volume is mL.
The method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid is characterized in that the temperature of evaporation and concentration in the fourth step is 60-90 ℃, and the vacuum degree is 0.09-0.1 MPa.
Compared with the prior art, the invention has the following advantages:
1. the method is simple and convenient to operate, does not generate secondary waste gas and waste water, is green and environment-friendly, the recovery rate of the rhodium can reach more than 95%, and the prepared rhodium trichloride can meet the requirement of first-grade rhodium trichloride.
2. According to the invention, the speed of rhodium desorbed from the polymeric adsorbent and enters the acidic solution is greatly increased by adding stannous chloride in the desorption process.
3. The invention preferably selects the macromolecular adsorbent containing sulfydryl and imino groups or the macromolecular adsorbent containing sulfoxide groups and imino groups, can efficiently capture rhodium in the rhodium-containing organic waste liquid, and has large adsorption capacity and high adsorption rate.
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and embodiments.
Drawings
FIG. 1 is a schematic flow diagram of the process of the present invention.
Detailed Description
The method mainly comprises the following four steps:
step one, adsorption: adsorbing rhodium in rhodium-containing organic waste liquid generated in the production process of a rhodium homogeneous catalyst to a high-molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the mass content of rhodium in the rhodium-containing organic waste liquid is 10 ppm-1000 ppm; the rhodium-containing organic waste liquid is produced in the process of producing homogeneous catalysts of rhodium park, rhodium acetylacetonate carbonyl, rhodium octanoate or Wilkinson; the macromolecular adsorbent is a macromolecular adsorbent containing sulfydryl and imino groups, or a macromolecular adsorbent containing sulfoxide groups and imino groups, such as a macromolecular polymer bonded with dialkyl sulfide or dialkyl sulfoxide, wherein the macromolecular polymer is a polymer of N, N-methylene diacrylamide and vinyl imidazole, or a polymer of ethylene glycol dimethacrylate and acrylic acid; the mass ratio of the high molecular adsorbent to rhodium in the rhodium-containing organic waste liquid is 50 (1-5); the adsorption temperature is 25-60 ℃; the flow rate of the rhodium-containing organic waste liquid in the adsorption process is 1 mL/min-30 mL/min;
step two, desorption: drying the rhodium-containing adsorbent in the step one, then placing the rhodium-containing adsorbent in an acid solution, then adding stannous chloride, refluxing and stirring for 4-8 h at the temperature of 80-120 ℃, and filtering to obtain a rhodium-containing aqueous phase solution; the acid solution is hydrochloric acid or aqua regia, and the mass of the acid solution is 5-10 times of that of the dried rhodium-containing adsorbent; the mass concentration of the hydrochloric acid is 36-38%; the molar ratio of the stannous chloride to the rhodium is 0.05 (1-5);
step three, purification: adding alkali liquor into the rhodium-containing aqueous phase solution in the second step until the pH value is 7.5-9 to generate a precipitate, and filtering and washing the precipitate; then dissolving the precipitate with hydrochloric acid solution, adjusting the pH value to 1.0-1.5, and filtering to remove insoluble substances; purifying the solution after filtering and removing insoluble substances by adopting cation exchange resin; the alkali liquor is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or sodium carbonate aqueous solution, and the mass concentration of the alkali liquor is 5-20%; the mass concentration of the hydrochloric acid solution is 1-2%; the cation exchange resin is formed by that sulfonic acid groups (-SO) are carried on a styrene-divinyl copolymer with 7 percent of crosslinking3H) The flow rate of the solution per hour is 1-4 times of the volume of the cation exchange resin (namely 732 cation exchange resin), wherein the unit of the flow rate is mL/h, and the unit of the volume is mL;
step four, concentration: putting the solution purified in the third step into a rotary evaporator for evaporation and concentration to obtain rhodium trichloride; the temperature of the evaporation concentration is 60-90 ℃, and the vacuum degree is 0.09-0.1 MPa.
Example 1
Step one, adsorption: rhodium-containing organic waste generated in the production process of rhodium homogeneous catalystRhodium in the liquid is adsorbed on a high molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the specific process is as follows: 10g of a polymeric adsorbent having mercapto and imino groups (e.g., a polymeric polymer having a dihydrocarbyl sulfide bonded thereto, the polymeric polymer being a polymer of N, N-methylenebisacrylamide and vinylimidazole, or a polymer of ethylene glycol dimethacrylate and acrylic acid) was charged
In the adsorption column, 1500mL of rhodium-containing organic waste liquid passes through the adsorption column at the speed of 1mL/min by using a peristaltic pump, and rhodium in the rhodium-containing organic waste liquid is adsorbed onto a high molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the adsorption temperature is 25 ℃, and the mass content of rhodium in the rhodium-containing organic waste liquid is 156 ppm; the rhodium-containing organic waste liquid is organic waste liquid generated in the process of producing homogeneous catalyst rhodium park;
step two, desorption: drying the rhodium-containing adsorbent in the step one, then placing the rhodium-containing adsorbent in an acid solution, then adding 0.015g of stannous chloride dihydrate, refluxing and stirring for 4 hours at the temperature of 80 ℃, and filtering to obtain a rhodium-containing aqueous phase solution; the acid solution is hydrochloric acid, and the mass of the acid solution is 5 times of that of the dried rhodium-containing adsorbent; the mass concentration of the hydrochloric acid is 36%;
step three, purification: adding alkali liquor into the rhodium-containing aqueous phase solution in the step two until the pH value is 7.5 to generate a precipitate, and washing the precipitate after filtering; then dissolving the precipitate with hydrochloric acid solution, adjusting pH to 1.5, and filtering to remove insoluble substances; purifying the solution after filtering and removing insoluble substances by adopting cation exchange resin, reducing a small amount of the purified solution by hydrazine hydrate, quantitatively detecting the impurity content by adopting a spectrum, completing the purification if the impurity content meets the standard of the first-grade rhodium trichloride in YS/T363-2006, or repeatedly purifying by adopting the cation exchange resin until the impurity content is quantitatively detected by adopting the spectrum and meets the standard of the first-grade rhodium trichloride in YS/T363-2006; the alkali liquor isA 5% sodium hydroxide aqueous solution; the mass concentration of the hydrochloric acid solution is 1%; the cation exchange resin is formed by that sulfonic acid groups (-SO) are carried on a styrene-divinyl copolymer with 7 percent of crosslinking3H) The flow rate of the solution per hour is 1 times the volume of the cation exchange resin (i.e. 732 cation exchange resin), wherein the flow rate is in mL/h and the volume is in mL;
step four, concentration: and (3) putting the solution purified in the third step into a rotary evaporator for evaporation and concentration, wherein the temperature of the evaporation and concentration is 60 ℃, and the vacuum degree is 0.1MPa, so as to obtain 0.582g of rhodium trichloride. The content of rhodium in rhodium trichloride measured by ICP was 38.5%, and the recovery rate of rhodium was 95.76%.
TABLE 1 results of impurity content in rhodium trichloride prepared in example 1 (YS/T363-2006)
As can be seen from Table 1, the rhodium trichloride prepared in this example meets the requirements for first-order rhodium trichloride.
Example 2
Step one, adsorption: adsorbing rhodium in rhodium-containing organic waste liquid generated in the production process of a rhodium homogeneous catalyst to a high-molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the specific process is as follows: 10g of a polymer adsorbent (e.g., a polymer having a dialkyl sulfoxide bonded thereto, wherein the polymer is a polymer of N, N-methylenebisacrylamide and vinylimidazole, or a polymer of ethylene glycol dimethacrylate and acrylic acid) containing sulfoxide groups and imino groups was charged into a reactor
In the adsorption column, 30000mL of rhodium-containing organic waste liquid passes through the adsorption column at the speed of 30mL/min by using a peristaltic pump, and rhodium in the rhodium-containing organic waste liquid is adsorbed onto a high molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the adsorption temperature is 40 ℃, and the mass content of rhodium in the rhodium-containing organic waste liquid is 10 ppm; the rhodium-containing compoundThe organic waste liquid is produced in the process of producing homogeneous catalyst acetylacetonatocarbonylrhodium;
step two, desorption: drying the rhodium-containing adsorbent in the step one, then placing the rhodium-containing adsorbent in an acid solution, adding 0.01g of stannous chloride dihydrate, refluxing and stirring for 5 hours at the temperature of 100 ℃, transferring rhodium from the solid adsorbent to the solution, and filtering to obtain a rhodium-containing aqueous phase solution; the acid solution is hydrochloric acid with the mass concentration of 37%, and the mass of the acid solution is 8 times of that of the dried rhodium-containing adsorbent;
step three, a purification process: adding alkali liquor into the rhodium-containing aqueous phase solution in the step two until the pH value is 8 to generate a precipitate, and washing the precipitate after filtering; then dissolving the precipitate with hydrochloric acid solution, adjusting pH to 1.0, and filtering to remove insoluble substances; purifying the solution after filtering and removing insoluble substances by adopting cation exchange resin, reducing a small amount of the purified solution by hydrazine hydrate, quantitatively detecting the impurity content by adopting a spectrum, completing the purification if the impurity content meets the standard of the first-grade rhodium trichloride in YS/T363-2006, or repeatedly purifying by adopting the cation exchange resin until the impurity content is quantitatively detected by adopting the spectrum and meets the standard of the first-grade rhodium trichloride in YS/T363-2006; the alkali liquor is a potassium hydroxide aqueous solution with the mass concentration of 10%; the mass concentration of the hydrochloric acid solution is 2%; the cation exchange resin is formed by that sulfonic acid groups (-SO) are carried on a styrene-divinyl copolymer with 7 percent of crosslinking3H) The flow rate of the solution per hour is 2 times the volume of the cation exchange resin (i.e. 732 cation exchange resin), wherein the flow rate is in mL/h and the volume is in mL;
step four, concentration: and (3) putting the solution purified in the third step into a rotary evaporator for evaporation and concentration, wherein the temperature of the evaporation and concentration is 90 ℃, and the vacuum degree is 0.09MPa, so that 0.750g of rhodium trichloride is obtained. The content of rhodium in rhodium trichloride measured by ICP was 38.9%, and the recovery rate of rhodium was 97.20%.
TABLE 2 results of impurity content in rhodium trichloride prepared in example 2 (YS/T363-2006)
As can be seen from Table 2, the rhodium trichloride prepared in this example meets the requirements for first-order rhodium trichloride.
Example 3
Step one, adsorption: adsorbing rhodium in rhodium-containing organic waste liquid generated in the production process of a rhodium homogeneous catalyst to a high-molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the specific process is as follows: 50g of a polymer adsorbent (e.g., a polymer having a dialkyl sulfoxide bonded thereto, wherein the polymer is a polymer of N, N-methylenebisacrylamide and vinylimidazole, or a polymer of ethylene glycol dimethacrylate and acrylic acid) containing sulfoxide groups and imino groups was charged
In the adsorption column, 5000mL of rhodium-containing organic waste liquid passes through the adsorption column at the speed of 1mL/min by using a peristaltic pump, and rhodium in the rhodium-containing organic waste liquid is adsorbed onto a high molecular adsorbent in a dynamic adsorption mode to obtain the rhodium-containing adsorbent; the adsorption temperature is 60 ℃, and the mass content of rhodium in the rhodium-containing organic waste liquid is 1000 ppm; the rhodium-containing organic waste liquid is organic waste liquid generated in the process of producing homogeneous catalyst rhodium octanoate;
step two, desorption: drying the rhodium-containing adsorbent in the step one, then placing the rhodium-containing adsorbent in an acid solution, adding 0.11g of stannous chloride dihydrate, refluxing and stirring for 8 hours at the temperature of 120 ℃, transferring rhodium from the solid adsorbent to the solution, and filtering to obtain a rhodium-containing aqueous phase solution; the acid solution is aqua regia, and the mass of the acid solution is 5 times of that of the dried rhodium-containing adsorbent;
step three, purification: adding alkali liquor into the rhodium-containing aqueous phase solution in the step two until the pH value is 9 to generate a precipitate, and washing the precipitate after filtering; then dissolving the precipitate with hydrochloric acid solution, adjusting pH to 1.2, and filtering to remove insoluble substances; using cation exchange resinsPurifying the solution after filtering to remove insoluble substances, reducing a small amount of the purified solution by hydrazine hydrate, quantitatively detecting the impurity content by adopting a spectrum, completing the purification if the impurity content meets the standard of the first-class rhodium trichloride in YS/T363-2006, or repeatedly purifying by adopting cation exchange resin until the impurity content is quantitatively detected by the spectrum and meets the standard of the first-class rhodium trichloride in YS/T363-2006; the alkali liquor is a sodium carbonate aqueous solution with the mass concentration of 20%; the mass concentration of the hydrochloric acid solution is 1.5%; the cation exchange resin is formed by that sulfonic acid groups (-SO) are carried on a styrene-divinyl copolymer with 7 percent of crosslinking3H) The flow rate of the solution per hour is 4 times the volume of the cation exchange resin (i.e. 732 cation exchange resin), wherein the flow rate is in mL/h and the volume is in mL;
step four, concentration: and (3) putting the solution purified in the third step into a rotary evaporator for evaporation and concentration, wherein the temperature of the evaporation and concentration is 80 ℃, and the vacuum degree is 0.09MPa, so that 12.413g of rhodium trichloride is obtained. The content of rhodium in rhodium trichloride measured by ICP was 39.0%, and the recovery rate of rhodium was 96.82%.
TABLE 3 results of impurity content in rhodium trichloride prepared in example 3 (YS/T363-2006)
As can be seen from Table 3, the rhodium trichloride prepared in this example meets the requirements for first-order rhodium trichloride.
Example 4
Step one, adsorption: adsorbing rhodium in rhodium-containing organic waste liquid generated in the production process of a rhodium homogeneous catalyst to a high-molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the specific process is as follows: 200g of a polymeric adsorbent having mercapto and imino groups (e.g., a polymeric polymer having a dihydrocarbyl sulfide bonded thereto, the polymeric polymer being a polymer of N, N-methylenebisacrylamide and vinylimidazole, or a polymer of ethylene glycol dimethacrylate and acrylic acid) was charged
In the adsorption column, 4700mL of rhodium-containing organic waste liquid is passed through the adsorption column at a speed of 20mL/min by a peristaltic pump, and rhodium in the rhodium-containing organic waste liquid is adsorbed onto a high molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the adsorption temperature is 60 ℃, and the mass content of rhodium in the rhodium-containing organic waste liquid is 855 ppm; the rhodium-containing organic waste liquid is organic waste liquid generated in the process of producing a homogeneous catalyst, namely Wilkinson;
step two, desorption: drying the rhodium-containing adsorbent in the step one, then placing the rhodium-containing adsorbent in an acid solution, adding 0.44g of stannous chloride dihydrate, refluxing and stirring for 6 hours at the temperature of 100 ℃, transferring rhodium from the solid adsorbent to the solution, and filtering to obtain a rhodium-containing water phase solution; the acid solution is hydrochloric acid with the mass concentration of 38%, and the mass of the acid solution is 10 times of that of the dried rhodium-containing adsorbent;
step three, purification: adding alkali liquor into the rhodium-containing aqueous phase solution in the step two until the pH value is 8.5 to generate a precipitate, and washing the precipitate after filtering; then dissolving the precipitate with hydrochloric acid solution, adjusting pH to 1.5, and filtering to remove insoluble substances; purifying the solution after filtering and removing insoluble substances by adopting cation exchange resin, reducing a small amount of the purified solution by hydrazine hydrate, quantitatively detecting the impurity content by adopting a spectrum, completing the purification if the impurity content meets the standard of the first-grade rhodium trichloride in YS/T363-2006, or repeatedly purifying by adopting the cation exchange resin until the impurity content is quantitatively detected by adopting the spectrum and meets the standard of the first-grade rhodium trichloride in YS/T363-2006; the alkali liquor is a sodium hydroxide aqueous solution with the mass concentration of 15%; the mass concentration of the hydrochloric acid solution is 2%; the cation exchange resin is formed by that sulfonic acid groups (-SO) are carried on a styrene-divinyl copolymer with 7 percent of crosslinking3H) The flow rate of the solution per hour is 3 times the volume of the cation exchange resin (i.e. 732 cation exchange resin), wherein the flow rate is in mL/h and the volume is in mL;
step four, concentration: and (3) putting the solution purified in the third step into a rotary evaporator for evaporation and concentration, wherein the temperature of the evaporation and concentration is 70 ℃, and the vacuum degree is 0.1MPa, so that 10.057g of rhodium trichloride is obtained. The content of rhodium in rhodium trichloride measured by ICP was 38.5%, and the recovery rate of rhodium was 96.35%.
TABLE 4 results of impurity content in rhodium trichloride prepared in example 4 (YS/T363-2006)
As can be seen from Table 4, the rhodium trichloride prepared in this example meets the requirements for first-order rhodium trichloride.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and all simple modifications, changes and equivalent structural changes made to the above embodiment according to the technical spirit of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (8)
1. A method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid is characterized by comprising the following steps:
step one, adsorption: adsorbing rhodium in rhodium-containing organic waste liquid generated in the production process of a rhodium homogeneous catalyst to a high-molecular adsorbent in a dynamic adsorption mode to obtain a rhodium-containing adsorbent; the mass content of rhodium in the rhodium-containing organic waste liquid is 10 ppm-1000 ppm; the rhodium-containing organic waste liquid is produced in the process of producing homogeneous catalysts of rhodium park, rhodium acetylacetonate carbonyl, rhodium octanoate or Wilkinson; the mass ratio of the high molecular adsorbent to rhodium in the rhodium-containing organic waste liquid is 50 (1-5);
step two, desorption: drying the rhodium-containing adsorbent in the step one, then placing the rhodium-containing adsorbent in an acid solution, then adding stannous chloride, refluxing and stirring for 4-8 h at the temperature of 80-120 ℃, and filtering to obtain a rhodium-containing aqueous phase solution; the acid solution is hydrochloric acid or aqua regia, and the mass of the acid solution is 5-10 times of that of the dried rhodium-containing adsorbent;
step (ii) ofThirdly, purification: adding alkali liquor into the rhodium-containing aqueous phase solution in the second step until the pH value is 7.5-9 to generate a precipitate, and filtering and washing the precipitate; then dissolving the precipitate with hydrochloric acid solution, adjusting the pH value to 1.0-1.5, and filtering to remove insoluble substances; purifying the solution after filtering and removing insoluble substances by adopting cation exchange resin; the alkali liquor is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution or sodium carbonate aqueous solution, and the mass concentration of the alkali liquor is 5-20%; the mass concentration of the hydrochloric acid solution is 1-2%; the cation exchange resin is formed by that sulfonic acid groups (-SO) are carried on a styrene-divinyl copolymer with 7 percent of crosslinking3H) The flow rate of the solution per hour is 1-4 times of the volume of the cation exchange resin, wherein the unit of the flow rate is mL/h, and the unit of the volume is mL;
step four, concentration: and (4) putting the solution purified in the third step into a rotary evaporator for evaporation and concentration to obtain the rhodium trichloride.
2. The method for preparing rhodium trichloride according to claim 1, wherein in the step one, the polymeric adsorbent is a polymeric adsorbent containing mercapto groups and imino groups, or a polymeric adsorbent containing sulfoxide groups and imino groups.
3. The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid according to claim 2, wherein the high molecular adsorbent is a high molecular polymer bonded with dialkyl sulfide or dialkyl sulfoxide, and the high molecular polymer is a polymer of N, N-methylene bisacrylamide and vinyl imidazole, or a polymer of ethylene glycol dimethacrylate and acrylic acid;
4. the method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid according to claim 1, wherein the adsorption temperature in the first step is 25-60 ℃.
5. The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid according to claim 1, wherein the flow rate of the rhodium-containing organic waste liquid in the adsorption process in the step one is 1mL/min to 30 mL/min.
6. The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid according to claim 1, wherein the mass concentration of the hydrochloric acid in the second step is 36-38%.
7. The method for preparing rhodium trichloride by recovering rhodium from the rhodium-containing organic waste liquid according to claim 1, wherein the molar ratio of stannous chloride in the second step to rhodium in the rhodium-containing organic waste liquid in the first step is 0.05 (1-5).
8. The method for preparing rhodium trichloride by recovering rhodium from rhodium-containing organic waste liquid according to claim 1, wherein the temperature of evaporation and concentration in the fourth step is 60-90 ℃, and the vacuum degree is 0.09-0.1 MPa.
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