CN114105230A - Preparation method of rhodium trichloride hydrate - Google Patents
Preparation method of rhodium trichloride hydrate Download PDFInfo
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Abstract
The invention belongs to the technical field of catalyst synthesis. The invention provides a preparation method of rhodium trichloride hydrate, which comprises the following steps: reacting a chlororhodate solution with a reducing agent to obtain rhodium powder; reacting rhodium powder with chlorine to obtain a rhodium-containing mixture; reacting a rhodium-containing mixture with hydrochloric acid, and filtering to obtain a chlororhodic acid solution; and (3) performing rotary evaporation on the chlororhodic acid solution to obtain the rhodium trichloride hydrate. The raw materials of the invention adopt the intermediate product of the chlorine rhodium acid sodium or the chlorine rhodium acid potassium in the rhodium recovery process, and rhodium powder with higher activity is prepared by a reducing agent, thereby improving the single reaction yield; according to the invention, rhodium trichloride which is insoluble in water is directly converted into a chlororhodium acid solution which is soluble in water by using the positive pressure reactor, and then rhodium trichloride hydrate can be obtained by rotary evaporation, so that washing with a large amount of deionized water can be avoided, and the generation of waste liquid is reduced.
Description
Technical Field
The invention relates to the technical field of catalyst synthesis, in particular to a preparation method of rhodium trichloride hydrate.
Background
Rhodium chloride hydrate is an important catalyst precursor, and because metal rhodium is very insoluble in various acids, many important rhodium catalysts, such as triphenylphosphine chloride rhodium, triphenylphosphine acetylacetonatocarbonyl rhodium, rhodium acetate and the like, are prepared from rhodium chloride. The most common preparation method of rhodium trichloride is that rhodium powder and sodium (potassium) chloride are chlorinated at medium temperature to obtain sodium (potassium) chlororhodate, then alkali is added to obtain rhodium hydroxide precipitate, and the chloride ions in the precipitate are washed clean, then hydrochloric acid is added to dissolve and evaporate so as to obtain the rhodium trichloride. Or dissolving rhodium powder with sodium (potassium) sulfate to obtain sodium (potassium) sulfate, hydrolyzing to obtain rhodium hydroxide, washing, adding hydrochloric acid, dissolving, and evaporating to obtain rhodium trichloride hydrate.
In the prior art, a moderate-temperature chlorination method is used for preparing hexachlororhodate, rhodium powder and chlorine react at 400-800 ℃ to generate anhydrous rhodium chloride, then the anhydrous rhodium chloride and sodium (potassium) chloride solid are ground and mixed, and then the mixture is heated to 600-900 ℃ to convert the anhydrous rhodium chloride into water-soluble hexachlororhodate. The method is complex to operate, and rhodium trichloride hydrate is not obtained at last.
In the prior art, a moderate temperature chlorination method is used to obtain a sodium chlororhodate solution, the solution is further hydrolyzed to form a rhodium hydroxide solution, deionized water is used for rinsing and precipitating to remove sodium ions, concentrated hydrochloric acid is added into the precipitate and heated to obtain a rhodium trichloride solution, and finally a spray drying method is used to obtain a rhodium trichloride hydrate. Although the method mentions that rhodium trichloride crystals in tail gas can be recovered by alkali liquor after being dissolved by acid, the needed alkali quantity is very large, and the recovered rhodium trichloride solution has large volume, so that the rhodium content is lower, the recovery rate is reduced, and the recovery efficiency is reduced.
The prior art also mentions that rhodium powder is dissolved in hydrochloric acid solution in a U-shaped electrolytic cell by alternating current to obtain rhodium chloride acid aqueous solution, and then crystallization is carried out to obtain rhodium chloride hydrate or anhydrous rhodium chloride. The method has simple flow, but has long treatment period, is easy to generate chlorine gas to pollute the environment in the electrolytic process, and is not suitable for batch production.
In the prior art, rhodium hydroxide precipitate is usually obtained firstly, then impurity ions are removed by washing, and finally hydrochloric acid is added for dissolving to obtain rhodium trichloride hydrate, so that the process is complex, a large amount of reagents are consumed, and a large amount of wastewater is generated; the electrolysis method has long treatment period, small treatment amount and large amount of waste gas.
Therefore, the research and development of the preparation method of rhodium trichloride hydrate, which reduces waste liquid, improves the material utilization rate and the reaction efficiency and has no pollution to the environment, has important value and significance.
Disclosure of Invention
The invention aims to provide a preparation method of rhodium trichloride hydrate aiming at the defects of the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of rhodium trichloride hydrate, which comprises the following steps:
1) reacting a chlororhodate solution with a reducing agent to obtain rhodium powder;
2) reacting rhodium powder with chlorine to obtain a rhodium-containing mixture;
3) reacting a rhodium-containing mixture with hydrochloric acid, and filtering to obtain a chlororhodic acid solution;
4) and (3) performing rotary evaporation on the chlororhodic acid solution to obtain the rhodium trichloride hydrate.
Preferably, the chlororhodanate used in the step 1) is sodium chlororhodanate or potassium chlororhodanate; the reducing agent comprises formic acid, hydrazine hydrate, or sodium formate dihydrate.
Preferably, when the reducing agent is formic acid or sodium formate dihydrate, the molar ratio of chlororhodate to reducing agent is 2: 3-9; when the reducing agent is hydrazine hydrate, the molar ratio of the chlororhodate to the reducing agent is 4: 3 to 9.
Preferably, the reaction temperature in the step 2) is 300-600 ℃, and the reaction time is 1-5 h.
Preferably, the flow rate of the chlorine in the step 2) is 0.1-5L/min, and the rhodium-containing mixture contains anhydrous rhodium trichloride and rhodium powder.
Preferably, in the step 3), the mass ratio of rhodium to hydrochloric acid is 1: 20-1000, and the mass concentration of the hydrochloric acid is 5-37%.
Preferably, the reaction temperature in the step 3) is 30-90 ℃, and the reaction time is 0.5-3 h.
Preferably, the reaction in step 3) is carried out at a pressure of 10 to 100 KPa.
Preferably, the temperature of the rotary evaporation in the step 4) is 50-85 ℃.
The beneficial effects of the invention include the following:
1) the raw materials of the invention adopt the intermediate product of the chlorine rhodium acid sodium or the chlorine rhodium acid potassium in the rhodium recovery process, and rhodium powder with higher activity is prepared by a reducing agent.
2) According to the invention, rhodium trichloride which is insoluble in water is directly converted into a chlororhodium acid solution which is soluble in water by using the positive pressure reactor, and then rhodium trichloride hydrate can be obtained by rotary evaporation, so that washing with a large amount of deionized water can be avoided, and the generation of waste liquid is reduced.
3) The condensate generated in the rotary evaporation process can be reused as a dissolving solution, so that the generation of waste liquid is effectively reduced.
Detailed Description
The invention provides a preparation method of rhodium trichloride hydrate, which comprises the following steps:
1) reacting a chlororhodate solution with a reducing agent to obtain rhodium powder;
2) reacting rhodium powder with chlorine to obtain a rhodium-containing mixture;
3) reacting a rhodium-containing mixture with hydrochloric acid, and filtering to obtain a chlororhodic acid solution;
4) and (3) performing rotary evaporation on the chlororhodic acid solution to obtain the rhodium trichloride hydrate.
In the step 1), the pH value of a chlororhodate solution is preferably adjusted to obtain a mixed solution; the mixed liquor preferably comprises a clarified solution and a precipitate; slowly adding a reducing agent into the boiled precipitate for reaction to obtain rhodium powder; the reagent used for adjusting the pH value is preferably an alkali solution; the pH value is preferably adjusted to 7-12, more preferably 8-11, and even more preferably 9-10; the mass concentration of the alkali solution is preferably 5-20%, more preferably 8-16%, and even more preferably 10-13%; the alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution.
When a reducing agent is added in the step 1), the precipitation temperature is preferably 90-150 ℃, more preferably 100-140 ℃, and more preferably 110-120 ℃; the adding speed of the reducing agent is preferably 0.5-20 g/min, more preferably 2-10 g/min, and even more preferably 5-8 g/min.
The chlororhodate used in the step 1) of the invention is preferably sodium chlororhodate or potassium chlororhodate; the reducing agent preferably comprises formic acid, hydrazine hydrate or sodium formate dihydrate; the hydrazine hydrate is preferably a hydrazine hydrate solution, the mass fraction of the hydrazine hydrate in the hydrazine hydrate solution is preferably 75-85%, more preferably 78-82%, and even more preferably 80%, and the solvent of the hydrazine hydrate solution is water.
In step 1) of the present invention, when the reducing agent is formic acid or sodium formate dihydrate, the molar ratio of chlororhodate to the reducing agent is preferably 2: 3 to 9, and more preferably 2: 4-8, more preferably 2: 5-6; when the reducing agent is hydrazine hydrate, the molar ratio of chlororhodate to reducing agent is preferably 4: 3-9, more preferably 4: 4-8, more preferably 4: 5 to 6.
In the chlororhodate solution of the present invention, the mass fraction of rhodium is preferably 3 to 7%, more preferably 4 to 6%, and still more preferably 5%.
The chemical equation of the reaction of the sodium chlororhodate and the sodium hydroxide solution is shown as (1); the chemical equation for the reaction of the precipitate and the reducing agent of the present invention is shown in (2) to (4):
Na3RhCl6(l)+3NaOH(l)+H2O(l)＝Rh(OH)3·H2O(s)+6NaCl(l) (1)
2Rh(OH)3·H2O(s)+3HCOONa·2H2O(s)＝2Rh(s)+7H2O(l)+3CO2(g)+3NaOH(l) (2)
2Rh(OH)3·H2O(s)+3HCOOH(l)＝2Rh(s)+8H2O(l)+3CO2(g) (3)
4Rh(OH)3·H2O(s)+3N2H4·H2O(s)＝4Rh(s)+19H2O(l)+3N2(g) (4)
after the reaction in the step 1) is finished, preferably sequentially cleaning the rhodium powder to be neutral, and drying in vacuum, wherein the reagent used for cleaning is preferably water, and the temperature for vacuum drying is preferably 50-80 ℃, more preferably 55-75 ℃, and more preferably 60-70 ℃; the time for vacuum drying is preferably 1-5 h, more preferably 2-4 h, and even more preferably 3 h; the degree of vacuum is preferably not less than 49KPa, more preferably not less than 55 KPa.
The reaction temperature in the step 2) of the invention is preferably 300-600 ℃, more preferably 350-550 ℃, more preferably 400-500 ℃, and still more preferably 430-460 ℃; the reaction time is preferably 1 to 5 hours, more preferably 2 to 4 hours, and even more preferably 2.5 to 3.5 hours.
The reaction in step 2) of the present invention is preferably carried out in a moderate temperature chlorination furnace.
The flow rate of the chlorine gas in the step 2) is preferably 0.1-5L/min, more preferably 1-4L/min, and even more preferably 2-3L/min; the rhodium-containing mixture contains anhydrous rhodium trichloride and rhodium powder.
The chemical equation of the reaction of rhodium powder and chlorine gas is shown as (5):
2Rh(s)+3Cl2(g)＝2RhCl3(s) (5)
in step 3) of the present invention, the mass ratio of rhodium to hydrochloric acid in the rhodium-containing mixture is preferably 1: 20 to 1000, and more preferably 1: 80-500, more preferably 1: 200-400; the mass concentration of the hydrochloric acid is preferably 5-37%, more preferably 10-30%, and even more preferably 15-20%.
The reaction temperature in the step 3) of the invention is preferably 30-90 ℃, more preferably 40-80 ℃, and more preferably 50-70 ℃; the reaction time is preferably 0.5-3 h, more preferably 1-2.5 h, and even more preferably 1.5-2 h.
The reaction in step 3) of the present invention is preferably carried out at a pressure of 10 to 100KPa, more preferably at a pressure of 20 to 80KPa, and still more preferably at a pressure of 40 to 70 KPa.
The reaction in step 3) of the present invention is preferably carried out in a positive pressure reactor under stirring conditions.
The chemical equation of the reaction of anhydrous rhodium chloride and hydrochloric acid of the invention is shown in (6):
RhCl3(s)+3HCl(l)＝H3RhCl6(l) (6)
filtering in step 3) to obtain chlororhodic acid solution and filter residue; the filter residue is rhodium powder; if filter residues are contained after the reaction in the step 3), drying the filter residues, and repeating the operation in the step 2) and the step 3) until no filter residues are visible to naked eyes, wherein the operation conditions are completely the same as those in the step 2) and the step 3); the number of repetition is preferably 1 to 3.
The rotary evaporation temperature in the step 4) of the invention is preferably 50-85 ℃, more preferably 55-80 ℃, and more preferably 60-70 ℃.
The chemical equation for obtaining the rhodium trichloride hydrate by rotary evaporation is shown as (7):
H3RhCl6(l)+xH2O(l)＝RhCl3·xH2O(s)+3HCl(g) (7)
the technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The pH of 100g of an aqueous solution of sodium chlororhodate (the mass fraction of rhodium in the aqueous solution of sodium chlororhodate is 5%) was adjusted to 7.5 with a sodium hydroxide solution having a mass concentration of 5% to obtain a mixed solution, which was then allowed to stand and clarified. Decanting the supernatant, boiling the rest precipitate, adding 15.0g sodium formate dihydrate at 130 deg.C at a rate of 3g/min for reduction, filtering to obtain rhodium powder, washing with deionized water to neutrality, and vacuum drying at 70 deg.C and 85KPa for 2 hr for use.
And (3) placing the obtained rhodium powder in a quartz boat, placing the quartz boat in a medium-temperature chlorination furnace, and reacting with chlorine at the flow rate of 1L/min for 2h at the temperature of 400 ℃ to obtain a mixture of anhydrous rhodium trichloride and rhodium powder. Putting the mixture into a positive pressure reactor, adding 110g of hydrochloric acid with the mass concentration of 20%, reacting for 1h at the temperature of 80 ℃ and under the pressure of 50KPa, and filtering to obtain chlororhodic acid solution and filter residue.
Drying the filter residue, and reacting with chlorine again under the same conditions to obtain a rhodium-containing mixture; the rhodium-containing mixture is reacted again with hydrochloric acid, and the above operation is repeated until no filter residue is visible to the naked eye after the reaction with hydrochloric acid. And (3) rotationally evaporating the chlororhodic acid solution at 80 ℃ to obtain rhodium trichloride hydrate, and collecting the condensate for later use.
The mass of rhodium trichloride hydrate in example 1 was 12.5g, the rhodium content was 39.5% by detection, and the yield was 98.75%.
Example 2
15.0g of sodium formate dihydrate in example 1 was changed to 8.4g of formic acid, and the other conditions were the same as in example 1.
The mass of rhodium trichloride hydrate in example 2 was 12.0g, the rhodium content was 39.6% by detection, and the yield was 95.04%.
Example 3
The 15.0g of sodium formate dihydrate in example 1 was changed to 4.5g of 80% by mass hydrazine hydrate solution, and the other conditions were the same as in example 1.
The mass of rhodium trichloride hydrate in example 3 was 12.1g, the rhodium content was 39.7% by detection, and the yield was 96.07%.
Example 4
The pH value of 400g of an aqueous solution of potassium chlororhodate (the mass fraction of rhodium in the aqueous solution of potassium chlororhodate is 5%) was adjusted to 10.0 with a potassium hydroxide solution having a mass concentration of 15%, and a mixed solution was obtained and was left to stand for clarification. Decanting the supernatant, boiling the rest precipitate, adding formic acid 30.0g at 5g/min at 100 deg.C for reduction, filtering to obtain rhodium powder, washing with deionized water to neutrality, and vacuum drying at 60 deg.C and 75KPa for 3 hr.
Putting the obtained rhodium powder into a quartz boat, putting the quartz boat into a medium-temperature chlorination furnace, and reacting with chlorine gas with the flow rate of 2.5L/min for 3.5h at 550 ℃ to obtain a mixture of anhydrous rhodium trichloride and rhodium powder. Putting the mixture into a positive pressure reactor, adding 800g of hydrochloric acid with the mass concentration of 10%, reacting for 2h at 50 ℃ and under the pressure of 80KPa, and filtering to obtain chlororhodic acid solution and filter residue.
Drying the filter residue, and reacting with chlorine again under the same conditions to obtain a rhodium-containing mixture; the rhodium-containing mixture is reacted again with hydrochloric acid, and the above operation is repeated until no filter residue is visible to the naked eye after the reaction with hydrochloric acid. And (3) rotationally evaporating the chlororhodic acid solution at the temperature of 60 ℃ to obtain rhodium trichloride hydrate, and collecting the condensate for later use.
The mass of rhodium trichloride hydrate in example 4 was 49.6g, the rhodium content was 39.8% by detection, and the yield was 98.56%.
Example 5
The pH of 400g of an aqueous solution of sodium chlororhodate (5% by mass of rhodium in the aqueous solution of sodium chlororhodate) was adjusted to 8.0 with a sodium hydroxide solution having a mass concentration of 10% to obtain a mixed solution, which was then allowed to stand and clarified. Decanting the supernatant, boiling the rest precipitate, adding 70.0g sodium formate dihydrate at 120 deg.C at a rate of 10g/min for reduction, filtering to obtain rhodium powder, washing with deionized water to neutrality, and vacuum drying at 55 deg.C and 70KPa for 4 hr for use.
Putting the obtained rhodium powder into a quartz boat, putting the quartz boat into a medium-temperature chlorination furnace, and reacting with chlorine gas with the flow rate of 1.5L/min for 2.5h at 450 ℃ to obtain a mixture of anhydrous rhodium trichloride and rhodium powder. And putting the mixture into a positive pressure reactor, adding 400g of hydrochloric acid with the mass concentration of 20%, reacting for 2 hours at the temperature of 80 ℃ and under the pressure of 60KPa, and filtering to obtain chlororhodic acid solution and filter residue.
Drying the filter residue, and reacting with chlorine again under the same conditions to obtain a rhodium-containing mixture; the rhodium-containing mixture is reacted again with hydrochloric acid, and the above operation is repeated until no filter residue is visible to the naked eye after the reaction with hydrochloric acid. And (3) rotationally evaporating the chlororhodic acid solution at 85 ℃ to obtain rhodium trichloride hydrate, and collecting the condensate for later use.
The mass of rhodium trichloride hydrate in example 5 was 49.4g, the rhodium content was 39.7% by detection, and the yield was 98.06%.
Comparative example 1
The procedure for preparing rhodium powder in example 1 was omitted, and commercially available 5g of rhodium powder was directly used, and the temperature of the rotary evaporation of chlororhodic acid solution was changed from 80 ℃ to 85 ℃ under the same conditions as in example 1.
The mass of rhodium trichloride hydrate of comparative example 1 was 7.78g, the rhodium content was found to be 39.7%, and the yield was 61.77%.
Comparative example 2
The positive pressure reactor in example 1 was changed to an atmospheric pressure reactor, and the other conditions were the same as in example 1.
The mass of rhodium trichloride hydrate of comparative example 2 was 8.0g, the rhodium content was 39.8% by detection, and the yield was 63.68%.
Comparative example 3
A mixture of the rotary evaporation condensate and commercially available concentrated hydrochloric acid (1: 1 by mass) was fed to the positive pressure reactor of example 1 as a solution for the positive pressure reactor, and the other conditions were the same as in example 1.
The mass of rhodium trichloride hydrate in comparative example 3 was 8.0g, the rhodium content was 39.8% by detection, and the yield was 98.46%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A preparation method of rhodium trichloride hydrate is characterized by comprising the following steps:
1) reacting a chlororhodate solution with a reducing agent to obtain rhodium powder;
2) reacting rhodium powder with chlorine to obtain a rhodium-containing mixture;
3) reacting a rhodium-containing mixture with hydrochloric acid, and filtering to obtain a chlororhodic acid solution;
4) and (3) performing rotary evaporation on the chlororhodic acid solution to obtain the rhodium trichloride hydrate.
2. The preparation method of claim 1, wherein the chlororhodanate used in step 1) is sodium chlororhodanate or potassium chlororhodanate; the reducing agent comprises formic acid, hydrazine hydrate, or sodium formate dihydrate.
3. The process according to claim 2, wherein when the reducing agent is formic acid or sodium formate dihydrate, the molar ratio of chlororhodate to the reducing agent is 2: 3-9; when the reducing agent is hydrazine hydrate, the molar ratio of the chlororhodate to the reducing agent is 4: 3 to 9.
4. The preparation method according to claim 2 or 3, wherein the reaction temperature in the step 2) is 300-600 ℃ and the reaction time is 1-5 h.
5. The preparation method of claim 4, wherein the flow rate of the chlorine gas in the step 2) is 0.1-5L/min, and the rhodium-containing mixture comprises anhydrous rhodium trichloride and rhodium powder.
6. The preparation method according to claim 4, wherein in the step 3), the mass ratio of rhodium to hydrochloric acid is 1: 20-1000, and the mass concentration of the hydrochloric acid is 5-37%.
7. The preparation method according to claim 5 or 6, wherein the reaction temperature in the step 3) is 30-90 ℃ and the reaction time is 0.5-3 h.
8. The method according to claim 7, wherein the reaction in step 3) is carried out at a pressure of 10 to 100 KPa.
9. The method according to claim 8, wherein the temperature of the rotary evaporation in the step 4) is 50 to 85 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115072809A (en) * | 2022-06-28 | 2022-09-20 | 浙江微通催化新材料有限公司 | Method for preparing rhodium trichloride hydrate from thiourea-containing rhodium material |
| CN115536082A (en) * | 2022-11-04 | 2022-12-30 | 郴州高鑫材料有限公司 | Method for preparing rhodium trichloride and ammonium chloroiridate from rhodium-iridium/silica gel adsorbent |
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| CN102557155A (en) * | 2011-10-25 | 2012-07-11 | 中国海洋石油总公司 | Method for recovering rhodium from rhodium-containing waste liquid and preparing rhodium chloride hydrate |
| CN107540025A (en) * | 2017-10-31 | 2018-01-05 | 中南大学 | A kind of method for preparing hydrate ruthenium trichloride |
| CN111410242A (en) * | 2020-03-12 | 2020-07-14 | 鲁西催化剂有限公司 | Method for recovering rhodium chloride from rhodium slag |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2007154252A (en) * | 2005-12-05 | 2007-06-21 | Nikko Kinzoku Kk | Method for collecting rhodium |
| CN101275184A (en) * | 2007-03-30 | 2008-10-01 | 日矿金属株式会社 | Method for recovering rhodium |
| CN102557155A (en) * | 2011-10-25 | 2012-07-11 | 中国海洋石油总公司 | Method for recovering rhodium from rhodium-containing waste liquid and preparing rhodium chloride hydrate |
| CN107540025A (en) * | 2017-10-31 | 2018-01-05 | 中南大学 | A kind of method for preparing hydrate ruthenium trichloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115072809A (en) * | 2022-06-28 | 2022-09-20 | 浙江微通催化新材料有限公司 | Method for preparing rhodium trichloride hydrate from thiourea-containing rhodium material |
| CN115536082A (en) * | 2022-11-04 | 2022-12-30 | 郴州高鑫材料有限公司 | Method for preparing rhodium trichloride and ammonium chloroiridate from rhodium-iridium/silica gel adsorbent |
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