CN113020615A - Method for preparing high-purity rhodium powder by using rhodium trichloride - Google Patents
Method for preparing high-purity rhodium powder by using rhodium trichloride Download PDFInfo
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- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 46
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 title claims abstract description 25
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 title claims abstract description 25
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 60
- 239000010948 rhodium Substances 0.000 claims abstract description 60
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 47
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 47
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 44
- 238000005406 washing Methods 0.000 claims abstract description 44
- 230000009467 reduction Effects 0.000 claims abstract description 40
- 239000008367 deionised water Substances 0.000 claims abstract description 36
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 33
- 239000002253 acid Substances 0.000 claims abstract description 28
- 238000001291 vacuum drying Methods 0.000 claims abstract description 26
- 239000012670 alkaline solution Substances 0.000 claims abstract description 25
- 239000003929 acidic solution Substances 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 20
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002244 precipitate Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 9
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 150000001768 cations Chemical class 0.000 claims abstract description 7
- 238000004321 preservation Methods 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 44
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000003637 basic solution Substances 0.000 claims 2
- 238000011946 reduction process Methods 0.000 claims 2
- 238000007670 refining Methods 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- -1 silver-white transition metals Chemical class 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- XJUCCGJZENLZSA-UHFFFAOYSA-M [Rh]Cl Chemical compound [Rh]Cl XJUCCGJZENLZSA-UHFFFAOYSA-M 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a method for preparing high-purity rhodium powder by using rhodium trichloride, which comprises the following steps: dissolving solid rhodium trichloride powder by using a first acid solution to obtain a chlororhodic acid solution; removing cation impurities in the chlororhodic acid solution through ion exchange resin to obtain pure rhodium solution; adding a first alkaline solution into the pure rhodium solution to generate rhodium hydroxide precipitate, adding deionized water for washing, and adjusting the pH value to a target value to obtain rhodium hydroxide; separating the rhodium hydroxide by adopting a pressurized hydrogen reduction method to obtain rhodium reduction powder; putting the rhodium reducing powder into a hydrogen furnace, and carrying out heat preservation reduction sintering to obtain sintered rhodium powder; and washing the rhodium powder by using a second acidic solution, a second alkaline solution and deionized water, and then carrying out vacuum drying to obtain pure rhodium powder. The method provided by the invention improves the preparation efficiency of the rhodium powder and the purity of the rhodium powder obtained by refining.
Description
Technical Field
The invention relates to the field of material preparation, in particular to a method for preparing high-purity rhodium powder by using rhodium trichloride.
Background
Rhodium is one of silver-white transition metals and platinum group noble metals, is hard and brittle, has strong reflection capacity, and is particularly soft in a heating state. The rhodium has good chemical stability and strong oxidation resistance, and can keep metallic luster for a long time in the air. The noble metal alloy containing rhodium has more excellent physicochemical properties and is widely applied to the fields of industry, electronic information, aerospace, military industry and the like. For example, Rh, Pt catalytic mesh for nitric acid production; rh, Pt and Pd purifying catalyst for automobile exhaust, etc. The expansion of the application field of the noble metal industry makes the noble metal industry listed as strategic materials by many countries.
Because the stability of the rhodium-containing alloy/rhodium compound is stronger, compared with other platinum metals, the recovery difficulty is high, and the purity of the rhodium powder obtained by recovery is lower.
Chinese patent ZL200910073730.3 discloses a method for removing base metals from platinum rhodium ion exchange resins. Chinese patents CN101275184B and CN100410395C disclose a method for recovering rhodium. The method comprises the steps of adding formic acid into ammonium hexachlororhodate chlorate aqueous solution, reducing and recovering rhodium in the form of rhodium black, and sintering the rhodium black in a hydrogen atmosphere at 700-900 ℃ to obtain sponge rhodium. The process flow for refining rhodium is long, and other platinum metals are easy to settle in the process of adding the settling agent, so that the requirements on the types and the contents of impurities in the raw material liquid are high.
From the above, it can be seen that how to improve the preparation efficiency and purity of rhodium powder is a problem to be solved at present.
Disclosure of Invention
The invention aims to provide a method for preparing high-purity rhodium powder by using rhodium trichloride, which aims to solve the problems that the existing process for refining rhodium is long in flow and the purity of rhodium powder obtained by refining is low.
In order to solve the technical problem, the invention provides a method for preparing high-purity rhodium powder by using rhodium trichloride, which comprises the following steps: dissolving solid rhodium trichloride powder by using a first acid solution to obtain a chlororhodic acid solution; removing cation impurities in the chlororhodic acid solution through ion exchange resin to obtain pure rhodium solution; adding a first alkaline solution into the pure rhodium solution to generate rhodium hydroxide precipitate, adding deionized water for washing, and adjusting the pH value to a target value to obtain rhodium hydroxide; separating the rhodium hydroxide by adopting a pressurized hydrogen reduction method to obtain rhodium reduction powder; putting the rhodium reducing powder into a hydrogen furnace, and carrying out heat preservation reduction sintering to obtain sintered rhodium powder; and washing the rhodium powder by using a second acidic solution, a second alkaline solution and deionized water, and then carrying out vacuum drying to obtain pure rhodium powder.
Preferably, the first acidic solution is one of hydrochloric acid, nitric acid and sulfuric acid, and the concentration of the first acidic solution is 30-80 g/L.
Preferably, the first acidic solution is a mixed solution of at least two acidic solutions of hydrochloric acid, nitric acid and nitric acid.
Preferably, the ion exchange resin is a strong acid type cation exchange resin.
Preferably, after the first alkaline solution is added to the pure rhodium solution to generate a rhodium hydroxide precipitate, deionized water is added for washing, and the PH value is adjusted to a target value, so as to obtain rhodium hydroxide, wherein the step of adding deionized water comprises:
adding at least one alkaline solution of sodium hydroxide, potassium hydroxide and potassium carbonate into the pure rhodium solution to generate rhodium hydroxide precipitate, then adding deionized water for washing, and adjusting the pH value to a target value to obtain rhodium hydroxide;
wherein the value range of the target value is 8 to 12.
Preferably, the separating the rhodium hydroxide by using a pressurized hydrogen reduction method to obtain rhodium reduction powder comprises the following steps:
putting the rhodium hydroxide in a high-pressure reaction kettle, heating to a preset temperature value, introducing hydrogen to keep hydrogen partial pressure reduction, and performing solid-liquid separation on the rhodium hydroxide;
fully washing the solid obtained by solid-liquid separation by using deionized water, and then carrying out vacuum drying to obtain rhodium reducing powder;
wherein the value range of the preset temperature value is 120-250 ℃, the range of the hydrogen partial pressure is 0.2-2.0MPa, and the reduction time is 1-8 h.
Preferably, the separating the rhodium hydroxide by using a pressurized hydrogen reduction method to obtain rhodium reduction powder comprises the following steps:
putting the rhodium hydroxide into a high-pressure reaction kettle, heating to 180 ℃, introducing hydrogen to keep the partial pressure of 2MPa, and reducing for 5 hours to separate the rhodium hydroxide from solid;
and fully washing the solid obtained by solid-liquid separation by using deionized water, and then carrying out vacuum drying at the temperature of 120 ℃ to obtain rhodium reducing powder.
Preferably, the rhodium reducing powder is put into a hydrogen furnace, and is subjected to heat preservation reduction sintering to obtain sintered rhodium powder;
and (3) putting the rhodium reducing powder into a hydrogen furnace, heating to 950 ℃, introducing hydrogen to maintain the partial pressure of 2MPa for reduction for 2h, introducing nitrogen to maintain the partial pressure of 2MPa for replacement for 2h, cooling and taking out to obtain the sintered rhodium powder.
Preferably, after the rhodium powder is washed by the second acidic solution, the second alkaline solution and deionized water, vacuum drying is performed to obtain pure rhodium powder, and the method includes:
washing the sintered rhodium powder by using at least one acid solution of hydrochloric acid, nitric acid and sulfuric acid, and washing the rhodium powder by using at least one alkaline solution of sodium hydroxide and potassium hydroxide;
washing the rhodium powder by using an alkaline solution, and then fully washing the rhodium powder by using deionized water;
carrying out vacuum drying on the washed rhodium powder to obtain pure rhodium powder;
wherein the temperature range of the washed rhodium powder for vacuum drying is 100-250 ℃, and the vacuum drying time is 8-30 h.
Preferably, after the rhodium powder is washed by the second acidic solution, the second alkaline solution and deionized water, vacuum drying is performed to obtain pure rhodium powder, and the method includes:
boiling and washing the sintered rhodium powder for 1h by using an acid solution obtained by mixing hydrogen peroxide and hydrochloric acid, boiling and washing the rhodium powder for 1h by using sodium hydroxide with the concentration of 20%, boiling and washing the rhodium powder for 1h by using deionized water, and carrying out vacuum drying on the washed rhodium powder to obtain pure rhodium powder.
Adding a first alkaline solution into the pure rhodium solution to generate rhodium hydroxide precipitate, adding deionized water for washing, and adjusting the pH value to a target value to obtain rhodium hydroxide; separating the rhodium hydroxide by adopting a pressurized hydrogen reduction method to obtain rhodium reduction powder; putting the rhodium reducing powder into a hydrogen furnace, and carrying out heat preservation reduction sintering to obtain sintered rhodium powder; and washing the rhodium powder by using a second acidic solution, a second alkaline solution and deionized water, and then carrying out vacuum drying to obtain pure rhodium powder.
The method for preparing high-purity rhodium powder by using rhodium trichloride provided by the invention is characterized in that rhodium trichloride solid is dissolved by using an acid solution to obtain a chlororhodium acid solution. And removing cation impurities in the chlororhodic acid solution through ion exchange resin to obtain pure rhodium solution. And adding alkali into the pure rhodium solution to produce rhodium hydroxide precipitate, then adding deionized water for washing, and adjusting the pH value to obtain rhodium hydroxide. Reducing the rhodium hydroxide by adopting pressurized hydrogen, and obtaining rhodium reducing powder by adjusting the pressure and the temperature of the hydrogen; and then sintering, introducing hydrogen, washing with acid and alkali, fully washing with an ion tree, and drying in vacuum to obtain pure rhodium powder. The method provided by the invention does not introduce new impurities, and improves the production efficiency; and the impurity content of the pure rhodium powder obtained by refining is less than 100ppm, the direct yield is more than 99 percent, and the production requirement of the rhodium powder is met.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained based on these drawings without creative efforts.
FIG. 1 is a flow chart of a first embodiment of the process for producing high purity rhodium powder from rhodium trichloride in accordance with the present invention;
FIG. 2 is a flow chart of a second embodiment of the process for producing high purity rhodium powder from rhodium trichloride;
FIG. 3 is a flow chart of a third embodiment of the method for preparing high-purity rhodium powder from rhodium trichloride.
Detailed Description
The core of the invention is to provide a method for preparing high-purity rhodium powder by using rhodium trichloride, which improves the preparation efficiency of the high-purity rhodium powder and the purity of the extracted rhodium powder.
In order that those skilled in the art will better understand the disclosure, the invention will be described in further detail with reference to the accompanying drawings and specific embodiments. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to FIG. 1, FIG. 1 is a flow chart of a first embodiment of the present invention of a method for preparing high purity rhodium powder from rhodium trichloride; the specific operation steps are as follows:
step S101: dissolving solid rhodium trichloride powder by using a first acid solution to obtain a chlororhodic acid solution;
in this embodiment, the first acidic solution may be one of hydrochloric acid, nitric acid and sulfuric acid, and the concentration thereof is 30-80 g/L; the first acidic solution may be a mixed solution of at least two acidic solutions of hydrochloric acid, nitric acid, and nitric acid.
Step S102: removing cation impurities in the chlororhodic acid solution through ion exchange resin to obtain pure rhodium solution;
the ion exchange resin is strong acid type cation exchange resin.
Step S103: adding a first alkaline solution into the pure rhodium solution to generate rhodium hydroxide precipitate, adding deionized water for washing, and adjusting the pH value to a target value to obtain rhodium hydroxide;
the first alkaline solution can be one or more of sodium hydroxide, potassium hydroxide and potassium carbonate.
And adding an alkaline solution into the pure rhodium solution to generate a precipitate, adding deionized water for washing, and adjusting the pH value to be 8-12.
Step S104: separating the rhodium hydroxide by adopting a pressurized hydrogen reduction method to obtain rhodium reduction powder;
when the rhodium hydroxide is separated by adopting a pressurized hydrogen reduction method, the rhodium hydroxide is placed in a high-pressure reaction kettle and heated to the temperature of 120 ℃ and 250 ℃, and then hydrogen is introduced to keep the hydrogen partial pressure reduction, so that the rhodium hydroxide is subjected to solid-liquid separation, wherein the hydrogen partial pressure range is 0.2-2.0MPa, and the reduction time is 1-8 h. And after the rhodium hydroxide is subjected to solid-liquid separation, fully washing the rhodium hydroxide by using deionized water, and drying in vacuum to obtain the rhodium reducing powder.
Step S105: putting the rhodium reducing powder into a hydrogen furnace, and carrying out heat preservation reduction sintering to obtain sintered rhodium powder;
step S106: and washing the rhodium powder by using a second acidic solution, a second alkaline solution and deionized water, and then carrying out vacuum drying to obtain pure rhodium powder.
In this embodiment, the second acidic solution is one or more of hydrochloric acid, nitric acid, and sulfuric acid. The second alkaline solution is one or more of sodium hydroxide and potassium hydroxide.
The method for preparing high-purity rhodium provided by the embodiment is simple in process, no new impurities are introduced, and the production efficiency is improved; the obtained rhodium powder has low impurity content, the direct yield is more than 99 percent, and the production requirement of the rhodium powder is met.
Based on the above embodiment, in this embodiment, the first acidic solution may be a mixed solution of nitric acid and hydrochloric acid, and the mixing ratio is 3: 1. the first alkaline solution is sodium hydroxide. The second acidic solution is a mixed solution of hydrogen peroxide and hydrochloric acid, and the mixing ratio is 3: 1. the second alkaline solution is sodium hydroxide.
Referring to FIG. 2, FIG. 2 is a flow chart of a second embodiment of the method for preparing high purity rhodium powder from rhodium trichloride; the specific operation steps are as follows:
step S201: dissolving 10g of rhodium trichloride solid in 500ml of mixed solution of nitric acid and hydrochloric acid to obtain chlororhodic acid solution, wherein the ratio of the nitric acid to the hydrochloric acid is 3: 1;
step S202: removing cation impurities in the chlororhodic acid solution by using strong acid type cation exchange resin to obtain pure rhodium solution;
step S203: adding sodium hydroxide into the pure rhodium solution until no rhodium hydroxide precipitate is produced, and adding deionized water to wash until the pH value is 9 to obtain rhodium hydroxide;
step S204: putting the rhodium hydroxide into a high-pressure reaction kettle, heating to 180 ℃, introducing hydrogen to keep the partial pressure of 2MPa for reduction for 5 hours, carrying out solid-liquid separation on the rhodium hydroxide, fully washing the solid obtained by the solid-liquid separation by using deionized water, and carrying out vacuum drying at the temperature of 120 ℃ to obtain rhodium reduction powder;
based on the embodiment, in other embodiments of the present invention, the rhodium hydroxide may also be heated to 150 ℃ in a high pressure reactor, and hydrogen is introduced to maintain a partial pressure of 2MPa for reduction for 10 hours, so as to separate the rhodium hydroxide from the solid. Or putting the rhodium hydroxide into a high-pressure reaction kettle, heating to 250 ℃, introducing hydrogen to keep the partial pressure of 0.5MPa, and reducing for 8 hours to separate the rhodium hydroxide from the solid.
In other embodiments of the present invention, the hydrogen partial pressure and the reduction time may be changed without changing the operation temperature of the hydrogenation reduction, for example: putting the rhodium hydroxide into a high-pressure reaction kettle, heating to 180 ℃, introducing hydrogen to keep the partial pressure of 0.8MPa, and reducing for 3 hours to separate the rhodium hydroxide from solid; vacuum drying is carried out at the temperature of 150 ℃ to obtain rhodium reducing powder.
Step S205: putting the rhodium reducing powder into a hydrogen furnace, heating to 950 ℃, introducing hydrogen to maintain the partial pressure of 2MPa for reduction for 2h, introducing nitrogen to maintain the partial pressure of 2MPa for replacement for 2h, cooling and taking out to obtain sintered rhodium powder;
step S206: the rhodium powder is boiled and washed for 1h by using a mixed solution of hydrogen peroxide and hydrochloric acid, the rhodium powder is boiled and washed for 1h by using sodium hydroxide with the concentration of 20%, the rhodium powder is boiled and washed for 1h by using deionized water, and the washed rhodium powder is subjected to vacuum drying to obtain pure rhodium powder, wherein the ratio of hydrogen peroxide to hydrochloric acid is 3: 1.
in the present example, a rhodium trichloride solid was dissolved in hydrochloric acid in the above examples. Referring to FIG. 3, FIG. 3 is a flow chart of a third embodiment of the method for preparing high purity rhodium powder from rhodium trichloride; the specific operation steps are as follows:
step S301: dissolving 10g of rhodium trichloride solid in 45g/L hydrochloric acid to obtain a chlororhodic acid solution;
it should be noted that in other embodiments of the present invention, other concentrations of hydrochloric acid can be used to dissolve the rhodium trichloride solid, such as 75g/L, with a concentration range of 30-80 g/L.
Step S302: removing cation impurities in the chlororhodic acid solution by using cation exchange resin to obtain pure rhodium solution;
step S303: adding sodium hydroxide into the pure rhodium solution until no rhodium hydroxide precipitate is produced, and adding deionized water to wash until the pH value is 10 to obtain rhodium hydroxide;
step S304: putting the rhodium hydroxide into a high-pressure reaction kettle, heating to 180 ℃, introducing hydrogen to keep the partial pressure of 1.5MPa for reduction for 7.5h, carrying out solid-liquid separation on the rhodium hydroxide, fully washing the solid obtained by the solid-liquid separation by using deionized water, and carrying out vacuum drying at the temperature of 120 ℃ to obtain rhodium reduction powder;
in step 304, if the hydrogen partial pressure is 1.3MPa, the reduction time can be increased to 8.5 h.
Step S305: putting the rhodium reducing powder into a hydrogen furnace, heating to 950 ℃, introducing hydrogen to maintain the partial pressure of 1.5MPa for reduction for 3h, introducing nitrogen to maintain the partial pressure of 2MPa for replacement for 2h, cooling and taking out to obtain the sintered rhodium powder;
step S306: boiling and washing the rhodium powder for 1h by using a mixed solution of hydrogen peroxide and hydrochloric acid, boiling and washing the rhodium powder for 1h by using sodium hydroxide with the concentration of 20%, boiling and washing the rhodium powder for 1h by using deionized water, and carrying out vacuum drying on the washed rhodium powder to obtain pure rhodium powder.
In this embodiment, the ratio of the hydrogen peroxide to the hydrochloric acid may be 1:1 or 1: 2.
The method for preparing high-purity rhodium powder by using rhodium trichloride provided by the invention is described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A method for preparing high-purity rhodium powder by using rhodium trichloride is characterized by comprising the following steps:
dissolving solid rhodium trichloride powder by using a first acid solution to obtain a chlororhodic acid solution;
removing cation impurities in the chlororhodic acid solution through ion exchange resin to obtain pure rhodium solution;
adding a first alkaline solution into the pure rhodium solution to generate rhodium hydroxide precipitate, adding deionized water for washing, and adjusting the pH value to a target value to obtain rhodium hydroxide;
separating the rhodium hydroxide by adopting a pressurized hydrogen reduction method to obtain rhodium reduction powder;
putting the rhodium reducing powder into a hydrogen furnace, and carrying out heat preservation reduction sintering to obtain sintered rhodium powder;
and washing the rhodium powder by using a second acidic solution, a second alkaline solution and deionized water, and then carrying out vacuum drying to obtain pure rhodium powder.
2. The method of claim 1, wherein the first acidic solution is one of hydrochloric acid, nitric acid, and sulfuric acid, and has a concentration of 30-80 g/L.
3. The method of claim 1, wherein the first acidic solution is a mixed solution of at least two acidic solutions of hydrochloric acid, nitric acid, and nitric acid.
4. The method of claim 1, wherein the ion exchange resin is a strong acid cation exchange resin.
5. The method of claim 1, wherein the adding of the first alkaline solution to the pure rhodium solution to form a rhodium hydroxide precipitate, and then washing with deionized water to adjust the PH to a target value to obtain rhodium hydroxide comprises:
adding at least one alkaline solution of sodium hydroxide, potassium hydroxide and potassium carbonate into the pure rhodium solution to generate rhodium hydroxide precipitate, then adding deionized water for washing, and adjusting the pH value to a target value to obtain rhodium hydroxide;
wherein the value range of the target value is 8 to 12.
6. The method of claim 1, wherein the separating the rhodium hydroxide using a pressurized hydrogen reduction process to obtain a rhodium-reduced powder comprises:
putting the rhodium hydroxide in a high-pressure reaction kettle, heating to a preset temperature value, introducing hydrogen to keep hydrogen partial pressure reduction, and performing solid-liquid separation on the rhodium hydroxide;
fully washing the solid obtained by solid-liquid separation by using deionized water, and then carrying out vacuum drying to obtain rhodium reducing powder;
wherein the value range of the preset temperature value is 120-250 ℃, the range of the hydrogen partial pressure is 0.2-2.0MPa, and the reduction time is 1-8 h.
7. The method of claim 6, wherein the separating the rhodium hydroxide using a pressurized hydrogen reduction process to obtain a rhodium-reduced powder comprises:
putting the rhodium hydroxide into a high-pressure reaction kettle, heating to 180 ℃, introducing hydrogen to keep the partial pressure of 2MPa, and reducing for 5 hours to separate the rhodium hydroxide from solid;
and fully washing the solid obtained by solid-liquid separation by using deionized water, and then carrying out vacuum drying at the temperature of 120 ℃ to obtain rhodium reducing powder.
8. The method of claim 1, wherein the rhodium reducing powder is placed into a hydrogen furnace, and is subjected to heat preservation reduction sintering to obtain sintered rhodium powder;
and (3) putting the rhodium reducing powder into a hydrogen furnace, heating to 950 ℃, introducing hydrogen to maintain the partial pressure of 2MPa for reduction for 2h, introducing nitrogen to maintain the partial pressure of 2MPa for replacement for 2h, cooling and taking out to obtain the sintered rhodium powder.
9. The method of claim 1, wherein the washing the rhodium powder with a second acidic solution, a second basic solution and deionized water, and then vacuum drying to obtain pure rhodium powder comprises:
washing the sintered rhodium powder by using at least one acid solution of hydrochloric acid, nitric acid and sulfuric acid, and washing the rhodium powder by using at least one alkaline solution of sodium hydroxide and potassium hydroxide;
washing the rhodium powder by using an alkaline solution, and then fully washing the rhodium powder by using deionized water;
carrying out vacuum drying on the washed rhodium powder to obtain pure rhodium powder;
wherein the temperature range of the washed rhodium powder for vacuum drying is 100-250 ℃, and the vacuum drying time is 8-30 h.
10. The method of claim 9, wherein the washing the rhodium powder with a second acidic solution, a second basic solution and deionized water, and then vacuum drying to obtain pure rhodium powder comprises:
boiling and washing the sintered rhodium powder for 1h by using an acid solution obtained by mixing hydrogen peroxide and hydrochloric acid, boiling and washing the rhodium powder for 1h by using sodium hydroxide with the concentration of 20%, boiling and washing the rhodium powder for 1h by using deionized water, and carrying out vacuum drying on the washed rhodium powder to obtain pure rhodium powder.
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