CN102976913B - Method for preparing high-purity acetylacetonatodicarbonyl rhodium through using rhodium trichloride - Google Patents
Method for preparing high-purity acetylacetonatodicarbonyl rhodium through using rhodium trichloride Download PDFInfo
- Publication number
- CN102976913B CN102976913B CN201210436179.6A CN201210436179A CN102976913B CN 102976913 B CN102976913 B CN 102976913B CN 201210436179 A CN201210436179 A CN 201210436179A CN 102976913 B CN102976913 B CN 102976913B
- Authority
- CN
- China
- Prior art keywords
- rhodium
- deionized water
- organic solvent
- dicarbonyl acetylacetonate
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for preparing high-purity acetylacetonatodicarbonyl rhodium through using rhodium trichloride. The method comprises the following steps: mixing rhodium trichloride containing metal impurities with N,N-dimethyl formamide and acetylacetone, heating to reaction completeness, cooling the obtained reaction solution to room temperature, adding deionized water, filtering the obtained precipitate, washing the precipitate to obtain crude acetylacetonatodicarbonyl rhodium, dissolving the crude acetylacetonatodicarbonyl rhodium in a sufficient amount of an organic solvent, washing the obtained organic phase by an aqueous solution of disodium ethylene diamine tetraacetate twice, and washing the organic phase by water once to obtain an acetylacetonatodicarbonyl rhodium solution. The method which adopts the acetylacetonatodicarbonyl rhodium containing the metal impurities as a reaction raw material enables the rhodium recovery process to be substantially shortened, so the production cost is reduced, and the economic benefit of the method is large.
Description
Technical field:
The present invention relates to catalysis technical field, it is a kind of method of preparing high-purity acetylacetone rhodium carbonyl with Trichlororhodium, be specifically related to use the Trichlororhodium of metal impurities, prepare the method for high purity homogeneous reaction catalyzer or catalyst precursor methyl ethyl diketone rhodium carbonyl.
Background of invention:
Rhodium homogeneous phase organic complex catalyzer has that catalytic activity is high, good selective, in the catalyzed reactions such as shortening, olefin hydroformylation, oxo process, has important application, and many industrial production that has been applied to.For example: three (triphenylphosphine) rhodium chloride is as efficient olefin hydrogenation catalyst at industrial application, and rhodium dicarbonyl acetylacetonate, triphenylphosphine methyl ethyl diketone rhodium carbonyl, three (triphenylphosphine) carbonyl hydrogen rhodium, three [three (m-sulfonate phenyl) phosphine] carbonyl hydrogenation Rh etc. use in olefin hydroformylation full scale plant as efficient olefin hydroformylation catalyzer.Wherein, rhodium dicarbonyl acetylacetonate is general can directly apply to catalyzed alkene hydroformylation reaction as the intermediate product of synthetic triphenylphosphine methyl ethyl diketone rhodium carbonyl or under corresponding part exists.Above-mentioned rhodium homogeneous phase organic complex catalyzer is prepared for raw material by highly purified rhodium trichloride hydrate (rhodium-containing of the metallic impurity such as iron wherein, nickel, calcium is extremely low, and massfraction is in ppm left and right) conventionally.According to Russ. J. Inorg. Chem., 12,899,1967 disclosed preparation methods, by RhCl
3nH
2o is dissolved in DMF and methyl ethyl diketone, is heated to 150
oc keeps 1 hour, and reaction solution adds the deionized water of 4 times of volumes to be settled out Rh (acac) (CO) after being cooled to room temperature
2, after filtration, make rhodium dicarbonyl acetylacetonate with 75% yield after washing, drying and other steps.Aforesaid method raw material rhodium trichloride hydrate used is generally the chlorine rhodate (chlordene rhodium acid sodium or chlordene rhodium acid potassium) that is converted into solubility by warm chlorination process in highly purified rhodium powder warp, after dissolving, react with sodium hydroxide and make aqua oxidation rhodium again, aqua oxidation rhodium, with obtaining rhodium chloride acid solution after dissolving with hydrochloric acid, then obtains rhodium trichloride hydrate solid through evaporation concentration.
But, the thick rhodium of metal impurities is purified to the technique very complicated of high purity rhodium.First the purifying technique of rhodium metal is liquid making, rhodium is dissolved together with base metal to formation solution, and recycling rhodium is different from both separation from base metal chemistry character.But due to metal rhodium utmost point indissoluble solution, be one of the most insoluble metal, be insoluble to any single acid, be only slightly soluble in chloroazotic acid.Therefore, the liquid making of rhodium metal need be carried out repeatedly, rhodium could be dissolved completely.By after rhodium and base metal dissolving, need to utilize various separation means that both are separated, have the methods such as the precipitator method, electrochemical reducing, resin adsorption method, but most methods can only drop to certain level by the content of foreign metal.At present, the way extensively adopting is a part of precious metal of loss, ensures that the impurity content in rhodium metal reaches requirement, and the reaction solution before the rhodium metal of removing with impurity returns is again purified again.This just makes the purifying technique of rhodium metal repeatedly tediously long.
At present, the source of rhodium metal mainly contains two kinds, and a kind of is to separate and extract from the Mineral resources of rhodium-containing, and the decaying catalyst that another kind of source is rhodium-containing obtains after processing recycling.In Mineral resources, the content of rhodium is on the low side, generally also only has the level of some thousandths of through its mass content after preliminary enrichment operation, and the platinum metals that association is of the same clan and other foreign metal, in order to obtain highly purified metal rhodium, need to pass through a large amount of purification process.In the decaying catalyst of rhodium-containing, the rhodium-containing of rhodium is higher, and generally more than percentum, and the impurity containing is also comparatively simple.Taking hydroformylation of olefin inactivation spent rhodium catalyst as example; rhodium mass content in residue after preliminary burning disposal can reach more than 10%; the kind of foreign metal is determined, generally only contains the metallic impurity such as sodium, iron, nickel, calcium, its mass content generally hundreds of between thousands of ppm.In order to ensure catalytic activity and the life-span of rhodium catalyst, the content requirement of the metallic impurity of catalyzer is very high, and the impurity of common metal requires below dozens of ppm.For example, the metal quality content requirement such as the iron in Catalyst for Hydroformylation of Olefin methyl ethyl diketone carbonyl phosphine rhodium, nickel, calcium is below 50ppm.Even the dopant species of rhodium is few in spent rhodium catalyst residue, content is low; Remove impurity but still need to carry out various purification process, thereby obtain highly purified rhodium metal compound, to meet the requirement of again preparing metal rhodium complex compound catalyst.According to the technique of preparing at present methyl ethyl diketone carbonyl phosphine rhodium, in order to prepare various metallic impurity rhodium catalyst up to standard, need hydration rhodium chloride that foreign matter content is extremely low as raw material.But, the difficulty of rhodium metal recovery complete processing is the purification removal of impurities of rhodium metal, reach requirement because current preparation technology requires the impurity level of the very low rhodium complex catalyst that just can make preparation of foreign matter content of rhodium metal, make rhodium metal need repeatedly to carry out just reaching the level that foreign matter content is very low in the process of processing.Due to metallic impurity in rhodium metal in very low content, be how the difficult problem aspect rhodium metal purification ensureing under the prerequisite that rhodium metal does not lose, impurity to be removed always.
Because rhodium metal and impurity are close aspect chemical property, and the content of metallic impurity is very low, and simple removal of impurities reaction is difficult to remove completely metallic impurity.For example, if remove the sulfate ion in solution, general thinking is to add barium chloride solution, forms barium sulfate precipitate.But the sulfate ion after this processing in solution is not still removed completely, its content still has several ppm left and right, and in solution, has also introduced the barium ion impurity previously not had; When carrying out subsequent step when concentrated, previously in solution, sl. sol. barium sulfate can be separated out again in solution.Therefore be, to be difficult to reach the object of removing impurity if want by adding reagent to react with impurity.If be also difficult in the time carrying out impurity to carry out removal of impurities reaction treatment, the metallic impurity in rhodium metal compound are dropped to certain level, can add reaction reagent by rhodium metal compound generation chemical reaction, change rhodium compound into another material, change its physicochemical property, thereby reach the object separating with original impurity.
Summary of the invention:
The object of this invention is to provide a kind of rhodium trichloride hydrate by metal impurities and prepare the method for rhodium dicarbonyl acetylacetonate, the method adopts the rhodium trichloride hydrate of metal impurities as raw material, avoiding using the high-purity hydrated Trichlororhodium that purification step is loaded down with trivial details is raw material, can simplify rhodium and reclaim process operation step.
The purification of before mentioning metal rhodium compound is comparatively complicated, in order to solve this difficult problem, can start with from developing new efficient separation means on the one hand, also can develop on the other hand new catalyst preparation process, by the preparation feedback of catalyzer, the impurity in rhodium metal be removed.For example, Chinese patent CN102391310A discloses and has utilized the chlordene rhodium acid sodium that sodium content is high to prepare methyl ethyl diketone rhodium carbonyl, and every analysis indexes of the rhodium complexing product obtaining all reaches requirement.Technical in this technology, we,, by the further optimization to preparation technology, have developed the technology of utilizing the rhodium trichloride hydrate of metal ion impurity to prepare rhodium dicarbonyl acetylacetonate.The Trichlororhodium raw material of using in the present invention is the crude product of not yet complete refining and edulcoration in rhodium removal process, contain iron, nickel, calcium metallic impurity ion that mass content is 0.0001%-1%, the processing condition after optimization of the present invention can be prepared metals content impurity rhodium dicarbonyl acetylacetonate up to standard.
The present invention is a kind of method of preparing high-purity acetylacetone rhodium carbonyl with Trichlororhodium, it is characterized in that:
Comprise following processing step:
(a) by the rhodium trichloride hydrate of contaminating metal ion and N, dinethylformamide and methyl ethyl diketone mix, and are heated to react completely, and reaction solution is cooled to room temperature, add deionized water, the precipitation of separating out after filtration, after deionized water wash rhodium dicarbonyl acetylacetonate crude product; Wherein in Trichlororhodium, the mass content of iron, nickel, calcium, sodium metallic impurity ion is 0.0001%-1%;
(b) rhodium dicarbonyl acetylacetonate crude product is with after enough organic solvent dissolutions, wash organic phase twice with adding disodium ethylene diamine tetra-acetic acid aqueous solution, use again deionized water wash organic phase once, wherein the mass concentration of disodium ethylene diamine tetra-acetic acid aqueous solution is 0.1%-2%, wherein the volume ratio of organic solvent and disodium ethylene diamine tetra-acetic acid aqueous solution is 1:1-20:1, the volume ratio of organic solvent and deionized water is 1:1-20:1, and organic solvent is benzene, toluene, ether, methylene dichloride;
(c) the rhodium dicarbonyl acetylacetonate organic solution that obtains of washing can reduce pressure and remove organic solvent and obtain rhodium dicarbonyl acetylacetonate solid product, or under certain reaction conditions, is directly reacting with triphenylphosphine and preparing Catalyst for Hydroformylation of Olefin methyl ethyl diketone carbonyl phosphine rhodium.
According to the method described in the present invention, it is characterized in that:
Comprise the following steps:
(a) by the rhodium trichloride hydrate of contaminating metal ion and N, dinethylformamide and methyl ethyl diketone mix, and are heated to react completely, and reaction solution is cooled to room temperature, add deionized water, the precipitation of separating out after filtration, after deionized water wash rhodium dicarbonyl acetylacetonate crude product; Wherein the mass content of the iron in Trichlororhodium, nickel, calcium, sodium metallic impurity ion is 0.0002%-0.8%;
(b) rhodium dicarbonyl acetylacetonate crude product is with after enough organic solvent dissolutions, wash organic phase twice with adding disodium ethylene diamine tetra-acetic acid aqueous solution, use again deionized water wash organic phase once, wherein the mass concentration of disodium ethylene diamine tetra-acetic acid aqueous solution is 0.2%-1.8%, the volume ratio of organic solvent and disodium ethylene diamine tetra-acetic acid aqueous solution is 5:1-10:1, the volume ratio of organic solvent and deionized water is 5:1-10:1, and described organic solvent is toluene;
(c) the rhodium dicarbonyl acetylacetonate organic solution that obtains of washing can reduce pressure and remove organic solvent and obtain solid rhodium dicarbonyl acetylacetonate product.
Method provided by the invention is to remove the metallic impurity of rhodium dicarbonyl acetylacetonate through two steps, first rhodium with N, when dinethylformamide and methyl ethyl diketone reaction, the metallic impurity such as iron in rhodium, nickel, calcium do not react with corresponding reagent, after having reacted, rhodium changes the rhodium compound of organic complex state into, and other metallic impurity still keep mineralized.In the time adding deionized water in reaction solution, the rhodium compound of organic complex state form with flocks from reaction solution is separated out, and metallic impurity are present in the aqueous solution with ionic condition, have reached the initial gross separation of rhodium and foreign metal.But can wrap up the foreign ion in solution while separating out with the form of precipitation in reaction solution due to rhodium complex, even a large amount of deionized water wash of the rhodium dicarbonyl acetylacetonate of separating out precipitation, its metals content impurity still exceeds standard, and need to carry out further removal of impurities processing to rhodium dicarbonyl acetylacetonate crude product.While carrying out further removal of impurities processing, rhodium dicarbonyl acetylacetonate crude product is with after enough organic solvent dissolutions, add disodium ethylene diamine tetra-acetic acid aqueous solution washing organic phase twice, due to the strong sequestering action to metal ions such as iron, nickel, calcium of EDTA, metallic impurity in organic phase will enter water, thereby realize and the separating of rhodium dicarbonyl acetylacetonate.The rhodium dicarbonyl acetylacetonate product obtaining through the two step processing requirement that sodium, iron, nickel, calcium plasma all touch the mark after testing, and the washing impurity-removing step increasing does not almost affect the yield of rhodium dicarbonyl acetylacetonate.
Embodiment:
Embodiment 1
Contain sodium by 1.00 grams, iron, nickel, hydration rhodium chloride (the rhodium of calcium metallic impurity, sodium, iron, nickel, the mass content of calcium is respectively: 35.21%, 0.97%, 0.0143%, 0.0014%, 0.0256%) and 15 milliliters of N, dinethylformamide, 4 milliliters of methyl ethyl diketones are placed in 50 milliliters of round-bottomed flasks, be heated to 80 DEG C, keep 0.5 hour, continuing to be warming up to 136 DEG C keeps 1 hour, after having reacted, reaction solution is naturally cooled to room temperature, add 100 ml deionized water, after mixing, filter out rhodium dicarbonyl acetylacetonate precipitation, deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product obtaining dissolves with 40 milliliters of toluene solvants, then use 40 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 0.1%) washing toluene, twice (40 × 2) mutually, again with 40 once (40 × 1) of ml deionized water washing toluene phase, can obtain rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains rhodium dicarbonyl acetylacetonate solid, yield 95.2%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid obtaining obtains after sulfuric acid, nitric acid are cleared up detects the mass content of sodium, iron, nickel, calcium metallic impurity through ICP-OES, be respectively 0.0011%, 0.0003%, 0.0002%, 0.0010%, all reach standard-required (mass content of foreign metal is less than 0.0005%).
Embodiment 2
Contain sodium by 1.00 grams, iron, nickel, hydration rhodium chloride (the rhodium of calcium metallic impurity, sodium, iron, nickel, the mass content of calcium is respectively: 34.87%, 0.69%, 0.0118%, 0.8920%, 0.0235%) and 15 milliliters of N, dinethylformamide, 4 milliliters of methyl ethyl diketones are placed in 50 milliliters of round-bottomed flasks, be heated to 80 DEG C, keep 0.5 hour, continuing to be warming up to 136 DEG C keeps 1 hour, after having reacted, reaction solution is naturally cooled to room temperature, add 100 ml deionized water, after mixing, filter out rhodium dicarbonyl acetylacetonate precipitation, deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product obtaining dissolves with 40 milliliters of toluene solvants, then use 2 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 2.0%) washing toluene, twice (2 × 2) mutually, again with 2 once (2 × 1) of ml deionized water washing toluene phase, can obtain rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains rhodium dicarbonyl acetylacetonate solid, yield 95.6%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid obtaining obtains after sulfuric acid, nitric acid are cleared up detects the mass content of sodium, iron, nickel, calcium metallic impurity through ICP-OES, be respectively 0.0028%, 0.0006%, 0.0005%, 0.0015%, all reaches standard-required.
Embodiment 3
Contain sodium by 1.00 grams, iron, nickel, hydration rhodium chloride (the rhodium of calcium metallic impurity, sodium, iron, nickel, the mass content of calcium is respectively: 34.30%, 0.54%, 0.0124%, 0.0018%, 0.8630%) and 15 milliliters of N, dinethylformamide, 4 milliliters of methyl ethyl diketones are placed in 50 milliliters of round-bottomed flasks, be heated to 80 DEG C, keep 0.5 hour, continuing to be warming up to 136 DEG C keeps 1 hour, after having reacted, reaction solution is naturally cooled to room temperature, add 100 ml deionized water, after mixing, filter out rhodium dicarbonyl acetylacetonate precipitation, deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product obtaining dissolves with 4 milliliters of toluene solvants, then use 8 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 0.6%) washing toluene, twice (8 × 2) mutually, again with 8 once (8 × 1) of ml deionized water washing toluene phase, can obtain rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains rhodium dicarbonyl acetylacetonate solid, yield 95.0%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid obtaining obtains after sulfuric acid, nitric acid are cleared up detects the mass content of sodium, iron, nickel, calcium metallic impurity through ICP-OES, be respectively 0.0018%, 0.0004%, 0.0003%, 0.0013%, all reaches standard-required.
Embodiment 4
Contain sodium by 1.00 grams, iron, nickel, hydration rhodium chloride (the rhodium of calcium metallic impurity, sodium, iron, nickel, the mass content of calcium is respectively: 34.02%, 0.51%, 0.9130%, 0.0016%, 0.0217%) and 15 milliliters of N, dinethylformamide, 4 milliliters of methyl ethyl diketones are placed in 50 milliliters of round-bottomed flasks, be heated to 80 DEG C, keep 0.5 hour, continuing to be warming up to 136 DEG C keeps 1 hour, after having reacted, reaction solution is naturally cooled to room temperature, add 100 ml deionized water, after mixing, filter out rhodium dicarbonyl acetylacetonate precipitation, deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product obtaining dissolves with 4 milliliters of toluene solvants, then use 4 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 1.0%) washing toluene, twice (4 × 2) mutually, again with 4 once (4 × 1) of ml deionized water washing toluene phase, can obtain rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains rhodium dicarbonyl acetylacetonate solid, yield 94.7%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid obtaining obtains after sulfuric acid, nitric acid are cleared up detects the mass content of sodium, iron, nickel, calcium metallic impurity through ICP-OES, be respectively 0.0021%, 0.0005%, 0.0002%, 0.0011%, all reaches standard-required.
Embodiment 5
Contain sodium by 1.00 grams, iron, nickel, hydration rhodium chloride (the rhodium of calcium metallic impurity, sodium, iron, nickel, the mass content of calcium is respectively: 33.46%, 0.51%, 0.8350%, 0.0031%, 0.812%) and 15 milliliters of N, dinethylformamide, 4 milliliters of methyl ethyl diketones are placed in 50 milliliters of round-bottomed flasks, be heated to 80 DEG C, keep 0.5 hour, continuing to be warming up to 136 DEG C keeps 1 hour, after having reacted, reaction solution is naturally cooled to room temperature, add 100 ml deionized water, after mixing, filter out rhodium dicarbonyl acetylacetonate precipitation, deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product obtaining dissolves with 5 milliliters of toluene solvants, then use 5 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 0.8%) washing toluene, twice (5 × 2) mutually, again with 5 once (5 × 1) of ml deionized water washing toluene phase, can obtain rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains rhodium dicarbonyl acetylacetonate solid, yield 95.3%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid obtaining obtains after sulfuric acid, nitric acid are cleared up detects the mass content of sodium, iron, nickel, calcium metallic impurity through ICP-OES, be respectively 0.0016%, 0.0006%, 0.0003%, 0.0015%, all reaches standard-required.
Comparative example 1
Contain sodium by 1.00 grams, iron, nickel, hydration rhodium chloride (the rhodium of calcium metallic impurity, sodium, iron, nickel, the mass content of calcium is respectively: 35.21%, 0.97%, 0.0143%, 0.0014%, 0.0256%) and 15 milliliters of N, dinethylformamide, 4 milliliters of methyl ethyl diketones are placed in 50 milliliters of round-bottomed flasks, be heated to 80 DEG C, keep 0.5 hour, continuing to be warming up to 136 DEG C keeps 1 hour, after having reacted, reaction solution is naturally cooled to room temperature, add 100 ml deionized water, after mixing, filter out rhodium dicarbonyl acetylacetonate precipitation, deionized water wash filter cake, dry, the rhodium dicarbonyl acetylacetonate product obtaining, yield 95.7%.The aqueous solution that the rhodium dicarbonyl acetylacetonate obtaining obtains after sulfuric acid, nitric acid are cleared up detects the content of sodium (0.0047%), iron (0.0076%), nickel (0.0013%), calcium (0.0098%) metallic impurity through ICP-OES, the requirement that is above standard of Qi Zhongtie, calcium contents.
Claims (2)
1. a method of preparing high-purity acetylacetone rhodium carbonyl with Trichlororhodium, is characterized in that:
Comprise following processing step:
(a) by the rhodium trichloride hydrate of contaminating metal ion and N, dinethylformamide and methyl ethyl diketone mix, and are heated to react completely, and reaction solution is cooled to room temperature, add deionized water, the precipitation of separating out after filtration, after deionized water wash rhodium dicarbonyl acetylacetonate crude product; Wherein in Trichlororhodium, the mass content of iron, nickel, calcium, sodium metallic impurity ion is 0.0001%-1%;
(b) rhodium dicarbonyl acetylacetonate crude product is with after enough organic solvent dissolutions, wash organic phase twice with adding disodium ethylene diamine tetra-acetic acid aqueous solution, use again deionized water wash organic phase once, wherein the mass concentration of disodium ethylene diamine tetra-acetic acid aqueous solution is 0.1%-2%, wherein the volume ratio of organic solvent and disodium ethylene diamine tetra-acetic acid aqueous solution is 1:1-20:1, the volume ratio of organic solvent and deionized water is 1:1-20:1, and organic solvent is benzene, toluene, ether, methylene dichloride;
(c) the rhodium dicarbonyl acetylacetonate organic solution that obtains of washing can reduce pressure and remove organic solvent and obtain rhodium dicarbonyl acetylacetonate solid product, or under certain reaction conditions, is directly reacting with triphenylphosphine and preparing Catalyst for Hydroformylation of Olefin methyl ethyl diketone carbonyl phosphine rhodium.
2. it is characterized in that in accordance with the method for claim 1:
Comprise the following steps:
(a) by the rhodium trichloride hydrate of contaminating metal ion and N, dinethylformamide and methyl ethyl diketone mix, and are heated to react completely, and reaction solution is cooled to room temperature, add deionized water, the precipitation of separating out after filtration, after deionized water wash rhodium dicarbonyl acetylacetonate crude product; Wherein the mass content of the iron in Trichlororhodium, nickel, calcium, sodium metallic impurity ion is 0.0002%-0.8%;
(b) rhodium dicarbonyl acetylacetonate crude product is with after enough organic solvent dissolutions, wash organic phase twice with adding disodium ethylene diamine tetra-acetic acid aqueous solution, use again deionized water wash organic phase once, wherein the mass concentration of disodium ethylene diamine tetra-acetic acid aqueous solution is 0.2%-1.8%, the volume ratio of organic solvent and disodium ethylene diamine tetra-acetic acid aqueous solution is 5:1-10:1, the volume ratio of organic solvent and deionized water is 5:1-10:1, and described organic solvent is toluene;
(c) the rhodium dicarbonyl acetylacetonate organic solution that obtains of washing can reduce pressure and remove organic solvent and obtain solid rhodium dicarbonyl acetylacetonate product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210436179.6A CN102976913B (en) | 2012-11-05 | 2012-11-05 | Method for preparing high-purity acetylacetonatodicarbonyl rhodium through using rhodium trichloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210436179.6A CN102976913B (en) | 2012-11-05 | 2012-11-05 | Method for preparing high-purity acetylacetonatodicarbonyl rhodium through using rhodium trichloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102976913A CN102976913A (en) | 2013-03-20 |
| CN102976913B true CN102976913B (en) | 2014-12-03 |
Family
ID=47851320
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210436179.6A Active CN102976913B (en) | 2012-11-05 | 2012-11-05 | Method for preparing high-purity acetylacetonatodicarbonyl rhodium through using rhodium trichloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102976913B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283063B (en) * | 2019-06-11 | 2020-06-16 | 中山华明泰科技股份有限公司 | Preparation method and application of lanthanum acetylacetonate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409149A (en) * | 1981-06-29 | 1983-10-11 | Union Carbide Corporation | Process for producing catalyst precursors |
| CN102093432A (en) * | 2011-01-29 | 2011-06-15 | 杭州凯大催化金属材料有限公司 | Method for synthesizing acetylacetonatodicarbonyl rhodium |
-
2012
- 2012-11-05 CN CN201210436179.6A patent/CN102976913B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4409149A (en) * | 1981-06-29 | 1983-10-11 | Union Carbide Corporation | Process for producing catalyst precursors |
| CN102093432A (en) * | 2011-01-29 | 2011-06-15 | 杭州凯大催化金属材料有限公司 | Method for synthesizing acetylacetonatodicarbonyl rhodium |
Non-Patent Citations (2)
| Title |
|---|
| 乙酰丙酮二羰基铑(I)的合成与表征;郇昌永等;《广州化工》;20120208;第40卷(第3期);77-78 * |
| 郇昌永等.乙酰丙酮二羰基铑(I)的合成与表征.《广州化工》.2012,第40卷(第3期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102976913A (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102557155B (en) | Method for recovering rhodium from rhodium-containing waste liquid and preparing rhodium chloride hydrate | |
| CN100549190C (en) | Use the recovery method that contains the platinum in the selenium waste liquid of hydrazine | |
| CN100575267C (en) | A kind of liquid phase method reclaims the method for high purity chlorination rhodium from the spent rhodium catalyst that carbongl group synthesis reaction produces | |
| CN102923796B (en) | Method for preparing rhodium chloride hydrate by recovering rhodium from dead rhodium catalyst of oxo synthesis | |
| CN102277499B (en) | Method for recovering rhodium from organic waste liquid produced in carbonyl synthesis reaction | |
| CN102373335B (en) | Method for recovering rhodium from inactivated rhodium-phosphine complex catalyst | |
| TW201439331A (en) | Methods of recovering scandium from titanium residue streams | |
| CN103343239B (en) | Method for separating and purifying rhodium | |
| CN104860358B (en) | A kind of recovery method of purification of high-purity rhodium | |
| CN105314689A (en) | Method for reclaiming rhodium from waste rhodium catalyst of oxo synthesis reaction to prepare rhodium chloride hydrate | |
| CN102515286B (en) | Method for preparing high-purity rhodium chloride by using waste rhodium catalyst digestion solution | |
| CN102976913B (en) | Method for preparing high-purity acetylacetonatodicarbonyl rhodium through using rhodium trichloride | |
| CN104478009A (en) | Method for recovering rhodium from rhodium-containing cationic resin exchange waste liquid | |
| CN105944768B (en) | A kind of method that rhodium catalyst is recycled in the waste water phase from rhodium-containing | |
| CN104402068A (en) | Method for preparing high-purity rhodium trichloride from carbonyl-synthetic-reaction waste rhodium catalyst degradation solution | |
| CN102492845A (en) | Method for digesting spent rhodium catalyst in carbonyl group synthetic reaction | |
| KR101323754B1 (en) | Recovery of acid and platinum group metals from leaching solution of waste catalyst | |
| CN114308131A (en) | Precious metal compound extracted from waste, method thereof and method for synthesizing tetrakis (triphenylphosphine) platinum/palladium | |
| JP5818315B2 (en) | Metal selective extractant | |
| CN106222437B (en) | A kind of method that palladium is refined from alkaline strip liquor | |
| KR100354980B1 (en) | Purification of the Platinum group | |
| CN105463202B (en) | A kind of method that impure chlorine rhodium acid solution removal of impurities prepares high-purity rhodium chloride | |
| CA1070504A (en) | Method for removing arsenic from copper electrolytic solutions or the like | |
| CN102912141A (en) | Method for digesting waste rhodium catalyst from olefin hydroformylation reaction | |
| JP5000678B2 (en) | Purification method of iridium aqueous solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| C56 | Change in the name or address of the patentee | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee after: CHINA NATIONAL OFFSHORE OIL Corp. Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20161009 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee after: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: CHINA NATIONAL OFFSHORE OIL Corp. Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE Co.,Ltd. Patentee before: CNOOC ENERGY TECHNOLOGY & SERVICES Ltd. |