CN102976913A - 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
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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 for preparing the 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 catalytic activity height, good selective, in the catalyzed reactions such as shortening, olefin hydroformylation, oxo process important application is arranged, and many industrial production that has been applied to.For example: three (triphenylphosphine) rhodium chloride is as olefin hydrogenation catalyst is at industrial application efficiently, and the conducts such as rhodium dicarbonyl acetylacetonate, triphenylphosphine methyl ethyl diketone rhodium carbonyl, three (triphenylphosphine) carbonyl hydrogen rhodium, three [three (meta-sulfonate phenyl) phosphine] carbonyl hydrogenation Rh efficiently olefin hydroformylation catalyzer are used in the olefin hydroformylation full scale plant.Wherein, the general conduct of rhodium dicarbonyl acetylacetonate is synthesized the intermediate product of triphenylphosphine methyl ethyl diketone rhodium carbonyl or can directly apply to the catalyzed alkene hydroformylation reaction in the presence of corresponding part.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 about ppm) usually.According to Russ. J. Inorg. Chem., 12,899,1967 disclosed preparation methods are with RhCl
3NH
2O is dissolved in DMF and the methyl ethyl diketone, is heated to 150
oC kept 1 hour, and reaction solution is cooled to the deionized water that adds 4 times of volumes after the room temperature and is settled out Rh (acac) (CO)
2, after filtration, the yield with 75% after the washing, drying and other steps makes rhodium dicarbonyl acetylacetonate.The used raw material rhodium trichloride hydrate of aforesaid method generally is the chlorine rhodate (chlordene rhodium acid sodium or chlordene rhodium acid potassium) that is converted into solubility by warm chlorination process in the highly purified rhodium powder warp, make the aqua oxidation rhodium with the sodium hydroxide reaction again after the dissolving, the aqua oxidation rhodium after with dissolving with hydrochloric acid rhodium chloride acid solution, then obtain the rhodium trichloride hydrate solid through evaporation concentration.
Yet, the thick rhodium of metal impurities is purified to the technique very complicated of high purity rhodium.The purifying technique of rhodium metal at first is liquid making, and rhodium and base metal are dissolved formation solution together, and the recycling rhodium separates both from base metal chemistry the different of character.But because metal rhodium utmost point indissoluble solution, be one of the most insoluble metal, be insoluble to any single acid, only be slightly soluble in chloroazotic acid.Therefore, the liquid making of rhodium metal need be carried out repeatedly, rhodium could be dissolved fully.After with rhodium and base metal dissolving, need to utilize various separation means that both are separated, the methods such as the precipitator method, electrochemical reducing, resin adsorption method are arranged, but most methods can only drop to the content of foreign metal certain level.At present, the way that extensively adopts is the precious metal of a loss part, guarantees that the impurity content in the rhodium metal reaches requirement, and the reaction solution before the rhodium metal of removing with impurity returns is again purified again.This is just so that the purifying technique of rhodium metal is repeatedly tediously long.
At present, the source of rhodium metal mainly contains two kinds, and a kind of is to separate to extract from the Mineral resources of rhodium-containing, and the decaying catalyst that another kind of source is rhodium-containing obtains after the processing recycling.The content of rhodium is on the low side in the Mineral resources, the level of generally also only having some thousandths of through its mass content after the 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 through a large amount of purification process.The rhodium-containing of rhodium is higher in the decaying catalyst of rhodium-containing, and generally more than percentum, and the impurity that contains is also comparatively simple.Take hydroformylation of olefin inactivation spent rhodium catalyst as example; rhodium mass content in the 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.For the catalytic activity and the life-span that guarantee 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 the Catalyst for Hydroformylation of Olefin methyl ethyl diketone carbonyl phosphine rhodium, nickel, calcium are below 50ppm.Even the dopant species of rhodium is few in the 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, in order to satisfy the requirement that again prepares the metal rhodium complex compound catalyst.According to the technique of present preparation methyl ethyl diketone carbonyl phosphine rhodium, in order to prepare various metallic impurity rhodium catalyst up to standard, need the extremely low hydration rhodium chloride of foreign matter content as raw material.Yet, the difficulty of rhodium metal recovery complete processing is the purification removal of impurities of rhodium metal, because present preparation technology requires the very low ability of foreign matter content of rhodium metal so that the impurity level of the rhodium complex catalyst of preparation reaches requirement, so that rhodium metal needs repeatedly to carry out just reaching the very low level of foreign matter content in the process of processing.Because metallic impurity have been in very low content in rhodium metal, be a difficult problem aspect the rhodium metal purification guaranteeing under the prerequisite that rhodium metal does not lose impurity removed how always.
Because rhodium metal is close aspect chemical property with impurity, and the content of metallic impurity is very low, simple removal of impurities reaction is difficult to remove fully metallic impurity.For example, if remove sulfate ion in the solution, general thinking is to add barium chloride solution, forms barium sulfate precipitate.But still do not remove fully through the sulfate ion in the solution after this processing, its content still has about several ppm, and has also introduced the barium ion impurity that had not before had in the solution; When carrying out subsequent step when concentrated, before sl. sol. barium sulfate can be separated out in solution again in solution.Therefore, react and be to be difficult to reach the purpose of removing impurity by adding reagent and impurity if want.If when carrying out that impurity carried out the removal of impurities reaction treatment, also be difficult to the metallic impurity in the rhodium metal compound are dropped in the situation of 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 purpose of separating with original impurity.
Summary of the invention:
The purpose of this invention is to provide the method that a kind of rhodium trichloride hydrate by metal impurities prepares rhodium dicarbonyl acetylacetonate, the method adopts the rhodium trichloride hydrate of metal impurities as raw material, avoid using the loaded down with trivial details high-purity hydrated Trichlororhodium of purification step to be raw material, can simplify rhodium and reclaim the process operation step.
The purification of before mentioning the 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 new catalyst preparation process on the other hand, by the preparation feedback of catalyzer the impurity in the rhodium metal be removed.For example, Chinese patent CN102391310A discloses and has utilized the high chlordene rhodium acid sodium of sodium content to prepare the methyl ethyl diketone rhodium carbonyl, and every analysis indexes of the rhodium complexing product that obtains all reaches requirement.Technical in this technology, we have developed the technology that the rhodium trichloride hydrate that utilizes metal ion impurity prepares rhodium dicarbonyl acetylacetonate by the further optimization to preparation technology.The Trichlororhodium raw material of using among the present invention is the crude product of not yet complete refining and edulcoration in the rhodium removal process, contain iron, nickel, calcium metallic impurity ion that mass content is 0.0001%-1%, can prepare metals content impurity rhodium dicarbonyl acetylacetonate up to standard through the processing condition after the optimization of the present invention.
The present invention a kind ofly prepares the method for high-purity acetylacetone rhodium carbonyl with Trichlororhodium, it is characterized in that:
Comprise following processing step:
(a) with rhodium trichloride hydrate and the N of contaminating metal ion, 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, behind the deionized water wash the rhodium dicarbonyl acetylacetonate crude product; Wherein the mass content of iron, nickel, calcium, sodium metallic impurity ion is 0.0001%-1% in the Trichlororhodium;
(b) the rhodium dicarbonyl acetylacetonate crude product is with behind the organic solvent dissolution of capacity, wash organic phase twice with the adding disodium ethylene diamine tetra-acetic acid aqueous solution, use again the 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 the rhodium dicarbonyl acetylacetonate solid product, perhaps directly prepares Catalyst for Hydroformylation of Olefin methyl ethyl diketone carbonyl phosphine rhodium with the triphenylphosphine reaction under certain reaction conditions.
According to the method described in the present invention, it is characterized in that:
May further comprise the steps:
(a) with rhodium trichloride hydrate and the N of contaminating metal ion, 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, behind the deionized water wash the rhodium dicarbonyl acetylacetonate crude product; Wherein the mass content of the iron in the Trichlororhodium, nickel, calcium, sodium metallic impurity ion is 0.0002%-0.8%;
(b) the rhodium dicarbonyl acetylacetonate crude product is with behind the organic solvent dissolution of capacity, wash organic phase twice with the adding disodium ethylene diamine tetra-acetic acid aqueous solution, use again the 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, at first rhodium with N, when dinethylformamide and methyl ethyl diketone reaction, the metallic impurity such as the iron in the rhodium, nickel, calcium do not react with corresponding reagent, after reaction is finished, rhodium changes the rhodium compound of organic complex state into, and other metallic impurity still keep mineralized.When adding deionized water in the 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 because rhodium complex can wrap up foreign ion in the solution when separating out with the form of precipitation in reaction solution, 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 to the rhodium dicarbonyl acetylacetonate crude product and process.When carrying out further removal of impurities processing, the rhodium dicarbonyl acetylacetonate crude product is with behind the organic solvent dissolution of capacity, add disodium ethylene diamine tetra-acetic acid aqueous solution washing organic phase twice, because the strong sequestering action to metal ions such as iron, nickel, calcium of EDTA, metallic impurity in the organic phase will enter water, thereby realize and the separating of rhodium dicarbonyl acetylacetonate.Process the after testing requirement that all touches the mark of sodium, iron, nickel, calcium plasma of the rhodium dicarbonyl acetylacetonate product obtain through two steps, and the washing impurity-removing step that increases is on the almost not impact of yield of rhodium dicarbonyl acetylacetonate.
Embodiment:
Embodiment 1
1.00 grams are contained sodium, 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 place 50 milliliters of round-bottomed flasks, be heated to 80 ℃, kept 0.5 hour, continuing to be warming up to 136 ℃ kept 1 hour, after reaction is finished reaction solution is naturally cooled to room temperature, add 100 ml deionized water, filter out the rhodium dicarbonyl acetylacetonate precipitation after mixing, the deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product that obtains dissolves with 40 milliliters of toluene solvants, then use mutually twice (40 * 2) of 40 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 0.1%) washing toluene, wash toluene phase once (40 * 1) with 40 ml deionized water again, can obtain the rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains the rhodium dicarbonyl acetylacetonate solid, yield 95.2%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid that obtains 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
1.00 grams are contained sodium, 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 place 50 milliliters of round-bottomed flasks, be heated to 80 ℃, kept 0.5 hour, continuing to be warming up to 136 ℃ kept 1 hour, after reaction is finished reaction solution is naturally cooled to room temperature, add 100 ml deionized water, filter out the rhodium dicarbonyl acetylacetonate precipitation after mixing, the deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product that obtains dissolves with 40 milliliters of toluene solvants, then use mutually twice (2 * 2) of 2 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 2.0%) washing toluene, wash toluene phase once (2 * 1) with 2 ml deionized water again, can obtain the rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains the rhodium dicarbonyl acetylacetonate solid, yield 95.6%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid that obtains obtains after sulfuric acid, nitric acid are cleared up detects the mass content of sodium, iron, nickel, calcium metallic impurity through ICP-OES, is respectively 0.0028%, 0.0006%, 0.0005%, 0.0015%, all reaches standard-required.
Embodiment 3
1.00 grams are contained sodium, 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 place 50 milliliters of round-bottomed flasks, be heated to 80 ℃, kept 0.5 hour, continuing to be warming up to 136 ℃ kept 1 hour, after reaction is finished reaction solution is naturally cooled to room temperature, add 100 ml deionized water, filter out the rhodium dicarbonyl acetylacetonate precipitation after mixing, the deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product that obtains dissolves with 4 milliliters of toluene solvants, then use mutually twice (8 * 2) of 8 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 0.6%) washing toluene, wash toluene phase once (8 * 1) with 8 ml deionized water again, can obtain the rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains the rhodium dicarbonyl acetylacetonate solid, yield 95.0%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid that obtains obtains after sulfuric acid, nitric acid are cleared up detects the mass content of sodium, iron, nickel, calcium metallic impurity through ICP-OES, is respectively 0.0018%, 0.0004%, 0.0003%, 0.0013%, all reaches standard-required.
Embodiment 4
1.00 grams are contained sodium, 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 place 50 milliliters of round-bottomed flasks, be heated to 80 ℃, kept 0.5 hour, continuing to be warming up to 136 ℃ kept 1 hour, after reaction is finished reaction solution is naturally cooled to room temperature, add 100 ml deionized water, filter out the rhodium dicarbonyl acetylacetonate precipitation after mixing, the deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product that obtains dissolves with 4 milliliters of toluene solvants, then use mutually twice (4 * 2) of 4 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 1.0%) washing toluene, wash toluene phase once (4 * 1) with 4 ml deionized water again, can obtain the rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains the rhodium dicarbonyl acetylacetonate solid, yield 94.7%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid that obtains obtains after sulfuric acid, nitric acid are cleared up detects the mass content of sodium, iron, nickel, calcium metallic impurity through ICP-OES, is respectively 0.0021%, 0.0005%, 0.0002%, 0.0011%, all reaches standard-required.
Embodiment 5
1.00 grams are contained sodium, 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 place 50 milliliters of round-bottomed flasks, be heated to 80 ℃, kept 0.5 hour, continuing to be warming up to 136 ℃ kept 1 hour, after reaction is finished reaction solution is naturally cooled to room temperature, add 100 ml deionized water, filter out the rhodium dicarbonyl acetylacetonate precipitation after mixing, the deionized water wash filter cake, after the rhodium dicarbonyl acetylacetonate crude product that obtains dissolves with 5 milliliters of toluene solvants, then use mutually twice (5 * 2) of 5 milliliters of disodium ethylene diamine tetra-acetic acid aqueous solutions (mass concentration 0.8%) washing toluene, wash toluene phase once (5 * 1) with 5 ml deionized water again, can obtain the rhodium dicarbonyl acetylacetonate toluene solution.After removing toluene, decompression obtains the rhodium dicarbonyl acetylacetonate solid, yield 95.3%.The aqueous solution that the rhodium dicarbonyl acetylacetonate solid that obtains obtains after sulfuric acid, nitric acid are cleared up detects the mass content of sodium, iron, nickel, calcium metallic impurity through ICP-OES, is respectively 0.0016%, 0.0006%, 0.0003%, 0.0015%, all reaches standard-required.
Comparative Examples 1
1.00 grams are contained sodium, 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 place 50 milliliters of round-bottomed flasks, be heated to 80 ℃, kept 0.5 hour, continuing to be warming up to 136 ℃ kept 1 hour, after reaction is finished reaction solution is naturally cooled to room temperature, add 100 ml deionized water, filter out the rhodium dicarbonyl acetylacetonate precipitation after mixing, the deionized water wash filter cake, drying, the rhodium dicarbonyl acetylacetonate product that obtains, yield 95.7%.The aqueous solution that the rhodium dicarbonyl acetylacetonate that obtains 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, wherein iron, the calcium contents requirement that is above standard.
Claims (2)
1. one kind prepares the method for high-purity acetylacetone rhodium carbonyl with Trichlororhodium, it is characterized in that:
Comprise following processing step:
(a) with rhodium trichloride hydrate and the N of contaminating metal ion, 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, behind the deionized water wash the rhodium dicarbonyl acetylacetonate crude product; Wherein the mass content of iron, nickel, calcium, sodium metallic impurity ion is 0.0001%-1% in the Trichlororhodium;
(b) the rhodium dicarbonyl acetylacetonate crude product is with behind the organic solvent dissolution of capacity, wash organic phase twice with the adding disodium ethylene diamine tetra-acetic acid aqueous solution, use again the 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 the rhodium dicarbonyl acetylacetonate solid product, perhaps directly prepares Catalyst for Hydroformylation of Olefin methyl ethyl diketone carbonyl phosphine rhodium with the triphenylphosphine reaction under certain reaction conditions.
2. it is characterized in that in accordance with the method for claim 1:
May further comprise the steps:
(a) with rhodium trichloride hydrate and the N of contaminating metal ion, 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, behind the deionized water wash the rhodium dicarbonyl acetylacetonate crude product; Wherein the mass content of the iron in the Trichlororhodium, nickel, calcium, sodium metallic impurity ion is 0.0002%-0.8%;
(b) the rhodium dicarbonyl acetylacetonate crude product is with behind the organic solvent dissolution of capacity, wash organic phase twice with the adding disodium ethylene diamine tetra-acetic acid aqueous solution, use again the 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.
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|---|---|---|---|---|
| CN110283063A (en) * | 2019-06-11 | 2019-09-27 | 中山华明泰科技股份有限公司 | A kind of preparation method and application of Acetylacetone lanthanum |
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 |
-
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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 (1)
| Title |
|---|
| 郇昌永等: "乙酰丙酮二羰基铑(I)的合成与表征", 《广州化工》, vol. 40, no. 3, 8 February 2012 (2012-02-08) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283063A (en) * | 2019-06-11 | 2019-09-27 | 中山华明泰科技股份有限公司 | A kind of preparation method and application of Acetylacetone lanthanum |
| 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 |
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