CN102351913B - Preparation method of tris[tri(3-sodium sulfonate-phenyl)phosphine]rhodium chloride - Google Patents
Preparation method of tris[tri(3-sodium sulfonate-phenyl)phosphine]rhodium chloride Download PDFInfo
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Abstract
The invention relates to a preparation method of tris[tri(3-sodium sulfonate-phenyl)phosphine]rhodium chloride, which comprises the following steps: adding a tri(3-sodium sulfonate-phenyl)phosphine water solution into a sodium hexachlororhodate hydrate alcoholic solution which has been replaced with nitrogen atmosphere; heating the reactant liquid until the reaction is complete; and separating and recycling the product. The method has the advantages of simple operational process and high yield; and since the sodium hexachlororhodate hydrate, which can be more easily prepared from rhodium powder, is used as the reaction material, the technical process of preparing tris[tri(3-sodium sulfonate-phenyl)phosphine]rhodium chloride from rhodium powder can be greatly simplified, thereby lowering the production cost and having higher economic benefit.
Description
Technical field the present invention relates to catalyst technical field; The preparation method of one three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride about homogeneous reaction catalyzer or catalyst precursor.
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.Wherein, water miscible three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride [RhCl (TPPTS)
3] be often used as the catalyzer that water is the alkene carbon-to-carbon double bond hydrogenation reaction of reaction solvent.US5057618 discloses rhodium trichloride hydrate (RhCl
33H
2o) prepare RhCl (TPPTS)
3method: by RhCl
33H
2o and three (3-sodium sulfonate-phenyl) phosphine (TPPTS) stirs and within 15 hours, obtains RhCl (TPPTS) in the aqueous solution
3, after separating-purifying, only can obtain RhCl (TPPTS) with 73% yield
3.
Aforesaid method raw material rhodium trichloride hydrate used is generally to be prepared by rhodium powder, the treated water-soluble rhodium salt that is converted into of rhodium powder, make aqua oxidation rhodium with sodium hydroxide neutralization again, aqua oxidation rhodium, with obtaining rhodium chloride acid solution after dissolving with hydrochloric acid, then obtains rhodium trichloride hydrate solid through evaporation concentration.Generally adopt sodium pyrosulfate scorification or middle temperature chlorination process and the processing of rhodium powder is converted into water miscible rhodium salt, the leaching yield of rhodium is in 98% left and right.While dissolving rhodium with sodium pyrosulfate scorification, melting at 500～550 DEG C of temperature after the sodium pyrosulfate of rhodium powder and 8～12 times of amounts is mixed in crucible, keeps 2～3 hours.Frit water leaches, and rhodium enters solution with the form of rhodium sulfate.While dissolving by a rear method, after rhodium powder and sodium-chlor are mixed, pack quartz boat into, in tube furnace, 750 DEG C of logical chlorinated with chlorine, be incubated 2～4 hours.Chlorination gained frit is with obtaining chlorine rhodium acid sodium solution after dilute hydrochloric acid leaching.Description by above technique can be found out, although rhodium powder can be converted into water-soluble rhodium salt efficiently via above-mentioned two kinds of method processing, but still need in alkali and aqua oxidation rhodium processed, aqua oxidation rhodium washing impurity-removing matter ion, dissolving with hydrochloric acid, after the step process such as evaporation concentration, just can make rhodium trichloride hydrate, whole technological process is comparatively complicated, and in alkali and in the technique of aqua oxidation rhodium processed, rhodium in solution can not be converted into rhodium gel completely, also have part to be present among solution, and every step process process all has a certain amount of rhodium loss, thereby cause, to prepare the once through yield of rhodium trichloride hydrate lower, the yield that aforesaid method makes hydration rhodium chloride is generally no more than 65%.
Summary of the invention
The object of this invention is to provide a kind of method of being prepared three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride by hydration chlordene rhodium acid sodium, the method adopts hydration chlordene rhodium acid sodium as raw material, and avoiding using the loaded down with trivial details rhodium trichloride hydrate of preparation is raw material.Prepare chlorine rhodium acid sodium yield by rhodium powder high, simple to operate; And it is low to prepare rhodium trichloride hydrate yield by rhodium powder, complex operation complexity.Use present method can simplify the operation steps of being prepared three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride by rhodium powder, thereby shorten the production cycle, reduce production costs.
The present invention is a kind of preparation method of three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride, it is characterized in that: three (3-sodium sulfonate-phenyl) phosphine aqueous solution is joined in the hydration chlordene rhodium acid sodium alcoholic solution that is replaced as nitrogen atmosphere, reaction solution is heated to 70-90 DEG C, keep 1-2 hour, the cooling rear Separation and Recovery product of reaction solution; Described alcohol is selected from ethanol, 1-propyl alcohol, 2-propyl alcohol; The volumetric molar concentration of described hydration chlordene rhodium acid sodium alcoholic solution is 0.1-1.0mol/L, the volumetric molar concentration of three (3-sodium sulfonate-phenyl) phosphine aqueous solution is 1.0-2.0mol/L, and the mol ratio of three (3-sodium sulfonate-phenyl) phosphines and hydration chlordene rhodium acid sodium is: 6-12.
According to method for making of the present invention, it is characterized in that: three (3-sodium sulfonate-phenyl) phosphine aqueous solution is joined in the hydration chlordene rhodium acid sodium alcoholic solution that is replaced as nitrogen atmosphere, reaction solution is heated to 70-90 DEG C, keeps 1-2 hour, the cooling rear Separation and Recovery product of reaction solution; Described alcohol is 2-propyl alcohol; The volumetric molar concentration of described hydration chlordene rhodium acid sodium alcoholic solution is 0.2-0.6mol/L, the volumetric molar concentration of three (3-sodium sulfonate-phenyl) phosphine aqueous solution is 1.0-2.0mol/L, and the mol ratio of three (3-sodium sulfonate-phenyl) phosphines and hydration chlordene rhodium acid sodium is: 8-10.
Adopt alcohol-water mixed solution as solvent, can reduce the content of water in solvent, make to separate out in water miscible three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride product reaction solution more complete, thereby improve product yield.Rising temperature of reaction is accelerated rhodium and three (3-sodium sulfonate-phenyl) the phosphine reaction speed in reaction solution, Reaction time shorten.Simultaneous reactions temperature also can make the reaction intermediate existing at normal temperatures transform to product after raising, thereby reduces by-product impurities, simplifies aftertreatment purification step, only needs simple washing can make product purity meet service requirements.
Method provided by the invention makes the process of being prepared three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride by rhodium powder not need the intermediate steps through rhodium trichloride hydrate, and whole operating process is more simple, has more economic benefit.Use hydration chlordene rhodium acid sodium as raw material, reaction conditions gentleness, the sodium-chlor by product of generation can improve the ionic strength of reaction solution, product is separated out from reaction solution more complete, and reaction yield is higher.Three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride detects by analysis indices and all reaches service requirements.
Embodiment
Embodiment 1
By by rhodium powder through in 0.60 gram, the hydration chlordene rhodium acid sodium that makes of warm chlorination join after mixing with 1 milliliter of 1-propyl alcohol reflux condensing tube be housed, in the round-bottomed flask of nitrogen air inlet/outlet, be replaced as nitrogen (99.999%, wt) after atmosphere, add and be dissolved with 33.7 grams of TPPTS (95%, wt) 5 ml water solution, reaction solution is fully uniformly mixed, be heated to 90 DEG C, keep 1 hour, reaction solution is cooled to room temperature, add after 30 milliliters of dehydrated alcohols, be cooled to 5-10 DEG C with ice-water bath, decompress filter, 5 milliliters of absolute ethanol washings 3 times, filter cake vacuum-drying at 50 DEG C obtains yellow crystals, collect rate 83.5% with rhodium.
Embodiment 2
By by rhodium powder through in 0.60 gram, the hydration chlordene rhodium acid sodium that makes of warm chlorination join after mixing with 1 milliliter of ethanol reflux condensing tube be housed, in the round-bottomed flask of nitrogen air inlet/outlet, be replaced as nitrogen (99.999%, wt) after atmosphere, add and be dissolved with 4.0 grams of TPPTS (95%, wt) 6 ml water solution, reaction solution is fully uniformly mixed, be heated to 70 DEG C, keep 2 hours, reaction solution is cooled to room temperature, add after 30 milliliters of dehydrated alcohols, be cooled to 5-10 DEG C with ice-water bath, decompress filter, 5 milliliters of absolute ethanol washings 3 times, filter cake vacuum-drying at 50 DEG C obtains yellow crystals, collect rate 81.4% with rhodium.
Embodiment 3
By by rhodium powder through in 3.0 grams, the hydration chlordene rhodium acid sodium that makes of warm chlorination join after mixing with 25 milliliters of 2-propyl alcohol reflux condensing tube be housed, in the round-bottomed flask of nitrogen air inlet/outlet, be replaced as nitrogen (99.999%, wt) after atmosphere, add and be dissolved with 27.0 grams of TPPTS (95%, wt) 20 ml water solution, reaction solution is fully uniformly mixed, be heated to 80 DEG C, keep 90 minutes, reaction solution is cooled to room temperature, add after 200 milliliters of dehydrated alcohols, be cooled to 5-10 DEG C with ice-water bath, decompress filter, 25 milliliters of absolute ethanol washings 3 times, filter cake vacuum-drying at 50 DEG C obtains yellow crystals, collect rate 88.3% with rhodium.
Embodiment 4
By by rhodium powder through in 1.2 grams, the hydration chlordene rhodium acid sodium that makes of warm chlorination join after mixing with 3 milliliters of 1-propyl alcohol reflux condensing tube be housed, in the round-bottomed flask of nitrogen air inlet/outlet, be replaced as nitrogen (99.999%, wt) after atmosphere, add and be dissolved with 16.2 grams of TPPTS (95%, wt) 15 ml water solution, reaction solution is fully uniformly mixed, be heated to 90 DEG C, keep 1 hour, reaction solution is cooled to room temperature, add after 30 milliliters of dehydrated alcohols, be cooled to 5-10 DEG C with ice-water bath, decompress filter, 10 milliliters of absolute ethanol washings 3 times, filter cake vacuum-drying at 50 DEG C obtains yellow crystals, collect rate 85.2% with rhodium.
Embodiment 5
By by rhodium powder through in 3.0 grams, the hydration chlordene rhodium acid sodium that makes of warm chlorination join after mixing with 5 milliliters of 2-propyl alcohol reflux condensing tube be housed, in the round-bottomed flask of nitrogen air inlet/outlet, be replaced as nitrogen (99.999%, wt) after atmosphere, add and be dissolved with 30.3 grams of TPPTS (95%, wt) 30 ml water solution, reaction solution is fully uniformly mixed, be heated to 80 DEG C, keep 90 minutes, reaction solution is cooled to room temperature, add after 200 milliliters of dehydrated alcohols, be cooled to 5-10 DEG C with ice-water bath, decompress filter, 25 milliliters of absolute ethanol washings 3 times, filter cake vacuum-drying at 50 DEG C obtains yellow crystals, collect rate 83.7% with rhodium.
Get the synthetic product of embodiment 3 and carry out analysis and characterization: IR (KBr) v
co: 1208cm
-1, 1183cm
-1, 1,027cm
-1, 742cm
-1there is charateristic avsorption band at place;
31p-NMR (CDCl
3, 162MHz, 298K): δ 34.5, δ 52.6; Carry out C, H, O constituent content analysis: theoretical value C 32.34, H 2.71, O 28.72 test value C 32.36, H 2.77, O 28.78; Carry out metal content analysis: Rh 5.10%, Na 0.0010% with ICP-OES.
Claims (2)
1. the preparation method of three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride, is characterized in that:
After being mixed with 25 milliliters of 2-propyl alcohol, 3.0 grams, hydration chlordene rhodium acid sodium joins in the round-bottomed flask that reflux condensing tube, nitrogen air inlet/outlet are housed, be replaced as after nitrogen atmosphere, add the 20 ml water solution of the TPPTS that is dissolved with 27.0 grams of 95wt%, reaction solution is fully uniformly mixed, be heated to 80 DEG C, keep 90 minutes, reaction solution is cooled to room temperature, add after 200 milliliters of dehydrated alcohols, be cooled to 5-10 DEG C with ice-water bath, decompress filter, 25 milliliters of absolute ethanol washings 3 times, filter cake makes after vacuum-drying at 50 DEG C.
2. the preparation method of three [three (3-sodium sulfonate-phenyl) phosphine] rhodium chloride, is characterized in that:
After being mixed with 3 milliliters of 1-propyl alcohol, 1.2 grams, hydration chlordene rhodium acid sodium joins in the round-bottomed flask that reflux condensing tube, nitrogen air inlet/outlet are housed, be replaced as after nitrogen atmosphere, add the 15 ml water solution that are dissolved with 16.2 grams of 95wt%TPPTS, reaction solution is fully uniformly mixed, be heated to 90 DEG C, keep 1 hour, reaction solution is cooled to room temperature, add after 30 milliliters of dehydrated alcohols, be cooled to 5-10 DEG C with ice-water bath, decompress filter, 10 milliliters of absolute ethanol washings 3 times, filter cake makes after vacuum-drying at 50 DEG C.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057618A (en) * | 1988-12-02 | 1991-10-15 | Hoechst Aktiengesellschaft | Complex compounds containing sulfonated phenyl phosphanes |
| CN1250053A (en) * | 1998-09-29 | 2000-04-12 | 三菱化学株式会社 | Double-tooth chelate ligand synrhodium dinuclear compounding ingrediend and method for preparing aldehyde |
| CN101463103A (en) * | 2007-12-17 | 2009-06-24 | 朗盛公司 | Hydrogenation of a diene-based polymer latex |
-
2011
- 2011-10-25 CN CN201110327044.1A patent/CN102351913B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5057618A (en) * | 1988-12-02 | 1991-10-15 | Hoechst Aktiengesellschaft | Complex compounds containing sulfonated phenyl phosphanes |
| CN1250053A (en) * | 1998-09-29 | 2000-04-12 | 三菱化学株式会社 | Double-tooth chelate ligand synrhodium dinuclear compounding ingrediend and method for preparing aldehyde |
| CN101463103A (en) * | 2007-12-17 | 2009-06-24 | 朗盛公司 | Hydrogenation of a diene-based polymer latex |
Non-Patent Citations (6)
| Title |
|---|
| F. Neatu等,.Hydrotalcite docked Rh-TPPTS complexes as efficient catalysts for the arylation of 2-cyclohexen-1-one in neat water.《Catalysis Today》.2008,第139卷第161-167页. |
| Hydrotalcite docked Rh-TPPTS complexes as efficient catalysts for the arylation of 2-cyclohexen-1-one in neat water;F. Neatu等,;《Catalysis Today》;20080911;第139卷;第161-167页 * |
| N.Sudheesh等,.RhCl(TPPTS)3 encapsulated into the hexagonal mesoporous silica as an efficient heterogeneous catalyst for hydroformylation of vinyl esters.《Applied Catalysis A: General》.2011,第409-410卷第99-105页. |
| RhCl(TPPTS)3 encapsulated into the hexagonal mesoporous silica as an efficient heterogeneous catalyst for hydroformylation of vinyl esters;N.Sudheesh等,;《Applied Catalysis A: General》;20111001;第409-410卷;第99-105页 * |
| Syntheses of Water-Soluble Phosphines and their Transition Metal Complexes;Wolfgang A. Herrmann等,;《Inorganic Syntheses》;19981231;第32卷;第8-25页，尤其是第21页第1段 * |
| Wolfgang A. Herrmann等,.Syntheses of Water-Soluble Phosphines and their Transition Metal Complexes.《Inorganic Syntheses》.1998,第32卷第8-25页，尤其是第21页第1段. |
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: CNOOC Tianjin Chemical Research & Design Institute Patentee before: China National Offshore Oil Corporation |
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