CN102351913A - 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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- CN102351913A CN102351913A CN2011103270441A CN201110327044A CN102351913A CN 102351913 A CN102351913 A CN 102351913A CN 2011103270441 A CN2011103270441 A CN 2011103270441A CN 201110327044 A CN201110327044 A CN 201110327044A CN 102351913 A CN102351913 A CN 102351913A
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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; Be preparation method about a kind of three [three (3-sodium sulfonate group phenyl) phosphine] rhodium chloride of homogeneous reaction catalyzer or catalyst precursor.
Background of invention rhodium homogeneous phase organic complex catalyzer has catalytic activity height, good selective, in catalyzed reactions such as shortening, olefin hydroformylation, oxo process, important use is arranged, and many industrial production that has been applied to.Wherein, water miscible three [three (3-sodium sulfonate group phenyl) phosphine] rhodium chloride [RhCl (TPPTS)
3] often be 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) preparation RhCl (TPPTS)
3Method: with RhCl
33H
2O and three (3-sodium sulfonate group phenyl) phosphine (TPPTS) stirs in the aqueous solution and obtained RhCl (TPPTS) in 15 hours
3, only can obtain RhCl (TPPTS) after separate purifying with 73% yield
3
The used raw material rhodium trichloride hydrate of aforesaid method generally is to be prepared by the rhodium powder; The treated water-soluble rhodium salt that is converted into of rhodium powder; Make the aqua oxidation rhodium with sodium hydroxide neutralization again, the aqua oxidation rhodium after with dissolving with hydrochloric acid rhodium chloride acid solution, obtain the rhodium trichloride hydrate solid through evaporation concentration then.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 about 98%.During with sodium pyrosulfate scorification dissolving rhodium, the sodium pyrosulfate fusion under 500～550 ℃ of temperature behind the mixing in crucible with rhodium powder and 8～12 times of amounts kept 2～3 hours.The frit water leaches, and rhodium gets into solution with the form of rhodium sulfate.During with back one method dissolving,, in tube furnace,, be incubated 2～4 hours 750 ℃ of logical chlorinated with chlorine with the quartz boat of packing into behind rhodium powder and the sodium-chlor mixing.Chlorination gained frit promptly gets chlorine rhodium acid sodium solution after leaching with dilute hydrochloric acid.Description by above technology can be found out; Though the rhodium powder is handled and can be converted into water-soluble rhodium salt efficiently via above-mentioned two kinds of methods; But still need in the alkali and system aqua oxidation rhodium; Aqua oxidation rhodium washing impurity-removing matter ion; Dissolving with hydrochloric acid; Just can make rhodium trichloride hydrate after the step process such as evaporation concentration; Whole technological process is comparatively complicated; And in alkali and in the technology of system aqua oxidation rhodium; Rhodium in the solution can not be converted into the rhodium gel fully; Also have part to be present among the solution; And every step process process all has a certain amount of rhodium loss; Thereby cause the once through yield of preparation rhodium trichloride hydrate lower, the yield that aforesaid method makes the hydration rhodium chloride generally is no more than 65%.
Summary of the invention
The purpose of this invention is to provide a kind of method by hydration chlordene rhodium acid sodium preparation three [three (3-sodium sulfonate group phenyl) phosphine] rhodium chloride, this method adopts hydration chlordene rhodium acid sodium as raw material, and avoiding the use of the loaded down with trivial details rhodium trichloride hydrate of preparation is raw material.It is high, simple to operate to prepare chlorine rhodium acid sodium yield by the rhodium powder; And it is low to prepare the rhodium trichloride hydrate yield by the rhodium powder, and complex operation is complicated.Use present method can simplify operation steps, thereby shorten the production cycle, reduce production costs by rhodium powder preparation three [three (3-sodium sulfonate group phenyl) phosphine] rhodium chloride.
The present invention is the preparation method of a kind of three [three (3-sodium sulfonate group phenyl) phosphine] rhodium chloride; It is characterized in that: three (3-sodium sulfonate group 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 ℃; Kept reaction solution cooling back Separation and Recovery product 1-2 hour; Said alcohol is selected from ethanol, 1-propyl alcohol, 2-propyl alcohol; The volumetric molar concentration of said hydration chlordene rhodium acid sodium alcoholic solution is 0.1-1.0mol/L, and the volumetric molar concentration of three (3-sodium sulfonate group phenyl) phosphine aqueous solution is 1.0-2.0mol/L, and the mol ratio of three (3-sodium sulfonate group 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 group 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 ℃, kept 1-2 hour, reaction solution cooling back Separation and Recovery product; Said alcohol is the 2-propyl alcohol; The volumetric molar concentration of said hydration chlordene rhodium acid sodium alcoholic solution is 0.2-0.6mol/L, and the volumetric molar concentration of three (3-sodium sulfonate group phenyl) phosphine aqueous solution is 1.0-2.0mol/L, and the mol ratio of three (3-sodium sulfonate group 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 the solvent, make separate out in water miscible three [three (3-sodium sulfonate group phenyl) phosphine] rhodium chloride product reaction solution more complete, thereby improve product yield.The rising temperature of reaction makes rhodium and three (the 3-sodium sulfonate group phenyl) phosphine reaction in the reaction solution speed up, and shortens the reaction times.After temperature of reaction raises simultaneously, also can make the reaction intermediate that exists at normal temperatures transform, thereby reduce by-product impurities, simplify the aftertreatment purification step, only need simple washing can make product purity satisfy service requirements to product.
Method provided by the invention makes need not pass through the intermediate steps of rhodium trichloride hydrate by rhodium powder preparation three [three (3-sodium sulfonate group phenyl) phosphine] process of rhodium chloride, and the entire operation process is more simple, has more economic benefit.Use hydration chlordene rhodium acid sodium as raw material, reaction conditions is gentle, and the sodium-chlor by product of generation can improve the ionic strength of reaction solution, and it is more complete that product is separated out from reaction solution, and reaction yield is higher.Three [three (3-sodium sulfonate group phenyl) phosphine] rhodium chloride all reaches service requirements through analyzing and testing each item index.
Embodiment
Embodiment 1
Will by the rhodium powder through in hydration chlordene rhodium acid sodium 0.60 gram that makes of warm chlorination reflux condensing tube is housed with joining after 1 milliliter of 1-propyl alcohol mixes; In the round-bottomed flask of nitrogen air inlet/outlet; Be replaced as nitrogen (99.999%; Wt) after the atmosphere; Add and be dissolved with 33.7 gram TPPTS (95%; Wt) 5 ml water solution; Reaction solution fully mixes; Be heated to 90 ℃, kept 1 hour, reaction solution is cooled to room temperature; After adding 30 milliliters of dehydrated alcohols; Be cooled to 5-10 ℃ with ice-water bath, decompress filter, 5 milliliters of absolute ethanol washings 3 times; Filter cake gets yellow crystals in 50 ℃ of following vacuum-dryings, collects rate 83.5% with rhodium.
Embodiment 2
Will by the rhodium powder through in hydration chlordene rhodium acid sodium 0.60 gram that makes of warm chlorination reflux condensing tube is housed with joining after 1 milliliter of ethanol mixes; In the round-bottomed flask of nitrogen air inlet/outlet; Be replaced as nitrogen (99.999%; Wt) after the atmosphere; Add and be dissolved with 4.0 gram TPPTS (95%; Wt) 6 ml water solution; Reaction solution fully mixes; Be heated to 70 ℃, kept 2 hours, reaction solution is cooled to room temperature; After adding 30 milliliters of dehydrated alcohols; Be cooled to 5-10 ℃ with ice-water bath, decompress filter, 5 milliliters of absolute ethanol washings 3 times; Filter cake gets yellow crystals in 50 ℃ of following vacuum-dryings, collects rate 81.4% with rhodium.
Embodiment 3
Will by the rhodium powder through in hydration chlordene rhodium acid sodium 3.0 grams that make of warm chlorination reflux condensing tube is housed with joining after 25 milliliters of 2-propyl alcohol mix; In the round-bottomed flask of nitrogen air inlet/outlet; Be replaced as nitrogen (99.999%; Wt) after the atmosphere; Add and be dissolved with 27.0 gram TPPTS (95%; Wt) 20 ml water solution; Reaction solution fully mixes; Be heated to 80 ℃, kept 90 minutes, reaction solution is cooled to room temperature; After adding 200 milliliters of dehydrated alcohols; Be cooled to 5-10 ℃ with ice-water bath, decompress filter, 25 milliliters of absolute ethanol washings 3 times; Filter cake gets yellow crystals in 50 ℃ of following vacuum-dryings, collects rate 88.3% with rhodium.
Embodiment 4
Will by the rhodium powder through in hydration chlordene rhodium acid sodium 1.2 grams that make of warm chlorination reflux condensing tube is housed with joining after 3 milliliters of 1-propyl alcohol mix; In the round-bottomed flask of nitrogen air inlet/outlet; Be replaced as nitrogen (99.999%; Wt) after the atmosphere; Add and be dissolved with 16.2 gram TPPTS (95%; Wt) 15 ml water solution; Reaction solution fully mixes; Be heated to 90 ℃, kept 1 hour, reaction solution is cooled to room temperature; After adding 30 milliliters of dehydrated alcohols; Be cooled to 5-10 ℃ with ice-water bath, decompress filter, 10 milliliters of absolute ethanol washings 3 times; Filter cake gets yellow crystals in 50 ℃ of following vacuum-dryings, collects rate 85.2% with rhodium.
Embodiment 5
Will by the rhodium powder through in hydration chlordene rhodium acid sodium 3.0 grams that make of warm chlorination reflux condensing tube is housed with joining after 5 milliliters of 2-propyl alcohol mix; In the round-bottomed flask of nitrogen air inlet/outlet; Be replaced as nitrogen (99.999%; Wt) after the atmosphere; Add and be dissolved with 30.3 gram TPPTS (95%; Wt) 30 ml water solution; Reaction solution fully mixes; Be heated to 80 ℃, kept 90 minutes, reaction solution is cooled to room temperature; After adding 200 milliliters of dehydrated alcohols; Be cooled to 5-10 ℃ with ice-water bath, decompress filter, 25 milliliters of absolute ethanol washings 3 times; Filter cake gets yellow crystals in 50 ℃ of following vacuum-dryings, collects rate 83.7% with rhodium.
Get embodiment 3 synthetic products and carry out analysis and characterization: IR (KBr) v
Co: 1208cm
-1, 1183cm
-1, 1,027cm
-1, 742cm
-1There is charateristic avsorption band at the place;
31P-NMR (CDCl
3, 162MHz, 298K): δ 34.5, and 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, and H 2.77, and O 28.78; Carry out metal content analysis: Rh 5.10% with ICP-OES, Na 0.0010%.
Claims (2)
1. the preparation method of one kind three [three (3-sodium sulfonate group phenyl) phosphine] rhodium chloride is characterized in that:
Three (3-sodium sulfonate group 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 ℃, kept 1-2 hour, reaction solution cooling back Separation and Recovery product; Said alcohol is selected from ethanol, 1-propyl alcohol, 2-propyl alcohol; The volumetric molar concentration of said hydration chlordene rhodium acid sodium alcoholic solution is 0.1-1.0mol/L, and the volumetric molar concentration of three (3-sodium sulfonate group phenyl) phosphine aqueous solution is 1.0-2.0mol/L, and the mol ratio of three (3-sodium sulfonate group phenyl) phosphines and hydration chlordene rhodium acid sodium is: 6-12.
2. according to the described method of claim 1, it is characterized in that:
Three (3-sodium sulfonate group 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 ℃, kept 1-2 hour, reaction solution cooling back Separation and Recovery product; Said alcohol is the 2-propyl alcohol; The volumetric molar concentration of said hydration chlordene rhodium acid sodium alcoholic solution is 0.2-0.6mol/L, and the volumetric molar concentration of three (3-sodium sulfonate group phenyl) phosphine aqueous solution is 1.0-2.0mol/L, and the mol ratio of three (3-sodium sulfonate group phenyl) phosphines and hydration chlordene rhodium acid sodium is: 8-10.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618145A (en) * | 2014-11-07 | 2016-06-01 | 中国石油天然气股份有限公司 | Tris[tris(m-sodium sulfonate phenyl)phosphine]rhodium chloride catalyst preparation method |
Citations (3)
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|---|---|---|---|---|
| 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 (3)
| 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》, vol. 139, 11 September 2008 (2008-09-11), pages 161 - 167, XP025685543, DOI: doi:10.1016/j.cattod.2008.07.028 * |
| 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》, vol. 409410, 1 October 2011 (2011-10-01), pages 99 - 105 * |
| WOLFGANG A. HERRMANN等,: "Syntheses of Water-Soluble Phosphines and their Transition Metal Complexes", 《INORGANIC SYNTHESES》, vol. 32, 31 December 1998 (1998-12-31) * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105618145A (en) * | 2014-11-07 | 2016-06-01 | 中国石油天然气股份有限公司 | Tris[tris(m-sodium sulfonate phenyl)phosphine]rhodium chloride catalyst preparation method |
| CN105618145B (en) * | 2014-11-07 | 2017-11-07 | 中国石油天然气股份有限公司 | A kind of preparation method of three [three (a sodium sulfonate phenyl) phosphines] chlorination rhodium catalysts |
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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 |