CN103709205B - A kind of preparation method of acetylacetonatodicarrhodium rhodium and the method for olefin hydroformylation - Google Patents
A kind of preparation method of acetylacetonatodicarrhodium rhodium and the method for olefin hydroformylation Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of acetylacetonatodicarrhodium rhodium, it is characterized in that, the method comprises: the Trichlororhodium aqueous solution, under the condition of precipitin reaction, contacts with precipitation agent by (1), to make rhodium element precipitate, obtain the precipitation containing rhodium element; (2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm; (3) under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, contact with methyl ethyl diketone after the described resolution of precipitate containing rhodium element that step (2) is obtained, obtain the reaction solution containing rhodium dicarbonyl acetylacetonate; (4) under the condition of the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, contact described with triphenylphosphine containing the rhodium dicarbonyl acetylacetonate in the reaction solution of rhodium dicarbonyl acetylacetonate.The invention also discloses a kind of method of olefin hydroformylation.The present invention can realize reducing product chloride ion content, improves product synthesis yield, improves the goal of the invention of the catalytic activity of acetylacetonatodicarrhodium rhodium.
Description
Technical field
The present invention relates to a kind of preparation method of acetylacetonatodicarrhodium rhodium and the method for olefin hydroformylation; being specifically related to a kind of employing Trichlororhodium hydrate is raw material; by forming the method preparing acetylacetonatodicarrhodium rhodium containing the precipitation of rhodium element again, and include the method that the alkene of preparation method of acetylacetonatodicarrhodium rhodium and synthetic gas carry out hydroformylation reaction.
Background technology
Acetylacetonatodicarrhodium rhodium (Rh (acac) (PPh
3) (CO)) be alpha-olefin and synthetic gas (CO and H
2mixed gas) occur that hydroformylation reaction is just generating, the good catalyst precursor of isomery aldehyde.Such as, propylene and synthetic gas are at Rh (acac) (PPh
3) (CO) homogeneous catalyst precursor existence under generate butyraldehyde-n and isobutyric aldehyde; Production of Acetic Acid by Methanol Carbonylation can also be used in addition.
Prior art is at synthesis Rh (acac) (PPh
3) (CO) process in general point of two steps: the first step is with Trichlororhodium hydrate (RhCl
3xH
2o) be starting raw material, react with methyl ethyl diketone, synthesis of acetyl acetone dicarbonyl rhodium (Rh (CO)
2(acac)).Second step is by Rh (CO)
2(acac) and triphenylphosphine reaction generate Rh (acac) (PPh
3) (CO).
" preparing the simple method of rhodium dicarbonyl acetylacetonate (I) " (Russian Chinese Journal of Inorganic Chemistry, Wa Shaweisi is based on sand etc., 1967,12 (6), 1709) (Simplemethodofpreparingacetylacetonatedicarbonylrhodium (I), VarshavskiiYu.S., ZhurnalNeorganicheskoiKhimii, 1967,12 (6), 1709) refer to RhCl in
3xH
2o is raw material one-step synthesis Rh (CO)
2(acac).By RhCl
3xH
2o joins in dimethyl formamide (DMF) as starting raw material and dissolves, and is heated to 150 DEG C, treats RhCl
3xH
2add methyl ethyl diketone again after O all dissolves, reflux 1 hour, after cooling, add the deionized water of more than several times, Rh (CO)
2(acac) flocks that takes on a red color is separated out.Red and green color needle crystal is obtained with hexane recrystallization, Rh (CO) after filtering
2(acac) yield is 75%.
" dicarbapentaborane-beta-diketon of rhodium (I) and related compound " (the Fu Bona base of a fruit and outstanding Wilkinson, Chemical Society's proceedings, 1964,3156-3160) (Dicarbonyl-β-diketonato-andRelatedComplexesofRhodium (I), F.BonatiandG.Wilkinson, J.Chem.Soc.1964,3156-3160) in refer to RhCl
3xH
2o is raw material two step synthesis Rh (CO)
2(acac).At 100 DEG C, toward the RhCl of porphyrize
3xH
2pass into carbon monoxide in O, obtain [Rh (CO)
2cl]
2, then with [Rh (CO)
2cl]
2for raw material, sherwood oil are solvent, add methyl ethyl diketone and barium carbonate refluxes 1 week at 100 DEG C.Red and green color needle-like Rh (CO) is obtained through concentrating under reduced pressure
2(acac) crystallization.Two steps synthesis Rh (CO)
2(acac) total recovery is 85%.
In prior art, Rh (CO)
2(acac) and triphenylphosphine reaction generate Rh (acac) (PPh
3) (CO) be first by Rh (CO)
2(acac) and triphenylphosphine be dissolved in benzene solvent respectively, then the benzole soln of triphenylphosphine is joined Rh (CO)
2(acac), in benzole soln, after reaction no longer includes CO effusion, cooling solution separates out yellow crystals, filters, uses benzene recrystallization, productive rate more than 96%.
CN102093432A discloses a kind of synthetic method of acetylacetonatodicarrhodium rhodium, described method is: (1) is by rhodium trichloride hydrate and N, dinethylformamide mixes, and under nitrogen protection, is heated to 130-150 DEG C, after Trichlororhodium all dissolves, adding methyl ethyl diketone, be heated to back flow reaction 0.5-1.5h, reaction solution room temperature is being placed cooling, add sedimentation-enhancing agents and separate out precipitation, precipitation aftertreatment obtains rhodium dicarbonyl acetylacetonate; (2) by rhodium dicarbonyl acetylacetonate organic solvent dissolution prepared by step (1), add triphenylphosphine, namely have bubble to produce, after no longer including bubble and producing, reaction solution aftertreatment obtains acetylacetonatodicarrhodium rhodium; Described organic solvent is straight-chain paraffin or the C6-C8 naphthenic hydrocarbon of C5-C10.In synthesis Rh (CO) in the method for this disclosure of the invention
2(acac) adding KCl or NaCl time is precipitation agent, improves Rh (CO)
2(acac) yield.
Although above-mentioned existing method can obtain higher Rh (acac) (PPh
3) (CO) yield, but use above-mentioned Rh (acac) (PPh
3) (CO) when carrying out propylene and synthetic gas generation hydroformylation reaction as catalyzer, finds that the catalytic activity of catalyzer in the lower or reaction process of the catalytic activity of catalyzer declines clearly.Therefore, Rh (acac) (PPh is solved
3) the catalytic activity problem of (CO) is the important problem that propylene and synthetic gas carry out hydroformylation reaction and face.
Summary of the invention
The object of the invention is to carry out the low or catalytic activity of hydroformylation reaction catalytic activity for propylene and synthetic gas to decline obvious problem to overcome existing acetylacetonatodicarrhodium rhodium catalyzer; a kind of method preparing the high acetylacetonatodicarrhodium rhodium of catalytic activity is provided, a kind of method of the olefin hydroformylation containing this acetylacetonatodicarrhodium rhodium preparation method is provided in addition.
The present inventor is found by research, existing rhodium dicarbonyl acetylacetonate and acetylacetonatodicarrhodium rhodium catalytic activity is low or catalytic activity reduces obviously, because in intermediate acetyl acetone dicarbonyl rhodium, the content of impurity chlorine ion is higher, often be greater than 0.1 % by weight, and chlorion is the toxicant of catalyzer in hydroformylation reaction, even if the chlorion (in cl content in reaction solution) carrying out bringing into hydroformylation reaction system 1ppm to propylene and synthetic gas from acetylacetonatodicarrhodium rhodium itself or other raw material also can make rhodium catalyst poisoning rapidly.For this reason, the chloride ion content as far as possible reduced in acetylacetonatodicarrhodium rhodium is needed.
Although prior art also can reduce the chloride ion content in acetylacetonatodicarrhodium rhodium by the mode of recrystallization intermediate acetyl acetone dicarbonyl rhodium, this reduces the synthesis yield of acetylacetonatodicarrhodium rhodium product.And rhodium is the precious metal that a kind of price is extremely expensive, therefore higher yield is the key point realizing acetylacetonatodicarrhodium rhodium batch production.
To this, the present inventor is by studying discovery further, in the process of acetylacetonatodicarrhodium rhodium preparation method, first Trichlororhodium is prepared into precipitation containing rhodium element through precipitin reaction, chloride ions displace is got off, and by further filtering, washing reduces the content of chlorion in the precipitation containing rhodium element, carry out the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl again, can ensure like this in the process of follow-up synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, less introducing chlorion in product, therefore the chloride ion content of acetylacetonatodicarrhodium rhodium product not only can be made qualified, and owing to decreasing the repeatedly recrystallization carried out for reducing chloride ion content in prior art, thus also improve the synthesis yield obtaining acetylacetonatodicarrhodium rhodium product.Complete the present invention thus.
To achieve these goals, the invention provides a kind of preparation method of acetylacetonatodicarrhodium rhodium, it is characterized in that, the method comprises:
(1) under precipitin reaction condition, the Trichlororhodium aqueous solution is contacted with precipitation agent, to make rhodium element precipitate, obtain the precipitation containing rhodium element;
(2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm;
(3) under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, contact with methyl ethyl diketone after the described resolution of precipitate containing rhodium element that step (2) is obtained, obtain the reaction solution containing rhodium dicarbonyl acetylacetonate;
(4) under the condition of the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, contact described with triphenylphosphine containing the rhodium dicarbonyl acetylacetonate in the reaction solution of rhodium dicarbonyl acetylacetonate.
The present invention also provides a kind of method of olefin hydroformylation; the method comprises prepares acetylacetonatodicarrhodium rhodium; and obtained described acetylacetonatodicarrhodium rhodium is used for the hydroformylation reaction of alkene and synthetic gas; it is characterized in that, the preparation method of the acetylacetonatodicarrhodium rhodium that the method preparing acetylacetonatodicarrhodium rhodium provides for the invention described above.
By technique scheme provided by the invention, the content of the chlorion in the acetylacetonatodicarrhodium rhodium product prepared is less than 10ppm, and the synthesis yield of acetylacetonatodicarrhodium rhodium is greater than 95%.As in embodiment 3, through Trichlororhodium is precipitated as through precipitin reaction the reaction carrying out synthesis of acetyl acetone triphenylphosphine rhodium carbonyl after rhodium hydroxide precipitation again, chloride ion content in the acetylacetonatodicarrhodium rhodium product obtained only has 6.5ppm, and in rhodium, synthesis yield reaches 98.2%.And the acetylacetonatodicarrhodium rhodium using prior art to prepare in comparative example 2, not only need recrystallization, and in the product obtained, chloride ion content reaches 95ppm, in rhodium, yield also only has 87.4%.Therefore, technical scheme provided by the invention can solve the problem that detrimental impurity chloride ion content is high and synthesis of acetyl acetone triphenylphosphine rhodium carbonyl yield is low effectively, realizes goal of the invention of the present invention.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of preparation method of acetylacetonatodicarrhodium rhodium, it is characterized in that, the method comprises:
(1) under precipitin reaction condition, the Trichlororhodium aqueous solution is contacted with precipitation agent, to make rhodium element precipitate, obtain the precipitation containing rhodium element;
(2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm;
(3) under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, contact with methyl ethyl diketone after the described resolution of precipitate containing rhodium element that step (2) is obtained, obtain the reaction solution containing rhodium dicarbonyl acetylacetonate;
(4) under the condition of the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, contact described with triphenylphosphine containing the rhodium dicarbonyl acetylacetonate in the reaction solution of rhodium dicarbonyl acetylacetonate.
According to the present invention, in the preparation method of described acetylacetonatodicarrhodium rhodium, step (1) is for by Trichlororhodium hydrate deposition being the precipitation containing containing rhodium element, can comprise and first make the Trichlororhodium aqueous solution by Trichlororhodium hydrate dissolution to water, then under precipitin reaction condition, in the Trichlororhodium aqueous solution, add precipitation agent and carry out precipitin reaction, obtain the precipitation containing rhodium element, control the temperature of precipitin reaction, control the pH value of the reaction mixture of the precipitation containing rhodium element that precipitin reaction obtains, to ensure that the rhodium in the Trichlororhodium aqueous solution precipitates completely, obtain the reaction mixture containing the precipitation containing rhodium element.
According to the present invention, the described precipitation agent of use can be any can by precipitation agent that rhodium is precipitated out with the form of the precipitation containing rhodium element from Trichlororhodium hydrate.Under preferable case, described precipitation agent is ammoniacal liquor and/or alkali metal hydroxide, one or more in preferred NaOH, KOH and ammoniacal liquor.In these cases, the described yellow rhodium hydroxide that is precipitated as containing rhodium element precipitates.
According to the present invention, the described precipitation agent of use can use in the form of a solution, and the concentration of precipitant solution can be selected in relative broad range, and under preferable case, described precipitation agent is that the solution form of 0.1-5mol/L uses with volumetric molar concentration; Preferred described precipitation agent is that the solution form of 1-3mol/L uses with volumetric molar concentration.Wherein, when described precipitation agent is ammoniacal liquor, described precipitation agent is that the solution form of 1-3mol/L uses and refers to that the ammoniacal liquor that uses volumetric molar concentration to be 1-3mol/L is as precipitation agent with volumetric molar concentration.In the present invention, the concentration of ammoniacal liquor continues to use the common implication in this area.
According to the present invention, when Trichlororhodium hydrate dissolution and water form the described Trichlororhodium aqueous solution, under preferable case, in the described Trichlororhodium aqueous solution, the volumetric molar concentration of rhodium is 0.1-5mol/L; In the preferred described Trichlororhodium aqueous solution, the volumetric molar concentration of rhodium is 1-3mol/L.
According to the present invention, the condition of described precipitin reaction is complete with the precipitation that can be conducive to containing rhodium element, and the loss of rhodium can be reduced, under preferable case, the condition of described precipitin reaction comprises: precipitation temperature is 5-10 DEG C, the consumption of precipitation agent makes the pH value after precipitin reaction between 7-10, and preferable ph is between 7-8.
According to the present invention, under precipitin reaction condition, in the Trichlororhodium aqueous solution, add precipitation agent carry out precipitin reaction, described in add and can carry out by any way, under preferable case, described in be incorporated as dropping.
According to the present invention, in the preparation method of described acetylacetonatodicarrhodium rhodium, step (2) is described containing the chlorion in the precipitation of rhodium element for reducing further on the basis of precipitin reaction, can comprise and first the reaction mixture containing the precipitation containing rhodium element be carried out solid-liquid separation, isolate the precipitation containing rhodium element, then washing and filtering obtain containing the precipitation of rhodium element, control wash temperature, control medium and the number of times of washing use, to make the content containing chlorion in the precipitation of rhodium element after washing lower than 1000ppm, preferably lower than 500ppm.In the present invention, ppm refers to quality hundred content very much.
In the present invention, the content of chlorion in the precipitation that can detect containing rhodium element by inductivity coupled plasma mass spectrometry (ICP-MS) mode.The precipitation containing rhodium element after washing preferably carries out vacuum-drying in order to follow-up use at 25 DEG C.
According to the present invention, described washing can use conventional washing methods, controls wash conditions to realize better washing effect and to make rhodium lose few, under preferable case, make successively to wash with water 2-5 time, hexanaphthene washs 1 time, wash temperature is 5-10 DEG C.
According to the present invention, the described solid-liquid separation of being carried out by the reaction mixture containing the precipitation containing rhodium element can be any method, and under preferable case, described solid-liquid separation is filtration under diminished pressure.
According to the present invention, in the preparation method of described acetylacetonatodicarrhodium rhodium, step (3) is for the building-up reactions of rhodium dicarbonyl acetylacetonate, can comprise and first add organic solvent containing the precipitation of rhodium element dissolve what washed, obtain the mixture containing the precipitation containing rhodium element, by the solution containing the precipitation containing rhodium element is heated to more than 140 DEG C, the solution boiling containing the precipitation containing rhodium element can be kept, the precipitation containing rhodium element all dissolved; Then, under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, slowly add methyl ethyl diketone under reflux state and carry out building-up reactions in the solution containing the precipitation containing rhodium element.After adding methyl ethyl diketone, continue to keep the reaction of synthesis of acetyl acetone dicarbonyl rhodium at boiling, reflux state, control reaction times and temperature of reaction, obtain the reaction solution containing rhodium dicarbonyl acetylacetonate.Stop building-up reactions, carry out aftertreatment, first the reaction solution of cooling containing rhodium dicarbonyl acetylacetonate, then the chilled reaction solution containing rhodium dicarbonyl acetylacetonate is poured in deionized water, produce the precipitation of red cotton-shaped rhodium dicarbonyl acetylacetonate, then filter the precipitation of rhodium dicarbonyl acetylacetonate, the organic solvent of the precipitation containing rhodium element is dissolved in removing, then with other organic solvent washing, final drying obtains rhodium dicarbonyl acetylacetonate.
According to the present invention, after described precipitin reaction, with the reaction carrying out synthesis of acetyl acetone dicarbonyl rhodium and synthesis of acetyl acetone triphenylphosphine rhodium carbonyl described in obtaining containing the precipitation of rhodium element as starting raw material successively.The condition of described building-up reactions can be the condition known to those skilled in the art.
According to the present invention, the described precipitation containing rhodium element is joined in organic solvent and dissolves, obtain the solution containing the precipitation containing rhodium element, under preferable case, the organic solvent dissolving the described precipitation containing rhodium element is dimethylformamide, relative to the rhodium element of 1 mole, the consumption of dimethylformamide is 1-3L; The consumption of preferred dimethylformamide is 1.5-2L.Described dimethylformamide can be DMF and/or N,N-dimethylacetamide, is preferably DMF.
According to the present invention, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium, described rhodium dicarbonyl acetylacetonate can be obtained, under preferable case, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium comprises: the mol ratio of described methyl ethyl diketone and rhodium is 8-15:1, temperature of reaction is 140-160 DEG C, and the reaction times is 50-90 minute; The mol ratio of preferred described methyl ethyl diketone and rhodium is 9-12:1, and temperature of reaction is 150 DEG C.
According to the present invention, after the reaction completing described synthesis of acetyl acetone dicarbonyl rhodium, the reaction solution containing rhodium dicarbonyl acetylacetonate described in being obtained by reacting is carried out aftertreatment.First be cooled to 5-10 DEG C, then import the red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation of generation in 5-10 DEG C of water, described water is preferably deionized water.Then by filtering the described organic solvent removed containing the precipitation of rhodium element described in above-mentioned dissolving, the crude product of described rhodium dicarbonyl acetylacetonate is obtained.
According to the present invention, in order to remove the impurity of rhodium dicarbonyl acetylacetonate precipitation surface further, under preferable case, also the rhodium dicarbonyl acetylacetonate obtained precipitation is washed, the solvent that described washing uses is the organic solvent not dissolving described rhodium dicarbonyl acetylacetonate precipitation, under preferable case, described organic solvent is normal hexane or hexanaphthene.
According to the present invention, in the preparation method of described acetylacetonatodicarrhodium rhodium, step (4) is for by rhodium dicarbonyl acetylacetonate synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, can comprise and first the rhodium dicarbonyl acetylacetonate obtained is dissolved in organic solvent, obtain the solution containing rhodium dicarbonyl acetylacetonate; Triphenylphosphine dissolved is obtained in organic solvent the organic solution containing triphenylphosphine simultaneously.Then the solution of heating containing rhodium dicarbonyl acetylacetonate is to the temperature of reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, then the organic solution containing triphenylphosphine is slowly added the reaction carrying out synthesis of acetyl acetone triphenylphosphine rhodium carbonyl in the solution containing rhodium dicarbonyl acetylacetonate.Have CO bubble to produce when carrying out the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, the condition controlling the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, until no longer produce CO bubble, obtains the reaction solution containing acetylacetonatodicarrhodium rhodium.Stop the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, carry out aftertreatment, first the reaction solution cooling containing acetylacetonatodicarrhodium rhodium is separated out the yellow crystals of acetylacetonatodicarrhodium rhodium, then carry out filtering, washing and drying, obtain the finished product of acetylacetonatodicarrhodium rhodium.
According to the present invention, the described solution containing rhodium dicarbonyl acetylacetonate obtained respectively and the described organic solvent containing using in the organic solution of triphenylphosphine can be the same or different, the organic solvent that preferred use is identical, described organic solvent is one or more in normal hexane, hexanaphthene, Benzene and Toluene.Described rhodium dicarbonyl acetylacetonate volumetric molar concentration is in organic solvent 0.2-0.5mol/L, and described triphenylphosphine volumetric molar concentration is in organic solvent 0.5-1.0mol/L.
According to the present invention, when the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is carried out, under preferable case, the mol ratio of described rhodium dicarbonyl acetylacetonate and described triphenylphosphine is 1:1.1-2.0.
According to the present invention, when carrying out the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, the described solution containing rhodium dicarbonyl acetylacetonate of heating, then the described organic solvent containing triphenylphosphine is slowly added, and have CO bubble to produce, reaction stirring is carried out until no longer include the generation of CO bubble, stopped reaction.Under optimum condition, the temperature of reaction of carrying out the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is 70-80 DEG C.
According to the present invention, in the reaction of the reaction and described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl of carrying out described synthesis of acetyl acetone dicarbonyl rhodium, rare gas element can be used to prevent the rhodium in described rhodium dicarbonyl acetylacetonate and described acetylacetonatodicarrhodium rhodium and the oxygen generation oxidizing reaction in air, under preferable case, the reaction of described synthesis of acetyl acetone dicarbonyl rhodium and the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl are carried out separately in a nitrogen atmosphere.
According to the present invention, after the reaction completing described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, by the reaction solution containing acetylacetonatodicarrhodium rhodium described in being obtained by reacting, be cooled to 5-10 DEG C, separate out yellow crystals, then carry out filtration and obtain acetylacetonatodicarrhodium rhodium crystal, and with organic solvent washing at 5-10 DEG C, described organic solvent is the material not dissolving described acetylacetonatodicarrhodium rhodium, under preferable case, described organic solvent is one or more in normal hexane, hexanaphthene, benzene.Finally by the vacuum-drying at 25 DEG C of described acetylacetonatodicarrhodium rhodium crystal, obtain described acetylacetonatodicarrhodium rhodium finished product.
According to the present invention, by the preparation method of described acetylacetonatodicarrhodium rhodium, the chloride ion content in the described acetylacetonatodicarrhodium rhodium obtained is lower than 10ppm.
The present invention also provides a kind of olefin hydroformylation method; the method comprises prepares acetylacetonatodicarrhodium rhodium; and obtained described acetylacetonatodicarrhodium rhodium is used for the hydroformylation reaction of alkene and synthetic gas; it is characterized in that, the method preparing acetylacetonatodicarrhodium rhodium is the preparation method of described acetylacetonatodicarrhodium rhodium.
According to the present invention, the method preparing acetylacetonatodicarrhodium rhodium is the preparation method of described acetylacetonatodicarrhodium rhodium described above, does not repeat them here.
According to the present invention, the method for described hydroformylation of olefin and condition are content known in those skilled in the art, can be any can realize this reaction method and corresponding condition.In the present invention, described hydroformylation of olefin adopts rhythmic reaction method, and the method comprises: acetylacetonatodicarrhodium rhodium, part and organic solvent are put into autoclave by a certain amount of by (1); (2) under certain temperature, pressure condition, by raw material olefin, H
2continue by a certain percentage to pass in autoclave to react with CO.
By under certain catalyst solution concentration (in rhodium element), the mole number that in the unit time, in per volume of catalyst solution, reaction mass (in alkene) consumes calculates the rate of catalysis reaction of hydroformylation of olefin.The rate of catalysis reaction obtained is the initial reaction rate of the hydroformylation of olefin under this catalyst solution concentration.
Described part is can form the P contained compound of rhodium-phosphine complex with acetylacetonatodicarrhodium rhodium, and can be single phosphine or biphosphine ligand, part can have one or more identical or different substituted radical, and under preferable case, described part is triphenylphosphine.
Described organic solvent is to dissolve the butyraldehyde-n and isobutyric aldehyde that described propene hydroformylation reaction obtains, and can be one or more in benzene, toluene and trimerization butyraldehyde, be preferably trimerization butyraldehyde.
Described alkene can be the alkene of various routine, such as, can be the alkene of C2-C8.Most preferably, described alkene is propylene.
It is 100 DEG C that described reaction conditions comprises temperature, and pressure is 0.55MPa.The ratio that described raw material passes into is propylene: H
2: CO=1:1:1(mol ratio).In the present invention, described pressure refers to absolute pressure.
According to the present invention, the method for described olefin hydroformylation is the hydroformylation reaction of alkene and synthetic gas, and under preferable case, described hydroformylation of olefin is the reaction that propylene and synthetic gas generation hydroformylation reaction generate butyraldehyde-n and isobutyric aldehyde.
Precipitin reaction is passed through in the present invention, rhodium in the Trichlororhodium aqueous solution is transformed into the precipitation containing rhodium element, make in the chemical constitution of the building-up reactions raw material preparing rhodium dicarbonyl acetylacetonate not containing chlorine element, further washing step can remove chlorion residual in precipitation, thus reduces the content of chlorion in the finished product acetylacetonatodicarrhodium rhodium.Owing to decreasing rhodium dicarbonyl acetylacetonate re-crystallization step in the present invention, improve the synthesis yield of acetylacetonatodicarrhodium rhodium, and the chloride ion content in product significantly reduces.
Below will be described the present invention by embodiment, but the present invention is not limited to this.
In following examples, chlorine ions content uses the 7500CX icp ms (ICP-MS) of Agilent company to analyze.
The rhodium dicarbonyl acetylacetonate product prepared is measured by Fourier transformation infrared spectrometer, contrast with the standard spectrogram (AldrichAlcoholsandPhenols composes storehouse) of rhodium dicarbonyl acetylacetonate, determine that the product prepared is rhodium dicarbonyl acetylacetonate.Infrared spectroscopy adopts THERMOFISHERSCIENTIFIC company NICOLETNEXUS470FT-IR instrument, adopts KBr pressed disc method to measure.
The finished product prepared are measured by Fourier transformation infrared spectrometer, contrast with the standard spectrogram (AldrichAlcoholsandPhenols composes storehouse) of acetylacetonatodicarrhodium rhodium, determine that the product prepared is acetylacetonatodicarrhodium rhodium.Infrared spectroscopy adopts THERMOFISHERSCIENTIFIC company NICOLETNEXUS470FT-IR instrument, adopts KBr pressed disc method to measure.
The content of rhodium in analysed preparation acetylacetonatodicarrhodium rhodium, Perkinelmer Inc. AAnalyst400 type Atomic Absorption Spectroscopy AAS is analyzed.In the catalyzer used in hydroformylation of olefin rhodium element quality (g)=acetylacetonatodicarrhodium rhodium in content (quality the %) × acetylacetonatodicarrhodium rhodium of rhodium add quality (g).
The content of rhodium in analysed preparation rhodium dicarbonyl acetylacetonate, Perkinelmer Inc. AAnalyst400 type Atomic Absorption Spectroscopy AAS is analyzed.In the catalyzer used in hydroformylation of olefin rhodium element quality (g)=rhodium dicarbonyl acetylacetonate in content (quality the %) × rhodium dicarbonyl acetylacetonate of rhodium add quality (g).
The synthesis yield of acetylacetonatodicarrhodium rhodium product, in rhodium element, calculates according to the following formula:
The synthesis yield of rhodium dicarbonyl acetylacetonate product, in rhodium element, calculates according to the following formula:
The all commercially available acquisition of raw material used in following examples and comparative example.
Embodiment 1
The present embodiment is for illustration of the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention.
(1) precipitin reaction: in 1500ml beaker, add the Trichlororhodium aqueous solution that 250.00mlRh concentration is 1.000mol/L, under magnetic stirring, controlling temperature of reaction is 10 DEG C, dropping concentration is that the NaOH solution of 1.00mol/L is about 750ml, the change of monitoring solution ph, stops when solution ph=8.0 dripping, obtains the reaction soln containing rhodium hydroxide precipitation.
(2) washing precipitation: by the reaction soln filtration under diminished pressure precipitated containing rhodium hydroxide, isolates rhodium hydroxide precipitation.With the deionized water wash three times that temperature is 10 DEG C, finally wash one time with 10 DEG C of hexanaphthenes.25 DEG C of vacuum-dryings, obtain yellow rhodium hydroxide precipitation.The content measuring chlorion in rhodium hydroxide precipitation is 495ppm.
(3) synthesis of acetyl acetone dicarbonyl rhodium: first the rhodium hydroxide of gained precipitation is put into three mouthfuls of reaction flasks that 1000ml is provided with reflux exchanger.Add 375ml analytical pure DMF; Stir; Be heated to 150 DEG C, boiling; Under total reflux state, treat that rhodium hydroxide precipitation is dissolved completely, obtain the solution containing rhodium hydroxide precipitation, solvent is DMF, and in solution, the volumetric molar concentration of rhodium is 0.666mol/L.
Then the reaction of synthesis of acetyl acetone dicarbonyl rhodium is carried out.In the solution precipitated containing rhodium hydroxide, slowly add 225 grams of analytical pure methyl ethyl diketones, the mol ratio of methyl ethyl diketone and rhodium is 9:1.Control reaction heating 150 DEG C, backflow, and pass into nitrogen protection react after 50 minutes stop.Obtain the reaction solution containing rhodium dicarbonyl acetylacetonate.
After cooling reaction solution to 10 DEG C, being poured into and filling 3100ml temperature is in the beaker of 10 DEG C of deionized waters, generates red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation.Cross and filter DMF solvent, obtain rhodium dicarbonyl acetylacetonate crude product.By the rhodium dicarbonyl acetylacetonate crude product prepared, with 10 DEG C of n-hexane, then vacuum-drying at 25 DEG C, namely obtain the crystal finished product 62.0 grams in red and green color.Fourier infrared spectrograph is measured the spectrogram that crystal finished product obtains, contrast with the standard spectrogram of rhodium dicarbonyl acetylacetonate, determine that crystal finished product is rhodium dicarbonyl acetylacetonate.
(4) synthesis of acetyl acetone triphenylphosphine rhodium carbonyl: first rhodium dicarbonyl acetylacetonate crystal 62.0g is added the heating of 1.2L hexanaphthene, stir, be warming up to 70 DEG C, it is made to dissolve completely, obtain the solution containing rhodium dicarbonyl acetylacetonate, wherein the volumetric molar concentration of rhodium dicarbonyl acetylacetonate is 0.20mol/L.Simultaneously by 70g triphenylphosphine dissolved in 530ml hexanaphthene, obtain the organic solvent containing triphenylphosphine, wherein the volumetric molar concentration of triphenylphosphine is 0.50mol/L.
Then the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is carried out.Under agitation; isothermal reaction at 70 DEG C; drip containing in the solution of rhodium dicarbonyl acetylacetonate the cyclohexane solution 530ml that above-mentioned triphenylphosphine concentration is 0.50mol/L to obtained above; wherein the mol ratio of rhodium dicarbonyl acetylacetonate and triphenylphosphine is 1:1.11; carry out building-up reactions; and passing into nitrogen protection, reaction carries out having CO bubble to produce.After question response does not have CO bubble to produce, stopped reaction, obtains the reaction solution containing acetylacetonatodicarrhodium rhodium.
Reaction solution is cooled to 10 DEG C, separates out yellow crystals.Filtration obtains yellow crystals, washs 3 times with the cyclohexane solutions of 10 DEG C, then 25 DEG C of vacuum-dryings, obtains the finished product 117.8 grams.Fourier infrared spectrograph is measured the spectrogram that the finished product obtain, contrast with the standard spectrogram of acetylacetonatodicarrhodium rhodium, determine that the finished product are acetylacetonatodicarrhodium rhodium.Product analysis the results are shown in Table 1.
Embodiment 2
The present embodiment is for illustration of the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention.
(1) precipitin reaction: in 1000ml beaker, adds the Trichlororhodium aqueous solution that 150.0mlRh concentration is 2.000mol/L.Under magnetic stirring, controlling temperature of reaction is 7 DEG C, and dropping concentration is that the KOH solution of 3.00mol/L is about 300ml, and the change of monitoring solution ph stops when solution ph=7.0 dripping, obtains the reaction soln precipitated containing rhodium hydroxide.
(2) washing precipitation: by the reaction soln filtration under diminished pressure precipitated containing rhodium hydroxide, isolates rhodium hydroxide precipitation.With the deionized water wash three times that temperature is 8 DEG C, finally with 7 DEG C of hexanaphthenes washing washings one time.25 DEG C of vacuum-dryings, the yellow rhodium hydroxide precipitation obtained.The content measuring chlorion in rhodium hydroxide precipitation is 450ppm.
(3) synthesis of acetyl acetone dicarbonyl rhodium: first gained rhodium hydroxide precipitation is put into three mouthfuls of reaction flasks that 1500ml is provided with reflux exchanger.Add 600ml analytical pure DMF, stir, be heated to 150 DEG C, boiling; Under total reflux state, treat that rhodium hydroxide precipitation is dissolved completely, obtain the solution containing rhodium hydroxide precipitation, solvent is DMF, and in solution, the volumetric molar concentration of rhodium is 0.50mol/L.
Then the reaction of synthesis of acetyl acetone dicarbonyl rhodium is carried out.In the solution precipitated containing rhodium hydroxide, slowly add 360 grams of analytical pure methyl ethyl diketones, the mol ratio of methyl ethyl diketone and rhodium is 12:1.Control reaction heating 150 DEG C, backflow, reaction 90 minutes after stop, obtaining the reaction solution containing rhodium dicarbonyl acetylacetonate.
After cooling reaction solution to 7 DEG C, being poured into and filling 5800ml temperature is in the beaker of 7 DEG C of deionized waters, generates red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation.Cross and filter DMF solvent, obtain rhodium dicarbonyl acetylacetonate crude product.By the rhodium dicarbonyl acetylacetonate crude product prepared, with 7 DEG C of n-hexane, vacuum-drying at 25 DEG C, namely obtain the crystal finished product 76.0 grams in red and green color.Determine that crystal finished product is rhodium dicarbonyl acetylacetonate.
(4) synthesis of acetyl acetone triphenylphosphine rhodium carbonyl: first rhodium dicarbonyl acetylacetonate crystal 76.0g is added the heating of 0.59L normal hexane, stir, be warming up to 75 DEG C, it is made to dissolve completely, obtain the solution containing rhodium dicarbonyl acetylacetonate, wherein the volumetric molar concentration of rhodium dicarbonyl acetylacetonate is 0.50mol/L.Simultaneously by 154g triphenylphosphine dissolved in 587ml normal hexane, obtain the organic solvent containing triphenylphosphine, wherein the volumetric molar concentration of triphenylphosphine is 1.00mol/L.
Then the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is carried out.Under agitation, isothermal reaction at 80 DEG C, drip containing in the solution of rhodium dicarbonyl acetylacetonate the cyclohexane solution 587ml that above-mentioned triphenylphosphine concentration is 1.00mol/L to obtained above, wherein the mol ratio of rhodium dicarbonyl acetylacetonate and triphenylphosphine is 1:2.0, carry out building-up reactions, and have CO bubble to produce.After question response does not have CO bubble to produce, stopped reaction, obtains the reaction solution containing acetylacetonatodicarrhodium rhodium.
Reaction solution is cooled to 7 DEG C, separates out yellow crystals.Filtration obtains yellow crystals, washs 3 times with the hexane solutions of 7 DEG C, then 25 DEG C of vacuum-dryings, obtains the finished product 144.5 grams.Determine that the finished product are acetylacetonatodicarrhodium rhodium.Product analysis the results are shown in Table 1.
Embodiment 3
The present embodiment is for illustration of the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention.
(1) precipitin reaction: in 1000ml tri-mouthfuls of reaction flasks, adds the Trichlororhodium aqueous solution that 80mlRh concentration is 2.500mol/L.Under magnetic stirring, controlling temperature of reaction is 5 DEG C, and dropping concentration is that the ammonia soln of 2.00mol/L is about 300ml, and the change of monitoring solution ph stops when solution ph=7.5 dripping, obtains the reaction soln precipitated containing rhodium hydroxide.
(2) washing precipitation: by the reaction soln filtration under diminished pressure precipitated containing rhodium hydroxide, isolates rhodium hydroxide precipitation.With the deionized water wash three times that temperature is 5 DEG C, finally wash one time with 5 DEG C of hexanaphthenes.25 DEG C of vacuum-dryings, the yellow rhodium hydroxide precipitation obtained.The content measuring chlorion in rhodium hydroxide precipitation is 410ppm.
(3) synthesis of acetyl acetone dicarbonyl rhodium: first gained rhodium hydroxide precipitation is put into three mouthfuls of reaction flasks that 1000ml is provided with reflux exchanger, add 360ml analytical pure DMF, stir, be heated to 150 DEG C, boiling, under total reflux state, treats that rhodium hydroxide precipitation is dissolved completely, obtain the solution containing rhodium hydroxide precipitation, solvent is DMF, and in solution, the volumetric molar concentration of rhodium is 0.55mol/L.
Then the reaction of synthesis of acetyl acetone dicarbonyl rhodium is carried out.In the solution precipitated containing rhodium hydroxide, slowly add 210 grams of analytical pure methyl ethyl diketones, the mol ratio of methyl ethyl diketone and rhodium is 10.5:1.Control reaction heating 150 DEG C, backflow, reaction 80 minutes after stop, obtaining the reaction solution containing rhodium dicarbonyl acetylacetonate.
After cooling reaction solution to 5 DEG C, being poured into and filling 5800ml temperature is in the beaker of 5 DEG C of deionized waters, generates red cotton-shaped rhodium dicarbonyl acetylacetonate precipitation.Cross and filter DMF solvent, obtain rhodium dicarbonyl acetylacetonate crude product.By the rhodium dicarbonyl acetylacetonate crude product prepared, with 5 DEG C of hexanaphthene washings, then vacuum-drying at 25 DEG C, namely obtain the crystal finished product 51.2 grams in red and green color.Determine that crystal finished product is rhodium dicarbonyl acetylacetonate.
(4) synthesis of acetyl acetone triphenylphosphine rhodium carbonyl: first rhodium dicarbonyl acetylacetonate crystal 51.2g is added the heating of 0.566L benzene, stir, be warming up to 80 DEG C, it is made to dissolve completely, obtain the solution containing rhodium dicarbonyl acetylacetonate, wherein the volumetric molar concentration of rhodium dicarbonyl acetylacetonate is 0.35mol/L.Simultaneously by 83g triphenylphosphine dissolved in 422ml benzene, obtain the organic solvent containing triphenylphosphine, wherein the volumetric molar concentration of triphenylphosphine is 0.75mol/L.
Then the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl is carried out.Under agitation, isothermal reaction at 75 DEG C, drip containing in the solution of rhodium dicarbonyl acetylacetonate the benzole soln 422ml that above-mentioned triphenylphosphine concentration is 0.75mol/L to obtained above, wherein the mol ratio of rhodium dicarbonyl acetylacetonate and triphenylphosphine is 1:1.6, carry out building-up reactions, and have CO bubble to produce.After question response does not have CO bubble to produce, stopped reaction, obtains the reaction solution containing acetylacetonatodicarrhodium rhodium.
Reaction solution is cooled to 5 DEG C, separates out yellow crystals.Filtration obtains yellow crystals, washs 3 times with the benzole solns of 5 DEG C, then 25 DEG C of vacuum-dryings, obtains the finished product 97.7 grams.Determine that the finished product are acetylacetonatodicarrhodium rhodium.Product analysis the results are shown in Table 1.
Embodiment 4
The present embodiment is for illustration of the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention.
According to the method for embodiment 3, unlike, in precipitin reaction, the change of monitoring solution ph, stops when solution ph=10 dripping, obtains the reaction soln containing rhodium hydroxide.Product analysis the results are shown in Table 1.
Comparative example 1
According to the method for embodiment 3, unlike, there is no precipitin reaction step, washing precipitation step and synthesis of acetyl acetone triphenylphosphine rhodium carbonyl step.
In synthesis of acetyl acetone dicarbonyl rhodium step, the Trichlororhodium aqueous solution being 2.500mol/L with 80mlRh concentration substitutes rhodium hydroxide precipitation; Simultaneously after obtaining rhodium dicarbonyl acetylacetonate crude product, carry out recrystallization secondary with normal hexane.Measure the chloride ion content of the rhodium dicarbonyl acetylacetonate of synthesis, analytical results is in table 1.
Comparative example 2
According to the method for embodiment 3, unlike, there is no precipitin reaction step and washing precipitation step.
In synthesis of acetyl acetone dicarbonyl rhodium step, the Trichlororhodium aqueous solution being 2.500mol/L with 80mlRh concentration substitutes rhodium hydroxide precipitation; Simultaneously after obtaining rhodium dicarbonyl acetylacetonate crude product, carry out recrystallization secondary with normal hexane.Measure the chloride ion content of the acetylacetonatodicarrhodium rhodium of synthesis.Product analysis the results are shown in Table 1.
Embodiment 5
The present embodiment is for illustration of the method for olefin hydroformylation.
The acetylacetonatodicarrhodium rhodium 0.0477g that Example 1 prepares; 6.00 grams of triphenylphosphines and 44.00 grams of trimerization butyraldehyde are put into 100ml autoclave and are formed 50ml catalyst solution, pass into propylene, hydrogen and CO and carry out propene hydroformylation reaction in autoclave.Carrying out propene hydroformylation reaction condition is: temperature 100 DEG C, pressure 0.55MPa, propylene: H
2: CO=1:1:1(mol ratio), measure the initial catalyst speed of reaction of propene hydroformylation reaction.The results are shown in Table 2.
Embodiment 6
The present embodiment is for illustration of the method for olefin hydroformylation.
The acetylacetonatodicarrhodium rhodium 0.0477g that Example 2 prepares, measures the initial catalyst speed of reaction of propene hydroformylation reaction according to the condition of embodiment 5.The results are shown in Table 2.
Embodiment 7
The present embodiment is for illustration of the method for olefin hydroformylation.
The acetylacetonatodicarrhodium rhodium 0.0477g that Example 3 prepares, measures the initial catalyst speed of reaction of propene hydroformylation reaction according to the condition of embodiment 5.The results are shown in Table 2.
Comparative example 3
Get the rhodium dicarbonyl acetylacetonate 0.0254g that comparative example 1 prepares, measure the initial catalyst speed of reaction of propene hydroformylation reaction according to the condition of embodiment 5.The results are shown in Table 2.
Comparative example 4
Get the acetylacetonatodicarrhodium rhodium 0.0477g that comparative example 2 prepares, measure the initial catalyst speed of reaction of propene hydroformylation reaction according to the condition of embodiment 5.The results are shown in Table 2.
Table 1
Table 2
Can be found out by the data of above-mentioned experimental result table 1 and table 2, adopt the preparation method of acetylacetonatodicarrhodium rhodium provided by the invention, the acetylacetonatodicarrhodium rhodium product obtained, has synthesis yield high, the feature that chloride ion content is low.As can be seen here, be rhodium precipitation by the converting feedstock of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl in technical scheme provided by the invention, really can realize the present invention and reduce product chloride ion content, improve the goal of the invention of product synthesis yield.
The acetylacetonatodicarrhodium rhodium product will preparation method provided by the invention being adopted to obtain further; apply to propene hydroformylation reaction; under the condition identical in quality of the rhodium used; because chlorine ion concentration is lower in reactor; initial catalyst speed of reaction faster can be obtained, illustrate that the acetylacetonatodicarrhodium rhodium that preparation method of the present invention obtains can have better catalytic activity.
Embodiment 4 and the difference of embodiment 1 are control pH value in precipitin reaction different.As can be seen from experimental result, making the pH value of precipitin reaction be 7-8 is the preferred implementation obtaining preparation method's best effect of the present invention.
Claims (13)
1. a preparation method for acetylacetonatodicarrhodium rhodium, is characterized in that, the method comprises:
(1) under the condition of precipitin reaction, the Trichlororhodium aqueous solution is contacted with precipitation agent, to make rhodium element precipitate, obtain the precipitation containing rhodium element;
(2) the described precipitation containing rhodium element is washed, washing to described containing chloride ion content in the precipitation of rhodium element lower than 1000ppm;
(3) under the condition of the reaction of synthesis of acetyl acetone dicarbonyl rhodium, contact with methyl ethyl diketone after the described resolution of precipitate containing rhodium element that step (2) is obtained, obtain the reaction solution containing rhodium dicarbonyl acetylacetonate;
(4) under the condition of the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl, contact described with triphenylphosphine containing the rhodium dicarbonyl acetylacetonate in the reaction solution of rhodium dicarbonyl acetylacetonate.
2. method according to claim 1, wherein, described precipitation agent is ammoniacal liquor and/or alkali metal hydroxide.
3. method according to claim 1 and 2, wherein, in the described Trichlororhodium aqueous solution, the volumetric molar concentration of rhodium element is 0.1-5mol/L, and described precipitation agent is that the solution form of 0.1-5mol/L uses with volumetric molar concentration.
4. method according to claim 1, wherein, the condition of described precipitin reaction comprises: precipitation temperature is 5-10 DEG C; The consumption of precipitation agent makes the pH value after precipitin reaction between 7-10.
5. method according to claim 1, wherein, washing is lower than 500ppm to the chloride ion content in the described precipitation containing rhodium element.
6. method according to claim 5, wherein, described washing washing composition used is water or hexanaphthene, and wash temperature is 5-10 DEG C.
7. method according to claim 1, wherein, be dimethylformamide for dissolving the solvent of the described precipitation containing rhodium element, relative to the rhodium element of 1 mole, the consumption of dimethylformamide is 1-3L.
8. method according to claim 1, wherein, the condition of the reaction of described synthesis of acetyl acetone dicarbonyl rhodium comprises: the mol ratio of described methyl ethyl diketone and rhodium element is 8-15:1; Temperature of reaction is 140-160 DEG C, and the reaction times is 50-90 minute.
9. method according to claim 1, wherein, the condition of the reaction of described synthesis of acetyl acetone triphenylphosphine rhodium carbonyl comprises: the mol ratio of described rhodium dicarbonyl acetylacetonate and described triphenylphosphine is 1:1.1-2, and temperature of reaction is 70-80 DEG C.
10. according to the method in claim 1-2 and 4-9 described in any one, wherein, the reaction of described synthesis of acetyl acetone dicarbonyl rhodium and the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl are carried out separately in a nitrogen atmosphere.
11. methods according to claim 3, wherein, the reaction of described synthesis of acetyl acetone dicarbonyl rhodium and the reaction of synthesis of acetyl acetone triphenylphosphine rhodium carbonyl are carried out separately in a nitrogen atmosphere.
The method of 12. 1 kinds of olefin hydroformylations; the method comprises prepares acetylacetonatodicarrhodium rhodium; and obtained described acetylacetonatodicarrhodium rhodium is used for the hydroformylation reaction of alkene and synthetic gas; it is characterized in that, prepare the method for acetylacetonatodicarrhodium rhodium for the method in claim 1-11 described in any one.
13. methods according to claim 12, wherein, described hydroformylation of olefin is the reaction that propylene and synthetic gas generation hydroformylation reaction generate butyraldehyde-n and isobutyric aldehyde.
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| CN104370972A (en) * | 2014-11-07 | 2015-02-25 | 北京高新利华催化材料制造有限公司 | Preparation method of acetylacetone triphenylphosphine carbonyl rhodium (I) |
| CN105289736B (en) * | 2015-11-11 | 2017-11-03 | 天津渤化永利化工股份有限公司 | A kind of preparation method of acetylacetone,2,4-pentanedione Lian Feifusi rhodium catalysts |
| CN106749419A (en) * | 2016-11-18 | 2017-05-31 | 江西省汉氏贵金属有限公司 | Acetylacetone,2,4-pentanedione triphenyl phosphorus carbonyl closes the synthesis technique of rhodium |
| CN111333683B (en) * | 2020-04-09 | 2022-08-23 | 中国海洋石油集团有限公司 | Preparation method of acetylacetonatodicarbonylrhodium and mixed carbon-four hydroformylation method |
| CN111978353A (en) * | 2020-07-30 | 2020-11-24 | 西安凯立新材料股份有限公司 | Preparation method of rhodium complex |
| CN114573640A (en) * | 2022-03-17 | 2022-06-03 | 金川集团股份有限公司 | Preparation of acetylacetonatocarbonylrhodium and method for synthesizing butyraldehyde by propylene carbonyl |
| CN114591373B (en) * | 2022-03-17 | 2024-03-19 | 金川集团股份有限公司 | Preparation method of acetyl acetone triphenylphosphine rhodium carbonyl |
| CN115651030B (en) * | 2022-10-28 | 2024-04-26 | 四川大学 | Method for synthesizing triphenylphosphine rhodium carbonyl acetylacetonate by one-pot method |
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| EP0505339A1 (en) * | 1991-03-20 | 1992-09-23 | Tanaka Kikinzoku Kogyo K.K. | Process of preparing rhodium nitrate solution |
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| EP0505339A1 (en) * | 1991-03-20 | 1992-09-23 | Tanaka Kikinzoku Kogyo K.K. | Process of preparing rhodium nitrate solution |
| CN1769187A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Rhodium triiodid preparation method |
| CN102702270A (en) * | 2012-05-25 | 2012-10-03 | 杭州凯大催化金属材料有限公司 | Solvent-free synthesis method of acetylacetonatocarbonyltriphenylphosphine |
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