CN105503601A - Method for synthesis of 3-acetoxy propionaldehyde by vinyl acetate hydroformylation - Google Patents
Method for synthesis of 3-acetoxy propionaldehyde by vinyl acetate hydroformylation Download PDFInfo
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Abstract
The invention relates to a synthesis method of 3-acetoxy propionaldehyde, and mainly solves the problems of low activity and selectivity of catalysts for synthesis of 3-acetoxy propionaldehyde by vinyl acetate hydroformylation in the prior art. According to a technical scheme, vinyl acetate, carbon monoxide and hydrogen are adopted as the raw materials, and toluene is taken as the solvent to carry out reaction in the presence of a catalyst to synthesize 3-acetoxy propionaldehyde. The catalyst comprises a main catalyst and a promoter, the main catalyst comprises a carrier and an active component, the active component adopts a compound of rhodium, the promoter is selected from at least one of organic amine and organic phosphorus, the carrier is fluorine containing compound modified silica with the surface containing a coating, the coating is composed of a modifying metal element and a silica binder bonding the modifying metal element to the carrier surface, and the modifying metal element is selected from at least one of alkali metal elements. The method provided by the invention well solves the problems, and can be used in the industrial production of 1.3-propanediol.
Description
Technical field
The present invention relates to the method for vinyl acetate between to for plastic hydroformylation synthesis 3-acetoxyl group propionic aldehyde.
Background technology
1.3-propylene glycol (1.3-PDO) is a kind of important industrial chemicals, is mainly used in the synthesis of softening agent, washing composition, sanitas, emulsifying agent, also for industries such as food, makeup and pharmacy.Because it is a kind of important trevira monomer, its topmost purposes is as monomer and terephthalic acid synthesizing new polyester material one polytrimethylene terephthalate (PTT).
The preparation method of 1.3-propylene glycol has oxyethane single stage method, oxyethane two-step approach, acrolein hydration method, acetaldehyde stiasny method, vinylformic acid ester process, biological process, vinyl acetate between to for plastic hydroformylation etc.At present, the industrialized preparing process of 1.3-PDO is chemical synthesis, and world market is primarily of German Degussa company, shell Shell company of the U.S. and the monopolization of three, du pont company.Degussa company adopt be acrolein hydration hydrogenation method (AC method), Shell Co. Ltd adopt be oxirane carbonyl method (EO method), E.I.Du Pont Company adopt be oneself innovation thorugh biologic engineering method (MF method).Its ethylene oxide two-step process and acrolein hydration method technique are current prevailing technology.
As everyone knows, having a carbon-carbon double bond in vinyl acetate between to for plastic, can there is hydroformylation reaction in this key, a carbon atom of double bond adds an aldehyde radical, generates the isomers of acetoxyl group propionic aldehyde.This aldehyde can become hydroxyl by hydrogenation, and ester group can become hydroxyl by hydrolysis and form glycol, and such vinyl acetate between to for plastic just can prepare 1.3-propylene glycol through hydroformylation, hydrogenation and hydrolysis.
Teaching in the patents such as patent US4072709 (Productionoflacticacid) utilizes vinyl-acetic ester or propionate to be raw material; by adopting homogeneous phase rhodium compound to be catalyzer; by hydroformylation reaction, obtain α-acetoxyl group propionic aldehyde or α-propionyloxy propionic aldehyde.Be separated or be not separated, then obtain 1.3-PDO by hydrogenation and hydrolytic process, or oxidation and hydrolysis obtain lactic acid.But all there is the problem that 3-acetoxyl group propionic aldehyde yield is low and selectivity is not high in aforesaid method in preparation 3-acetoxyl group propionic aldehyde process.
Summary of the invention
One of technical problem to be solved by this invention is the problem that 3-acetoxyl group propionic aldehyde yield is low and selectivity is not high; there is provided a kind of new vinyl acetate between to for plastic hydroformylation to synthesize the method for 3-acetoxyl group propionic aldehyde, the method has high and high to the 3-acetoxyl group propionic aldehyde selectivity feature of 3-acetoxyl group propionic aldehyde yield.
Two of technical problem to be solved by this invention is preparation methods of the described catalyzer of one of above-mentioned technical problem.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the method for vinyl acetate between to for plastic hydroformylation synthesis 3-acetoxyl group propionic aldehyde, with vinyl acetate between to for plastic, carbon monoxide and hydrogen for raw material, take toluene as solvent, catalyzer carries out Reactive Synthesis 3-acetoxyl group propionic aldehyde under existing, described catalyzer comprises Primary Catalysts and promotor, and described Primary Catalysts comprises carrier, active ingredient; Described active ingredient adopts the compound of rhodium; Described promotor is selected from least one in organic amine and organophosphorus; Described carrier is for containing cated silicon-dioxide with fluorochemicals its surface modified; Described coating forms by modified metal element and by the silica binder that described modified metal element is bonded in described carrier surface; Described fluorine-containing constituent content is 0.50 ~ 5.00g/L; Modified metal constituent content is 0.010 ~ 1.00g/L; Described modified metal element is selected from least one in alkali metal.Preferred described organophosphorus has the structure as shown in the formula (I), more preferably R
1, R
2and R
3for alkyl, be independently selected from C further
1~ C
20alkyl, further independent preferred from C
6~ C
20aryl or alkyl substituting aromatic base, such as phenyl, tolyl, naphthyl etc.
The compound of rhodium described in technique scheme is preferably RhCl
3.. described promotor is preferably at least one in pyridine and triphenyl phosphorus.At least one in the preferred ammonium silicofluoride of described fluorine-containing compound, Neutral ammonium fluoride, hydrofluoric acid and Sodium Fluoride.At least one of described alkali metal preferably in Li, Na, K, Rb and Cs.More preferably described alkali metal comprises Rb and Cs simultaneously.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: Primary Catalysts preparation method described in the technical scheme of one of above-mentioned technical problem, comprises the steps:
1. fluorine-containing compound is mixed with aqueous impregnation silicon-dioxide, drying obtains described catalyst carrier precursor I;
2. the oxyhydroxide of described modified metal element or oxide compound and silicon sol are mixed to get coating liquid;
3. above-mentioned coating liquid is coated to precursor carrier I surface, dry, roasting obtains described support of the catalyst II;
4. the composition of catalyzer is pressed by RhCl
3solution mixes with described support of the catalyst II;
5. standing, dry, roasting, obtains described Primary Catalysts.
The preparation key of catalyzer of the present invention is the preparation of Primary Catalysts after obtaining Primary Catalysts, can obtain catalyzer of the present invention by making Primary Catalysts with described promotor contact.The mode that Primary Catalysts contacts with promotor is not particularly limited, and is also not particularly limited the opportunity of contact making both.Both such as can be made before catalyzer of the present invention is used for chemical reaction contact to form described catalyzer, and in the reaction system that both can also be made to apply at catalyzer of the present invention, contact makes catalyzer in-situ preparation.
The present inventor finds, in technique scheme, activity component impregnation used at the same time ammonium silicofluoride, hydrofluoric acid, no matter be that selectivity or 3-acetoxyl group propionic aldehyde yield all reach best containing Rb with containing the catalyzer that obtains on the compound modified carrier of Cs.
Key of the present invention is the selection of catalyzer, those skilled in the art will know that the proportioning determining suitable temperature of reaction, reaction times, reaction pressure and material how according to actual needs.But the temperature of reacting in technique scheme is preferably 50 ~ 180 DEG C; The pressure of reaction is preferably 1.0 ~ 15.0MPa; The time of reaction is preferably 1.0 ~ 15.0h.The mol ratio of carbon monoxide and hydrogen is preferably 0.10 ~ 10.0.
Product of the present invention through cooling, decompression, be separated after adopt gas chromatograph-mass spectrometer (GC-MASS) to analyze, by the transformation efficiency of following formulae discovery vinyl acetate between to for plastic and the yield of 3-acetoxyl group propionic aldehyde and selectivity:
Compared with prior art, key of the present invention is that support of the catalyst uses fluorine-containing compound and alkali metal to carry out modified, is conducive to the activity and the stability that improve Primary Catalysts, thus improves yield and the selectivity of 3-acetoxyl group propionic aldehyde.
Experimental result shows, when adopting of the present invention, 3-acetoxyl group propionic aldehyde yield reaches 85.16%, and selectivity reaches 95.08%, achieves good technique effect.Especially in support of the catalyst modifying process, use ammonium silicofluoride, hydrofluoric acid simultaneously, containing Rb and work in coordination with containing Cs time, achieve more outstanding technique effect.Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the ammonium silicofluoride aqueous solution 0.80L of 2.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 0.60g rubidium hydroxide powder and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after retort furnace 500 DEG C of roastings, obtain described support of the catalyst II.Carrier is through with IC and icp analysis, and F content is 2.45g/L, Rb content is 0.49g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.16% as calculated, selectivity is 95.08%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1].
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 72.47% as calculated, selectivity is 89.62%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[comparative example 2]
For the comparative example of [embodiment 1].
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the ammonium silicofluoride aqueous solution 0.80L of 2.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Then after retort furnace 500 DEG C of roastings, support of the catalyst II is obtained.Carrier is through by IC analysis, and F content is 2.45g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 72.86% as calculated, selectivity is 91.28%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[comparative example 3]
For the comparative example of [embodiment 1].
The preparation of support of the catalyst II: be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 0.60g rubidium hydroxide powder and concentration, coating liquid is sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, obtain described support of the catalyst II after retort furnace 500 DEG C of roastings.Carrier is through with icp analysis, and Rb content is 0.49g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 74.59% as calculated, selectivity is 90.38%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
By finding out compared with embodiment 1, the support of the catalyst that the present invention adopts, use Performance Ratio containing F and alkali metals modified rear catalyst without the carrier of any modification, than only with the compound modified carrier, more excellent than the performance of the catalyzer only made with the carrier of alkali metals modified containing F simultaneously, the selectivity of 3-acetoxyl group propionic aldehyde and yield all want high, this is as can be seen from the data of embodiment 1, comparative example 1 ~ 3, describes and is present in good synergy containing between the compound of F and basic metal.
[embodiment 2]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the ammonium fluoride aqueous solution 0.80L of 2.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 1.07g Lithium Oxide 98min powder and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after retort furnace 500 DEG C of roastings, obtain described support of the catalyst II.Carrier is through with IC and icp analysis, and F content is 2.45g/L, Li content is 0.49g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.27% as calculated, selectivity is 95.03%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[embodiment 3]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the hydrofluoric acid aqueous solution 0.80L of 0.52gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 1.0g is fully mixed to get coating liquid by 0.16g sodium oxide powder and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after retort furnace 500 DEG C of roastings, obtain described support of the catalyst II.Carrier is through with IC and icp analysis, and F content is 0.51g/L, Na content is 0.11g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.44% as calculated, selectivity is 95.12%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[embodiment 4]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the ammonium bifluoride aqueous solution 0.80L of 5.00gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 1.43g potassium hydroxide powder and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after retort furnace 500 DEG C of roastings, obtain described support of the catalyst II.Carrier is through with IC and icp analysis, and F content is 4.90g/L, K content is 0.99g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.38% as calculated, selectivity is 95.26%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[embodiment 5]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the 5-fluorosalicylic acid aqueous solution 0.80L of 2.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 0.56g cesium hydroxide powder and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after retort furnace 500 DEG C of roastings, obtain described support of the catalyst II.Carrier is through with IC and icp analysis, and F content is 2.45g/L, Cs content is 0.49g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.73% as calculated, selectivity is 95.11%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[embodiment 6]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the ammonium silicofluoride aqueous solution 0.80L of 2.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 0.56g cesium hydroxide powder and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after retort furnace 500 DEG C of roastings, obtain described support of the catalyst II.Carrier is through with IC and icp analysis, and F content is 2.45g/L, Cs content is 0.49g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.09% as calculated, selectivity is 95.37%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[embodiment 7]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the ammonium silicofluoride aqueous solution 0.80L of 2.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 0.60g rubidium hydroxide powder and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after retort furnace 500 DEG C of roastings, obtain described support of the catalyst II.Carrier is through with IC and icp analysis, and F content is 2.45g/L, Rb content is 0.49g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 0.3MPa after air, then carbon monoxide and hydrogen is passed into until pressure 1.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 50 DEG C, and the mol ratio of hydrogen and carbon monoxide is 1:10, after sustained reaction 1.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 76.16% as calculated, selectivity is 93.79%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[embodiment 8]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the ammonium silicofluoride aqueous solution 0.80L of 2.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 0.60g rubidium hydroxide powder and concentration, coating liquid be sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, after retort furnace 500 DEG C of roastings, obtain described support of the catalyst II.Carrier is through with IC and icp analysis, and F content is 2.45g/L, Rb content is 0.49g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 15.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 180 DEG C, the mol ratio of hydrogen and carbon monoxide is 10:1, after sustained reaction 15.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 84.39% as calculated, selectivity is 92.47%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[embodiment 9]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the ammonium silicofluoride aqueous solution 0.80L of 2.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 0.30g cesium hydroxide, 0.29g rubidium hydroxide powder and concentration, coating liquid is sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, obtain described support of the catalyst II after retort furnace 500 DEG C of roastings.Carrier is through with IC and icp analysis, and F content is 2.45g/L, Rb content be 0.23g/L, Cs content is 0.26g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 86.95% as calculated, selectivity is 97.24%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 9 and embodiment 1 and embodiment 6, in the selectivity improving 3-acetoxyl group propionic aldehyde and yield, Rb and Cs has synergy.
[embodiment 10]
The preparation of support of the catalyst II: will be the spherical SiO of 5.6mm containing the 5-fluorosalicylic acid aqueous solution 0.80L of 2.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 0.30g cesium hydroxide, 0.29g rubidium hydroxide powder and concentration, coating liquid is sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, obtain described support of the catalyst II after retort furnace 500 DEG C of roastings.Carrier is through with IC and icp analysis, and F content is 2.45g/L, Rb content be 0.23g/L, Cs content is 0.26g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 87.04% as calculated, selectivity is 97.06%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
[embodiment 11]
The preparation of support of the catalyst II: be the spherical SiO of 5.6mm by the ammonium silicofluoride containing 1.00gF and the aqueous solution 0.8L of 5-fluorosalicylic acid containing 1.50gF and 1.0L diameter
2carrier mixes, and 100 DEG C of dryings, obtain described catalyst carrier precursor I.Be that 35wt% silicon sol 5.0g is fully mixed to get coating liquid by 0.30g cesium hydroxide, 0.29g rubidium hydroxide powder and concentration, coating liquid is sprayed on 1.0L catalyst carrier precursor I uniformly, 100 DEG C of dryings, obtain support of the catalyst II after retort furnace 500 DEG C of roastings.Carrier is through with IC and icp analysis, and F content is 2.45g/L, Rb content be 0.23g/L, Cs content is 0.26g/L.
The preparation of Primary Catalysts: by the RhCl containing 6.50gRh
33H
2o is dissolved in pure water, obtains steeping fluid 500ml, is immersed in by support of the catalyst II described in 1.0L in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, at N
2be warming up to 500 DEG C of roasting 5h in atmosphere, obtain Primary Catalysts.Primary Catalysts is through icp analysis, and Rh content is 6.44g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 800rpm, stirring heating is warming up to temperature of reaction simultaneously, and controlling temperature of reaction is 110 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained reaction 5.0h, stopped reaction.
Product analysis: the above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 88.79% as calculated, selectivity is 98.15%, for convenience of explanation and compare, the yield of the preparation condition of support modification condition, catalyzer, reaction conditions, material feeding amount, 3-acetoxyl group propionic aldehyde and selectivity are listed in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 9 and embodiment 10, in the selectivity improving 3-acetoxyl group propionic aldehyde and yield, ammonium silicofluoride and 5-fluorosalicylic acid and basic metal Rb, Cs have synergy.
Table 1
Table 2
Claims (10)
1. the method for vinyl acetate between to for plastic hydroformylation synthesis 3-acetoxyl group propionic aldehyde, with vinyl acetate between to for plastic, carbon monoxide and hydrogen for raw material, take toluene as solvent, catalyzer carries out Reactive Synthesis 3-acetoxyl group propionic aldehyde under existing, described catalyzer comprises Primary Catalysts and promotor, and described Primary Catalysts comprises carrier, active ingredient; Described active ingredient adopts the compound of rhodium; Described promotor is selected from least one in organic amine and organophosphorus; Described carrier is for containing cated silicon-dioxide with fluorochemicals its surface modified; Described coating forms by modified metal element and by the silica binder that described modified metal element is bonded in described carrier surface; Described fluorine-containing constituent content is 0.50 ~ 5.00g/L; Modified metal constituent content is 0.010 ~ 1.00g/L; Described modified metal element is selected from least one in alkali metal.
2. method according to claim 1, is characterized in that the compound of described rhodium is RhCl
3.
3. method according to claim 1, is characterized in that described promotor is selected from least one in pyridine and triphenyl phosphorus.
4. method according to claim 1, is characterized in that described fluorine-containing compound is selected from least one in ammonium silicofluoride, Neutral ammonium fluoride, hydrofluoric acid, ammonium bifluoride and 5-fluorosalicylic acid.
5. method according to claim 1, is characterized in that described alkali metal is selected from least one in Li, Na, K, Rb and Cs.
6. method according to claim 1, is characterized in that the temperature of reacting is 50 ~ 180 DEG C.
7. method according to claim 1, is characterized in that the pressure reacted is 1.0 ~ 15.0MPa.
8. method according to claim 1, is characterized in that the time of reacting is 1.0 ~ 15.0h.
9. method according to claim 1, is characterized in that carbon monoxide and hydrogen volume ratio are 0.10 ~ 10.0.
10., by the preparation method of Primary Catalysts according to claim 1, comprise the steps:
1. fluorine-containing compound is mixed with aqueous impregnation silicon-dioxide, drying obtains described catalyst carrier precursor I;
2. the oxyhydroxide of described modified metal element or oxide compound and silicon sol are mixed to get coating liquid;
3. above-mentioned coating liquid is coated to precursor carrier I surface, dry, roasting obtains described support of the catalyst II;
4. the composition of catalyzer is pressed by RhCl
3mix with described support of the catalyst II;
5. standing, dry, roasting, obtains described Primary Catalysts.
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| CN105585437A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Method for producing 1,3-propylene glycol through hydroformylation of vinyl acetate |
| CN107999061A (en) * | 2018-01-18 | 2018-05-08 | 南开大学 | A kind of preparation method and applications of preparing aldehyde by hydro formylating defin effective catalyst |
| CN108144602A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst |
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| CN105585437A (en) * | 2014-10-24 | 2016-05-18 | 中国石油化工股份有限公司 | Method for producing 1,3-propylene glycol through hydroformylation of vinyl acetate |
| CN108144602A (en) * | 2016-12-02 | 2018-06-12 | 中国科学院大连化学物理研究所 | A kind of preparation method of high abrasion micron noble-metal-supported silica support catalyst |
| CN108144602B (en) * | 2016-12-02 | 2020-11-10 | 中国科学院大连化学物理研究所 | Preparation method of high-wear-resistance micron noble metal loaded silicon oxide carrier catalyst |
| CN107999061A (en) * | 2018-01-18 | 2018-05-08 | 南开大学 | A kind of preparation method and applications of preparing aldehyde by hydro formylating defin effective catalyst |
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