CN105498764A - 3-acetoxy propionaldehyde catalyst and production method thereof - Google Patents
3-acetoxy propionaldehyde catalyst and production method thereof Download PDFInfo
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Abstract
The invention relates to a 3-acetoxy propionaldehyde catalyst and a production method thereof, and mainly solves the problems of low activity and selectivity of 3-acetoxy propionaldehyde catalyst in the prior art. According to a technical scheme, the 3-acetoxy propionaldehyde catalyst adopts SiO2, Al2O3 or a mixture thereof as the carrier, and the active component includes rhodium, alkali metal and at least one metal element selected from IVA and IVB, thus well solving the technical problems. And the 3-acetoxy propionaldehyde catalyst can be used in the industrial production of 1.3-propanediol.
Description
Technical field
The present invention relates to 3-acetoxyl group propionic aldehyde catalyst, the synthetic method of 3-acetoxyl group propionic aldehyde catalyst manufacturing process and 3-acetoxyl group propionic aldehyde.
Background technology
1.3-propane diols (1.3-PDO) is a kind of important industrial chemicals, is mainly used in the synthesis of plasticizer, washing agent, anticorrisive agent, emulsifying agent, also for industries such as food, cosmetics and pharmacy.Because it is a kind of important polyester fiber monomer, its topmost purposes is as monomer and terephthalic acid (TPA) synthesizing new polyester material one polytrimethylene terephthalate (PTT).
The preparation method of 1.3-propane diols has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehyde stiasny method, acrylic acid ester process, bioanalysis, vinyl acetate hydroformylation etc.At present, the industrialized preparing process of 1.3-PDO is chemical synthesis, and international 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, can there is hydroformylation reaction in this key, a carbon atom of double bond adds an aldehyde radical, generates the isomer 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 just can prepare 1.3-propane diols through hydroformylation, hydrogenation and hydrolysis.
Teaching in the patents such as patent US4072709 (Productionoflacticacid) utilizes vinyl acetate or propionate to be raw material; by adopting homogeneous phase rhodium compound to be catalyst; 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 low and selective not high problem of 3-acetoxyl group propionic aldehyde yield in said 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 low and selective low problem of 3-acetoxyl group propionic aldehyde yield, there is provided a kind of new 3-acetoxyl group propionic aldehyde catalyst, it is high to the selective high feature of 3-acetoxyl group propionic aldehyde that this catalyst has 3-acetoxyl group propionic aldehyde yield.
Two of technical problem to be solved by this invention is the production methods adopting one of above-mentioned technical problem described catalyst.
Three of technical problem to be solved by this invention is the synthetic methods of the 3-acetoxyl group propionic aldehyde adopting one of above-mentioned technical problem described catalyst.
In order to one of solve the problems of the technologies described above, the technical solution used in the present invention is as follows: 3-acetoxyl group propionic aldehyde catalyst, and described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active component comprises rhodium, alkali metal and is selected from least one metallic element in IVA and IVB.Preferred described active component comprises rhodium, alkali metal, at least one metallic element that is selected from least one metallic element in IVA and is selected from IVB simultaneously.Now there is synergy improving in the selective and yield of 3-acetoxyl group propionic aldehyde between the metallic element of IVA and the metallic element of IVB.
In technique scheme, at least one of described alkali metal preferably in lithium, sodium, potassium, rubidium and caesium.
In technique scheme, at least one of described IVA metal preferably in germanium, tin and lead.
In technique scheme, at least one of described IVB metal preferably in titanium, zirconium and hafnium.
In technique scheme, as most preferred technical scheme, described active component comprises rhodium metal element, alkali metal, IVA metallic element and IVB metallic element simultaneously; Such as described active component is made up of rhodium, lithium, rubidium, tin and hafnium, or is made up of rhodium, lithium, rubidium, tin and zirconium, or is made up of rhodium, lithium, rubidium, tin, zirconium and hafnium.
In technique scheme, in described catalyst, the content of rhodium is preferably 3.00 ~ 15.00g/L, is more preferably 5.00 ~ 10.00g/L; In described catalyst, alkali-metal content is preferably 0.10 ~ 3.00g/L, is more preferably 0.50 ~ 3.00g/L; At least one content being selected from metal in IVA and IVB in described catalyst is preferably 0.10 ~ 5.00g/L, is more preferably 1.00 ~ 5.00g/L.Described catalyst carrier specific surface used is preferably 50 ~ 300m
2/ g, is more preferably 150 ~ 200m
2/ g, pore volume is preferably 0.80 ~ 1.20, is more preferably 0.90 ~ 1.00.
For solve the problems of the technologies described above two, technical scheme of the present invention is as follows: the production method of catalyst described in the technical scheme of one of above-mentioned technical problem, comprises the steps:
The solution of metallic compound in rhodium compound, alkali metal compound, IVA and IVB mixes with carrier by the composition 1. pressing catalyst;
2. dry.
In technique scheme, step is at least one of described rhodium compound preferably in rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate 1.; Step is at least one of described alkali metal compound preferably in alkali metal oxide, alkali metal chloride, alkali nitrates, alkali metal sulfates and alkali metal acetate 1.; Step is at least one in the preferred germanium tetrachloride of described IVA metallic compound, stannous chloride, nitric acid sub-tin, stannous oxide, lead acetate and plumbi nitras 1.; Step is at least one of metallic compound preferably in titanium tetrachloride, ammonium titanium fluoride, hexafluorotitanic acid, zirconium chloride, acetic acid zirconium and oxychloride hafnium in described IVB 1.; Step 2. described baking temperature is 80 ~ 120 DEG C, is more preferably 100 ~ 120 DEG C.
For solve the problems of the technologies described above three, technical scheme of the present invention is as follows: the synthetic method of 3-acetoxyl group propionic aldehyde, with vinyl acetate, carbon monoxide and hydrogen for raw material, take toluene as solvent, under catalyst and promoter exist, reaction generates 3-acetoxyl group propionic aldehyde.At least one in the preferred pyridine of described promoter and triphenyl phosphorus.
Key of the present invention is the selection of catalyst, those skilled in the art will know that the proportioning determining suitable reaction temperature, reaction time, 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-MS) (GC-MASS) to analyze, by the conversion ratio of following formulae discovery vinyl acetate and the yield of 3-acetoxyl group propionic aldehyde and selective:
Compared with prior art, key of the present invention is that the active component of catalyst comprises rhodium, alkali metal and is selected from least one metallic element in IVA and IVB, be conducive to improving the activity of major catalyst and stability, thus improve the yield of 3-acetoxyl group propionic aldehyde and selective.
Experimental result shows, when adopting catalyst of the present invention, 3-acetoxyl group propionic aldehyde yield 85.26%, selectively reach 94.87%, achieve good technique effect, especially, when active component comprises rhodium, alkali metal simultaneously, is selected from least one metallic element in IVA and is selected from least one metallic element in IVB in catalyst, achieve more outstanding technique effect, can be used in the industrial production of 1.3-propane diols.Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of catalyst: by containing 6.50gRh, containing 1.50gLi with containing the RhCl of 3.50gSn
33H
2o, LiCl and SnCl
22H
2the abundant mixed dissolution of O is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L, Sn content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.26% as calculated, and selective is 94.87%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 2]
The preparation of catalyst: by containing 6.50gRh, containing 1.50gLi with containing the RhCl of 3.50gTi
33H
2o, LiCl and TiCl
4abundant mixed dissolution is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L, Ti content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.34% as calculated, and selective is 94.59%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of catalyst: will 6.50Rh and the RhCl containing 1.50gLi be contained
33H
2the abundant mixed dissolution of O and LiCl, in pure water, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 73.86% as calculated, and selective is 84.45%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
By finding out compared with embodiment 1 ~ 2, the catalyst that the present invention adopts, use simultaneously more excellent than the performance only containing Rh and Li active constituent catalyst containing Rh, Li and Sn active component, catalyst performance simultaneously containing Rh, Li and Ti active component, the selective and yield of 3-acetoxyl group propionic aldehyde all wants height.
[embodiment 3]
The preparation of catalyst: by containing 6.50gRh, containing 1.50gK with containing the Rh (OAc) of 3.50gGe
3, K
2sO
4and GeCl
4abundant mixed dissolution is in 10wt% aqueous acetic acid in concentration, obtains maceration extract 400ml, is 200m by 1.0L specific surface
2/ g, pore volume is 1.00, and diameter is the spherical Al of 5.6mm
2o
3carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, K content 1.50g/L, Ge content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.19% as calculated, and selective is 95.04%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 4]
The preparation of catalyst: by containing 6.50gRh, containing 1.50gRb with containing the RhCl of 3.50gSn
33H
2o, RbNO
3and SnCl
22H
2the abundant mixed dissolution of O is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 400ml, is 150m by 1.0L specific surface
2/ g, pore volume is 0.90, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Rb content 1.50g/L, Sn content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.21% as calculated, and selective is 95.17%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 5]
The preparation of catalyst: by containing 5.00gRh, containing 0.50gCs with containing the Rh of 1.00gPb
2(SO
4)
315H
2o, CsOAc and Pb (OAc)
23H
2the abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 80 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 5.00g/L, Cs content 0.50g/L, Pb content 1.00g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 80.15% as calculated, and selective is 89.63%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 6]
The preparation of catalyst: by containing 10.00gRh, containing 3.00gNa with containing the RhCl of 5.00gPb
33H
2o, Na
2o and Pb (NO
3)
2abundant mixed dissolution is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 120 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 10.00g/L, Na content 3.00g/L, Pb content 5.00g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.84% as calculated, and selective is 94.37%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 7]
The preparation of catalyst: by containing 6.50gRh, containing 1.50gLi with containing the RhCl of 3.50gTi
33H
2o, LiCl and ammonium titanium fluoride ((NH
4)
2tiF
6) fully mixed dissolution is in pure water, obtaining maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L, Ti content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate are added in 1L titanium material reactor, first discharge in still with argon gas and be pressurized to 0.2MPa after air, then carbon monoxide and hydrogen is passed into until pressure 1.0MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 50 DEG C, and the mol ratio of hydrogen and carbon monoxide is 1:10, after sustained response 1.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 76.27% as calculated, and selective is 94.46%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 8]
The preparation of catalyst: by containing 6.50gRh, containing 1.50gLi with containing the RhCl of 3.50gTi
33H
2o, LiCl and hexafluorotitanic acid (H
2tiF
6) fully mixed dissolution is in pure water, obtaining maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L, Ti content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 180 DEG C, and the mol ratio of hydrogen and carbon monoxide is 10:1, after sustained response 15.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.71% as calculated, and selective is 93.64%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 9]
The preparation of catalyst: by containing 6.50gRh, containing 1.50gLi with containing the RhCl of 3.50gZr
33H
2o, LiCl and ZrCl
4abundant mixed dissolution, in pure water, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L, Zr content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.22% as calculated, and selective is 94.59%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 10]
The preparation of catalyst: by containing 6.50gRh, containing 1.50gLi with containing the RhCl of 3.50gZr
33H
2o, LiCl and Zr (OA
c)
4abundant mixed dissolution, in pure water, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L, Zr content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.31% as calculated, and selective is 94.97%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 11]
The preparation of catalyst: by containing 6.50gRh, containing 1.50gLi with containing the RhCl of 3.50gHf
33H
2o, LiCl and oxychloride hafnium (HfOCl
28H
2o) fully mixed dissolution is in pure water, and obtaining maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L, Hf content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 85.17% as calculated, and selective is 95.14%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 12]
The preparation of catalyst: by containing 6.50gRh, containing 1.00gLi, containing 0.50gRb with containing the RhCl of 3.50gSn
33H
2o, LiCl, RbNO
3and SnCl
22H
2the abundant mixed dissolution of O is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.00g/L, Rb content 0.50g/L, Sn content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 86.45% as calculated, and selective is 95.87%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
Found out, in the selective and yield improving 3-acetoxyl group propionic aldehyde, between alkali metal Li, Rb and IVA metal Sn, to there is synergy on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 4.
[embodiment 13]
The preparation of catalyst: by containing 6.50gRh, containing 1.00gLi, containing 0.50gRb with containing the RhCl of 3.50gZr
33H
2o, LiCl, RbNO
3with Zr (OA
c)
4abundant mixed dissolution, in water, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.00g/L, Rb content 0.50g/L, Zr content 3.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 86.39% as calculated, and selective is 95.91%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 14]
The preparation of catalyst: by containing 6.50gRh, containing 1.00gLi, containing 0.50gRb, containing 2.00gSn with containing the RhCl of 1.50gZr
33H
2o, LiCl, RbNO
3, SnCl
22H
2o and Zr (OA
c)
4abundant mixed dissolution is in the aqueous hydrochloric acid solution of 8wt% in concentration, obtains maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.00g/L, Rb content 0.50g/L, Sn content 2.00g/L, Zr content 1.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 87.33% as calculated, and selective is 96.41%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
Found out, in the selective and yield improving 3-acetoxyl group propionic aldehyde, between IVA metal Sn and IVB metallic Z r, to there is synergy on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13.
[embodiment 15]
The preparation of catalyst: by containing 6.50gRh, containing 1.00gLi, containing 0.50gRb, containing 2.00gSn with containing the RhCl of 1.50gHf
33H
2o, LiCl, RbNO
3, SnCl
22H
2o and oxychloride hafnium (HfOCl
28H
2o) fully mixed dissolution is in the aqueous hydrochloric acid solution of 8wt% in concentration, and obtaining maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.00g/L, Rb content 0.50g/L, Sn content 2.00g/L, Hf content 1.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 87.48% as calculated, and selective is 96.23%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
[embodiment 16]
The preparation of catalyst: by containing 6.50gRh, containing 1.00gLi, containing 0.50gRb, containing 2.00gSn, containing 0.50gZr with containing the RhCl of 1.00gHf
33H
2o, LiCl, RbNO
3, SnCl
22H
2o, Zr (OA
c)
4with oxychloride hafnium (HfOCl
28H
2o) fully mixed dissolution is in the aqueous hydrochloric acid solution of 8wt% in concentration, and obtaining maceration extract 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyst.The Rh content measuring this catalyst through ICP is 6.50g/L, Li content 1.00g/L, Rb content 0.50g/L, Sn content 2.00g/L, Zr content 0.50g/L, Hf content 1.00g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.02mol catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate 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 5.2MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 98 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stop reaction.
Product analysis: the above-mentioned reactant mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) analysis.
The yield of 3-acetoxyl group propionic aldehyde is 88.17% as calculated, and selective is 97.09%, for convenience of explanation and compare, and the yield of the preparation condition of catalyst, reaction condition, material feeding amount, 3-acetoxyl group propionic aldehyde and selectively list in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, IVA metal Sn and have synergy between IVB metallic Z r, Hf, describes between Rh, Li, Rb, Sn, Zr and Hf six kinds of active components and there is well synergy.
Table 1
Table 2
Claims (10)
1.3-acetoxyl group propionic aldehyde catalyst, described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active component comprises rhodium, alkali metal and is selected from least one metallic element in IVA and IVB.
2. catalyst according to claim 1, is characterized in that described alkali metal is selected from least one in lithium, sodium, potassium, rubidium and caesium.
3. catalyst according to claim 1, is characterized in that described IVA metal is selected from least one in germanium, tin and lead.
4. catalyst according to claim 1, is characterized in that described IVB metal is selected from least one in titanium, zirconium and hafnium.
5. catalyst according to claim 1, is characterized in that the content of rhodium in catalyst is: 3.00 ~ 15.00g/L, alkali-metal content is: 0.10 ~ 3.00g/L.
6. catalyst according to claim 1, at least one content that it is characterized in that being selected from described in catalyst metal in IVA and IVB is 0.10 ~ 5.00g/L.
7., by the production method of catalyst according to claim 1, comprise the steps:
The solution of metallic compound in rhodium compound, alkali metal compound, IVA and IVB mixes with carrier by the composition 1. pressing catalyst;
2. dry.
8. the production method of catalyst according to claim 7, it is characterized in that step 1. described rhodium compound be selected from least one in rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate.
The synthetic method of 9.3-acetoxyl group propionic aldehyde, with vinyl acetate, carbon monoxide and hydrogen for raw material, is solvent with toluene, and according to any one of claim 1 ~ 6, catalyst and promoter synthesize 3-acetoxyl group propionic aldehyde under existing.
10. synthetic method according to claim 9, is characterized in that described promoter is selected from least one in pyridine and triphenyl phosphorus.
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| CN1116816A (en) * | 1993-01-22 | 1996-02-14 | 高士机械工厂有限公司 | Blow-off cock for a steam vessel |
| CN101898130A (en) * | 2009-05-25 | 2010-12-01 | 中国石油化工股份有限公司 | Method for preparing dehydrogenation catalyst |
| WO2011075905A1 (en) * | 2009-12-25 | 2011-06-30 | Chen Xiaozhou | Methods for preparing ester of 1,3-propylene glycol and 1,3- propylene glycol |
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