CN105498786A - Catalyst for synthesis of 3-acetoxy propionaldehyde - Google Patents
Catalyst for synthesis of 3-acetoxy propionaldehyde Download PDFInfo
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Abstract
The invention relates to a catalyst for synthesis of 3-acetoxy propionaldehyde, and mainly solves the problems of low activity and selectivity of 3-acetoxy propionaldehyde catalysts in the prior art. According to a technical scheme, the catalyst for synthesis of 3-acetoxy propionaldehyde adopts SiO2, Al2O3 or a mixture thereof as the carrier, and the active component includes at least one of iron series elements, at least one of metalloid elements, at least one of VB and alkali metals. The catalyst provided by the invention well solves the technical problems and can be applied to the industrial production of 1.3-propanediol.
Description
Technical field
The present invention relates to the catalyst that synthesis 3-acetoxyl group propionic aldehyde is used, the preparation method of described catalyst and the synthetic method of 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 and synthesize 3-acetoxyl group propionic aldehyde catalyst used, 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: the catalyst that synthesis 3-acetoxyl group propionic aldehyde is used, and described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active component comprise chosen from Fe series elements at least one, be selected from least one in metalloid element and be selected from least one metallic element in VB and alkali metal.Preferred described active component comprises iron series element, metalloid element, at least one metallic element that is selected from least one metallic element in VB and is selected from alkali metal simultaneously.There is synergy improving in the selective and yield of 3-acetoxyl group propionic aldehyde between metallic element now in the metallic element of VB and alkali metal.
In technique scheme, at least one in the excellent chosen from Fe of described iron series element, cobalt and nickel.
In technique scheme, at least one of described metalloid element preferably in boron, arsenic and tellurium.。
In technique scheme, at least one of described VB metal preferably in vanadium, niobium and tantalum.
In technique scheme, at least one of described alkali metal preferably in lithium, sodium, potassium, rubidium and caesium.
In technique scheme, as most preferred technical scheme, described active component comprises iron series element, metalloid element, VB metallic element and alkali metal simultaneously; Such as described active component is made up of cobalt, boron, vanadium and rubidium (or potassium), or be made up of cobalt, boron, vanadium (or tantalum), rubidium and potassium, or be made up of cobalt, boron (or tellurium), vanadium, tantalum, rubidium and potassium, or be made up of cobalt (or nickel), boron, tellurium, vanadium, tantalum, rubidium and potassium.The most preferred described active component is made up of cobalt, nickel, boron, tellurium, vanadium, tantalum, rubidium and potassium.
In technique scheme, in described catalyst, the content of iron series element is preferably 3.00 ~ 15.00g/L, is more preferably 7.00 ~ 12.00g/L; In described catalyst, the content of metalloid element is preferably 0.10 ~ 3.00g/L, is more preferably 0.50 ~ 3.00g/L; At least one content being selected from metal in VB and alkali metal 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:
1. the solution pressing the compound of metallic element in the compound of composition by iron series element of catalyst, the compound of metalloid element, VB and alkali metal mixes with carrier;
2. dry.
In technique scheme, at least one of compound preferably in ferrocene, carbonyl cobalt, cobalt acetate, cobalt chloride, carbonyl nickel and nickel chloride of step 1. described iron series element.At least one of compound preferably in boric acid, ammonium pentaborate, dimethylamino monoborane, arsenic acid, arsenic trichloride, ammonium tellurate, tellurium dioxide and telluric acid of step 1. described metalloid element; Step is at least one of metallic compound preferably in vanadium trichloride, vanadic anhydride, columbium pentachloride and tantalic chloride in described VB 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 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 according to any one of the technical scheme of one of above-mentioned technical problem 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 iron series element, metalloid element and is selected from least one metallic element in VB and alkali metal, 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, 3-acetoxyl group propionic aldehyde yield 59.86% prepared by the present invention, selectively reach 93.84%, achieve good technique effect, especially when in catalyst, active component comprises iron series element, metalloid element simultaneously, is selected from least one metallic element in VB and is selected from least one metallic element in alkali metal, 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 8.40gCo, containing 1.50gB with containing the Co of 2.90gV
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2and ammonium metavanadate (NH O)
4vO
3) fully mixed dissolution be in the aqueous acetic acid of 10wt% in concentration, 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, V content 2.90g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 59.86% as calculated, and selective is 93.84%, 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 8.40gCo, containing 1.50gB with containing the Co of 2.90gRb
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2and RbNO O)
3abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, Rb content 2.90g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 59.91% as calculated, and selective is 93.77%, 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 8.40gCo and the Co containing 1.50gB be contained
2(CO)
8with ammonium metaborate (NH
4hB
4o
73H
2o) fully mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 50.04% as calculated, and selective is 85.68%, 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 Co and B active constituent catalyst containing Co, B and V active component, catalyst performance simultaneously containing Co, B and Rb active component, the selective and yield of 3-acetoxyl group propionic aldehyde all wants height.
[embodiment 3]
The preparation of catalyst: by containing 7.00gCo, containing 0.50gB with containing the Co (OAc) of 1.00gV
24H
2o, ammonium pentaborate ((NH
4) B
5o
88H
2and Cl O)
3the abundant mixed dissolution of V 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 80 DEG C of dryings, obtains described catalyst.The Co content measuring this catalyst through ICP and ICP-MS is 7.00g/L, B content 0.50g/L, V content 1.00g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 55.33% as calculated, and selective is 92.14%, 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 4]
The preparation of catalyst: by containing 12.00gFe, containing 3.00gB with containing the ferrocene (Fe (C of 5.00gV
5h
5)
2), dimethylamino monoborane (C
2h
6and V BN)
2o
5abundant mixed dissolution is in the aqueous solution of nitric acid 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 120 DEG C of dryings, obtains described catalyst.The Fe content measuring this catalyst through ICP and ICP-MS is 12.00g/L, B content 3.00g/L, V content 5.00g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 60.25% as calculated, and selective is 93.78%, 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 8.40gNi, containing 1.50gAs with containing the Ni (CO) of 2.90gNb
4, arsenic acid (H
3asO
40.5H
2and NbCl O)
5abundant mixed dissolution, in ethanol, 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 Ni content measuring this catalyst through ICP is 8.40g/L, As content 1.50g/L, Nb content 2.90g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 60.03% as calculated, and selective is 93.73%, 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 8.40gNi, containing 1.50gTe with containing the Ni (NO of 2.90gTa
3)
26H
2o, ammonium tellurate ((NH
4)
2teO
4) and TaCl
5abundant mixed dissolution is in the aqueous sulfuric acid 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 Ni content measuring this catalyst through ICP is 8.40g/L, Te content 1.50g/L, Ta content 2.90g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 59.83% as calculated, and selective is 94.04%, 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 7]
The preparation of catalyst: by containing 8.40gCo, containing 1.50gTe with containing the CoCl of 2.90gLi
26H
2o, telluric acid (H
6teO
6) and the abundant mixed dissolution of LiCl 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 Co content measuring this catalyst through ICP is 8.40g/L, Te content 1.50g/L, Li content 2.90g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 59.93% as calculated, and selective is 93.83%, 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 8.40gCo, containing 1.50gB with containing the Co (NO of 2.90gNa
3)
26H
2o, ammonium metaborate (NH
4hB
4o
73H
2and Na O)
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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, Na content 2.90g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 59.90% as calculated, and selective is 94.10%, 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 8.40gCo, containing 1.50gB with containing the Co of 2.90gK
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2and K O)
2sO
4abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, K content 2.90g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 55.78% as calculated, and selective is 93.49%, 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 8.40gCo, containing 1.50gB with containing the Co of 2.90gCs
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2o) and the abundant mixed dissolution of CsOAc be in the aqueous acetic acid of 10wt% in concentration, 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, Cs content 2.90g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 60.92% as calculated, and selective is 93.59%, 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 11]
The preparation of catalyst: by containing 8.40gCo, containing 1.50gB, containing 1.10gV with containing the Co of 1.80gRb
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2o), ammonium metavanadate (NH
4vO
3) and RbNO
3abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, V content 1.10g/L, Rb content 1.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 61.94% as calculated, and selective is 95.63%, 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.
Found out, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, between VB metal V and alkali metal Rb, to there is synergy on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 2.
[embodiment 12]
The preparation of catalyst: by containing 8.40gCo, containing 1.50gB, containing 1.10gV with containing the Co of 1.80gK
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2o), ammonium metavanadate (NH
4vO
3) and K
2sO
4abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, V content 1.10g/L, K content 1.80g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 61.88% as calculated, and selective is 95.72%, 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 13]
The preparation of catalyst: by containing 8.40gCo, containing 1.50gB, containing 1.10gV, containing 1.25gRb with containing the Co of 0.55gK
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2o), ammonium metavanadate (NH
4vO
3), RbNO
3and K
2sO
4abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, V content 1.10g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 63.02% as calculated, and selective is 96.97%, 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.
Found out, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, in alkali metal, between Rb and K, to there is synergy on year-on-year basis by embodiment 13 and embodiment 11 and embodiment 12.Describe between Co, B, V, Rb and K five kinds of active components and there is well synergy.
[embodiment 14]
The preparation of catalyst: by containing 8.40gCo, containing 1.50gB, containing 1.10gTa, containing 1.25gRb with containing the Co of 0.55gK
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2o), TaCl
5, RbNO
3and K
2sO
4abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, Ta content 1.10g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 62.91% as calculated, and selective is 97.05%, 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 15]
The preparation of catalyst: by containing 8.40gCo, containing 1.50gB, containing 0.40gV, containing 0.70gTa, containing 1.25gRb with containing the Co of 0.55gK
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2o), ammonium metavanadate (NH
4vO
3), TaCl
5, RbNO
3and K
2sO
4abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 1.50g/L, V content 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 63.78% as calculated, and selective is 97.85%, 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 15 and embodiment 13 and embodiment 14, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, between VB metal V, Ta, there is synergy, describe between Co, B, V, Ta, Rb and K six kinds of active components and there is well synergy.
[embodiment 16]
The preparation of catalyst: by containing 8.40gCo, containing 1.50gTe, containing 0.40gV, containing 0.70gTa, containing 1.25gRb with containing the Co of 0.55gK
2(CO)
8, ammonium tellurate ((NH
4)
2teO
4), ammonium metavanadate (NH
4vO
3), TaCl
5, RbNO
3and K
2sO
4abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP is 8.40g/L, Te content 1.50g/L, V content 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 63.66% as calculated, and selective is 97.86%, 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 17]
The preparation of catalyst: by containing 8.40gCo, containing 0.60gB, containing 0.90gTe, containing 0.40gV, containing 0.70gTa, containing 1.25gRb with containing the Co of 0.55gK
2(CO)
8, ammonium metaborate (NH
4hB
4o
73H
2o), ammonium tellurate ((NH
4)
2teO
4), ammonium metavanadate (NH
4vO
3), TaCl
5, RbNO
3and K
2sO
4abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 0.60g/L, Te content 0.90g/L, V content 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 64.82% as calculated, and selective is 98.55%, 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 17 and embodiment 15 and embodiment 16, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, between metalloid B, Te, there is synergy, describe between Co, B, Te, V, Ta, Rb and K seven kinds of active components and there is well synergy.
[embodiment 18]
The preparation of catalyst: by containing 8.40gNi, containing 0.60gB, containing 0.90gTe, containing 0.40gV, containing 0.70gTa, containing 1.25gRb with containing the Ni (NO of 0.55gK
3)
26H
2o, ammonium metaborate (NH
4hB
4o
73H
2o), ammonium tellurate ((NH
4)
2teO
4), ammonium metavanadate (NH
4vO
3), TaCl
5, RbNO
3and K
2sO
4abundant mixed dissolution is in the aqueous sulfuric acid 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 Ni content measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 0.60g/L, Te content 0.90g/L, V content 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 64.76% as calculated, and selective is 98.62%, 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 19]
The preparation of catalyst: by containing 6.30gCo, containing 2.10gNi, containing 0.60gB, containing 0.90gTe, containing 0.40gV, containing 0.70gTa, containing 1.25gRb with containing the Co of 0.55gK
2(CO)
8, Ni (NO
3)
26H
2o, ammonium metaborate (NH
4hB
4o
73H
2o), ammonium tellurate ((NH
4)
2teO
4), ammonium metavanadate (NH
4vO
3), TaCl
5, RbNO
3and K
2sO
4abundant mixed dissolution is in the aqueous acetic acid of 10wt% 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 Co content measuring this catalyst through ICP and ICP-MS is 6.30g/L, Ni content 2.10g/L, B content 0.60g/L, Te content 0.90g/L, V content 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K content 0.55g/L.
The synthesis of 3-acetoxyl group propionic aldehyde: 2.50mol toluene, 0.15mol 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 2.0MPa after air, then carbon monoxide and hydrogen is passed into until pressure 12.5MPa, improve mixing speed to 800rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 120 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, 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 66.04% as calculated, and selective is 99.17%, 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.
Found out on year-on-year basis by embodiment 19 and embodiment 17 and embodiment 18, in the selective and yield improving 3-acetoxyl group propionic aldehyde, in the catalyst that the present invention uses, between Ferrious material Ni, Co, there is synergy, describe between Co, Ni, B, Te, V, Ta, Rb and K eight kinds of active components and there is well synergy.
Table 1
Table 2 (continued)
Table 2 (Continued)
Claims (10)
1. synthesize the catalyst that 3-acetoxyl group propionic aldehyde is used, described catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active component comprise chosen from Fe series elements at least one, be selected from least one in metalloid element and be selected from least one metallic element in VB and alkali metal.
2. catalyst according to claim 1, is characterized in that at least one in described iron series element chosen from Fe, cobalt and nickel.
3. catalyst according to claim 1, is characterized in that described metalloid element is selected from least one in boron, arsenic and tellurium.
4. catalyst according to claim 1, is characterized in that described VB metal is selected from least one in vanadium, niobium and tantalum.
5. catalyst according to claim 1, is characterized in that described alkali metal is selected from least one in lithium, sodium, potassium, rubidium and caesium.
6. catalyst according to claim 1, it is characterized in that the content of iron series element in catalyst is: 3.00 ~ 15.00g/L, the content of metalloid element is: 0.10 ~ 3.00g/L.
7. catalyst according to claim 1, at least one content that it is characterized in that being selected from described in catalyst metal in VB and alkali metal is 0.10 ~ 5.00g/L.
8., by the production method of catalyst according to claim 1, comprise the steps:
1. the solution pressing the compound of metallic element in the compound of composition by iron series element of catalyst, the compound of metalloid element, VB and alkali metal mixes with carrier;
2. dry.
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 ~ 7, 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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| US4072709A (en) * | 1975-05-27 | 1978-02-07 | Monsanto Company | Production of lactic acid |
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| US4072709A (en) * | 1975-05-27 | 1978-02-07 | Monsanto Company | Production of lactic acid |
| CN101121130A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Ammoxidation method to manufacturing unsaturated nitrile catalyst |
| CN102372603A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol |
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