CN105585434A - Method for preparing 1,3-propanediol from vinyl acetate - Google Patents

Abstract

The invention relates to a method for preparing 1,3-propanediol from vinyl acetate. The method is mainly used for solving the problem in the prior art that 1,3-propanediol catalysts are relatively low in activity and selectivity. Through adopting the technical scheme that the method for preparing 1,3-propanediol comprises the following steps: subjecting vinyl acetate to hydroformylation, so as to obtain 3-acetoxypropanal; hydrogenating 3-acetoxypropanal, so as to obtain 3-acetoxypropanol; and hydrolyzing 3-acetoxypropanol so as to obtain 1,3-propanediol, wherein a hydroformylation catalyst adopts SiO2, Al2O3 or a mixture of SiO2 and Al2O3 as a carrier, and active ingredients comprise at least one element selected from ferrous elements, at least one element selected from metalloid elements and at least one metal element selected from VB and alkali metal elements, the technical problem is better solved, and the method can be applied to the industrial production of 1,3-propanediol.

Description

Vinyl acetate is prepared the method for 1,3-PD

Technical field

The present invention relates to vinyl acetate and prepare the method for 1,3-PD.

Background technology

1,3-PD (1.3-PDO) is a kind of important industrial chemicals, be mainly used in plasticizer, washing agent, anticorrisive agent,Synthesizing of 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-PD has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehydeStiasny method, acrylate method, bioanalysis, vinyl acetate hydroformylation etc. At present, the industrialization of 1.3-PDO is rawProduct method is chemical synthesis, and international market is mainly by German Degussa company, shell Shell company of the U.S. and the U.S.Three monopolizations of E.I.Du Pont Company. What Degussa company adopted is that acrolein hydration hydrogenation method (AC method), Shell Co. Ltd adoptWhat be that oxirane carbonyl method (EO method), E.I.Du Pont Company adopt is the own thorugh biologic engineering method (MF method) of innovating. WhereinOxirane two-step process and acrolein hydration method technique are current main flow technique.

It is former in the patents such as patent US4072709 (ProductionofLacticAcid), having told about and having utilized vinyl acetateMaterial, is catalyst by adopting homogeneous phase rhodium compound, by hydroformylation reaction, obtains 2 (or 3)-acetoxyl groups thirdAldehyde. Separate or do not separate, then 3-acetoxyl group propionic aldehyde obtains 1.3-PDO by hydrogenation and hydrolytic process. But above-mentioned sideIn preparation 1.3-PDO process, all there is the low and selective not high problem of 1.3-PDO yield in method.

Summary of the invention

Technical problem to be solved by this invention is yield and the selective low problem of 1,3-PD, provides a kind of newVinyl acetate is prepared the method for 1,3-PD, and the method has 1,3-PD yield height and selective high feature.

In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: vinyl acetate is prepared 1,3-PDMethod, comprises the following steps: (1) is taking vinyl acetate, carbon monoxide and hydrogen as raw material, at hydroformylation catalystUnder existing with promoter, carry out hydroformylation reaction and obtain 3-acetoxyl group propionic aldehyde; (2) under hydrogenation catalyst exists,Hydrogen is reacted with 3-acetoxyl group propionic aldehyde and obtain 3-acetoxyl group propyl alcohol; (3) hydrolysis of 3-acetoxyl group propyl alcohol obtains 1,3-Propane diols; Wherein, described hydroformylation catalyst adopts SiO₂、Al₂O₃Or its mixture is carrier, active componentComprise chosen from Fe series elements at least one, be selected from least one in metalloid element and be selected from VB and alkali metalIn at least one metallic element. Preferred described active component comprises iron series element, metalloid element simultaneously, is selected from VBIn at least one metallic element and be selected from least one metallic element in alkali metal. The now metallic element of VB and alkaliBetween metallic element in metal, selectively and aspect yield there is synergy at raising 1,3-PD.

In technique scheme, at least one in the excellent chosen from Fe of described iron series element, cobalt and nickel.

In technique scheme, described metalloid element is at least one in boron, arsenic and tellurium preferably. .

In technique scheme, preferably at least one in vanadium, niobium and tantalum of described VB metal.

In technique scheme, described alkali metal is at least one in lithium, sodium, potassium, rubidium and caesium preferably.

In technique scheme, as most preferred technical scheme, described active component comprises iron series element, accurate gold simultaneouslyBelong to element, VB metallic element and alkali metal; For example described active component is by cobalt, boron, vanadium and rubidium (or potassium) groupBecome, or formed by cobalt, boron, vanadium (or tantalum), rubidium and potassium, or by cobalt, boron (or tellurium), vanadium, tantalum, rubidium and potassiumComposition, or formed by cobalt (or nickel), boron, tellurium, vanadium, tantalum, rubidium and potassium. The most preferred described active component by cobalt,Nickel, boron, tellurium, vanadium, tantalum, rubidium and potassium composition.

In technique scheme, in described hydroformylation catalyst, the content of iron series element is preferably 3.00～15.00g/L, moreBe preferably 7.00～12.00g/L; In described hydroformylation catalyst, the content of metalloid element is preferably 0.10～3.00g/L,More preferably 0.50～3.00g/L; In described hydroformylation catalyst, be selected from least one of metal in VB and alkali metalContent is preferably 0.10～5.00g/L, more preferably 1.00～5.00g/L. The carrier ratio table that described hydroformylation catalyst is usedFace is preferably 50～300m²/ g, more preferably 150～200m²/ g, pore volume is preferably 0.80～1.20, and more preferably 0.90～1.00.At least one in the preferred pyridine of described promoter and triphenyl phosphorus.

In technique scheme, the concrete technology condition of the hydroformylation reaction of step (1) is not key of the present invention,And those skilled in the art can rationally determine according to actual needs. The concrete work of the hydroformylation reaction of step (1)Skill condition, such as but not limited to: the temperature of hydroformylation reaction is 50～180 DEG C; The pressure of reaction is 1.0～15.0MPa;The time of reaction is 1.0～15.0h; Carbon monoxide and hydrogen volume ratio are 0.10～10.0.

In technique scheme, described hydroformylation catalyst, the optional production method comprising the steps obtains:

1. press the composition of catalyst by gold in the compound of the compound of iron series element, metalloid element, VB and alkali metalThe solution that belongs to the compound of element mixes with carrier;

2. dry.

In technique scheme, step 1. described iron series element compound preferably from ferrocene, carbonyl cobalt, cobalt acetate,At least one in cobalt chloride, carbonyl nickel and nickel chloride. Step 1. described metalloid element compound preferably from boric acid,At least one in ammonium pentaborate, dimethylamino monoborane, arsenic acid, arsenic trichloride, ammonium tellurate, tellurium dioxide and telluric acid;Step 1. in described VB metallic compound preferably in vanadium trichloride, vanadic anhydride, columbium pentachloride and tantalic chlorideAt least one; Step 1. described alkali metal compound preferably from alkali metal oxide, alkali metal chloride, alkali metal nitric acidAt least one in salt, alkali metal sulfates and alkali metal acetate. Step 2. described baking temperature is 80～120 DEG C, moreBe preferably 100～120 DEG C.

The preparation key of catalyst of the present invention is the preparation of hydroformylation major catalyst, after obtaining major catalyst, logicalCross and make major catalyst can obtain catalyst of the present invention with described promoter contact. The side that major catalyst contacts with promoterFormula is not particularly limited, to be also not particularly limited the opportunity that both contact. For example catalyst of the present invention can usedBefore chemical reaction, make both contact and form described catalyst, can also make both applied anti-at catalyst of the present inventionAnswer contact in system that catalyst original position is generated.

In the method for the synthetic 1,3-PD of the present invention, after step (1) finishes, can be to the mixing of hydroformylation reactionThing separates acquisition target product 3-acetoxyl group propionic aldehyde and carries out step (2) again, also can step (1) generate 3-After acetoxyl group propionic aldehyde, do not separate and directly carry out step (2). Those skilled in the art know the suitable hydrogenation of selection and urgeAgent and definite suitable hydrogenation reaction temperature, time and material proportion. Conventional hydrogenation catalyst has transition metal unitThe metallic catalyst, metal oxide catalyst, metal sulfide catalyst, complex catalyst of element etc., for example platinum, palladium,Nickel, ruthenium carried catalyst, cupric oxide-copper chromite, aluminium oxide-zinc oxide-chromium oxide catalyst, nickel-molybdenum sulphide withAnd RhCl[P (C₆H₅)₃]. In the present invention preferably Raney's nickel as hydrogenation catalyst, suitable hydrogenation temperature is preferably 30～100 DEG C; Preferably 0.5～8.0MPa of hydrogenation reaction pressure; The hydrogenation reaction time is preferably 10～200min; Aldehyde and hydrogenMol ratio preferably 0.10～2.0; Solvent preferred water, at least one in toluene.

After step (2) finishes, can separate and obtain target product 3-acetoxyl group third mixture of hydrogenation reactionAlcohol carries out step (3) again, also can step (2) generates after 3-acetoxyl group propyl alcohol and does not separate and directly carry out step(3). Those skilled in the art know select suitable hydrolyst and determine suitable hydrolysising reacting temperature, time andMaterial proportion. Conventional hydrolyst can be inorganic acid, inorganic base, organic acid and organic base. For example hydrochloric acid, nitreAcid, sulfuric acid, phosphoric acid, NaOH, potassium hydroxide, benzene sulfonic acid and ion exchange resin. Suitable hydrolysis temperatureDegree is preferably 50～100 DEG C; Preferably 0～2.0MPa of hydrolysis pressure; Solvent preferred water, benzene, cyclohexane, tolueneIn at least one.

End product of the present invention adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) point after cooling, decompression, separationAnalyse, calculate the conversion ratio of vinyl acetate and the yield of 1,3-PD and selective by following formula:

Compared with prior art, key of the present invention is that the active component of hydroformylation catalyst comprises iron series element, standardMetallic element and be selected from least one metallic element in VB and alkali metal, is conducive to improve the activity of major catalyst and steadyQualitative, thus the yield that has improved 1,3-PD is with selective.

Experimental result shows, the 1,3-PD yield 70.25% that the present invention is prepared, selectively reaches 85.50%, obtainsIn good technique effect, especially hydroformylation catalyst active component comprise simultaneously iron series element, metalloid element,When being selected from least one metallic element in VB and being selected from least one metallic element in alkali metal, obtain more prominentThe technique effect going out, can be used in the industrial production of 1,3-PD. Below by embodiment, the present invention is further explainedState.

Detailed description of the invention

[embodiment 1]

The preparation of hydroformylation catalyst: will contain 8.40gCo, contain 1.50gB and the Co containing 2.90gV₂(CO)₈, boron partiallyAcid ammonium (NH₄HB₄O₇·3H₂And ammonium metavanadate (NH O)₄VO₃) acetic acid that fully mixed dissolution is 10wt% in concentrationIn the aqueous solution, obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/ g, pore volume is 0.94, diameter is 5.6mmSpherical SiO₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Through ICPThe Co content of measuring this catalyst with ICP-MS is 8.40g/L, B content 1.50g/L, V content 2.90g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 70.25% as calculated, is selectively 85.50%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 2]

The preparation of hydroformylation catalyst: will contain 8.40gCo, contain 1.50gB and the Co containing 2.90gRb₂(CO)₈, boron partiallyAcid ammonium (NH₄HB₄O₇·3H₂And RbNO O)₃In the aqueous acetic acid that fully mixed dissolution is 10wt% in concentration,To maceration extract 400ml, be 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂CarryBody is immersed in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Survey through ICP and ICP-MSThe Co content of fixed this catalyst is 8.40g/L, B content 1.50g/L, Rb content 2.90g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 70.45% as calculated, is selectively 85.31%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[comparative example 1]

For the comparative example of [embodiment 1] and [embodiment 2].

The preparation of hydroformylation catalyst: will contain 8.40gCo and the Co containing 1.50gB₂(CO)₈And ammonium metaborate(NH₄HB₄O₇·3H₂O), in the aqueous acetic acid that fully mixed dissolution is 10wt% in concentration, obtain maceration extract 400ml,Be 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation is above-mentionedIn maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Measure this catalyst through ICP and ICP-MSCo content is 8.40g/L, B content 1.50g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 59.35% as calculated, is selectively 78.39%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

By finding out compared with embodiment 1～2, the catalyst that the present invention adopts, uses simultaneously containing Co, B and VActive component, simultaneously containing the catalyst performance of Co, B and Rb active component than only containing Co and B active constituent catalystPerformance more excellent, the selective and yield of 1,3-PD is all wanted height.

[embodiment 3]

The preparation of hydroformylation catalyst: will contain 7.00gCo, contain 0.50gB and the Co (OAc) containing 1.00gV₂·4H₂O、Ammonium pentaborate ((NH₄)B₅O₈·8H₂And Cl O)₃The abundant mixed dissolution of V is in 10wt% aqueous acetic acid in concentration,To maceration extract 400ml, be 200m by 1.0L specific surface²/ g, pore volume is 1.00, the spherical Al that diameter is 5.6mm₂O₃Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 80 DEG C dry, obtain described catalyst. Through ICP and ICP-MSThe Co content of measuring this catalyst is 7.00g/L, B content 0.50g/L, V content 1.00g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 65.13% as calculated, is selectively 82.32%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 4]

The preparation of hydroformylation catalyst: will contain 12.00gFe, contain 3.00gB and the ferrocene containing 5.00gV(Fe(C₅H₅)₂), dimethylamino monoborane (C₂H₆And V BN)₂O₅The nitric acid that fully mixed dissolution is 8wt% in concentrationIn the aqueous solution, obtaining maceration extract 400ml, is 150m by 1.0L specific surface²/ g, pore volume is 0.90, diameter is 5.6mmSpherical SiO₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 120 DEG C dry, obtain described catalyst. Through ICPThe Fe content of measuring this catalyst with ICP-MS is 12.00g/L, B content 3.00g/L, V content 5.00g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 71.02% as calculated, is selectively 84.85%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 5]

The preparation of hydroformylation catalyst: will contain 8.40gNi, contain 1.50gAs and the Ni (CO) containing 2.90gNb₄, arsenic acid(H₃AsO₄·0.5H₂And NbCl O)₅Fully mixed dissolution, in ethanol, obtains maceration extract 400ml, by 1.0L ratio tableFace is 168m²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation is in above-mentioned maceration extract, quietPut 3h in 100 DEG C dry, obtain described catalyst. The Ni content of measuring this catalyst through ICP is 8.40g/L, AsContent 1.50g/L, Nb content 2.90g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 70.41% as calculated, is selectively 85.12%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 6]

The preparation of hydroformylation catalyst: will contain 8.40gNi, contain 1.50gTe and the Ni (NO containing 2.90gTa₃)₂·6H₂O、Ammonium tellurate ((NH₄)₂TeO₄) and TaCl₅In the aqueous sulfuric acid that fully mixed dissolution is 8wt% in concentration, floodedLiquid 400ml is 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier soaksStain in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Measure this catalyst through ICPNi content is 8.40g/L, Te content 1.50g/L, Ta content 2.90g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 70.36% as calculated, is selectively 85.20%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 7]

The preparation of hydroformylation catalyst: will contain 8.40gCo, contain 1.50gTe and the CoCl containing 2.90gLi₂·6H₂O、Telluric acid (H₆TeO₆) and the abundant mixed dissolution of LiCl in pure water, obtain maceration extract 400ml, by 1.0L specific surface be168m²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation, in above-mentioned maceration extract, leaves standstill 3hIn 100 DEG C dry, obtain described catalyst. The Co content of measuring this catalyst through ICP is 8.40g/L, Te content1.50g/L, Li content 2.90g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 70.24% as calculated, is selectively 85.38%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 8]

The preparation of hydroformylation catalyst: will contain 8.40gCo, contain 1.50gB and the Co (NO containing 2.90gNa₃)₂·6H₂O、Ammonium metaborate (NH₄HB₄O₇·3H₂And Na O)₂In the aqueous hydrochloric acid solution that the abundant mixed dissolution of O is 8wt% in concentration,Obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Through ICP and ICP-MSThe Co content of measuring this catalyst is 8.40g/L, B content 1.50g/L, Na content 2.90g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 70.33% as calculated, is selectively 85.29%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 9]

The preparation of hydroformylation catalyst: will contain 8.40gCo, contain 1.50gB and the Co containing 2.90gK₂(CO)₈, boron partiallyAcid ammonium (NH₄HB₄O₇·3H₂And K O)₂SO₄In the aqueous acetic acid that fully mixed dissolution is 10wt% in concentration,To maceration extract 400ml, be 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂CarryBody is immersed in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Survey through ICP and ICP-MSThe Co content of fixed this catalyst is 8.40g/L, B content 1.50g/L, K content 2.90g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 0.2MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 1.0MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 50 DEG C, the mol ratio of hydrogen and carbon monoxide is 1:10, after sustained response 1.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 61.16% as calculated, is selectively 82.71%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 10]

The preparation of hydroformylation catalyst: will contain 8.40gCo, contain 1.50gB and the Co containing 2.90gCs₂(CO)₈, boron partiallyAcid ammonium (NH₄HB₄O₇·3H₂O) and in the abundant mixed dissolution of the CsOAc aqueous acetic acid that is 10wt% in concentration,To maceration extract 400ml, be 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂CarryBody is immersed in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Survey through ICP and ICP-MSThe Co content of fixed this catalyst is 8.40g/L, B content 1.50g/L, Cs content 2.90g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 15MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 180 DEG C, the mol ratio of hydrogen and carbon monoxide is 10:1, after sustained response 15.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 70.68% as calculated, is selectively 84.86%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 11]

The preparation of hydroformylation catalyst: will contain 8.40gCo, contain 1.50gB, contain 1.10gV and contain 1.80gRb'sCo₂(CO)₈, ammonium metaborate (NH₄HB₄O₇·3H₂O), ammonium metavanadate (NH₄VO₃) and RbNO₃Fully mix moltenIn the aqueous acetic acid that solution is 10wt% in concentration, obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/g，Pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h dry in 100 DEG CDry, obtain described catalyst. The Co content of measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content1.50g/L, V content 1.10g/L, Rb content 1.80g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 71.29% as calculated, is selectively 86.17%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

Find out on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 2, improving the selective of 1,3-PD and receivingRate aspect, in the catalyst that the present invention uses, has synergy between VB metal V and alkali metal Rb.

[embodiment 12]

The preparation of hydroformylation catalyst: will contain 8.40gCo, contain 1.50gB, contain 1.10gV and contain 1.80gK'sCo₂(CO)₈, ammonium metaborate (NH₄HB₄O₇·3H₂O), ammonium metavanadate (NH₄VO₃) and K₂SO₄Fully mixed dissolutionIn the aqueous acetic acid that is 10wt% in concentration, obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/ g, holeAppearance is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,Obtain described catalyst. The Co content of 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.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 71.36% as calculated, is selectively 86.04%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 13]

The preparation of hydroformylation catalyst: will be containing 8.40gCo, containing 1.50gB, containing 1.10gV, containing 1.25gRb with containing 0.55gKCo₂(CO)₈, ammonium metaborate (NH₄HB₄O₇·3H₂O), ammonium metavanadate (NH₄VO₃)、RbNO₃And K₂SO₄In the aqueous acetic acid that fully mixed dissolution is 10wt% in concentration, obtain maceration extract 400ml, by 1.0L specific surface be168m²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation, in above-mentioned maceration extract, leaves standstill 3hIn 100 DEG C dry, obtain described catalyst. The Co content of 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.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 71.95% as calculated, is selectively 87.21%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

Find out on year-on-year basis by embodiment 13 and embodiment 11 and embodiment 12, improve the selective of 1,3-PD andYield aspect, in the catalyst that the present invention uses, has synergy between Rb and K in alkali metal. Illustrated Co,Between B, V, Rb and five kinds of active components of K, there is well synergy.

[embodiment 14]

The preparation of hydroformylation catalyst: will be containing 8.40gCo, containing 1.50gB, containing 1.10gTa, containing 1.25gRb and containingThe Co of 0.55gK₂(CO)₈, ammonium metaborate (NH₄HB₄O₇·3H₂O)、TaCl₅、RbNO₃And K₂SO₄Fully mixBeing dissolved in the aqueous acetic acid that concentration is 10wt%, obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/g，Pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h dry in 100 DEG CDry, obtain described catalyst. The Co content of measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content1.50g/L, Ta content 1.10g/L, Rb content 1.25g/L, K content 0.55g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 72.09% as calculated, is selectively 87.05%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 15]

The preparation of hydroformylation catalyst: will be containing 8.40gCo, containing 1.50gB, containing 0.40gV, containing 0.70gTa, containing 1.25gRbWith the Co containing 0.55gK₂(CO)₈, ammonium metaborate (NH₄HB₄O₇·3H₂O), ammonium metavanadate (NH₄VO₃)、TaCl₅、 RbNO₃And K₂SO₄In the aqueous acetic acid that fully mixed dissolution is 10wt% in concentration, obtain maceration extract 400ml, will1.0L specific surface is 168m²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation is at above-mentioned dippingIn liquid, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Measure the Co of this catalyst through ICP and ICP-MSContent is 8.40g/L, B content 1.50g/L, and V content 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L,K content 0.55g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 72.91% as calculated, is selectively 88.14%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

Find out on year-on-year basis by embodiment 15 and embodiment 13 and embodiment 14, improve the selective of 1,3-PD andYield aspect, the present invention use catalyst in, between VB metal V, Nb, there is synergy, illustrated Co, B,Between V, Nb, Rb and six kinds of active components of K, there is well synergy.

[embodiment 16]

The preparation of hydroformylation catalyst: will be containing 8.40gCo, containing 1.50gTe, containing 0.40gV, containing 0.70gTa, containing 1.25gRbWith the Co containing 0.55gK₂(CO)₈, ammonium tellurate ((NH₄)₂TeO₄), ammonium metavanadate (NH₄VO₃)、TaCl₅、RbNO₃And K₂SO₄In the aqueous acetic acid that fully mixed dissolution is 10wt% in concentration, obtain maceration extract 400ml, by 1.0L ratioSurface is 168m²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation in above-mentioned maceration extract,Leave standstill 3h in 100 DEG C dry, obtain described catalyst. The Co content of 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.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 73.10% as calculated, is selectively 88.02%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 17]

The preparation of hydroformylation catalyst: will containing 8.40gCo, containing 0.60gB, containing 0.90gTe, containing 0.40gV, containing 0.70gTa,Contain 1.25gRb and the Co containing 0.55gK₂(CO)₈, ammonium metaborate (NH₄HB₄O₇·3H₂O), ammonium tellurate ((NH₄)₂TeO₄)、Ammonium metavanadate (NH₄VO₃)、TaCl₅、RbNO₃And K₂SO₄The acetic acid water that fully mixed dissolution is 10wt% in concentrationIn solution, obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/ g, pore volume is 0.94, diameter is 5.6mmSpherical SiO₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Through ICPThe Co content of measuring this catalyst with ICP-MS is 8.40g/L, B content 0.60g/L, Te content 0.90g/L, VContent 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K content 0.55g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 74.34% as calculated, is selectively 88.94%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

Find out on year-on-year basis by embodiment 17 and embodiment 15 and embodiment 16, improve the selective of 1,3-PD andYield aspect, the present invention use catalyst in, between metalloid B, Te, there is synergy, illustrated Co, B,Between Te, V, Nb, Rb and seven kinds of active components of K, there is well synergy.

[embodiment 18]

The preparation of hydroformylation catalyst: will containing 8.40gNi, containing 0.60gB, containing 0.90gTe, containing 0.40gV, containing 0.70gTa,Contain 1.25gRb and the Ni (NO containing 0.55gK₃)₂·6H₂O, ammonium metaborate (NH₄HB₄O₇·3H₂O), ammonium tellurate((NH₄)₂TeO₄), ammonium metavanadate (NH₄VO₃)、TaCl₅、RbNO₃And K₂SO₄Fully mixed dissolution in concentration isIn the aqueous sulfuric acid of 8wt%, obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/ g, pore volume is 0.94,Diameter is the spherical SiO of 5.6mm₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, described in obtainingCatalyst. The Ni content of measuring this catalyst through ICP and ICP-MS is 8.40g/L, B content 0.60g/L, and Te containsAmount 0.90g/L, V content 0.40g/L, Ta content 0.70g/L, Rb content 1.25g/L, K content 0.55g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 74.21% as calculated, is selectively 89.07%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

[embodiment 19]

The preparation of hydroformylation catalyst: will containing 6.30gCo, containing 2.10gNi, containing 0.60gB, containing 0.90gTe, containing 0.40gV,Contain 0.70gTa, contain 1.25gRb and the Co containing 0.55gK₂(CO)₈、Ni(NO₃)₂·6H₂O, ammonium metaborate (NH₄HB₄O₇·3H₂O), ammonium tellurate ((NH₄)₂TeO₄), ammonium metavanadate (NH₄VO₃)、TaCl₅、RbNO₃And K₂SO₄Fully mixedClosing and be dissolved in the aqueous acetic acid that concentration is 10wt%, obtain maceration extract 400ml, is 168m by 1.0L specific surface²/g，Pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h dry in 100 DEG CDry, obtain described catalyst. The Co content of measuring this catalyst through ICP and ICP-MS is 6.30g/L, Ni content2.10g/L, B content 0.60g/L, Te content 0.90g/L, V content 0.40g/L, Ta content 0.70g/L, Rb content1.25g/L, K content 0.55g/L.

Synthesizing of 1,3-PD:

Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 12.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 120 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.

Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.

Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.

Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.

The yield of 1,3-PD is 75.05% as calculated, is selectively 90.29%, for convenience of explanation and relatively, and willThe yield of the preparation condition of carrier physical property, catalyst, reaction condition, material feeding amount, 1,3-PD and selectively dividingDo not list in table 1 and table 2.

Find out on year-on-year basis by embodiment 19 and embodiment 17 and embodiment 18, improve the selective of 1,3-PD andYield aspect, the present invention use catalyst in, between Ferrious material Ni, Co, there is synergy, illustrated Co,Between Ni, B, Te, V, Nb, Rb and eight kinds of active components of K, there is well synergy.

Table 1

Table 2 (continued)

Table 2 (Continued)

Claims (10)

1. vinyl acetate is prepared the method for 1.3-propane diols, comprises the following steps: (1) is with vinyl acetate, carbon monoxide and hydrogenGas is raw material, carries out hydroformylation reaction and obtain 3-acetoxyl group third under hydroformylation catalyst and promoter existence(2), under hydrogenation catalyst exists, hydrogen is reacted with 3-acetoxyl group propionic aldehyde and obtain 3-acetoxyl group propyl alcohol;(3) hydrolysis of 3-acetoxyl group propyl alcohol obtains 1.3-propane diols; Wherein, described hydroformylation catalyst adopts SiO₂、Al₂O₃Or its mixture is carrier, active component comprise chosen from Fe series elements at least one, be selected from metalloid unitAt least one in element and be selected from VB and alkali metal at least one metallic element.

2. method according to claim 1, is characterized in that at least one in described iron series element chosen from Fe, cobalt and nickelKind.

3. method according to claim 1, is characterized in that described metalloid element is selected from boron, arsenic and tellurium at leastA kind of.

4. method according to claim 1, is characterized in that described VB metal is selected from least one in vanadium, niobium and tantalumKind.

5. method according to claim 1, is characterized in that described alkali metal is selected from lithium, sodium, potassium, rubidium and caesiumAt least one.

6. method according to claim 1, is characterized in that the content of iron series element in hydroformylation catalyst is:3.00～15.00g/L, the content of metalloid element is: 0.10～3.00g/L.

7. method according to claim 1, is characterized in that being selected from described in hydroformylation catalyst VB and alkali metalAt least one content of middle metal is 0.10～5.00g/L.

8. method according to claim 1, is characterized in that the described promoter of step (1) is selected from pyridine and triphenyl phosphorusIn at least one.

9. method according to claim 1, is characterized in that the temperature of step (1) hydroformylation reaction is 50～180 DEG C.

10. method according to claim 1, is characterized in that the production method of described hydroformylation catalyst, comprise asLower step:

1. press the composition of catalyst by gold in the compound of the compound of iron series element, metalloid element, VB and alkali metalThe solution that belongs to the compound of element mixes with carrier;

2. dry.