CN105585437A

CN105585437A - Method for producing 1,3-propylene glycol through hydroformylation of vinyl acetate

Info

Publication number: CN105585437A
Application number: CN201410573641.6A
Authority: CN
Inventors: 查晓钟; 杨运信
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2014-10-24
Filing date: 2014-10-24
Publication date: 2016-05-18
Anticipated expiration: 2034-10-24
Also published as: CN105585437B

Abstract

The invention relates to a method for producing 1,3-propylene glycol through hydroformylation of vinyl acetate to mainly solve the problems of relatively low catalyst activity and selectivity of 1,3-propylene glycol in the prior art. By adoption of the technical scheme that the preparation method of 1,3-propylene glycol comprises the following steps: carrying out hydroformylation on vinyl acetate to obtain 3-acetoxypropanal, carrying out hydrogenation on 3-acetoxypropanal to obtain 3-acetoxypropanol, and hydrolyzing 3-acetoxypropanol to obtain 1,3-propylene glycol, wherein a hydroformylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and the active components comprise at least one of platinum group metal elements, at least one of alkali metal elements, and at least one metal element selected from VIIB and VA metals, the technical problems are well solved, and the method can be used for industrial production of 1,3-propylene glycol.

Description

Vinyl acetate hydroformylation is produced the method for 1,3-PD

Technical field

The present invention relates to vinyl acetate hydroformylation and produce 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 newThe synthetic method of 1,3-PD, 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 hydroformylation is produced 1,3-The method of propane diols, comprises the following steps: (1) is taking vinyl acetate, carbon monoxide and hydrogen as raw material, at hydrogen formylChange catalyst and promoter are carried out hydroformylation reaction and are obtained 3-acetoxyl group propionic aldehyde under existing; (2) at hydrogenation catalystUnder existence, hydrogen is reacted with 3-acetoxyl group propionic aldehyde and obtain 3-acetoxyl group propyl alcohol; (3) 3-acetoxyl group propyl alcohol waterSeparate and obtain 1,3-PD; Wherein, described hydroformylation catalyst adopts SiO₂、Al₂O₃Or its mixture is carrier,Active component comprise be selected from platinum bunch metallic element at least one, be selected from least one in alkali metal and be selected fromAt least one metallic element in VIIB and VA. Preferred described active component comprises platinum bunch metallic element, alkali metal simultaneouslyElement, be selected from least one metallic element in VIIB and be selected from least one metallic element in VA metal. NowBetween metallic element in metallic element and the VA of VIIB, improving 1,3-PD selectively and aspect yield, having collaborativeEffect.

In technique scheme, preferably at least one in platinum, palladium, osmium, iridium, ruthenium and rhodium of described platinum bunch metallic element.

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

In technique scheme, preferably at least one in manganese and rhenium of described VIIB metal.

In technique scheme, preferably at least one in antimony and bismuth of described VA metal.

In technique scheme, as most preferred technical scheme, described active component comprise simultaneously platinum bunch metallic element,Alkali metal, VIIB metallic element and VA metallic element; For example described active component by rhodium, caesium, rhenium and bismuth (orAntimony) composition, or formed by rhodium, caesium, rhenium (or manganese), bismuth and antimony, or by rhodium, caesium (or potassium), rhenium, manganese,Bismuth and antimony composition, or formed by rhodium (or ruthenium), caesium, potassium, rhenium, manganese, bismuth and antimony. The most preferred described active groupDivide and formed by rhodium, ruthenium, caesium, potassium, rhenium, manganese, bismuth and antimony.

In technique scheme, in described hydroformylation catalyst, the content of platinum bunch metallic element is preferably3.00～15.00g/L, more preferably 5.00～10.00g/L; In described hydroformylation catalyst, the content of alkali metal is preferredBe 0.10～3.00g/L, more preferably 0.50～3.00g/L; In described hydroformylation catalyst, be selected from gold in VIIB and VAAt least one content belonging to is preferably 0.10～5.00g/L, more preferably 1.00～5.00g/L. Described hydroformylation catalyst instituteWith carrier specific surface be preferably 50～300m²/ g, more preferably 150～200m²/ g, pore volume is preferably 0.80～1.20, moreBe 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 the compound of the compound of platinum bunch metallic element, alkali metal, VIIB and VAThe solution of the compound of middle metallic element mixes with carrier;

2. dry.

In technique scheme, step 1. described platinum bunch metallic element compound preferably from radium chloride, acetic acid rhodium two parts,Triphenylphosphine chlorine rhodium, rhodium nitrate, palladium bichloride, dichloro four ammonia palladiums, palladium, ammonium chloropalladite, ruthenic chloride, mistake ruthenic acidAt least one in four interior amine, platinous chloride, ammonium chloroplatinite, chloroplatinic acid, osmium trichloride, iridous chloride and chloro-iridic acid;Step 1. described alkali metal compound preferably from alkali metal oxide, alkali metal chloride, alkali nitrates, alkali metalAt least one in sulfate and alkali metal acetate; The step 1. compound of described VIIB metallic element is selected from acetic acidAt least one in manganese, manganese chloride, manganese sulfate, methyl rhenium trioxide and ammonium perrhenate; Step is described VA metal unit 1.Preferably at least one in antimony chloride, antimony sulfate, bismuth chloride, bismuth and ammonium citrate, bismuth nitrate and bismuth sulfate of the compound of elementKind. Step 2. described baking temperature is 80～120 DEG C, more 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 platinum bunch metal unitElement, alkali metal and be selected from VIIB and VA at least one metallic element, be conducive to improve hydroformylation catalystActivity and stability, thereby improved the yield of 1,3-PD and selective.

Experimental result shows, while adopting catalyst of the present invention, 1,3-PD yield 74.43%, selectively reaches 88.56%,Obtained good technique effect, especially in hydroformylation catalyst, active component comprises platinum bunch metallic element, alkali simultaneouslyMetallic element, when being selected from least one metallic element in VIIB and being selected from least one metallic element in VA, obtainMore outstanding technique effect, can be used in the industrial production of 1,3-PD. Below by embodiment, the present invention is doneFurther set forth.

Detailed description of the invention

[embodiment 1]

The preparation of hydroformylation catalyst: will contain 6.20gRh, contain 2.00gCs and acetic acid rhodium two parts containing 2.80gRe(Rh₂(OAc)₄), CsCl and methyl rhenium trioxide (be called for short MTO, molecular formula CH₃ReO₃) fully mixed dissolution inIn pure water, 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 Rh content of measuring this catalyst is 6.20g/L, Cs content 2.00g/L, Re content 2.80g/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 5.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 96 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 5.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure 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 74.43% as calculated, is selectively 88.56%, 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 6.20gRh, contain 2.00gCs and acetic acid rhodium two parts containing 2.80gBi(Rh₂(OAc)₄), CsCl and bismuth subsalicylate (C₇H₅BiO₄) fully mixed dissolution in pure water, obtain maceration extract400ml is 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnationIn above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Measure the Rh of this catalyst through ICPContent is 6.20g/L, Cs content 2.00g/L, Bi content 2.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 74.52% as calculated, is selectively 88.39%, 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.

[comparative example 1]

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

The preparation of hydroformylation catalyst: will contain 6.20gRh and the acetic acid rhodium two part (Rh containing 2.00gCs₂(OAc)₄)In pure water, obtaining maceration extract 400ml with the abundant mixed dissolution of CsCl, is 168m by 1.0L specific surface²/ g, pore volumeBe 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 Rh content of measuring this catalyst through ICP is 6.20g/L, Cs content 2.00g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 63.27% as calculated, is selectively 79.83%, 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 Rh, Cs and ReActive component, simultaneously containing the catalyst performance of Rh, Cs and Bi active component than only containing Rh and the catalysis of Cs active componentThe performance of agent is more excellent, and the selective and yield of 1,3-PD all wants high.

[embodiment 3]

The preparation of hydroformylation catalyst: will contain 5.00gRh, contain 0.50gLi and the RhCl containing 1.00gRe₃·6H₂O、LiCl and ammonium perrhenate (H₄NO₄Re) fully mixed dissolution, in pure water, obtains maceration extract 400ml, by 1.0L ratioSurface is 200m²/ 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. The Rh content of measuring this catalyst through ICP is 5.00g/L, LiContent 0.50g/L, Re content 1.00g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 67.84% as calculated, is selectively 86.05%, 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 4]

The preparation of hydroformylation catalyst: will contain 10.00gRh, contain 3.00gNa and the Rh containing 5.00gMn₂(SO₄)₃·15H₂O、Na₂O and MnSO₄·H₂In the aqueous hydrochloric acid solution that the abundant mixed dissolution of O is 8wt% in concentration, floodedLiquid 400ml is 150m by 1.0L specific surface²/ g, pore volume is 0.90, the spherical SiO that diameter is 5.6mm₂Carrier soaksStain in above-mentioned maceration extract, leave standstill 3h in 120 DEG C dry, obtain described catalyst. Measure this catalyst through ICPRh content is 10.00g/L, Na content 3.00g/L, Mn content 5.00g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 74.95% as calculated, is selectively 88.06%, 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 6.20gRh, contain 2.00gK and the Rh (NO containing 2.80gMn₃)₃、K₂SO₄And MnCl₂·4H₂The abundant mixed dissolution of O, in pure water, obtains 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 Rh content of measuring this catalyst through ICP is 6.20g/L, K content 2.00g/L,Mn content 2.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 74.27% as calculated, is selectively 88.53%, 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 6.20gPd, contain 2.00gRb and the dichloro four ammonia palladium (Pd containing 2.80gMn(NH₃)₄Cl₂·H₂O)、RbNO₃And Mn (OAc)₂·4H₂The abundant mixed dissolution of O, in pure water, obtains 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. The Pd content of measuring this catalyst through ICP is6.20g/L, Rb content 2.00g/L, Mn content 2.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 74.41% as calculated, is selectively 88.43%, 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 6.20gPd, contain 2.00gCs and the Pd (OAc) containing 2.80gBi₂、CsClAnd bismuth and ammonium citrate (Bi (NH₃)₂C₆H₇O₇·H₂O), in the acetic acid that fully mixed dissolution is 10wt% in concentration, soakedStain liquid 400ml is 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂CarrierBe immersed in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Measure this catalyst through ICPPd content be 6.20g/L, Cs content 2.00g/L, Bi content 2.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 74.30% as calculated, is selectively 88.42%, 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 6.20gRu, contain 2.00gCs and the RuCl containing 2.80gBi₃·XH₂O、CsCl and BiCl₃In the hydrochloric acid that fully mixed dissolution is 8wt% in concentration, obtain 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 Ru content of measuring this catalyst through ICP is 6.20g/L, CsContent 2.00g/L, Bi content 2.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 74.36% as calculated, is selectively 88.35%, 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 6.20gPt, contain 2.00gCs and the ammonium chloroplatinite containing 2.80gBi((NH₄)₂PtCl₄), CsCl and Bi₂(SO₄)₃In the hydrochloric acid that fully mixed dissolution is 8wt% in concentration, obtain maceration extract400ml is 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnationIn above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Measure the Pt of this catalyst through ICPContent is 6.20g/L, Cs content 2.00g/L, Bi content 2.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 74.38% as calculated, is selectively 88.31%, 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.

[embodiment 10]

The preparation of hydroformylation catalyst: will contain 6.20gOs, contain 2.00gCs and the OsCl containing 2.80gSb₃·3H₂O、CsCl and Sb₂(SO₄)₃In the hydrochloric acid that fully mixed dissolution is 8wt% 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 Os content of measuring this catalyst through ICP is 6.20g/L,Cs content 2.00g/L, Sb content 2.80g/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 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.

The yield of 1,3-PD is 64.74% as calculated, is selectively 84.29%, 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 11]

The preparation of hydroformylation catalyst: will contain 6.20gIr, contain 2.00gCs and the IrCl containing 2.80gSb₃·XH₂O、CsClAnd Cl₃In the aqueous hydrochloric acid solution that the abundant mixed dissolution of Sb is 8wt% 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 Ir content of measuring this catalyst through ICP is 6.20g/L, CsContent 2.00g/L, Sb content 2.80g/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 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.

The yield of 1,3-PD is 74.82% as calculated, is selectively 87.88%, 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 12]

The preparation of hydroformylation catalyst: will contain 6.20gRh, contain 2.00gCs, contain 1.30gRe and the vinegar containing 1.50gBiAcid rhodium two part (Rh₂(OAc)₄), CsCl, methyl rhenium trioxide (be called for short MTO, molecular formula CH₃ReO₃) and timeBismuth salicylate (C₇H₅BiO₄) fully mixed dissolution 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 Rh content of measuring this catalyst through ICP is 6.20g/L, Cs content2.00g/L, Re content 1.30g/L, Bi content 1.50g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 75.53% as calculated, is selectively 89.77%, 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 VIIB metal Re and VA metal Bi.

[embodiment 13]

The preparation of hydroformylation catalyst: will contain 6.20gRh, contain 2.00gCs, contain 1.30gRe and the vinegar containing 1.50gSbAcid rhodium two part (Rh₂(OAc)₄), CsCl, methyl rhenium trioxide (be called for short MTO, molecular formula CH₃ReO₃) and Cl₃SbIn the aqueous hydrochloric acid solution that fully mixed dissolution is 8wt% in concentration, obtaining maceration extract 400ml, is 168 by 1.0L specific surfacem²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in100 DEG C dry, obtains described catalyst. The Rh content of measuring this catalyst through ICP is 6.20g/L, Cs content 2.00G/L, Re content 1.30g/L, Sb content 1.50g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 75.62% as calculated, is selectively 89.59%, 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 14]

The preparation of hydroformylation catalyst: will be containing 6.20gRh, containing 2.00gCs, containing 1.30gRe, containing 0.95gBi and containingThe acetic acid rhodium two part (Rh of 0.55gSb₂(OAc)₄), CsCl, methyl rhenium trioxide (be called for short MTO, molecular formulaCH₃ReO₃), bismuth subsalicylate (C₇H₅BiO₄) and Cl₃The hydrochloric acid that the abundant mixed dissolution of Sb is 8wt% in concentration is water-solubleIn liquid, 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 Rh content of measuring this catalyst is 6.20g/L, Cs content 2.00g/L, and Re content 1.30g/L, Bi content 0.95g/L,Sb content 0.55g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 76.68% as calculated, is selectively 90.89%, 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 14 and embodiment 12 and embodiment 13, improve the selective of 1,3-PD andYield aspect, in the catalyst that the present invention uses, has synergy between Bi and Sb in VA metal. Illustrated Rh,Between Cs, Re, Bi and five kinds of active components of Sb, there is well synergy.

[embodiment 15]

The preparation of hydroformylation catalyst: will be containing 6.20gRh, containing 2.00gCs, containing 1.30gMn, containing 0.95gBi and containingThe acetic acid rhodium two part (Rh of 0.55gSb₂(OAc)₄)、CsCl、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄)And Cl₃In the aqueous hydrochloric acid solution that the abundant mixed dissolution of Sb is 8wt% 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 Rh content of measuring this catalyst through ICP is 6.20g/L,Cs content 2.00g/L, Mn content 1.30g/L, Bi content 0.95g/L, Sb content 0.55g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 76.71% as calculated, is selectively 90.74%, 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 16]

The preparation of hydroformylation catalyst: will containing 6.20gRh, containing 2.00gCs, containing 0.80gRe, containing 0.50gMn, contain0.95gBi and containing the acetic acid rhodium two part (Rh of 0.55gSb₂(OAc)₄), CsCl, methyl rhenium trioxide (be called for short MTO,Molecular formula CH₃ReO₃)、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄) and Cl₃The abundant mixed dissolution of SbIn the aqueous hydrochloric acid solution that is 8wt% in concentration, obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/ g, pore volumeBe 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 Rh content of measuring this catalyst through ICP is 6.20g/L, Cs content 2.00g/L, and Re containsAmount 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L, Sb content 0.55g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 77.76% as calculated, is selectively 91.63%, 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 16 and embodiment 14 and embodiment 15, improve the selective of 1,3-PD andYield aspect, the present invention use catalyst in, between VIIB metal Re, Mn, there is synergy, illustrated Rh,Between Cs, Re, Mn, Bi and six kinds of active components of Sb, there is well synergy.

[embodiment 17]

The preparation of hydroformylation catalyst: will containing 6.20gRh, containing 2.00gK, containing 0.80gRe, containing 0.50gMn, contain0.95gBi and containing the acetic acid rhodium two part (Rh of 0.55gSb₂(OAc)₄)、K₂SO₄, methyl rhenium trioxide (be called for short MTO,Molecular formula CH₃ReO₃)、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄) and Cl₃The abundant mixed dissolution of SbIn the aqueous hydrochloric acid solution that is 8wt% in concentration, obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/ g, pore volumeBe 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 Rh content of measuring this catalyst through ICP is 6.20g/L, K content 2.00g/L, and Re containsAmount 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L, Sb content 0.55g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 77.81% as calculated, is selectively 91.50%, 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 18]

The preparation of hydroformylation catalyst: will containing 6.20gRh, containing 1.55gCs, containing 0.45gK, containing 0.80gRe, contain0.50gMn, containing 0.95gBi with containing the acetic acid rhodium two part (Rh of 0.55gSb₂(OAc)₄)、CsCl、K₂SO₄, methylRhenium trioxide (is called for short MTO, molecular formula CH₃ReO₃)、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄)And Cl₃In the aqueous hydrochloric acid solution that the abundant mixed dissolution of Sb is 8wt% 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 Rh content of measuring this catalyst through ICP is 6.20g/L,Cs content 1.55g/L, K content 0.45g/L, Re content 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L,Sb content 0.55g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 78.63% as calculated, is selectively 92.70%, 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 18 and embodiment 16 and embodiment 17, improve the selective of 1,3-PD andYield aspect, the present invention use catalyst in, between alkali metal Cs, K, there is synergy, illustrated Rh, Cs,Between K, Re, Mn, Bi and seven kinds of active components of Sb, there is well synergy.

[embodiment 19]

The preparation of hydroformylation catalyst: will containing 6.20gRu, containing 1.55gCs, containing 0.45gK, containing 0.80gRe, contain0.50gMn, containing 0.95gBi with containing the RuCl of 0.55gSb₃·XH₂O、CsCl、K₂SO₄, methyl rhenium trioxide (letterClaim MTO, molecular formula CH₃ReO₃)、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄) and Cl₃Sb is abundantIn the aqueous hydrochloric acid solution that mixed dissolution is 8wt% in concentration, obtaining maceration extract 400ml, is 168 by 1.0L specific surfacem²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in100 DEG C dry, obtains described catalyst. The Ru content of measuring this catalyst through ICP is 6.20g/L, Cs content 1.55g/L,K content 0.45g/L, Re content 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L, Sb content 0.55g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 78.69% as calculated, is selectively 92.57%, 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 20]

The preparation of hydroformylation catalyst: will containing 5.00gRh, containing 1.20gRu, containing 1.55gCs, containing 0.45gK, contain0.80gRe, containing 0.50gMn, containing 0.95gBi with containing the acetic acid rhodium two part (Rh of 0.55gSb₂(OAc)₄)、RuCl₃·XH₂O、CsCl、K₂SO₄, methyl rhenium trioxide (be called for short MTO, molecular formula CH₃ReO₃)、Mn(OAc)₂·4H₂O、Bismuth subsalicylate (C₇H₅BiO₄) and Cl₃In the aqueous hydrochloric acid solution that the abundant mixed dissolution of Sb is 8wt% in concentration, obtainMaceration extract 400ml is 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. Measure this catalysis through ICPThe Rh content of agent is 5.00g/L, Ru content 1.20g/L, Cs content 1.55g/L, K content 0.45g/L, Re content0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L, Sb content 0.55g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 79.85% as calculated, is selectively 93.54%, 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 20 and embodiment 18 and embodiment 19, improve the selective of 1,3-PD andYield aspect, the present invention use catalyst in, between platinum bunch metal Rh, Ru, there is synergy, illustrated Rh,Between Ru, Cs, K, Re, Mn, Bi and eight kinds of active components of Sb, there is well synergy.

Table 1

Table 2 (continued)

Table 2 (Continued)

Claims

1. vinyl acetate hydroformylation is produced the method for 1.3-propane diols, comprises the following steps: (1) is with vinyl acetate,Carbonoxide and hydrogen are raw material, carry out hydroformylation reaction and obtain 3-under hydroformylation catalyst and promoter existenceAcetoxyl 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 is urgedAgent adopts SiO₂、Al₂O₃Or its mixture is carrier, active component comprises and is selected from platinum bunch metallic element at leastA kind of, be selected from least one in alkali metal and be selected from VIIB and VA at least one metallic element.

2. method according to claim 1, it is characterized in that a described platinum bunch metal be selected from platinum, palladium, osmium, iridium, ruthenium andAt least one in rhodium.

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

4. method according to claim 1, is characterized in that described VIIB metal is selected from least one in manganese and rhenium.

5. method according to claim 1, is characterized in that described VA metal is selected from least one in antimony and bismuth.

6. method according to claim 1, is characterized in that the content of platinum bunch metallic element in hydroformylation catalyst is:3.00～15.00g/L, the content of alkali metal is: 0.10～3.00g/L.

7. method according to claim 1, is characterized in that being selected from VIIB and VA described in hydroformylation catalystAt least one content of 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, the production method of the hydroformylation catalyst described in it is characterized in that, comprisesFollowing steps:

1. press the composition of catalyst by the compound of the compound of platinum bunch metallic element, alkali metal, VIIB and VA goldIn genus, the solution of the compound of metallic element mixes with carrier;

2. dry.