CN105585437B

CN105585437B - The method that vinyl acetate hydroformylation produces 1,3 propane diols

Info

Publication number: CN105585437B
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: 2017-12-15
Anticipated expiration: 2034-10-24
Also published as: CN105585437A

Abstract

The present invention relates to the method that vinyl acetate hydroformylation produces 1,3 propane diols, mainly solve the problem of 1,3 propane diols catalyst activity and selectivities are relatively low in the prior art, by using the preparation method of 1,3 propane diols, comprise the following steps：Vinyl acetate hydroformylation obtains 3 acetoxyl group propionic aldehyde；3 acetoxyl group hydrogenation of propionaldehyde obtain 3 acetoxyl group propyl alcohol；The hydrolysis of 3 acetoxyl group propyl alcohol obtains 1,3 propane diols；Hydroformylation catalyst uses SiO₂、Al₂O₃Or its mixture is carrier, active component includes at least one, the technical scheme selected from least one of alkali metal and selected from least one of VIIB and VA metals metallic element selected from platinum cluster metallic element, preferably resolve the technical problem, in industrial production available for 1,3 propane diols.

Description

The method that vinyl acetate hydroformylation produces 1,3- propane diols

Technical field

The present invention relates to the method for vinyl acetate hydroformylation production 1,3- propane diols.

Background technology

1,3-PD (1.3-PDO) is a kind of important industrial chemicals, be mainly used in plasticizer, detergent, preservative, The synthesis of emulsifying agent, it is also used for the industries such as food, cosmetics and pharmacy.Because it is a kind of important polyester fiber monomer, its Most important purposes is as monomer and the polytrimethylene terephthalate (PTT) of terephthalic acid (TPA) synthesizing new polyester material one.

The preparation method of 1,3- propane diols has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehyde Stiasny method, acrylic acid ester process, bioanalysis, vinyl acetate hydroformylation etc..At present, 1.3-PDO industrialized preparing process For chemical synthesis, international market is mainly by German Degussa companies, shell Shell companies of the U.S. and du pont company three Family's monopolization.Degussa companies are using acrolein hydration hydrogenation method (AC methods), Shell Co. Ltd using oxirane carbonyl The thorugh biologic engineering method (MF methods) that change method (EO methods), E.I.Du Pont Company innovate using oneself.Its ethylene oxide two-step process It is current prevailing technology with acrolein hydration method technique.

Taught in the patents such as patent US4072709 (Production of Lactic Acid) and utilize vinyl acetate It is catalyst by using homogeneous rhodium compound for raw material, by hydroformylation reaction, obtains 2 (or 3)-acetoxyl group propionic aldehyde. Whether separation or not, and then 3- acetoxyl groups propionic aldehyde obtains 1.3-PDO by hydrogenation and hydrolytic process.But prepared by the above method The problem of 1.3-PDO yields are low and selectivity is not high during 1.3-PDO be present.

The content of the invention

The problem of technical problems to be solved by the invention are the yield and low selectivity of 1,3-PD, there is provided Yi Zhongxin 1,3-PD synthetic method, this method have 1,3-PD high income and selectivity it is high the characteristics of.

In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Vinyl acetate hydroformylation production 1, The method of ammediol, comprises the following steps：(1) using vinyl acetate, carbon monoxide and hydrogen as raw material, it is catalyzed in hydroformylation Hydroformylation reaction is carried out in the presence of agent and accelerator and obtains 3- acetoxyl group propionic aldehyde；(2) in the presence of a hydrogenation catalyst, hydrogen is made Gas obtains 3- acetoxyl group propyl alcohol with the reaction of 3- acetoxyl groups propionic aldehyde；(3) 3- acetoxyl groups propyl alcohol hydrolysis obtains 1,3- propane diols； Wherein, the hydroformylation catalyst uses SiO₂、Al₂O₃Or its mixture is carrier, active component is included selected from platinum cluster gold Belong at least one of element, selected from least one of alkali metal and selected from least one of VIIB and VA metal Element.It is preferred that the active component is simultaneously including platinum cluster metallic element, alkali metal, selected from least one of VIIB metals Element and selected from least one of VA metals metallic element.Now between the metallic element in VIIB metallic element and VA There is synergy in terms of improving 1,3- propane diols selectivity and yield.

In above-mentioned technical proposal, the platinum cluster metallic element preferably is selected from least one of platinum, palladium, osmium, iridium, ruthenium and rhodium.

In above-mentioned technical proposal, the alkali metal preferably is selected from least one of lithium, sodium, potassium, rubidium and caesium..

In above-mentioned technical proposal, the VIIB metals preferably are selected from least one of manganese and rhenium.

In above-mentioned technical proposal, the VA metals preferably are selected from least one of antimony and bismuth.

In above-mentioned technical proposal, as most preferred technical scheme, the active component simultaneously including platinum cluster metallic element, Alkali metal, VIIB metallic elements and VA metallic elements；Such as the active component is made up of rhodium, caesium, rhenium and bismuth (or antimony), Either it is made up of rhodium, caesium, rhenium (or manganese), bismuth and antimony or is made up of rhodium, caesium (or potassium), rhenium, manganese, bismuth and antimony, or by rhodium (or ruthenium), caesium, potassium, rhenium, manganese, bismuth and antimony composition.The most the preferably active component is by rhodium, ruthenium, caesium, potassium, rhenium, manganese, bismuth and antimony Composition.

In above-mentioned technical proposal, in the hydroformylation catalyst content of platinum cluster metallic element be preferably 3.00~ 15.00g/L, more preferably 5.00~10.00g/L；The content of alkali metal is preferably in the hydroformylation catalyst 0.10~3.00g/L, more preferably 0.50~3.00g/L；Selected from golden in VIIB and VA in the hydroformylation catalyst At least one content of category is preferably 0.10~5.00g/L, more preferably 1.00~5.00g/L.The hydroformylation catalyst Load surface area per unit volume used is preferably 50~300m²/ g, more preferably 150~200m²/ g, pore volume are preferably 0.80~1.20, more Preferably 0.90~1.00.At least one of the preferred pyridine of the accelerator and triphenyl phosphorus.

In above-mentioned technical proposal, the concrete technology condition of the hydroformylation reaction of step (1) is not the key of the present invention, and And those skilled in the art can be according to being actually needed reasonable determination.The concrete technology condition of the hydroformylation reaction of step (1), 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；Reaction when Between be 1.0~15.0h；Carbon monoxide and hydrogen volume ratio are 0.10~10.0.

In above-mentioned technical proposal, the hydroformylation catalyst, the optional production method comprised the following steps obtains：

1. by the composition of catalyst by the compound of platinum cluster metallic element, the compound of alkali metal, VIIB and VA The solution of the compound of metallic element mixes with carrier；

2. dry.

In above-mentioned technical proposal, the compound of the step 1. platinum cluster metallic element preferably is selected from radium chloride, rhodium acetate two is matched somebody with somebody Body, triphenylphosphine chlorine rhodium, rhodium nitrate, palladium bichloride, the ammonia palladium of dichloro four, palladium, ammonium chloropalladite, ruthenic chloride, cross ruthenic acid four in At least one of amine, platinous chloride, ammonium chloroplatinite, chloroplatinic acid, osmium trichloride, iridous chloride and chloro-iridic acid；Step 1. institute State alkali metal compound and preferably be selected from alkali metal oxide, alkali metal chloride, alkali nitrates, alkali metal sulfates and alkali gold Belong at least one of acetate；The compound of step 1. VIIB metallic elements has selected from manganese acetate, manganese chloride, sulfuric acid At least one of manganese, methyl rhenium trioxide and ammonium perrhenate；The compound of step 1. VA metallic elements preferably is selected from chlorination At least one of antimony, antimony sulfate, bismuth chloride, bismuth and ammonium citrate, bismuth nitrate and bismuth sulfate.2. the drying temperature is 80 to step ~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 major catalyst is obtained, The catalyst of the present invention is can obtain by making major catalyst be contacted with the accelerator.The side that major catalyst contacts with accelerator Formula is not particularly limited, and the opportunity for contacting both is also not particularly limited.Such as it can be used for by catalyst of the present invention Contact both before chemical reaction and form the catalyst, the reactant that both can also be made to be applied in catalyst of the present invention Contact makes catalyst in-situ preparation in system.

, can be to the mixture of hydroformylation reaction after step (1) terminates in the method for present invention synthesis 1,3-PD Carry out separation acquisition target product 3- acetoxyl groups propionic aldehyde and carry out step (2) again, can also step (1) generation 3- acetoxyl groups third Do not separated after aldehyde and directly carry out step (2).The suitable hydrogenation catalyst of the known selection of those skilled in the art and determination are closed Suitable hydrogenation reaction temperature, time and material proportion.Conventional hydrogenation catalyst have transition metal metallic catalyst, Metal oxide catalyst, metal sulfide catalyst, complex catalyst etc., such as platinum, palladium, nickel, ruthenium carried catalyst, oxidation Copper-copper chromite, alumina-silica zinc-chromium oxide catalyst, nickel-molybdenum sulfide and RhCl [P (C₆H₅)₃].In the present invention It is preferred that Raney's nickel, as hydrogenation catalyst, suitable hydrogenation temperature is preferably 30~100 DEG C；Hydrogenation reaction pressure preferably 0.5~ 8.0MPa；The hydrogenation reaction time is preferably 10~200min；The mol ratio of aldehyde and hydrogen preferably 0.10~2.0；The preferred water of solvent, At least one of toluene.

After step (2) terminates, separation can be carried out to the mixture of hydrogenation reaction and obtains target product 3- acetoxyl groups third Alcohol carries out step (3) again, can not also separate directly progress step (3) after step (2) generation 3- acetoxyl group propyl alcohol.This The suitable hydrolyst of the known selection of art personnel and determination suitable hydrolysising reacting temperature, time and material proportion. Conventional hydrolyst can be inorganic acid, inorganic base, organic acid and organic base.Such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen Sodium oxide molybdena, potassium hydroxide, benzene sulfonic acid and ion exchange resin.Suitable hydrolysising reacting temperature is preferably 50~100 DEG C；Hydrolysis Reaction pressure preferably 0~2.0MPa；At least one of the preferred water of solvent, benzene, hexamethylene, toluene.

Final product of the present invention is analyzed after cooling down, depressurize, separate using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), The conversion ratio of vinyl acetate and the yield and selectivity of 1,3- propane diols are calculated by following equation：

Compared with prior art, key of the invention is that the active component of hydroformylation catalyst includes platinum cluster metal member Element, alkali metal and selected from least one of VIIB and VA metallic element, are advantageous to improve the work of hydroformylation catalyst Property and stability, so as to improve the yield of 1,3-PD and selectivity.

Test result indicates that during using catalyst of the present invention, 1,3-PD yield 74.43%, selectively reach 88.56%, achieve active component in preferable technique effect, especially hydroformylation catalyst while include platinum cluster metal member Element, alkali metal, selected from least one of VIIB metallic elements and selected from least one of VA metallic elements when, obtain More prominent technique effect, available in the industrial production of 1,3-PD.The present invention is made below by embodiment into One step illustrates.

Embodiment

【Embodiment 1】

The preparation of hydroformylation catalyst：By the part of rhodium acetate two containing 6.20gRh, containing 2.00gCs and containing 2.80gRe (Rh₂(OAc)₄), CsCl and methyl rhenium trioxide (abbreviation MTO, molecular formula CH₃ReO₃) be sufficiently mixed and be dissolved in pure water, obtain Maceration extract 400ml, than surface it is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation is upper State in maceration extract, stand 3h in 100 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.20g/ L, Cs content 2.00g/L, Re content 2.80g/L.

The synthesis of 1,3- propane diols：

Step (1)：By 2.50mol toluene, 0.02mol hydroformylations major catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetates are added in 1L titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 5.5MPa, while agitating and heating is warming up to reaction temperature, Controlling reaction temperature is 96 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, stop reaction.Will reaction Kettle is down to room temperature, and the product that reaction obtains is washed with water 3 times, and organic matter enters oil phase, and solvent, acetic acid are removed through rectification and purification Ethene and other accessory substances, obtain 3- acetoxyl group propionic aldehyde.

Step (2)：Above-mentioned 3- acetoxyl groups propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added into 100ml titaniums Reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 5.0MPa, improves stirring Speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 70 DEG C, after sustained response 100min, Stop reaction.Reactor is down to room temperature, purified removal of impurities obtains 3- acetoxyl group propyl alcohol.

Step (3)：By above-mentioned 3- acetoxyl groups propyl alcohol 18ml, 30ml toluene-water (10ml toluene and 20ml water mix and Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in 0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.

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

The yield for being computed 1,3-PD is 74.43%, and selectivity is 88.56%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 2】

The preparation of hydroformylation catalyst：By the part of rhodium acetate two containing 6.20gRh, containing 2.00gCs and containing 2.80gBi (Rh₂(OAc)₄), CsCl and bismuth subsalicylate (C₇H₅BiO₄) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, will 1.0L is 168m than surface²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation is quiet in above-mentioned maceration extract 3h is put in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Bi content 2.80g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 74.52%, and selectivity is 88.39%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Comparative example 1】

For【Embodiment 1】With【Embodiment 2】Comparative example.

The preparation of hydroformylation catalyst：By the part (Rh of rhodium acetate two containing 6.20gRh and containing 2.00gCs₂(OAc)₄) and CsCl, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 168m by 1.0L²/ g, pore volume 0.94, directly Footpath is 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through The Rh contents that ICP determines the catalyst are 6.20g/L, Cs contents 2.00g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 63.27%, and selectivity is 79.83%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Rh, Cs and Re work Property component and meanwhile performance of the catalyst performance ratio containing only Rh and Cs active constituent catalysts containing Rh, Cs and Bi active component will More excellent, the selectivity and yield of 1,3-PD will be high.

【Embodiment 3】

The preparation of hydroformylation catalyst：By the RhCl containing 5.00gRh, containing 0.50gLi and containing 1.00gRe₃·6H₂O、 LiCl and ammonium perrhenate (H₄NO₄Re) it is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, is than surface by 1.0L 200m²/ g, pore volume 1.00, a diameter of 5.6mm spherical Al₂O₃It is dry in 80 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation It is dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 5.00g/L, Li contents 0.50g/L, Re content 1.00g/L。

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 67.84%, and selectivity is 86.05%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 4】

The preparation of hydroformylation catalyst：By the Rh containing 10.00gRh, containing 3.00gNa and containing 5.00gMn₂(SO₄)₃· 15H₂O、Na₂O and MnSO₄·H₂O, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, Than surface it is 150m by 1.0L²/ g, pore volume 0.90, a diameter of 5.6mm spherical SiO₂Carrier impregnation in above-mentioned maceration extract, 3h is stood in 120 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 10.00g/L, Na contents 3.00g/L, Mn content 5.00g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 74.95%, and selectivity is 88.06%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 5】

The preparation of hydroformylation catalyst：By the Rh (NO containing 6.20gRh, containing 2.00gK and containing 2.80gMn₃)₃、K₂SO₄With MnCl₂·4H₂O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 168m by 1.0L²/ g, pore volume are 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract Agent.The Rh contents that the catalyst is determined through ICP are 6.20g/L, K contents 2.00g/L, Mn content 2.80g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 74.27%, and selectivity is 88.53%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 6】

The preparation of hydroformylation catalyst：By the ammonia palladium (Pd of dichloro four containing 6.20gPd, containing 2.00gRb and containing 2.80gMn (NH₃)₄Cl₂·H₂O)、RbNO₃With Mn (OAc)₂·4H₂O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, will 1.0L is 168m than surface²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation is quiet in above-mentioned maceration extract 3h is put in 100 DEG C of dryings, obtains the catalyst.The Pd contents that the catalyst is determined through ICP are 6.20g/L, Rb contents 2.00g/L, Mn content 2.80g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 74.41%, and selectivity is 88.43%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 7】

The preparation of hydroformylation catalyst：By the Pd (OAc) containing 6.20gPd, containing 2.00gCs and containing 2.80gBi₂、CsCl With bismuth and ammonium citrate (Bi (NH₃)₂C₆H₇O₇·H₂O) it is sufficiently mixed and is dissolved in the acetic acid that concentration is 10wt%, obtains maceration extract 400ml, than surface it is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation is in above-mentioned dipping In liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Pd contents that the catalyst is determined through ICP are 6.20g/L, and Cs contains Measure 2.00g/L, Bi contents 2.80g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 74.30%, and selectivity is 88.42%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 8】

The preparation of hydroformylation catalyst：By the RuCl containing 6.20gRu, containing 2.00gCs and containing 2.80gBi₃·XH₂O、 CsCl and BiCl₃It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L 168m²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂It is dry in 100 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation It is dry, obtain the catalyst.The Ru contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Bi content 2.80g/L。

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 74.36%, and selectivity is 88.35%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 9】

The preparation of hydroformylation catalyst：By the ammonium chloroplatinite containing 6.20gPt, containing 2.00gCs and containing 2.80gBi ((NH₄)₂PtCl₄), CsCl and Bi₂(SO₄)₃It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract 400ml, Than surface it is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Pt contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Bi content 2.80g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 74.38%, and selectivity is 88.31%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 10】

The preparation of hydroformylation catalyst：By the OsCl containing 6.20gOs, containing 2.00gCs and containing 2.80gSb₃·3H₂O、 CsCl and Sb₂(SO₄)₃It is sufficiently mixed and is dissolved in the hydrochloric acid that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into surface For 168m²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C in above-mentioned maceration extract Dry, obtain the catalyst.The Os contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Sb content 2.80g/L。

The synthesis of 1,3- propane diols：

Step (1)：By 2.50mol toluene, 0.02mol hydroformylations major catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetates are added in 1L titanium reactors, first with 0.2MPa is pressurized to after air in argon gas discharge kettle, are then passed to Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 1.0MPa, while agitating and heating is warming up to reaction temperature, Controlling reaction temperature is 50 DEG C, and the mol ratio of hydrogen and carbon monoxide is 1:After 10, sustained response 1.0h, stop reaction.Will be anti- Answer kettle to be down to room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, and solvent, vinegar are removed through rectification and purification Sour ethene and other accessory substances, obtain 3- acetoxyl group propionic aldehyde.

The yield for being computed 1,3-PD is 64.74%, and selectivity is 84.29%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 11】

The preparation of hydroformylation catalyst：By the IrCl containing 6.20gIr, containing 2.00gCs and containing 2.80gSb₃·XH₂O、 CsCl and Cl₃Sb, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table Face is 168m²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 in above-mentioned maceration extract DEG C drying, obtains the catalyst.The Ir contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Sb content 2.80g/L。

The synthesis of 1,3- propane diols：

Step (1)：By 2.50mol toluene, 0.02mol hydroformylations major catalyst, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 15MPa, while agitating and heating is warming up to reaction temperature, Controlling reaction temperature is 180 DEG C, and the mol ratio of hydrogen and carbon monoxide is 10:After 1, sustained response 15.0h, stop reaction.Will Reactor is down to room temperature, will react obtained product and is washed with water 3 times, and organic matter enters oil phase, through rectification and purification removing solvent, Vinyl acetate and other accessory substances, obtain 3- acetoxyl group propionic aldehyde.

The yield for being computed 1,3-PD is 74.82%, and selectivity is 87.88%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 12】

The preparation of hydroformylation catalyst：By the acetic acid containing 6.20gRh, containing 2.00gCs, containing 1.30gRe and containing 1.50gBi Part (the Rh of rhodium two₂(OAc)₄), CsCl, methyl rhenium trioxide (abbreviation MTO, molecular formula CH₃ReO₃) and bismuth subsalicylate (C₇H₅BiO₄) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume are 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract Agent.The Rh contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Re content 1.30g/L, Bi content 1.50g/L。

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 75.53%, and selectivity is 89.77%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

Found out on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 2, improving the selectivity and yield of 1,3-PD Aspect, in the catalyst that uses of the present invention, there is synergy between VIIB metal Re and VA metals Bi.

【Embodiment 13】

The preparation of hydroformylation catalyst：By the acetic acid containing 6.20gRh, containing 2.00gCs, containing 1.30gRe and containing 1.50gSb Part (the Rh of rhodium two₂(OAc)₄), CsCl, methyl rhenium trioxide (abbreviation MTO, molecular formula CH₃ReO₃) and Cl₃Sb is sufficiently mixed dissolving In the aqueous hydrochloric acid solution that concentration is 8wt%, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume 0.94, A diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract. The Rh contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Re content 1.30g/L, Sb content 1.50g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 75.62%, and selectivity is 89.59%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 14】

The preparation of hydroformylation catalyst：To contain 6.20gRh, containing 2.00gCs, containing 1.30gRe, containing 0.95gBi and contain 0.55gSb part (the Rh of rhodium acetate two₂(OAc)₄), CsCl, methyl rhenium trioxide (abbreviation MTO, molecular formula CH₃ReO₃), secondary water Poplar acid bismuth (C₇H₅BiO₄) and Cl₃Sb, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, than surface it is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation is in above-mentioned dipping In liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.20g/L, and Cs contains Measure 2.00g/L, Re contents 1.30g/L, Bi content 0.95g/L, Sb content 0.55g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 76.68%, and selectivity is 90.89%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improving the selectivity and receipts of 1,3-PD In terms of rate, in the catalyst that the present invention uses, there is synergy in VA metals between Bi and Sb.Illustrate Rh, Cs, Re, Bi Synergy well between five kinds of active components of Sb be present.

【Embodiment 15】

The preparation of hydroformylation catalyst：To contain 6.20gRh, containing 2.00gCs, containing 1.30gMn, containing 0.95gBi and contain 0.55gSb part (the Rh of rhodium acetate two₂(OAc)₄)、CsCl、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄) and Cl₃Sb It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtain maceration extract 400ml, than surface is 168m by 1.0L²/ G, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtained in above-mentioned maceration extract To the catalyst.The Rh contents that the catalyst is determined through ICP are 6.20g/L, Cs contents 2.00g/L, Mn content 1.30g/L, Bi contents 0.95g/L, Sb content 0.55g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 76.71%, and selectivity is 90.74%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 16】

The preparation of hydroformylation catalyst：To contain 6.20gRh, containing 2.00gCs, containing 0.80gRe, containing 0.50gMn, contain The 0.95gBi and part (Rh of rhodium acetate two containing 0.55gSb₂(OAc)₄), CsCl, methyl rhenium trioxide (abbreviation MTO, molecular formula CH₃ReO₃)、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄) and Cl₃Sb is sufficiently mixed the salt for being dissolved in that concentration is 8wt% In aqueous acid, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm's is spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalyst is determined through ICP Rh contents be 6.20g/L, Cs contents 2.00g/L, Re content 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L, Sb Content 0.55g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 77.76%, and selectivity is 91.63%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, improving the selectivity and receipts of 1,3-PD In terms of rate, in the catalyst that the present invention uses, there is synergy between VIIB metals Re, Mn, illustrate Rh, Cs, Re, Mn, Synergy well between six kinds of active components of Bi and Sb be present.

【Embodiment 17】

The preparation of hydroformylation catalyst：To contain 6.20gRh, containing 2.00gK, containing 0.80gRe, containing 0.50gMn, contain The 0.95gBi and part (Rh of rhodium acetate two containing 0.55gSb₂(OAc)₄)、K₂SO₄, methyl rhenium trioxide (abbreviation MTO, molecular formula CH₃ReO₃)、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄) and Cl₃Sb is sufficiently mixed the salt for being dissolved in that concentration is 8wt% In aqueous acid, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm's is spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalyst is determined through ICP Rh contents be 6.20g/L, K contents 2.00g/L, Re content 0.80g/L, Mn content 0.50g/L, Bi content 0.95g/L, Sb contain Measure 0.55g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 77.81%, and selectivity is 91.50%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 18】

The preparation of hydroformylation catalyst：To contain 6.20gRh, containing 1.55gCs, containing 0.45gK, containing 0.80gRe, contain 0.50gMn, the part (Rh of rhodium acetate two containing 0.95gBi and containing 0.55gSb₂(OAc)₄)、CsCl、K₂SO₄, methyl rhenium trioxide (abbreviation MTO, molecular formula CH₃ReO₃)、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄) and Cl₃Sb, which is sufficiently mixed, to be dissolved in Concentration is in 8wt% aqueous hydrochloric acid solution, obtains maceration extract 400ml, than surface is 168m by 1.0L²/ g, pore volume 0.94, directly Footpath is 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through The Rh contents that ICP determines the catalyst are 6.20g/L, Cs contents 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.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 78.63%, and selectivity is 92.70%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

Found out on year-on-year basis by embodiment 18 and embodiment 16 and embodiment 17, improving the selectivity and receipts of 1,3-PD In terms of rate, in the catalyst that the present invention uses, there is synergy between alkali metal Cs, K, illustrate Rh, Cs, K, Re, Mn, Bi Synergy well between seven kinds of active components of Sb be present.

【Embodiment 19】

The preparation of hydroformylation catalyst：To contain 6.20gRu, containing 1.55gCs, containing 0.45gK, containing 0.80gRe, contain 0.50gMn, the RuCl containing 0.95gBi and containing 0.55gSb₃·XH₂O、CsCl、K₂SO₄, methyl rhenium trioxide (abbreviation MTO, molecule Formula CH₃ReO₃)、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄) and Cl₃It is 8wt%'s that Sb, which is sufficiently mixed and is dissolved in concentration, In aqueous hydrochloric acid solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm ball Shape SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalysis is determined through ICP The Ru contents of agent are 6.20g/L, Cs contents 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.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 78.69%, and selectivity is 92.57%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

【Embodiment 20】

The preparation of hydroformylation catalyst：To contain 5.00gRh, containing 1.20gRu, containing 1.55gCs, containing 0.45gK, contain 0.80gRe, the part (Rh of rhodium acetate two containing 0.50gMn, containing 0.95gBi and containing 0.55gSb₂(OAc)₄)、RuCl₃·XH₂O、 CsCl、K₂SO₄, methyl rhenium trioxide (abbreviation MTO, molecular formula CH₃ReO₃)、Mn(OAc)₂·4H₂O, bismuth subsalicylate (C₇H₅BiO₄) and Cl₃Sb, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, will 1.0L is 168m than surface²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation is quiet in above-mentioned maceration extract 3h is put in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 5.00g/L, Ru contents 1.20g/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 contents 0.55g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 79.85%, and selectivity is 93.54%, for convenience of description and is compared, will Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively In Tables 1 and 2.

Found out on year-on-year basis by embodiment 20 and embodiment 18 and embodiment 19, improving the selectivity and receipts of 1,3-PD In terms of rate, in the catalyst that the present invention uses, there is synergy between platinum cluster metal Rh, Ru, illustrate Rh, Ru, Cs, K, Synergy well between eight kinds of active components of Re, Mn, Bi and Sb be present.

Table 1

Table 2 (continued)

The (Continued) of table 2

Claims

1. the method that vinyl acetate hydroformylation produces 1.3- propane diols, comprises the following steps：(1) with vinyl acetate, an oxidation Carbon and hydrogen are raw material, and hydroformylation reaction is carried out in the presence of hydroformylation catalyst and accelerator and obtains 3- acetoxyl groups third Aldehyde；(2) in the presence of a hydrogenation catalyst, hydrogen is reacted with 3- acetoxyl groups propionic aldehyde and obtain 3- acetoxyl group propyl alcohol；(3) 3- second The hydrolysis of acyloxy propyl alcohol obtains 1.3- propane diols；Wherein, the hydroformylation catalyst uses SiO₂、Al₂O₃Or its mixture For carrier, active component includes at least one selected from platinum cluster metallic element, selected from least one of alkali metal and Selected from least one of VIIB and VA metallic element.

2. according to the method for claim 1, it is characterised in that the platinum cluster metal is in platinum, palladium, osmium, iridium, ruthenium and rhodium At least one.

3. according to the method for claim 1, it is characterised in that the alkali metal is in lithium, sodium, potassium, rubidium and caesium It is at least one.

4. according to the method for claim 1, it is characterised in that the VIIB metals are selected from least one of manganese and rhenium.

5. according to the method for claim 1, it is characterised in that the VA metals are selected from least one of antimony and bismuth.

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

7. according to the method for claim 1, it is characterised in that golden in VIIB and VA described in hydroformylation catalyst At least one content of category is 0.10~5.00g/L.

8. according to the method for claim 1, it is characterised in that step (1) described accelerator is in pyridine and triphenyl phosphorus At least one.

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

10. according to the method for claim 1, it is characterised in that the production method of described hydroformylation catalyst, including Following steps：

1. by the composition of catalyst by the compound of platinum cluster metallic element, the compound of alkali metal, VIIB and VA metals The solution of the compound of metallic element mixes with carrier；

2. dry.