CN105585438B

CN105585438B - The method of the propane diols of vinyl acetate production 1,3

Info

Publication number: CN105585438B
Application number: CN201410573644.XA
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: 2018-04-06
Anticipated expiration: 2034-10-24
Also published as: CN105585438A

Abstract

The present invention relates to the method for the propane diols of vinyl acetate production 1.3, mainly solves the problems, such as that 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, alkali earth metal and the technical scheme selected from least one of IVA and IIB metallic element selected from iron series element, the technical problem is preferably resolved, in the industrial production available for 1.3 propane diols.

Description

The method of vinyl acetate production 1,3- propane diols

Technical field

The present invention relates to the method for vinyl acetate 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 production 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 production 1,3- propane diols Method, comprise the following steps：(1) using vinyl acetate, carbon monoxide and hydrogen as raw material, in hydroformylation catalyst and promotion Hydroformylation reaction is carried out in the presence of agent and obtains 3- acetoxyl group propionic aldehyde；(2) in the presence of a hydrogenation catalyst, hydrogen and 3- second are made The reaction of acyloxy propionic aldehyde obtains 3- acetoxyl group propyl alcohol；(3) 3- acetoxyl groups propyl alcohol hydrolysis obtains 1,3- propane diols；Wherein, institute State hydroformylation catalyst and use SiO₂、Al₂O₃Or its mixture is carrier, active component is included selected from iron series element extremely Lack a kind of, alkali earth metal and selected from least one of IVA and IIB metallic element.It is preferred that the active component is wrapped simultaneously Include iron series element, alkali earth metal, selected from least one of IVA metallic elements and selected from least one of IIB metals Element.Now have between IVA metallic element and IIB metallic element in terms of 1,3- propane diols selectivity and yield is improved Synergy.

In above-mentioned technical proposal, the iron series element preferably is selected from least one of iron, cobalt and nickel.

In above-mentioned technical proposal, the alkali metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium.

In above-mentioned technical proposal, the IVA metals preferably are selected from least one of germanium, tin and lead.

In above-mentioned technical proposal, the IB metals preferably are selected from least one of zinc, cadmium and mercury.

In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including iron series element, alkaline earth Metallic element, IVA metallic elements and IIB metallic elements；Such as the active component is made up of cobalt, strontium, tin and zinc (or cadmium), or Person is made up of cobalt, strontium, tin (or lead), zinc and cadmium, be either made up of cobalt, strontium (or calcium), tin, lead, zinc and cadmium or by cobalt (or Nickel), strontium, calcium, tin, lead, zinc and cadmium composition.The most the preferably active component is by cobalt, nickel, strontium, calcium, tin, lead, zinc and cadmium group Into.

In above-mentioned technical proposal, the content of iron series element is preferably 3.00~15.00g/ in the hydroformylation catalyst L, more preferably 7.00~12.00g/L；In the hydroformylation catalyst content of alkali earth metal be preferably 0.10~ 3.00g/L, more preferably 0.50~3.00g/L；Selected from metal is extremely in IVA and IIB in the hydroformylation catalyst A kind of few content is preferably 0.10~5.00g/L, more preferably 1.00~5.00g/L.Used in the hydroformylation catalyst It is preferably 50~300m to carry surface area per unit volume²/ g, more preferably 150~200m²/ g, pore volume are preferably 0.80~1.20, more preferably 0.90~1.00.

In above-mentioned technical proposal, step (1) described accelerator is selected from those commonly used in the art, but preferably pyridine and triphen At least one of base 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.

Hydroformylation catalyst described in the technical scheme of one of above-mentioned technical problem, the life comprised the following steps can be used Production method obtains：

1. will be golden in the compound of iron series element, the compound of alkali earth metal, IVA and IIB by the composition of catalyst The solution for belonging to the compound of element mixes with carrier；

2. dry.

In above-mentioned technical proposal, the compound of the step 1. iron series element preferably be selected from ferrocene, carbonyl cobalt, cobalt acetate, At least one of cobalt chloride, carbonyl nickel and nickel chloride.1. the alkaline earth metal compound preferably is selected from alkaline-earth metal oxide to step At least one of thing, alkaline earth metal chloride, alkaline earth nitrate, alkali earth metal sulfate and Alkaline Earth Metal Acetate. The step 1. preferred germanium tetrachloride of the IVA metallic compounds, stannous chloride, nitric acid stannous, stannous oxide, lead acetate and plumbi nitras At least one of；Step 1. in the IIB metallic compound preferably be selected from zinc gluconate, zinc citrate, zinc acetate, cadmium acetate, At least one of cadmium nitrate, caddy and mercuric sulfate.Step 2. the drying temperature be 80~120 DEG C, more preferably 100~ 120℃。

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 be hydroformylation catalyst active component include iron series element, Alkali earth metal and selected from least one of IVA and IIB metallic element, be advantageous to improve the active of major catalyst and stably Property, so as to improve the yield of 1,3-PD and selectivity.

Test result indicates that the 1,3-PD yield 70.21% prepared by the present invention, selectively reaches 85.54%, takes Obtain active component in preferable technique effect, especially hydroformylation catalyst while include iron series element, alkaline-earth metal member Element, selected from least one of IVA metallic elements and selected from least one of IIB metallic elements when, achieve more prominent Technique effect, available in the industrial production of 1,3-PD.Below by embodiment, the present invention is further elaborated.

Embodiment

【Embodiment 1】

The preparation of hydroformylation catalyst：By the Co containing 8.60gCo, containing 1.80gSr and containing 3.00gSn₂(CO)₈、Sr (OA_C)₂·0.5H₂O and triphenyl tin chloride (C₁₈H₁₅ClSn) it is sufficiently mixed the aqueous acetic acid for being dissolved in that concentration is 10wt% In, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier It is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Co contents of the catalyst are determined through ICP For 8.60g/L, Sr contents 1.80g/L, Sn content 3.00g/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, while agitating and heating is warming up to reaction temperature until pressure 11.8MPa Degree, controlling reaction temperature are 122 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.

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 70.21%, and selectivity is 85.54%, 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.

【Embodiment 2】

The preparation of hydroformylation catalyst：By the Co containing 8.60gCo, containing 1.80gSr and containing 3.00gZn₂(CO)₈、Sr (OA_C)₂·0.5H₂O and zinc citrate (Zn₃(C₆H₅O₇)₂·2H₂O) be sufficiently mixed be dissolved in concentration be 10wt% acetic acid it is water-soluble In liquid, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carry Body is immersed in above-mentioned maceration extract, is stood 3h in 100 DEG C of dryings, is obtained the catalyst.The Co that the catalyst is determined through ICP contains Measure as 8.60g/L, Sr contents 1.80g/L, Zn content 3.00g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 70.35%, and selectivity is 85.55%, 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 Co containing 8.60gCo and containing 1.80gSr₂(CO)₈With Sr (OA_C)₂·0.5H₂O It is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, 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 Co contents that the catalyst is determined through ICP are 8.60g/L, Sr contents 1.80g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 59.49%, and selectivity is 78.77%, 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.

The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Co, Sr and Sn work Property component and meanwhile performance of the catalyst performance ratio containing only Co and Sr active constituent catalysts containing Co, Sr and Zn 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 Co (OAc) containing 7.00gCo, containing 0.50gBe and containing 1.00gSn₂·4H₂O、 BeCl₂And SnCl₂·2H₂O, which is sufficiently mixed, is dissolved in concentration in 8wt% aqueous hydrochloric acid solutions, maceration extract 400ml to be obtained, by 1.0L It is 200m than surface²/ g, pore volume 1.00, a diameter of 5.6mm spherical Al₂O₃Carrier impregnation stands 3h in above-mentioned maceration extract In 80 DEG C of dryings, the catalyst is obtained.The Co contents that the catalyst is determined through ICP are 7.00g/L, Be contents 0.50g/L, Sn Content 1.00g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 65.49%, and selectivity is 82.19%, 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 ferrocene (Fe containing 12.00gFe, containing 3.00gMg and containing 5.00gSn (C₅H₅)₂)、MgSO₄With stannous oxalate (SnC₂O₄) be sufficiently mixed be dissolved in concentration be 8wt% aqueous solution of nitric acid in, soaked Stain liquid 400ml, than surface it is 150m by 1.0L²/ g, pore volume 0.90, a diameter of 5.6mm spherical SiO₂Carrier impregnation is above-mentioned In maceration extract, 3h is stood in 120 DEG C of dryings, obtains the catalyst.The Fe contents that the catalyst is determined through ICP are 12.00g/ L, Mg content 3.00g/L, Sn content 5.00g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 71.36%, and selectivity is 84.27%, 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 Ni (CO) containing 8.60gNi, containing 1.80gCa and containing 3.00gGe₄、Ca (NO₃)₂And GeCl₄It is sufficiently mixed and is dissolved in concentration in 10wt aqueous acetic acids, to obtain maceration extract 400ml, 1.0L being 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 Ni contents that the catalyst is determined through ICP are 8.60g/L, Ca contents 1.80g/L, Ge content 3.00g/L。

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 70.28%, and selectivity is 85.41%, 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 Ni (NO containing 8.60gNi, containing 1.80gBa and containing 3.00gPb₃)₂·6H₂O、 BaO and Pb (OAc)₂·3H₂O, 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 Ni contents that the catalyst is determined through ICP are 8.60g/L, Ba contents 1.80g/L, Pb content 3.00g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 70.40%, and selectivity is 85.33%, 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 CoCl containing 8.60gCo, containing 1.80gSr and containing 3.00gPb₂·6H₂O、Sr (OA_C)₂·0.5H₂O and Pb (NO₃)₂It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, is 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 Co contents that the catalyst is determined through ICP are 8.60g/L, Sr contents 1.80g/L, Pb content 3.00g/L。

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 70.31%, and selectivity is 85.22%, 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 Co (NO containing 8.60gCo, containing 1.80gSr and containing 3.00gZn₃)₂·6H₂O、 Sr(OA_C)₂·0.5H₂O and zinc gluconate (C₁₂H₂₂O₁₄Zn₃·3H₂O) it is sufficiently mixed the hydrochloric acid water for being dissolved in that concentration is 8wt% In solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂ Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The Co of the catalyst is determined through ICP Content is 8.60g/L, Sr contents 1.80g/L, Zn content 3.00g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 70.42%, and selectivity is 85.07%, 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 Co containing 8.60gCo, containing 1.80gSr and containing 3.00gZn₂(CO)₈、Sr (OA_C)₂·0.5H₂O and Zn (OA_C)₂·2H₂O, which is sufficiently mixed, to be dissolved in the aqueous acetic acid that concentration is 10wt%, is impregnated Liquid 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 leaching In stain liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP are 8.60g/L, Sr Content 1.80g/L, Zn content 3.00g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 70.32%, and selectivity is 85.23%, 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 Co containing 8.60gCo, containing 1.80gSr and containing 3.00gCd₂(CO)₈、Sr (OA_C)₂·0.5H₂O and Cd (NO₃)₂·4H₂O, which is sufficiently mixed, to be dissolved in the aqueous acetic acid that concentration is 10wt%, is impregnated Liquid 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 leaching In stain liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP are that Co contents are 8.60g/L, Sr content 1.80g/L, Cd content 3.00g/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 61.58%, and selectivity is 82.92%, 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 Co containing 8.60gCo, containing 1.80gSr and containing 3.00gHg₂(CO)₈、Sr (OA_C)₂·0.5H₂O and HgSO₄It is sufficiently mixed and is dissolved in the aqueous 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 in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP are that Co contents are 8.60g/L, Sr contents 1.80g/L, Hg content 3.00g/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 70.75%, and selectivity is 84.82%, 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 Co containing 8.60gCo, containing 1.80gSr, containing 1.95gSn and containing 1.05gZn₂ (CO)₈、Sr(OA_C)₂·0.5H₂O, triphenyl tin chloride (C₁₈H₁₅) and zinc citrate (Zn ClSn₃(C₆H₅O₇)₂·2H₂O) fully Mixed dissolution obtains maceration extract 400ml in the aqueous acetic acid that concentration is 10wt%, than surface is 168m by 1.0L²/ g, hole Hold for 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract State catalyst.The Co contents that the catalyst is determined through ICP are 8.60g/L, Sr contents 1.80g/L, Sn content 1.95g/L, and Zn contains Measure 1.05g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 71.28%, and selectivity is 86.40%, 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 12 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 IVA metal Sn and IIB metals Zn.

【Embodiment 13】

The preparation of hydroformylation catalyst：By the Co containing 8.60gCo, containing 1.80gSr, containing 1.95gSn and containing 1.05gCd₂ (CO)₈、Sr(OA_C)₂·0.5H₂O, triphenyl tin chloride (C₁₈H₁₅) and Cd (NO ClSn₃)₂·4H₂O, which is sufficiently mixed, is dissolved in concentration Than surface it is 168m by 1.0L in 10wt% aqueous acetic acid, to obtain maceration extract 400ml²/ g, pore volume 0.94, diameter For 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through The Co contents that ICP determines the catalyst are 8.60g/L, Sr contents 1.80g/L, Sn content 1.95g/L, Cd content 1.05g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 71.43%, and selectivity is 86.35%, 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 14】

The preparation of hydroformylation catalyst：To contain 8.60gCo, containing 1.80gSr, containing 1.95gSn, containing 0.65gZn and contain 0.40gCd Co₂(CO)₈、Sr(OA_C)₂·0.5H₂O, triphenyl tin chloride (C₁₈H₁₅ClSn), zinc citrate (Zn₃ (C₆H₅O₇)₂·2H₂) and Cd (NO O₃)₂·4H₂O, which is sufficiently mixed, to be dissolved in the aqueous acetic acid that concentration is 10wt%, is soaked Stain liquid 400ml, than surface it is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation is above-mentioned In maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP are 8.60g/L, Sr contents 1.80g/L, Sn content 1.95g/L, Zn content 0.65g/L, Cd content 0.40g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 72.51%, and selectivity is 87.02%, 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 IIB metals between Zn and Cd.

【Embodiment 15】

The preparation of hydroformylation catalyst：To contain 8.60gCo, containing 1.80gSr, containing 1.95gPb, containing 0.65gZn and contain 0.40gCd Co₂(CO)₈、Sr(OA_C)₂·0.5H₂O、Pb(OAc)₂·3H₂O, zinc citrate (Zn₃(C₆H₅O₇)₂·2H₂O) and Cd(NO₃)₂·4H₂O, which is sufficiently mixed, to be dissolved in the aqueous acetic acid that concentration is 10wt%, maceration extract 400ml is obtained, by 1.0L It is 168m than surface²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in above-mentioned maceration extract In 100 DEG C of dryings, the catalyst is obtained.The Co contents that the catalyst is determined through ICP are 8.60g/L, Sr content 1.80g/L, Pb contents 1.95g/L, Zn content 0.65g/L, Cd content 0.40g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 72.30%, and selectivity is 87.14%, 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 8.60gCo, containing 1.80gSr, containing 1.25gSn, containing 0.70gPb, contain The 0.65gZn and Co containing 0.40gCd₂(CO)₈、Sr(OA_C)₂·0.5H₂O, triphenyl tin chloride (C₁₈H₁₅ClSn)、Pb (OAc)₂·3H₂O, zinc citrate (Zn₃(C₆H₅O₇)₂·2H₂) and Cd (NO O₃)₂·4H₂O, which is sufficiently mixed, to be dissolved in concentration and is In 10wt% aqueous acetic acid, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume 0.94 are a diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through ICP The Co contents for determining the catalyst are 8.60g/L, Sr contents 1.80g/L, Sn content 1.25g/L, Pb content 0.70g/L, and Zn contains Measure 0.65g/L, Cd contents 0.40g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 73.12%, and selectivity is 88.10%, 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 IVA metals Sn, Pb, illustrate Co, Sr, Sn, Pb, Zn Synergy well between six kinds of active components of Cd be present.

【Embodiment 17】

The preparation of hydroformylation catalyst：To contain 8.60gCo, containing 1.80gCa, containing 1.25gSn, containing 0.70gPb, contain The 0.65gZn and Co containing 0.40gCd₂(CO)₈、Ca(NO₃)₂, triphenyl tin chloride (C₁₈H₁₅ClSn)、Pb(OAc)₂·3H₂O, lemon Lemon acid zinc (Zn₃(C₆H₅O₇)₂·2H₂) and Cd (NO O₃)₂·4H₂O is sufficiently mixed the aqueous acetic acid for being dissolved in that concentration is 10wt% In, maceration extract 400ml is obtained, than surface is 168m by 1.0L²/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO₂Carrier It is immersed in above-mentioned maceration extract, stands 3h in 100 DEG C of dryings, obtain the catalyst.The Co contents of the catalyst are determined through ICP For 8.60g/L, Ca contents 1.80g/L, Sn content 1.25g/L, Pb content 0.70g/L, Zn content 0.65g/L, Cd content 0.40g/L。

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 73.37%, and selectivity is 87.93%, 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 8.60gCo, containing 1.20gSr, containing 0.60gCa, containing 1.25gSn, contain 0.70gPb, the Co containing 0.65gZn and containing 0.40gCd₂(CO)₈、Sr(OA_C)₂·0.5H₂O、Ca(NO₃)₂, triphenyl tin chloride (C₁₈H₁₅ClSn)、Pb(OAc)₂·3H₂O, zinc citrate (Zn₃(C₆H₅O₇)₂·2H₂) and Cd (NO O₃)₂·4H₂O is sufficiently mixed molten Solution obtains maceration extract 400ml in the aqueous acetic acid that concentration is 10wt%, 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 Co contents that the catalyst is determined through ICP are 8.60g/L, Sr contents 1.20g/L, Ca content 0.60g/L, Sn content 1.25g/L, Pb content 0.70g/L, Zn content 0.65g/L, Cd content 0.40g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 74.05%, and selectivity is 88.96%, 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 alkaline-earth metal Sr, Ca, illustrate Co, Sr, Ca, Sn, Synergy well between seven kinds of active components of Pb, Zn and Cd be present.

【Embodiment 19】

The preparation of hydroformylation catalyst：To contain 8.60gNi, containing 1.20gSr, containing 0.60gCa, containing 1.25gSn, contain 0.70gPb, the Ni (NO containing 0.65gZn and containing 0.40gCd₃)₂·6H₂O、Sr(OA_C)₂·0.5H₂O、Ca(NO₃)₂, triphenyl chlorine Change tin (C₁₈H₁₅ClSn)、Pb(OAc)₂·3H₂O, zinc citrate (Zn₃(C₆H₅O₇)₂·2H₂) and Cd (NO O₃)₂·4H₂O is fully mixed Close and be dissolved in the aqueous acetic acid that concentration is 10wt%, obtain maceration extract 400ml, than surface be 168m by 1.0L²/ g, pore volume For 0.94, a diameter of 5.6mm spherical SiO₂Carrier impregnation stands 3h in 100 DEG C of dryings, obtained described in above-mentioned maceration extract Catalyst.The Ni contents that the catalyst is determined through ICP are 8.60g/L, Sr contents 1.20g/L, Ca content 0.60g/L, Sn content 1.25g/L, Pb content 0.70g/L, Zn content 0.65g/L, Cd content 0.40g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 73.96%, and selectivity is 89.18%, 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 6.80gCo, containing 1.80gNi, containing 1.20gSr, containing 0.60gCa, contain 1.25gSn, the Co containing 0.70gPb, containing 0.65gZn and containing 0.40gCd₂(CO)₈、Ni(NO₃)₂·6H₂O、Sr(OA_C)₂· 0.5H₂O、Ca(NO₃)₂, triphenyl tin chloride (C₁₈H₁₅ClSn)、Pb(OAc)₂·3H₂O, zinc citrate (Zn₃(C₆H₅O₇)₂· 2H₂) and Cd (NO O₃)₂·4H₂O, which is sufficiently mixed, to be dissolved in the aqueous 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 in above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Co contents that the catalyst is determined through ICP are 6.80g/L, Ni contents 1.80g/L, Sr content 1.20g/L, Ca content 0.60g/L, Sn content 1.25g/L, Pb content 0.70g/L, Zn content 0.65g/ L, Cd content 0.40g/L.

The synthesis of 1,3- propane diols：

The yield for being computed 1,3-PD is 74.78%, and selectivity is 90.36%, 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 Ferrious material Ni, Co, illustrate Co, Ni, Sr, Ca, Synergy well between eight kinds of active components of Sn, Pb, Zn and Cd be present.

Table 1

Table 2 (continued)

The (Continued) of table 2

Claims

1. the method for vinyl acetate production 1,3-PD, comprises the following steps：(1) with vinyl acetate, carbon monoxide and hydrogen For raw material, hydroformylation reaction acquisition 3- acetoxyl group propionic aldehyde is carried out in the presence of hydroformylation catalyst and accelerator；(2) exist In the presence of hydrogenation catalyst, hydrogen is reacted with 3- acetoxyl groups propionic aldehyde and obtain 3- acetoxyl group propyl alcohol；(3) 3- acetoxyl groups third Alcohol hydrolysis obtains 1,3- propane diols；Wherein, the hydroformylation catalyst uses SiO₂、Al₂O₃Or its mixture is carrier, Active component includes selected from least one of iron series element, alkali earth metal, selected from least one of IVA metallic elements and Selected from least one of IIB metallic elements, the iron series element is selected from least one of iron, cobalt and nickel, the IVA metals Selected from least one of germanium, tin and lead, the IIB metals are selected from least one of zinc, cadmium and mercury.

2. according to the method for claim 1, it is characterized in that the alkaline-earth metal in beryllium, magnesium, calcium, strontium and barium at least It is a kind of.

3. according to the method for claim 1, it is characterized in that the content of iron series element is in hydroformylation catalyst：3.00~ 15.00g/L, the content of alkali earth metal are：0.10~3.00g/L.

4. according to the method for claim 1, it is characterized in that described in hydroformylation catalyst in IVA and IIB metal At least one content be 0.10~5.00g/L.

5. according to the method for claim 1, it is characterized in that step (1) described accelerator is in pyridine and triphenyl phosphorus It is at least one.

6. according to the method for claim 1, it is characterized in that the temperature of step (1) hydroformylation reaction is 50~180 DEG C；Instead The pressure answered is 1.0~15.0MPa；The time of reaction is 1.0~15.0h；Carbon monoxide and hydrogen volume ratio be 0.10~ 10.0。

7. the method according to claim 11, it is characterized in that the production method of the hydroformylation catalyst, including following step Suddenly：

It is 1. by the composition of catalyst that metal in the compound of iron series element, the compound of alkali earth metal, IVA and IIB is first The solution of the compound of element mixes with carrier；

2. dry.