CN105523892B - Produce the method used in 1,3 propane diols - Google Patents
Produce the method used in 1,3 propane diols Download PDFInfo
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Abstract
The present invention relates to the method used in 1.3 propane diols of production, mainly solves the problems, such as that the yield of 1.3 propane diols and selectivity are low when vinyl acetate successively prepares 1.3 propane diols through hydroformylation, hydrogenation and hydrolysis route.By using the method used in 1.3 propane diols of production：Vinyl acetate hydroformylation obtains 3 acetoxyl group propionic aldehyde；3 acetoxyl group hydrogenation of propionaldehyde obtain 3 acetoxyl group propyl alcohol；3 acetoxyl group propyl alcohol alcoholysis obtain 1.3 propane diols；Hydroformylation catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, lanthanide element and the technical scheme selected from least one of VA and VB metallic element, the technical problem is preferably resolved, in the industrial production available for 1.3 propane diols.
Description
Technical field
The present invention relates to the method used in 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
Production 1,3-PD used in 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：Produce the used of 1,3- propane diols
Method, comprise the following steps：(1) using vinyl acetate, carbon monoxide and hydrogen as raw material, in hydroformylation catalyst and accelerator
In the presence of carry out hydroformylation reaction obtain 3- acetoxyl group propionic aldehyde；(2) in the presence of a hydrogenation catalyst, hydrogen and 3- acetyl are made
The reaction of epoxide propionic aldehyde obtains 3- acetoxyl group propyl alcohol；(3) alcoholysis of 3- acetoxyl groups propyl alcohol obtains 1,3- propane diols；Wherein, it is described
Hydroformylation catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, lanthanide element and choosing
From at least one of VA and VB metallic element.It is preferred that the active component is simultaneously including rhodium, lanthanide element, in VA
At least one metallic element and selected from least one of VB metallic elements.Now VA metallic element and VB metallic element
Between improve 1,3- propane diols selectivity and yield in terms of have synergy.
In above-mentioned technical proposal, the lanthanide element preferably is selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium at least
It is a kind of.
In above-mentioned technical proposal, the VA metals preferably are selected from least one of antimony and bismuth.
In above-mentioned technical proposal, the VB metals preferably are selected from least one of vanadium, niobium and tantalum.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including rhodium metal element, lanthanum
It is metallic element, VA metallic elements and VB metallic elements；Such as the active component is made up of rhodium, cerium, antimony and vanadium, Huo Zheyou
Rhodium, cerium, antimony, bismuth and vanadium composition, are either made up of or by rhodium, cerium, lanthanum, antimony, bismuth, vanadium and niobium rhodium, cerium, antimony, bismuth, vanadium and niobium
Composition.
In above-mentioned technical proposal, the content of rhodium is preferably 3.00~15.00g/L in the hydroformylation catalyst, more excellent
Elect 5.00~10.00g/L as；The content of lanthanide element is preferably 0.10~3.00g/L in the hydroformylation catalyst,
More preferably 0.50~3.00g/L；At least one content selected from the metal in VA and VB in the hydroformylation catalyst
Preferably 0.10~5.00g/L, more preferably 1.00~5.00g/L.Load surface area per unit volume used in the hydroformylation catalyst
Preferably 50~300m2/ g, more preferably 150~200m2/ g, pore volume are preferably 0.80~1.20, more preferably 0.90~
1.00.The accelerator is preferably at least one of pyridine and triphenyl phosphorus.
The key of the present invention is the selection of hydroformylation catalyst, and skilled person will know how basis to be actually needed
It is determined that suitable reaction temperature, reaction time, the proportioning of reaction pressure and material.But hydroformylation in above-mentioned technical proposal
The temperature of reaction is preferably 50~180 DEG C；The pressure of reaction is preferably 1.0~15.0MPa；The time of reaction is preferably 1.0~
15.0h.The mol ratio of carbon monoxide and hydrogen is preferably 0.10~10.0.
In above-mentioned technical proposal, the hydroformylation catalyst, the optional production method comprised the following steps obtains：
1. by catalyst composition by rhodium compound, lanthanide element compound, VA and VB metallic compound it is molten
Liquid mixes with carrier；
2. dry.
In above-mentioned technical proposal, 1. the rhodium compound preferably is selected from rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate step
At least one；1. the lanthanide element compound preferably is selected from lanthanum acetate, lanthanum chloride, lanthanum nitrate, cerous acetate, nitric acid to step
At least one of cerium, cerium chloride, praseodymium acetate, acetic acid neodymium, samarium trichloride, ytterbium chloride, Europium chloride and lutecium chloride；The step 1. VA
The preferred basic bismuth carbonate of metallic compound, bismuth sulfate, bismuth chloride, bismuth and ammonium citrate, bismuth subsalicylate, antimony oxide, antimony sulfate and
At least one of antimony chloride；1. metallic compound preferably is selected from vanadium trichloride, vanadic anhydride, columbium pentachloride to step in the VB
At least one of with tantalic chloride；2. the drying temperature is 80~120 DEG C, more preferably 100~120 DEG C to step.
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 alcoholysis catalysts of the known selection of art personnel and determination suitable alcoholysis reaction temperature, time and material proportion.
But at least one of the preferred base catalyst of alcoholysis catalysts and acidic catalyst in alcoholysis reaction in above-mentioned technical proposal；
At least one of the low-carbon saturated alcohols of the preferred C1~C5 of alcohol in alcoholysis reaction.Alcoholysis reaction catalyst is more preferably dissolved in the first of alcohol
Sodium alkoxide；Alcohol more preferably methanol in alcoholysis reaction.In above-mentioned technical proposal, alcoholysis reaction temperature is preferably 30~100 DEG C；Alcoholysis
Reaction pressure preferably 0~2.0MPa.
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 rhodium, group of the lanthanides gold
Belong to element and selected from least one of VA and VB metallic element, be advantageous to improve the active of hydroformylation catalyst and stably
Property, 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 75.42%, selectively reach
89.43%, achieve active component in preferable technique effect, especially hydroformylation catalyst while include rhodium, group of the lanthanides gold
Belong to element, selected from least one of VA metallic elements and selected from least one of VB metallic elements when, achieve more prominent
The technique effect gone out, 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 major catalyst：By the RhCl containing 6.50gRh, containing 2.40gLa and containing 3.10gSb3·3H2O、
La(OAc)3·5H2O 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 in above-mentioned maceration extract,
3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, La contents
2.40g/L, Sb content 3.10g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 75.42%, and selectivity is 89.43%, 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 2】
The preparation of hydroformylation major catalyst：By the RhCl containing 6.50gRh, containing 2.40gLa and containing 3.10gNb3·3H2O、
La(OAc)3·5H2O and NbCl5It is sufficiently mixed and is 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 in above-mentioned maceration extract,
3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, La contents
2.40g/L, Nb content 3.10g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 75.38%, and selectivity is 89.47%, 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 major catalyst：By the RhCl containing 6.50gRh and containing 2.40gLa3·3H2O and La (OAc)3·
5H2O, 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, 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 Rh contents that ICP determines the catalyst are 6.50g/L, La contents 2.40g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 65.33%, and selectivity is 81.67%, 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.
By compared with embodiment 1~2 as can be seen that the hydroformylation catalyst that uses of the present invention, using simultaneously containing Rh,
La and Sb active components while catalyst performance ratio containing Rh, La and Nb active component is containing only Rh and La active constituent catalysts
Performance it is more excellent, the selectivity and yield of 1,3-PD will be high.
【Embodiment 3】
The preparation of hydroformylation major catalyst：By the Rh (OAc) containing 6.50gRh, containing 2.40gCe and containing 3.10gSb3、Ce
(OAc)3·6H2O and Sb2O3It is sufficiently mixed and is dissolved in concentration in 8wt% aqueous solution of nitric acid, to obtain maceration extract 400ml, will
1.0L is 200m than surface2/ g, pore volume 1.00, a diameter of 5.6mm spherical Al2O3Carrier impregnation is quiet in above-mentioned maceration extract
3h is put in 80 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Ce contents 2.40g/
L, Sb content 3.10g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 75.41%, and selectivity is 89.32%, 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 major catalyst：By the RhCl containing 6.50gRh, containing 2.40gCe and containing 3.10gSb3·3H2O、
CeCl3·6H2O and Sb2(SO4)3It is sufficiently mixed and is 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 6.50g/L, Ce contents
2.40g/L, Sb content 3.10g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 75.30%, and selectivity is 89.51%, 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 major catalyst：By the Rh containing 5.00gRh, containing 0.50gCe and containing 1.00gBi2(SO4)3·
15H2O、Ce(NO3)3·6H2O and (BiO)2CO3·0.5H2O, 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 Rh contents that the catalyst is determined through ICP are 5.00g/L, Ce contents
0.50g/L, Bi content 1.00g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 70.61%, and selectivity is 86.27%, 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 6】
The preparation of hydroformylation major catalyst：By the RhCl containing 10.00gRh, containing 3.00gPr and containing 5.00gBi3·3H2O、
Pr(OAc)3·5H2O and BiCl3It is sufficiently mixed and is 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 in above-mentioned maceration extract,
3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 10.00g/L, Pr contents
3.00g/L, Bi content 5.00g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 76.12%, and selectivity is 88.95%, 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 major catalyst：By the RhCl containing 6.50gRh, containing 2.40gNd and containing 3.10gBi3·3H2O、
Nd(OAc)3·5H2O and bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O) it is sufficiently mixed and is dissolved in pure water, 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 6.50g/L, and Nd contains
Measure 2.40g/L, Bi contents 3.10g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 75.34%, and selectivity is 89.40%, 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.
【Embodiment 8】
The preparation of hydroformylation major catalyst：By the RhCl containing 6.50gRh, containing 2.40gYb and containing 3.10gBi3·3H2O、
YbCl3·6H2O and bismuth subsalicylate (C7H5BiO4) be sufficiently mixed be dissolved in concentration be 8wt% aqueous hydrochloric acid solution in, 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 Rh contents that the catalyst is determined through ICP are 6.50g/L,
Yb contents 2.40g/L, Bi content 3.10g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 75.42%, and selectivity is 89.44%, 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 major catalyst：By the RhCl containing 6.50gRh, Eu containing 2.40g and containing 3.10gV3·3H2O、
EuCl3·6H2O and VCl3It is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%, 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 6.50g/L, Eu contents
2.40g/L, V content 3.10g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 75.39%, and selectivity is 89.52%, 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 major catalyst：By the RhCl containing 6.50gRh, containing 2.40gLu and containing 3.10gV3·3H2O、
LuCl3·6H2O and V2O5It is sufficiently mixed and is dissolved in the aqueous solution of nitric acid 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 6.50g/L, Lu contents
2.40g/L, V content 3.10g/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 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 71.36%, and selectivity is 88.26%, 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 major catalyst：By the RhCl containing 6.50gRh, containing 2.40gSm and containing 3.10gTa3·3H2O、
SmCl3·6H2O and TaCl5It is sufficiently mixed and is dissolved in the aqueous sulfuric acid 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 6.50g/L, Sm contents
2.40g/L, Ta content 3.10g/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, while agitating and heating is warming up to reaction temperature until pressure 15.0MPa
Degree, controlling reaction temperature are 180 DEG C, and the mol ratio of hydrogen and carbon monoxide is 10:After 1, sustained response 15.0h, stop reaction.
Reactor is down to room temperature, the product that reaction obtains is washed with water 3 times, organic matter enters oil phase, is removed through rectification and purification molten
Agent, 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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 75.89%, and selectivity is 89.12%, 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 major catalyst：By containing 6.50gRh, containing 2.40gLa, containing 1.70gSb and containing 1.40gNb's
RhCl3·3H2O、La(OAc)3·5H2O、Cl3Sb and NbCl5It is sufficiently mixed and is dissolved 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
In above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are
6.50g/L, La content 2.40g/L, Sb content 1.70g/L, Nb content 1.40g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 76.60%, and selectivity is 90.58%, 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 VA metal Sb and VB metals Nb.
【Embodiment 13】
The preparation of hydroformylation major catalyst：By containing 6.50gRh, containing 2.40gCe, containing 1.70gSb and containing 1.40gNb's
RhCl3·3H2O、CeCl3·6H2O、Cl3Sb and NbCl5It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains
Than surface it is 168m by 1.0L to maceration extract 400ml2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation exists
In above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are
6.50g/L, Ce content 2.40g/L, Sb content 1.70g/L, Nb content 1.40g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 76.72%, and selectivity is 90.67%, 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 major catalyst：To contain 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 1.70gSb and contain
1.40gNb RhCl3·3H2O、La(OAc)3·5H2O、CeCl3·6H2O、Cl3Sb and NbCl5It is sufficiently mixed and is dissolved in concentration and is
In 8wt% aqueous hydrochloric acid solution, 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 Rh contents for determining the catalyst are 6.50g/L, La contents 0.80g/L, Ce content 1.60g/L, Sb content 1.70g/L, and Nb contains
Measure 1.40g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 78.14%, and selectivity is 91.48%, 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 lanthanide series metal between La and Ce.
【Embodiment 15】
The preparation of hydroformylation major catalyst：To contain 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 1.70gBi and contain
1.40gNb RhCl3·3H2O、La(OAc)3·5H2O、CeCl3·6H2O, bismuth and ammonium citrate (Bi (NH3)2C6H7O7·H2O) and
NbCl5It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, La contents 0.80g/L, Ce content
1.60g/L, Bi content 1.70g/L, Nb content 1.40g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 78.05%, and selectivity is 91.54%, 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 16】
The preparation of hydroformylation major catalyst：To contain 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 0.60gSb, contain
The 1.10gBi and RhCl containing 1.40gNb3·3H2O、La(OAc)3·5H2O、CeCl3·6H2O、Cl3Sb, bismuth and ammonium citrate (Bi
(NH3)2C6H7O7·H2) and NbCl O5It is sufficiently mixed and is 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 6.50g/L, and La contains
Measure 0.80g/L, Ce contents 1.60g/L, Sb content 0.60g/L, Bi content 1.10g/L, Nb content 1.40g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 79.27%, and selectivity is 92.46%, 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 VA metals Sb, Bi, illustrate Rh, La, Ce, Sb, Bi
Synergy well between six kinds of active components of Nb be present.
【Embodiment 17】
The preparation of hydroformylation major catalyst：To contain 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 0.60gSb, contain
The 1.10gBi and RhCl containing 1.40gV3·3H2O、La(OAc)3·5H2O、CeCl3·6H2O、Cl3Sb, bismuth and ammonium citrate (Bi
(NH3)2C6H7O7·H2) and VCl O3It 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 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 6.50g/L, and La contains
Measure 0.80g/L, Ce contents 1.60g/L, Sb content 0.60g/L, Bi content 1.10g/L, V content 1.40g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 79.23%, and selectivity is 92.53%, 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 18】
The preparation of hydroformylation major catalyst：To contain 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 0.60gSb, contain
1.10gBi, the RhCl containing 0.90gNb and containing 0.50gV3·3H2O、La(OAc)3·5H2O、CeCl3·6H2O、Cl3Sb, lemon
Sour bismuth ammonium (Bi (NH3)2C6H7O7·H2O)、NbCl5And VCl3It is sufficiently mixed and is dissolved in the aqueous acetic acid that concentration is 10wt%,
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
In above-mentioned maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are
6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Sb content 0.60g/L, Bi content 1.10g/L, Nb content 0.90g/
L, V content 0.50g/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 5.3MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 102 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 4.5h, 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.
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 methanol, 0.02mol sodium methoxides (CH3ONa) add
100ml titanium reactors, first with 0.5MPa is pressurized to after air in argon gas discharge kettle, 65 DEG C are warming up to, stirring constant temperature 4h.
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 80.40%, and selectivity is 93.31%, 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.
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 VB metals V, Nb, illustrate Rh, La, Ce, Sb, Bi,
Synergy well between seven kinds of active components of Nb and V be present.
Table 1
Table 2 (continued)
The (Continued) of table 2
Claims (6)
1. producing the method used in 1,3-PD, comprise the following steps：(1) using vinyl acetate, carbon monoxide and hydrogen as original
Material, hydroformylation reaction acquisition 3- acetoxyl group propionic aldehyde is carried out in the presence of hydroformylation catalyst and accelerator；(2) it is being hydrogenated with
In the presence of catalyst, hydrogen is reacted with 3- acetoxyl groups propionic aldehyde and obtain 3- acetoxyl group propyl alcohol；(3) 3- acetoxyl groups propyl alcohol alcohol
Solution obtains 1,3-PD；Wherein, described hydroformylation catalyst uses SiO2、Al2O3It is living or its mixture is carrier
Property component include rhodium, lanthanide element and selected from least one of VA and VB metallic element；The lanthanide element choosing
From at least one of lanthanum, cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium；
The VA metals are selected from least one of antimony and bismuth；
The VB metals are selected from least one of vanadium, niobium and tantalum；The accelerator is triphenylphosphine.
2. according to the method for claim 1, it is characterised in that the content of rhodium is in hydroformylation catalyst：3.00~
15.00g/L, the content of lanthanide element are：0.10~3.00g/L, described in hydroformylation catalyst in VA and VB
At least one content of metal is 0.10~5.00g/L.
3. according to the method for claim 1, it is characterised in that the temperature of step (1) hydroformylation reaction is 50~180 DEG C.
4. according to the method for claim 1, it is characterised in that the preparation method of described hydroformylation catalyst, including such as
Lower step：
1. by catalyst composition by the solution of metallic compound in rhodium compound, lanthanide element compound, VA and VB with
Carrier mixes；
2. dry.
5. according to the method for claim 1, it is characterised in that step (3) alcoholysis catalysts are selected from base catalyst and acidity
At least one of catalyst.
6. according to the method for claim 1, it is characterised in that the alcohol in step (3) alcoholysis reaction is selected from C1~C5 low-carbon
At least one of saturated alcohols.
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| CN111533767A (en) * | 2020-04-30 | 2020-08-14 | 卢海元 | Tetradentate phosphine ligand and preparation method thereof, hydroformylation catalyst and reaction method, and preparation method of 1, 3-propylene glycol |
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| CN103120958A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Vinyl acetate catalyst and preparation method thereof |
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