CN105523886B - Synthesize the method used in 1,3 propane diols - Google Patents
Synthesize 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 synthesis, mainly solve the problems, such as that 1.3 propane diols catalyst activity and selectivities are relatively low in the prior art, by using the method used in 1.3 propane diols of synthesis, 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；3 acetoxyl group propyl alcohol alcoholysis obtain 1.3 propane diols；Hydroformylation catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, alkaline-earth metal and the technical scheme selected from least one of VA and IVB 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 synthesis 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
Synthesis 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：Synthesize the side used in 1,3- propane diols
Method, comprise the following steps：(1) using vinyl acetate, carbon monoxide and hydrogen as raw material, deposited in hydroformylation catalyst and accelerator
3- acetoxyl group propionic aldehyde is obtained in lower progress hydroformylation reaction；(2) in the presence of a hydrogenation catalyst, hydrogen and 3- acetyl oxygen are made
The reaction of base propionic aldehyde obtains 3- acetoxyl group propyl alcohol；(3) alcoholysis of 3- acetoxyl groups propyl alcohol obtains 1,3- propane diols；Wherein, the hydrogen
Hydroformylation catalyst uses SiO2、Al2O3Or its mixture is carrier, active component include rhodium, alkaline-earth metal and selected from VA and
At least one of IVB metallic elements.It is preferred that the active component is simultaneously including rhodium, alkaline-earth metal, at least one in VA
Plant metallic element and selected from least one of IVB metallic elements.Now between VA metallic element and IVB metallic element
There is synergy in terms of improving 1,3- propane diols selectivity and yield.
In above-mentioned technical proposal, the alkaline-earth metal preferably is selected from least one of beryllium, magnesium, calcium, strontium and barium.
In above-mentioned technical proposal, the VA metals preferably are selected from least one of antimony and bismuth.
In above-mentioned technical proposal, the IVB metals preferably are selected from least one of titanium, zirconium and hafnium.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including rhodium metal element, alkali
Earth metal, VA metallic elements and IVB metallic elements；Such as the active component is made up of rhodium, strontium, antimony and hafnium, or by rhodium,
Strontium, antimony, bismuth and hafnium composition, are either made up of or by rhodium, strontium, beryllium, antimony, bismuth, hafnium and titanium group rhodium, strontium, antimony, bismuth, hafnium and titanium
Into.
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 alkaline-earth metal is preferably 0.10~3.00g/L in the hydroformylation catalyst, more excellent
Elect 0.50~3.00g/L as；In the hydroformylation catalyst selected from VA and IVB at least one content of metal it is preferred
For 0.10~5.00g/L, more preferably 1.00~5.00g/L.Load surface area per unit volume used in the hydroformylation catalyst is preferred
For 50~300m2/ g, more preferably 150~200m2/ g, pore volume are preferably 0.80~1.20, and more preferably 0.90~1.00.Institute
State at least one of the preferred pyridine of accelerator 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 preparation method comprised the following steps obtains：
1. by catalyst composition by the solution of metallic compound in rhodium compound, alkaline earth metal compound, VA and IVB with
Carrier mixes；
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 alkaline earth metal compound preferably is selected from alkaline earth oxide, alkaline earth metal chloride, alkaline earth gold to step
At least one of genus nitrobacter, alkali earth metal sulfate and Alkaline Earth Metal Acetate；1. the VA metallic compounds are excellent for step
Select at least one of basic bismuth carbonate, bismuth sulfate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate and antimony chloride；Step 1. institute
Metallic compound in IVB is stated preferably to be selected from titanium tetrachloride, ammonium titanium fluoride, hexafluorotitanic acid, zirconium chloride, acetic acid zirconium and oxychloride hafnium
It is at least one；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, alkaline earth gold
Category and selected from least one of VA and IVB metallic element, is advantageous to improve the activity and stability of hydroformylation catalyst, from
And improve the yield and selectivity of 1,3- propane diols.
Test result indicates that using the hydroformylation catalyst of the present invention, 1,3-PD yield 75.52%, selectivity
Reach 89.31%, achieve active component in preferable technique effect, especially hydroformylation catalyst while include rhodium, alkali
Earth metal, selected from least one of VA metallic elements and selected from least one of IVB 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 catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gSb3·3H2O、Sr
(OAC)2·0.5H2O 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, Sr contents
2.00g/L, Sb content 3.30g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 75.52%, and selectivity is 89.31%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 2】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gHf3·3H2O、Sr
(OAC)2·0.5H2O and oxychloride hafnium (HfOCl2·8H2O) it is sufficiently mixed and is dissolved in the water, obtain maceration extract 400ml, 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr content 2.00g/L,
Hf contents 3.30g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 75.40%, and selectivity is 89.52%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh and containing 2.00gSr3·3H2O and Sr (OAC)2·
0.5H2O, which is sufficiently mixed, to be dissolved in the water, and 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, Sr contents 2.00g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 65.41%, and selectivity is 81.84%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
By compared with embodiment 1~2 as can be seen that the hydroformylation catalyst that uses of the present invention, using simultaneously containing Rh,
Sr and Sb active components while catalyst performance ratio containing Rh, Sr and Hf active component is containing only Rh and Sr 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 catalyst：By the Rh (OAc) containing 6.50gRh, containing 2.00gMg and containing 3.30gSb3、MgSO4
And Sb2O3It is sufficiently mixed and is dissolved in concentration in 8wt% aqueous solution of nitric acid, to obtain maceration extract 400ml, being than surface by 1.0L
200m2/ g, pore volume 1.00, a diameter of 5.6mm spherical Al2O3It is dry in 80 DEG C to stand 3h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Mg contents 2.00g/L, Sb content
3.30g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 75.35%, and selectivity is 89.57%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 4】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.00gCa and containing 3.30gSb3·3H2O、Ca
(NO3)2·4H2O 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, Ca contents
2.00g/L, Sb content 3.30g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 75.49%, and selectivity is 89.37%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 5】
The preparation of hydroformylation catalyst：By the Rh containing 5.00gRh, containing 0.50gBe and containing 1.00gBi2(SO4)3·
15H2O、BeCl2(BiO)2CO3·0.5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, and 1.0L is compared into surface
For 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C in above-mentioned maceration extract
Dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 5.00g/L, Be 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 70.56%, and selectivity is 85.44%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 6】
The preparation of hydroformylation catalyst：By the RhCl containing 10.00gRh, containing 3.00gBa and containing 5.00gBi3·3H2O、
BaO and BiCl3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table
Face is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 10.00g/L, Ba contents 3.00g/L, and Bi contains
Measure 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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 88.97%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 7】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gTi3·3H2O、Sr
(OAC)2·0.5H2O and ammonium titanium fluoride ((NH4)2TiF6) be sufficiently mixed and be dissolved in pure water, 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr content 2.00g/L,
Ti contents 3.30g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 89.46%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 8】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gTi3·3H2O、Sr
(OAC)2·0.5H2O and hexafluorotitanic acid (H2TiF6) be sufficiently mixed and be dissolved in pure water, maceration extract 400ml is obtained, 1.0L is compared into table
Face is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Ti content
3.30g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 75.54%, and selectivity is 89.32%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 9】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gZr3·3H2O、Sr
(OAC)2·0.5H2O and ZrCl4It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, than surface is 168m by 1.0L2/
G, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
To the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Zr content 3.30g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 75.50%, and selectivity is 89.35%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 10】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gZr3·3H2O、Sr
(OAC)2·0.5H2O and Zr (OAC)4It 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Zr content
3.30g/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.
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 71.04%, and selectivity is 88.91%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 11】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.00gSr and containing 3.30gTi3·3H2O、Sr
(OAC)2·0.5H2O and TiCl4It 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, Sr contents
2.00g/L, Ti content 3.30g/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 75.84%, and selectivity is 89.13%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 12】
The preparation of hydroformylation catalyst：By containing 6.50gRh, containing 2.00gSr, containing 1.50gSb and containing 1.80gHf's
RhCl3·3H2O、Sr(OAC)2·0.5H2O、Cl3Sb and oxychloride hafnium (HfOCl2·8H2O) it 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, and Sr contents 2.00g/L, Sb content 1.50g/L, Hf content is 1.80g/L.
The synthesis of 1,3- propane diols：
Step (1)：By 2.50mol toluene, 0.02mol hydroformylations major catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 76.77%, and selectivity is 90.82%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
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 IVB metals Hf.
【Embodiment 13】
The preparation of hydroformylation catalyst：By containing 6.50gRh, containing 2.00gSr, containing 1.50gBi and containing 1.80gHf's
RhCl3·3H2O、Sr(OAC)2·0.5H2O、BiCl3With oxychloride hafnium (HfOCl2·8H2O) it 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, and Sr contents 2.00g/L, Bi content 1.50g/L, Hf content is 1.80g/L.
The synthesis of 1,3- propane diols：
Step (1)：By 2.50mol toluene, 0.02mol hydroformylations major catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 76.81%, and selectivity is 90.72%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 14】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 2.00gSr, containing 0.50gSb, containing 1.00gBi and contain
1.80gHf RhCl3·3H2O、Sr(OAC)2·0.5H2O、Cl3Sb、BiCl3With oxychloride hafnium (HfOCl2·8H2O it is) fully mixed
Close and be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Sb content 0.50g/L, Bi content
1.00g/L, Hf content are 1.80g/L.
The synthesis of 1,3- propane diols：
Step (1)：By 2.50mol toluene, 0.02mol hydroformylations major catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 78.15%, and selectivity is 91.39%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improving the selectivity and receipts of 1,3-PD
In terms of rate, in the catalyst that the present invention uses, there is synergy in VA metals between Sb and Bi.
【Embodiment 15】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 2.00gSr, containing 0.50gSb, containing 1.00gBi and contain
1.80gTi RhCl3·3H2O、Sr(OAC)2·0.5H2O、Cl3Sb、BiCl3With ammonium titanium fluoride ((NH4)2TiF6) be sufficiently mixed
It is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, than surface is 168m by 1.0L2/ g, pore volume are
0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains described urge in above-mentioned maceration extract
Agent.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sr contents 2.00g/L, Sb content 0.50g/L, Bi content
1.00g/L, Ti content are 1.80g/L.
The synthesis of 1,3- propane diols：
Step (1)：By 2.50mol toluene, 0.02mol hydroformylations major catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 78.02%, and selectivity is 91.51%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 16】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 2.00gSr, containing 0.50gSb, containing 1.00gBi, contain
The 1.20gHf and RhCl containing 0.60gTi3·3H2O、Sr(OAC)2·0.5H2O、Cl3Sb、BiCl3, oxychloride hafnium (HfOCl2·
8H2) and ammonium titanium fluoride ((NH O4)2TiF6) be sufficiently mixed be dissolved in concentration be 8wt% aqueous hydrochloric acid solution in, obtain maceration extract
400ml, than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is 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 Sr contains
2.00g/L is measured, Sb contents 0.50g/L, Bi content 1.00g/L, Hf content is 1.20g/L, and Ti contents are 0.60g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 79.35%, and selectivity is 92.41%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
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 IVB metals Ti, Hf, illustrate Rh, Sr, Sb, Bi, Ti
Synergy well between six kinds of active components of Hf be present.
【Embodiment 17】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 2.00gBe, containing 0.50gSb, containing 1.00gBi, contain
The 1.20gHf and RhCl containing 0.60gTi3·3H2O、BeCl2、Cl3Sb、BiCl3, oxychloride hafnium (HfOCl2·8H2) and fluorine titanium O
Sour ammonium ((NH4)2TiF6) be sufficiently mixed be dissolved in concentration be 8wt% aqueous hydrochloric acid solution in, 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 Rh contents that the catalyst is determined through ICP are 6.50g/L, Be content 2.00g/L,
Sb contents 0.50g/L, Bi content 1.00g/L, Hf content is 1.20g/L, and Ti contents are 0.60g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 79.20%, and selectivity is 92.43%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
【Embodiment 18】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 1.60gSr, containing 0.40gBe, containing 0.50gSb, contain
1.00gBi, the RhCl containing 1.20gHf and containing 0.60gTi3·3H2O、Sr(OAC)2·0.5H2O、BeCl2、Cl3Sb、BiCl3, chlorine
Hafnium oxide (HfOCl2·8H2) and ammonium titanium fluoride ((NH O4)2TiF6) it is sufficiently mixed the aqueous hydrochloric acid solution for being dissolved in that concentration is 8wt%
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 Rh contents of the catalyst are determined through ICP
For 6.50g/L, Sr contents 1.60g/L, Be content 0.40g/L, Sb content 0.50g/L, Bi content 1.00g/L, Hf content is
1.20g/L, Ti content are 0.60g/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 4.5MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 104 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 80.31%, and selectivity is 93.38%, for convenience of description and is compared, will
Support modification condition, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity point
Tables 1 and 2 is not listed in it.
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, Be, illustrate Rh, Sr, Be, Sb,
Synergy well between seven kinds of active components of Bi, Ti and Hf be present.
Table 1
Table 2 (continued)
The (Continued) of table 2
Claims (10)
1. synthesizing 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) in the presence of a hydrogenation catalyst, hydrogen is reacted with 3- acetoxyl groups propionic aldehyde and obtain 3- acetoxyl group propyl alcohol；(3)3-
The alcoholysis of acetoxyl group propyl alcohol obtains 1,3- propane diols；Wherein, the hydroformylation catalyst uses SiO2、Al2O3Or its mixing
Thing is carrier, and active component is simultaneously including rhodium, alkaline-earth metal and selected from least one of VA metallic elements and in IVB
At least one metallic element.
2. according to the method for claim 1, it is characterised in that the alkaline-earth metal in beryllium, magnesium, calcium, strontium and barium extremely
Few one kind.
3. according to the method for claim 1, it is characterised in that the VA metals are selected from least one of antimony and bismuth.
4. according to the method for claim 1, it is characterised in that the IVB metals are selected from least one of titanium, zirconium and hafnium.
5. 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 alkaline-earth metal are：0.10~3.00g/L, described in hydroformylation catalyst in VA at least one
Plant metallic element and at least one content of metal is 0.10~5.00g/L in IVB.
6. according to the method for claim 1, it is characterised in that step (1) described accelerator is in pyridine and triphenyl phosphorus
At least one.
7. according to the method for claim 1, it is characterised in that the temperature of step (1) hydroformylation reaction is 50~180 DEG C.
8. according to the method for claim 1, it is characterised in that the preparation side of the hydroformylation catalyst described in step (1)
Method, comprise the following steps：
1. by the composition of catalyst by the solution and carrier of metallic compound in rhodium compound, alkaline earth metal compound, VA and IVB
Mixing；
2. dry.
9. 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 biology.
10. according to the method for claim 1, it is characterised in that the alcohol in step (3) alcoholysis reaction is selected from the low of C1~C5
At least one of carbon saturated alcohols.
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| CN101116816A (en) * | 2007-07-03 | 2008-02-06 | 中国石油大学(华东) | Method for preparing load type rhodium catalyst for making high-carbon aldehyde using hydroformylation of higher olefins |
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