CN105585445B - The preparation method of 1,3 propane diols - Google Patents
The preparation method of 1,3 propane diols Download PDFInfo
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Abstract
The present invention relates to the preparation method of 1.3 propane diols, mainly solves the problems, such as that 1.3 propane diols catalyst activity and selectivities are relatively low in the prior art, by using the preparation method of 1.3 propane diols, comprise the following steps：Vinyl acetate hydroformylation obtains 3 acetoxyl group propionic aldehyde；3 acetoxyl group hydrogenation of propionaldehyde obtain 3 acetoxyl group propyl alcohol；The hydrolysis of 3 acetoxyl group propyl alcohol obtains 1.3 propane diols；Hydroformylation catalyst uses SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, lanthanide element and the technical scheme selected from least one of IVA and VIB 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 preparation method of 1,3- propane diols.
Background technology
1,3-PD (1,3-PDO) is a kind of important industrial chemicals, be mainly used in plasticizer, detergent, preservative,
The synthesis of emulsifying agent, it is also used for the industries such as food, cosmetics and pharmacy.Because it is a kind of important polyester fiber monomer, its
Most important purposes is as monomer and the polytrimethylene terephthalate (PTT) of terephthalic acid (TPA) synthesizing new polyester material one.
The preparation method of 1,3- propane diols has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehyde
Stiasny method, acrylic acid ester process, bioanalysis, vinyl acetate hydroformylation etc..At present, 1,3-PDO industrialized preparing process
For chemical synthesis, international market is mainly by German Degussa companies, shell Shell companies of the U.S. and du pont company three
Family's monopolization.Degussa companies are using acrolein hydration hydrogenation method (AC methods), Shell Co. Ltd using oxirane carbonyl
The thorugh biologic engineering method (MF methods) that change method (EO methods), E.I.Du Pont Company innovate using oneself.Its ethylene oxide two-step process
It is current prevailing technology with acrolein hydration method technique.
Taught in the patents such as patent US4072709 (Production of Lactic Acid) and utilize vinyl acetate
It is catalyst by using homogeneous rhodium compound for raw material, by hydroformylation reaction, obtains 2 (or 3)-acetoxyl group propionic aldehyde.
Whether separation or not, and then 3- acetoxyl groups propionic aldehyde obtains 1,3-PDO by hydrogenation and hydrolytic process.But prepared by the above method
The problem of 1,3-PDO yields are low and selectivity is not high during 1,3-PDO be present.
The content of the invention
The problem of technical problems to be solved by the invention are the yield and low selectivity of 1,3-PD, there is provided Yi Zhongxin
1,3-PD preparation 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：The preparation method of 1,3-PD, bag
Include following steps：(1) using vinyl acetate, carbon monoxide and hydrogen as raw material, in the presence of hydroformylation catalyst and accelerator
Carry out hydroformylation reaction and obtain 3- acetoxyl group propionic aldehyde；(2) in the presence of a hydrogenation catalyst, hydrogen and 3- acetoxyl groups third are made
Aldehyde reaction obtains 3- acetoxyl group propyl alcohol；(3) 3- acetoxyl groups propyl alcohol hydrolysis obtains 1,3- propane diols；Wherein, the hydrogen formyl
Change catalyst and use SiO2、Al2O3Or its mixture is carrier, active component includes rhodium, lanthanide element and selected from IVA
With at least one of VIB metallic element.It is preferred that the active component is simultaneously including rhodium, lanthanide element, in IVA
At least one metallic element and selected from least one of VIB metallic elements.Now IVA metallic element and VIB metal member
There is synergy in terms of 1,3- propane diols selectivity and yield is improved between element.
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 IVA metals preferably are selected from least one of germanium, tin and lead.
In above-mentioned technical proposal, the vib metal preferably is selected from least one of chromium, molybdenum and tungsten.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including rhodium metal element, lanthanum
It is metallic element, IVA metallic elements and vib metal element；Such as the active component is made up of rhodium, samarium (or cerium), tin and chromium,
Either be made up of rhodium, samarium, cerium, tin and chromium (or molybdenum) or be made up of rhodium, cerium, samarium, tin, chromium and molybdenum, or by rhodium, cerium, samarium,
Tin, germanium, chromium and molybdenum 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 selected from the metal in IVA and VIB in the hydroformylation catalyst contains
Amount is preferably 0.10~5.00g/L, more preferably 1.00~5.00g/L.Carrier used in the hydroformylation catalyst compares table
Face is preferably 50~300m2/ g, more preferably 150~200m2/ g, pore volume are preferably 0.80~1.20, more preferably 0.90~
1.00.At least one of the preferred pyridine of step (1) described accelerator and triphenyl phosphorus.
In above-mentioned technical proposal, the concrete technology condition of the hydroformylation reaction of step (1) is not the key of the present invention, and
And those skilled in the art can be according to being actually needed reasonable determination.The concrete technology condition of the hydroformylation reaction of step (1),
Such as, but not limited to：The temperature of hydroformylation reaction is 50~180 DEG C；The pressure of reaction is 1.0~15.0MPa；Reaction when
Between be 1.0~15.0h；Carbon monoxide and hydrogen volume ratio are 0.10~10.0.
In above-mentioned technical proposal, the hydroformylation catalyst, the optional production method comprised the following steps obtains：
1. by the composition of catalyst by the change of metal in the compound of rhodium, the compound of lanthanide element, IVA and VIB
The solution of compound mixes with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. rhodium preferably is selected from rhodium acetate, rhodium nitrate, radium chloride and rhodium sulfate
At least one of；The compound of the step 1. lanthanide element preferably be selected from lanthanum acetate, lanthanum chloride, lanthanum nitrate, cerous acetate,
At least one of cerous nitrate, cerium chloride, praseodymium acetate, acetic acid neodymium, samarium trichloride, ytterbium chloride, Europium chloride and lutecium chloride；
The step 1. preferred stannous oxalate of compound of the IVA metals, germanium tetrachloride, stannous chloride, nitric acid stannous, oxidation
At least one of stannous, lead acetate and plumbi nitras；Step 1. in the VIB compound of metal preferably be selected from chromic acetate, chromic nitrate,
At least one of chromium chloride, ammonium molybdate, molybdenum pentachloride and ammonium tungstate；2. the drying temperature is 80~120 DEG C to step, more excellent
Elect 100~120 DEG C as.
The preparation key of catalyst of the present invention is the preparation of hydroformylation major catalyst, after major catalyst is obtained,
The catalyst of the present invention is can obtain by making major catalyst be contacted with the accelerator.The side that major catalyst contacts with accelerator
Formula is not particularly limited, and the opportunity for contacting both is also not particularly limited.Such as it can be used for by catalyst of the present invention
Contact both before chemical reaction and form the catalyst, the reactant that both can also be made to be applied in catalyst of the present invention
Contact makes catalyst in-situ preparation in system.
, can be to the mixture of hydroformylation reaction after step (1) terminates in the method for present invention synthesis 1,3-PD
Carry out separation acquisition target product 3- acetoxyl groups propionic aldehyde and carry out step (2) again, can also step (1) generation 3- acetoxyl groups third
Do not separated after aldehyde and directly carry out step (2).The suitable hydrogenation catalyst of the known selection of those skilled in the art and determination are closed
Suitable hydrogenation reaction temperature, time and material proportion.Conventional hydrogenation catalyst have transition metal metallic catalyst,
Metal oxide catalyst, metal sulfide catalyst, complex catalyst etc., such as platinum, palladium, nickel, ruthenium carried catalyst, oxidation
Copper-copper chromite, alumina-silica zinc-chromium oxide catalyst, nickel-molybdenum sulfide and RhCl [P (C6H5)3].In the present invention
It is preferred that Raney's nickel, as hydrogenation catalyst, suitable hydrogenation temperature is preferably 30~100 DEG C；Hydrogenation reaction pressure preferably 0.5~
8.0MPa；The hydrogenation reaction time is preferably 10~200min；The mol ratio of aldehyde and hydrogen preferably 0.10~2.0；The preferred water of solvent,
At least one of toluene.
After step (2) terminates, separation can be carried out to the mixture of hydrogenation reaction and obtains target product 3- acetoxyl groups third
Alcohol carries out step (3) again, can not also separate directly progress step (3) after step (2) generation 3- acetoxyl group propyl alcohol.This
The suitable hydrolyst of the known selection of art personnel and determination suitable hydrolysising reacting temperature, time and material proportion.
Conventional hydrolyst can be inorganic acid, inorganic base, organic acid and organic base.Such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, hydrogen
Sodium oxide molybdena, potassium hydroxide, benzene sulfonic acid and ion exchange resin.Suitable hydrolysising reacting temperature is preferably 50~100 DEG C；Hydrolysis
Reaction pressure preferably 0~2.0MPa；At least one of the preferred water of solvent, benzene, hexamethylene, toluene.
Final product of the present invention is analyzed after cooling down, depressurize, separate using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS),
The conversion ratio of vinyl acetate and the yield and selectivity of 1,3- propane diols are calculated by following equation：
Compared with prior art, key of the invention is that the active component of hydroformylation catalyst includes rhodium, group of the lanthanides gold
Belong to element and selected from least one of IVA and VIB metallic element, be advantageous to improve the active and steady of hydroformylation major catalyst
It is qualitative, so as to improve the yield of 1,3-PD and selectivity.
Test result indicates that during using catalyst of the present invention, the yield 75.51% of 1,3-PD, selectively reach
89.24%, 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 IVA metallic elements and selected from least one of VIB metallic elements when, achieve more
Prominent technique effect, available in the industrial production of 1,3-PD.The present invention is further explained below by embodiment
State.
Embodiment
【Embodiment 1】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.20gSm and containing 3.20gSn3·3H2O、
SmCl3·6H2O and stannous oxalate (SnC2O4) be sufficiently mixed be dissolved in concentration be 8wt% aqueous hydrochloric acid solution in, impregnated
Liquid 400ml, than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned leaching
In stain liquid, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sm
Content 2.20g/L, Sn content 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 75.51%, and selectivity is 89.24%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 2】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.20gSm and containing 3.20gCr3·3H2O、
SmCl3·6H2O and CrCl3·6H2O, which is sufficiently mixed, to be dissolved in pure water, obtains 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, Sm contents 2.20g/L, Cr content
3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 75.56%, and selectivity is 89.20%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh and containing 2.20gSm3·3H2O and SmCl3·6H2O
It 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 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, Sm contents 2.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 65.44%, and selectivity is 81.90%, 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,
Sm and Sn active components while catalyst performance ratio containing Rh, Sm and Cr active component is containing only Rh and Sm 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 2.20gCe and containing 3.20gGe3、Ce
(OAc)3·6H2O and GeCl4It is sufficiently mixed and is dissolved in concentration in 8wt%y aqueous hydrochloric acid solutions, 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 2.20g/
L, Ge content 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 75.44%, and selectivity is 89.30%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 4】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.20gCe and containing 3.20gSn3·3H2O、
CeCl3·6H2O and SnCl2·2H2O, which is sufficiently mixed, to be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract
400ml, than surface it is 150m by 1.0L2/ g, pore volume 0.90, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned dipping
In liquid, 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, and Ce contains
Measure 2.20g/L, Sn contents 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 75.47%, 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 5】
The preparation of hydroformylation catalyst：By the Rh containing 5.00gRh, containing 0.50gCe and containing 1.00gPb2(SO4)3·
15H2O、Ce(NO3)3·6H2O and Pb (OAc)2It is sufficiently mixed and is dissolved in pure water, obtain maceration extract 400ml, 1.0L is compared into surface
For 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 3h in 100 DEG C in above-mentioned maceration extract
Dry, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 5.00g/L, Ce contents 0.50g/L, Pb 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 70.63%, and selectivity is 86.15%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 6】
The preparation of hydroformylation catalyst：By the RhCl containing 10.00gRh, containing 3.00gPr and containing 5.00gPb3·3H2O、Pr
(OAc)3·5H2O and Pb (NO3)2·3H2O, which is sufficiently mixed, to be dissolved in pure water, obtains 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 10.00g/L, Pr contents 3.00g/L, Pb 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 76.21%, and selectivity is 88.96%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 7】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.20gNd and containing 3.20gPb3·3H2O、Nd
(OAc)3·5H2O and basic lead carbonate (2PbCO3-Pb(OH)2) be sufficiently mixed be dissolved in concentration be 8wt% nitric acid 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 upper
State in maceration extract, stand 3h in 100 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/
L, Nd content 2.20g/L, Pb content 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 75.39%, and selectivity is 89.42%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 8】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.20gYb and containing 3.20gCr3·3H2O、
YbCl3·6H2O and Cr (NO3)3·9H2O, which is sufficiently mixed, to be dissolved in pure water, obtains 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, Yb contents 2.20g/L, Cr content
3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 75.43%, and selectivity is 89.35%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 9】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, Eu containing 2.20g and containing 3.20gMo3·3H2O、
EuCl3·6H2O and MoCl5It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, will
1.0L is 168m than surface2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is quiet in above-mentioned maceration extract
3h is put in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Eu contents
2.20g/L, Mo content 3.20g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 75.35%, 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 catalyst：By the RhCl containing 6.50gRh, containing 2.20gLu and containing 3.20gMo3·3H2O、
LuCl3·6H2O and ammonium molybdate ((NH4)6Mo7O24·4H2O) it is sufficiently mixed and is 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 6.50g/L, Lu contents
2.20g/L, Mo content 3.20g/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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 71.14%, and selectivity is 88.21%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 11】
The preparation of hydroformylation catalyst：By the RhCl containing 6.50gRh, containing 2.20gLa and containing 3.20gW3·3H2O、La
(OAc)3·5H2O and ammonium tungstate ((NH4)10W12O41·4H2O) it is sufficiently mixed and is 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 6.50g/L, La contents
2.20g/L, W content 3.20g/L.
The synthesis of 1,3- propane diols：
Step (1)：By 2.50mol toluene, 0.02mol hydroformylations major catalyst, 0.20mol triphenyl phosphorus and
1.65mol vinyl acetates are added in 1L titanium reactors, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, are then passed to
Carbon monoxide and hydrogen improve mixing speed to 800rpm until pressure 15MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 180 DEG C, and the mol ratio of hydrogen and carbon monoxide is 10:After 1, sustained response 15.0h, stop reaction.Will
Reactor is down to room temperature, will react obtained product and is washed with water 3 times, and organic matter enters oil phase, through rectification and purification removing solvent,
Vinyl acetate and other accessory substances, obtain 3- acetoxyl group propionic aldehyde.
Step (2)：Above-mentioned 3- acetoxyl groups propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added into 100ml titaniums
Reactor, first with 1.0MPa is pressurized to after air in argon gas discharge kettle, hydrogen is then passed to until pressure 5.0MPa, improves stirring
Speed is to 600rpm, while agitating and heating is warming up to reaction temperature, and controlling reaction temperature is 70 DEG C, after sustained response 100min,
Stop reaction.Reactor is down to room temperature, purified removal of impurities obtains 3- acetoxyl group propyl alcohol.
Step (3)：By above-mentioned 3- acetoxyl groups propyl alcohol 18ml, 30ml toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 76.63%, and selectivity is 88.81%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 12】
The preparation of hydroformylation catalyst：By containing 6.50gRh, containing 2.20gSm, containing 2.20gSn and containing 1.00gCr's
RhCl3·3H2O、SmCl3·6H2O, stannous oxalate (SnC2O4) and CrCl3·6H2It is 8wt%'s that O, which is sufficiently mixed and is dissolved in concentration,
In aqueous hydrochloric acid solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm ball
Shape SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalysis is determined through ICP
The Rh contents of agent are 6.50g/L, Sm contents 2.20g/L, Sn content 2.20g/L, Cr 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 76.91%, and selectivity is 90.75%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2, improving the selectivity and yield of 1,3-PD
Aspect, in the catalyst that uses of the present invention, there is synergy between IVA metals Sn and vib metal Cr.
【Embodiment 13】
The preparation of hydroformylation catalyst：By containing 6.50gRh, containing 2.20gCe, containing 2.20gSn and containing 1.00gCr's
RhCl3·3H2O、CeCl3·6H2O, stannous oxalate (SnC2O4) and CrCl3·6H2It is 8wt%'s that O, which is sufficiently mixed and is dissolved in concentration,
In aqueous hydrochloric acid solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm ball
Shape SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalysis is determined through ICP
The Rh contents of agent are 6.50g/L, Ce contents 2.20g/L, Sn content 2.20g/L, Cr 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 76.83%, and selectivity is 90.82%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 14】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 1.15gSm, containing 1.05gCe, containing 2.20gSn and contain
1.00gCr RhCl3·3H2O、SmCl3·6H2O、CeCl3·6H2O, stannous oxalate (SnC2O4) and CrCl3·6H2O 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, Sm contents 1.15g/L, Ce content 1.05g/L, Sn content
2.20g/L, Cr 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 78.16%, and selectivity is 91.52%, 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.
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 Sm and Ce.
【Embodiment 15】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 1.15gSm, containing 1.05gCe, containing 2.20gSn and contain
1.00gMo RhCl3·3H2O、SmCl3·6H2O、CeCl3·6H2O, stannous oxalate (SnC2O4) and ammonium molybdate ((NH4)6Mo7O24·4H2O) it is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, maceration extract 400ml is obtained, by 1.0L ratios
Surface is 168m2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation in above-mentioned maceration extract, stand 3h in
100 DEG C of dryings, obtain the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L, Sm contents 1.15g/L, Ce
Content 1.05g/L, Sn content 2.20g/L, Mo 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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 77.97%, and selectivity is 91.64%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 16】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 1.15gSm, containing 1.05gCe, containing 2.20gSn, contain
The 0.60gCr and RhCl containing 0.40gMo3·3H2O、SmCl3·6H2O、CeCl3·6H2O, stannous oxalate (SnC2O4)、CrCl3·
6H2O and ammonium molybdate ((NH4)6Mo7O24·4H2O) it is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, is soaked
Stain liquid 400ml, than surface it is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm spherical SiO2Carrier impregnation is above-mentioned
In maceration extract, 3h is stood in 100 DEG C of dryings, obtains the catalyst.The Rh contents that the catalyst is determined through ICP are 6.50g/L,
Sm contents 1.15g/L, Ce content 1.05g/L, Sn content 2.20g/L, Cr content 0.6g/L, Mo content 0.40g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 79.54%, and selectivity is 92.34%, 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 vib metal Cr, Mo, illustrate Rh, Sm, Ce, Sn, Cr
Synergy well between six kinds of active components of Mo be present.
【Embodiment 17】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 1.15gSm, containing 1.05gCe, containing 2.20gGe, contain
The 0.60gCr and RhCl containing 0.40gMo3·3H2O、SmCl3·6H2O、CeCl3·6H2O、GeCl4、CrCl3·6H2O and molybdic acid
Ammonium ((NH4)6Mo7O24·4H2O) it 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, Sm contents
1.15g/L, Ce content 1.05g/L, Ge content 2.20g/L, Cr content 0.6g/L, Mo content 0.40g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 79.41%, and selectivity is 92.50%, for convenience of description and is compared, will
Carrier physical property, the preparation condition of catalyst, reaction condition, material inlet amount, the yield of 1,3- propane diols and selectivity arrange respectively
In Tables 1 and 2.
【Embodiment 18】
The preparation of hydroformylation catalyst：To contain 6.50gRh, containing 1.15gSm, containing 1.05gCe, containing 1.35gSn, contain
0.85gGe, the RhCl containing 0.60gCr and containing 0.40gMo3·3H2O、SmCl3·6H2O、CeCl3·6H2O, stannous oxalate
(SnC2O4)、GeCl4、CrCl3·6H2O and ammonium molybdate ((NH4)6Mo7O24·4H2O it is 8wt%'s) to be sufficiently mixed and be dissolved in concentration
In aqueous hydrochloric acid solution, maceration extract 400ml is obtained, than surface is 168m by 1.0L2/ g, pore volume 0.94, a diameter of 5.6mm ball
Shape SiO2Carrier impregnation stands 3h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.The catalysis is determined through ICP
The Rh contents of agent are 6.50g/L, Sm contents 1.15g/L, Ce content 1.05g/L, Sn content 1.35g/L, Ge content 0.85g/L,
Cr contents 0.6g/L, Mo content 0.40g/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 5.6MPa, while agitating and heating is warming up to reaction temperature,
Controlling reaction temperature is 103 DEG C, and the mol ratio of hydrogen and carbon monoxide is 2:After 1, sustained response 5.0h, 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 toluene-water (10ml toluene and 20ml water mix and
Into), the ion exchange resin of 0.015mol Amberlite IR 120 add 100ml titanium reactors, first with argon gas discharge kettle in
0.5MPa is pressurized to after air, is warming up to 75 DEG C, stirring constant temperature 7h.
Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas chromatograph-mass spectrometer (GC-MS)
(GC-MASS) analyze.
The yield for being computed 1,3-PD is 80.42%, and selectivity is 93.44%, 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.
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 IVA metals Sn, Ge, illustrate Rh, Sm, Ce, Sn,
Synergy well between seven kinds of active components of Ge, Cr and Mo be present.
Table 1
Table 2 (continued)
The (Continued) of table 2
Claims (10)
1.1, the preparation method of ammediol, comprise the following steps：(1) using vinyl acetate, carbon monoxide and hydrogen as raw material,
Hydroformylation reaction is carried out in the presence of hydroformylation catalyst and accelerator and obtains 3- acetoxyl group propionic aldehyde；(2) in hydrogenation catalyst
In the presence of agent, hydrogen is reacted with 3- acetoxyl groups propionic aldehyde and obtain 3- acetoxyl group propyl alcohol；(3) 3- acetoxyl groups propyl alcohol hydrolysis obtains
Obtain 1,3- propane diols；Wherein, the hydroformylation catalyst uses SiO2、Al2O3Or its mixture is carrier, active component
Including rhodium, lanthanide element and selected from least one of IVA and VIB metallic element.
2. preparation method according to claim 1, it is characterized in that the lanthanide element be selected from lanthanum, cerium, praseodymium, neodymium, samarium,
At least one of europium, ytterbium and lutetium.
3. preparation method according to claim 1, it is characterized in that the IVA metals in germanium, tin and lead at least one
Kind.
4. preparation method according to claim 1, it is characterized in that the vib metal in chromium, molybdenum and tungsten at least one
Kind.
5. preparation method according to claim 1, it is characterized in that the content of rhodium is in the hydroformylation catalyst：3.00
~15.00g/L, the content of lanthanide element are：0.10~3.00g/L.
6. preparation method according to claim 1, it is characterized in that described in hydroformylation catalyst in IVA and VIB
At least one content of metal is 0.10~5.00g/L.
7. preparation method according to claim 1, it is characterized in that step (1) described accelerator is selected from pyridine and triphenyl phosphorus
At least one of.
8. preparation method according to claim 1, it is characterized in that the temperature of step (1) hydroformylation reaction is 50~180
℃；The pressure of reaction is 1.0~15.0MPa；The time of reaction is 1.0~15.0h；Carbon monoxide and hydrogen volume ratio are 0.10
~10.0.
9. preparation method according to claim 1, it is characterized in that the production method of the hydroformylation catalyst, including such as
Lower step：
1. by the composition of catalyst by the compound of metal in the compound of rhodium, the compound of lanthanide element, IVA and VIB
Solution mixed with carrier；
2. dry.
10. preparation method according to claim 1, it is characterized in that the compound of the step 1. rhodium is selected from rhodium acetate, nitre
At least one of sour rhodium, radium chloride and rhodium sulfate.
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| CN103521268A (en) * | 2012-07-03 | 2014-01-22 | 中国科学院大连化学物理研究所 | Heterogeneous catalysts for alkene hydroformylation reaction and preparation method thereof |
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| US4072709A (en) * | 1975-05-27 | 1978-02-07 | Monsanto Company | Production of lactic acid |
| CN102372603A (en) * | 2010-08-26 | 2012-03-14 | 中国石油化工股份有限公司 | Method for simultaneously producing 1,3-propylene glycol and 1,2-propylene glycol |
| CN103521268A (en) * | 2012-07-03 | 2014-01-22 | 中国科学院大连化学物理研究所 | Heterogeneous catalysts for alkene hydroformylation reaction and preparation method thereof |
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