CN105523892A - Method for producing 1, 3-propanediol - Google Patents
Method for producing 1, 3-propanediol Download PDFInfo
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Abstract
The invention relates to a method for producing 1, 3-propanediol. The method mainly solves the problem that the prior art for preparing 1, 3-propanediol through vinyl acetate hydroformylation, hydrogenation and hydrolysis has a low yield and low selectivity. The method provided through the invention comprises vinyl acetate hydroformylation for 3-acetoxypropanal preparation, 3-acetoxypropanal hydrogenation for 3-acetoxypropanol preparation and 3-acetoxypropanol alcoholysis for 1, 3-propanediol preparation. A hydroformylation catalyst utilizes SiO2, Al2O3 or their mixture as a carrier and active ingredients comprise rhodium and lanthanide metal elements and at least one of VA and VB metals. The method well solves the technical problem and can be used for 1, 3-propanediol industrial production.
Description
Technical field
The present invention relates to and produce 1,3-PD method used.
Background technology
1,3-PD (1.3-PDO) is a kind of important industrial chemicals, is mainly used in the synthesis of softening agent, washing composition, sanitas, emulsifying agent, also for industries such as food, makeup and pharmacy.Because it is a kind of important trevira monomer, its topmost purposes is as monomer and terephthalic acid synthesizing new polyester material one polytrimethylene terephthalate (PTT).
The preparation method of 1,3-PD has oxyethane single stage method, oxyethane two-step approach, acrolein hydration method, acetaldehyde stiasny method, vinylformic acid ester process, biological process, vinyl acetate between to for plastic hydroformylation etc.At present, the industrialized preparing process of 1.3-PDO is chemical synthesis, and world market is primarily of German Degussa company, shell Shell company of the U.S. and the monopolization of three, du pont company.Degussa company adopt be acrolein hydration hydrogenation method (AC method), Shell Co. Ltd adopt be oxirane carbonyl method (EO method), E.I.Du Pont Company adopt be oneself innovation thorugh biologic engineering method (MF method).Its ethylene oxide two-step process and acrolein hydration method technique are current prevailing technology.
Teaching in the patents such as patent US4072709 (ProductionofLacticAcid) utilizes vinyl-acetic ester for raw material; by adopting homogeneous phase rhodium compound to be catalyzer; by hydroformylation reaction, obtain 2 (or 3)-acetoxyl group propionic aldehyde.Be separated or be not separated, then 3-acetoxyl group propionic aldehyde obtains 1.3-PDO by hydrogenation and hydrolytic process.But all there is the problem that 1.3-PDO yield is low and selectivity is not high in aforesaid method in preparation 1.3-PDO process.
Summary of the invention
Technical problem to be solved by this invention is the problem that the yield of 1,3-PD and selectivity are low, provides a kind of method that production 1,3-PD is newly used, and the method has the advantages that 1,3-PD yield is high and selectivity is high.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: produce 1, the method used of ammediol, comprise the following steps: (1) for raw material with vinyl acetate between to for plastic, carbon monoxide and hydrogen, is carried out hydroformylation reaction and obtained 3-acetoxyl group propionic aldehyde under hydroformylation catalyst and promotor exist; (2) in the presence of a hydrogenation catalyst, make hydrogen and 3-acetoxyl group propionic aldehyde react and obtain 3-acetoxyl group propyl alcohol; (3) alcoholysis of 3-acetoxyl group propyl alcohol obtains 1,3-PD; Wherein, described hydroformylation catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active ingredient comprises rhodium, lanthanide element and is selected from least one metallic element in VA and VB.Preferred described active ingredient comprises rhodium, lanthanide element, at least one metallic element that is selected from least one metallic element in VA and is selected from VB simultaneously.Now in the selectivity improving 1,3-PD and yield, there is synergy between the metallic element of VA and the metallic element of VB.
In technique scheme, at least one of described lanthanide element preferably in lanthanum, cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium.
In technique scheme, at least one of described VA metal preferably in antimony and bismuth.
In technique scheme, at least one of described VB metal preferably in vanadium, niobium and tantalum.
In technique scheme, as most preferred technical scheme, described active ingredient comprises rhodium metal element, lanthanide element, VA metallic element and VB metallic element simultaneously; Such as described active ingredient is made up of rhodium, cerium, antimony and vanadium, or is made up of rhodium, cerium, antimony, bismuth and vanadium, or is made up of rhodium, cerium, antimony, bismuth, vanadium and niobium, or is made up of rhodium, cerium, lanthanum, antimony, bismuth, vanadium and niobium.
In technique scheme, in described hydroformylation catalyst, the content of rhodium is preferably 3.00 ~ 15.00g/L, is more preferably 5.00 ~ 10.00g/L; In described hydroformylation catalyst, the content of lanthanide element is preferably 0.10 ~ 3.00g/L, is more preferably 0.50 ~ 3.00g/L; At least one content being selected from metal in VA and VB in described hydroformylation catalyst is preferably 0.10 ~ 5.00g/L, is more preferably 1.00 ~ 5.00g/L.Described hydroformylation catalyst carrier specific surface used is preferably 50 ~ 300m
2/ g, is more preferably 150 ~ 200m
2/ g, pore volume is preferably 0.80 ~ 1.20, is more preferably 0.90 ~ 1.00.. described promotor is preferably at least one in pyridine and triphenyl phosphorus.
Key of the present invention is the selection of hydroformylation catalyst, those skilled in the art will know that the proportioning determining suitable temperature of reaction, reaction times, reaction pressure and material how according to actual needs.But the temperature of hydroformylation reaction is preferably 50 ~ 180 DEG C in technique scheme; 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 technique scheme, described hydroformylation catalyst, the optional production method comprised the steps obtains:
The solution of metallic compound in rhodium compound, lanthanide element compound, VA and VB mixes with carrier by the composition 1. pressing catalyzer;
2. dry.
In technique scheme, step is at least one of described rhodium compound preferably in rhodium acetate, rhodium nitrate, rhodium chloride and rhodium sulfate 1.; Step is at least one of described lanthanide element compound preferably in lanthanum acetate, Lanthanum trichloride, lanthanum nitrate, cerous acetate, cerous nitrate, Cerium II Chloride, praseodymium acetate, acetic acid neodymium, samarium trichloride, Ytterbium trichloride, Europium trichloride and lutecium chloride 1.; At least one of step 1. in the preferred Bismuth Subcarbonate of described VA metallic compound, bismuth sulfate, bismuth chloride, bismuth and ammonium citrate, bismuth subsalicylate, weisspiessglanz, antimony trisulfate and antimony chloride; Step is at least one of metallic compound preferably in vanadium trichloride, Vanadium Pentoxide in FLAKES, columbium pentachloride and tantalum pentachloride in described VB 1.; Step 2. described drying temperature is 80 ~ 120 DEG C, is more preferably 100 ~ 120 DEG C.
The preparation key of catalyzer of the present invention is the preparation of hydroformylation Primary Catalysts after obtaining Primary Catalysts, can obtain catalyzer of the present invention by making Primary Catalysts with described promotor contact.The mode that Primary Catalysts contacts with promotor is not particularly limited, and is also not particularly limited the opportunity of contact making both.Both such as can be made before catalyzer of the present invention is used for chemical reaction contact to form described catalyzer, and in the reaction system that both can also be made to apply at catalyzer of the present invention, contact makes catalyzer in-situ preparation.
The present invention synthesizes 1; in the method for ammediol; after step (1) terminates; separation can be carried out to the mixture of hydroformylation reaction to obtain target product 3-acetoxyl group propionic aldehyde and carry out step (2) again, also can step (1) generate 3-acetoxyl group propionic aldehyde after do not separate and directly carry out step (2).Those skilled in the art know the suitable hydrogenation catalyst of selection and determine suitable hydrogenation reaction temperature, time and material proportion.Conventional hydrogenation catalyst has the metal catalyst, metal oxide catalyst, metal sulfide catalyst, complex catalyst etc. of transition metal, such as platinum, palladium, nickel, ruthenium carried catalyst, cupric oxide-copper chromite, alumina-silica zinc-chromium oxide catalyst, nickel-molybdenum sulphide and RhCl [P (C
6h
5)
3].In the present invention, preferred Raney's nickel is as hydrogenation catalyst, and 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; Solvent preferably water, at least one in toluene.
After step (2) terminates, separation can be carried out to the mixture of hydrogenation reaction to obtain target product 3-acetoxyl group propyl alcohol and carry out step (3) again, also can step (2) generate 3-acetoxyl group propyl alcohol after do not separate and directly carry out step (3).Those skilled in the art know the suitable alcoholysis catalysts of selection and determine suitable alcoholysis reaction temperature, time and material proportion.But at least one in technique scheme in alcoholysis reaction in the preferred basic catalyst of alcoholysis catalysts and an acidic catalyst; At least one of the low-carbon (LC) saturated alcohol of the preferred C1 ~ C5 of the alcohol in alcoholysis reaction.Alcoholysis reaction catalyzer is more preferably dissolved in the sodium methylate of alcohol; Alcohol in alcoholysis reaction more preferably methyl alcohol.In technique scheme, alcoholysis reaction temperature is preferably 30 ~ 100 DEG C; Alcoholysis reaction pressure preferably 0 ~ 2.0MPa.
Final product of the present invention through cooling, decompression, be separated after adopt gas chromatograph-mass spectrometer (GC-MASS) to analyze, by the following transformation efficiency of formulae discovery vinyl acetate between to for plastic and the yield of 1,3-PD and selectivity:
Compared with prior art; key of the present invention is that the active ingredient of hydroformylation catalyst comprises rhodium, lanthanide element and is selected from least one metallic element in VA and VB; be conducive to the activity and the stability that improve hydroformylation catalyst; thus improve yield and the selectivity of 1,3-PD.
Experimental result shows; when adopting catalyzer of the present invention; 1; ammediol yield 75.42%, selectivity reaches 89.43%, achieves good technique effect; especially when in hydroformylation catalyst, active ingredient comprises rhodium, lanthanide element simultaneously, is selected from least one metallic element in VA and is selected from least one metallic element in VB; achieve more outstanding technique effect, can be used in the industrial production of 1,3-PD.Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gLa with containing the RhCl of 3.10gSb
33H
2o, La (OAc)
35H
2o and Cl
3the abundant mixed dissolution of Sb is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 2.40g/L, Sb content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.42%, and selectivity is 89.43%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 2]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gLa with containing the RhCl of 3.10gNb
33H
2o, La (OAc)
35H
2o and NbCl
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 2.40g/L, Nb content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.38%, and selectivity is 89.47%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of hydroformylation Primary Catalysts: will 6.50gRh and the RhCl containing 2.40gLa be contained
33H
2o and La (OAc)
35H
2the abundant mixed dissolution of O, in pure water, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 2.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 65.33%, and selectivity is 81.67%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
By finding out compared with embodiment 1 ~ 2; the hydroformylation catalyst that the present invention adopts; use simultaneously more excellent than the performance only containing Rh and La active constituent catalyst containing Rh, La and Sb active ingredient, catalyst performance simultaneously containing Rh, La and Nb active ingredient; 1,3-PD selectivity and yield all want high.
[embodiment 3]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gCe with containing the Rh (OAc) of 3.10gSb
3, Ce (OAc)
36H
2o and Sb
2o
3abundant mixed dissolution is in 8wt% aqueous nitric acid in concentration, obtains steeping fluid 400ml, is 200m by 1.0L specific surface
2/ g, pore volume is 1.00, and diameter is the spherical Al of 5.6mm
2o
3carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 80 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Ce content 2.40g/L, Sb content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.41%, and selectivity is 89.32%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 4]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gCe with containing the RhCl of 3.10gSb
33H
2o, CeCl
36H
2o and Sb
2(SO
4)
3abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 150m by 1.0L specific surface
2/ g, pore volume is 0.90, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 120 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Ce content 2.40g/L, Sb content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.30%, and selectivity is 89.51%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 5]
The preparation of hydroformylation Primary Catalysts: by containing 5.00gRh, containing 0.50gCe with containing the Rh of 1.00gBi
2(SO
4)
315H
2o, Ce (NO
3)
36H
2o and (BiO)
2cO
30.5H
2the abundant mixed dissolution of O, in pure water, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 5.00g/L, Ce content 0.50g/L, Bi content 1.00g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 70.61%, and selectivity is 86.27%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 6]
The preparation of hydroformylation Primary Catalysts: by containing 10.00gRh, containing 3.00gPr with containing the RhCl of 5.00gBi
33H
2o, Pr (OAc)
35H
2o and BiCl
3abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 10.00g/L, Pr content 3.00g/L, Bi content 5.00g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 76.12%, and selectivity is 88.95%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 7]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gNd with containing the RhCl of 3.10gBi
33H
2o, Nd (OAc)
35H
2o and bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2o) fully mixed dissolution is in pure water, and obtaining steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Nd content 2.40g/L, Bi content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.34%, and selectivity is 89.40%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 8]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gYb with containing the RhCl of 3.10gBi
33H
2o, YbCl
36H
2o and bismuth subsalicylate (C
7h
5biO
4) fully mixed dissolution be in the aqueous hydrochloric acid of 8wt% in concentration, obtaining steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Yb content 2.40g/L, Bi content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.42%, and selectivity is 89.44%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 9]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gEu with containing the RhCl of 3.10gV
33H
2o, EuCl
36H
2o and VCl
3abundant mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Eu content 2.40g/L, V content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.39%, and selectivity is 89.52%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 10]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gLu with containing the RhCl of 3.10gV
33H
2o, LuCl
36H
2o and V
2o
5abundant mixed dissolution is in the aqueous nitric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Lu content 2.40g/L, V content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 0.2MPa after air; then carbon monoxide and hydrogen is passed into until pressure 1.0MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 50 DEG C; the mol ratio of hydrogen and carbon monoxide is 1:10; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 71.36%, and selectivity is 88.26%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 11]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gSm with containing the RhCl of 3.10gTa
33H
2o, SmCl
36H
2o and TaCl
5abundant mixed dissolution is in the aqueous sulfuric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Sm content 2.40g/L, Ta content 3.10g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 15.0MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 180 DEG C; the mol ratio of hydrogen and carbon monoxide is 10:1; after sustained reaction 15.0h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 75.89%, and selectivity is 89.12%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 12]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gLa, containing 1.70gSb with containing the RhCl of 1.40gNb
33H
2o, La (OAc)
35H
2o, Cl
3sb and NbCl
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 2.40g/L, Sb content 1.70g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 76.60%, and selectivity is 90.58%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
Found out, in the selectivity improving 1,3-PD and yield, in the catalyzer that the present invention uses, between VA metal Sb and VB metal Nb, to there is synergy on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2.
[embodiment 13]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 2.40gCe, containing 1.70gSb with containing the RhCl of 1.40gNb
33H
2o, CeCl
36H
2o, Cl
3sb and NbCl
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, Ce content 2.40g/L, Sb content 1.70g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 76.72%, and selectivity is 90.67%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 14]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 1.70gSb with containing the RhCl of 1.40gNb
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, Cl
3sb and NbCl
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Sb content 1.70g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 78.14%, and selectivity is 91.48%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
Found out, in the selectivity improving 1,3-PD and yield, in the catalyzer that the present invention uses, in lanthanide series metal, between La and Ce, to there is synergy on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13.
[embodiment 15]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 1.70gBi with containing the RhCl of 1.40gNb
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2and NbCl O)
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Bi content 1.70g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 78.05%, and selectivity is 91.54%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 16]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 0.60gSb, containing 1.10gBi with containing the RhCl of 1.40gNb
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, Cl
3sb, bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2and NbCl O)
5abundant mixed dissolution is in the aqueous hydrochloric acid of 8wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Sb content 0.60g/L, Bi content 1.10g/L, Nb content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 79.27%, and selectivity is 92.46%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, in raising 1, the selectivity of ammediol and yield aspect, in the catalyzer that the present invention uses, between VA metal Sb, Bi, there is synergy, describe between Rh, La, Ce, Sb, Bi and Nb six kinds of active ingredients and there is well synergy.
[embodiment 17]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 0.60gSb, containing 1.10gBi with containing the RhCl of 1.40gV
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, Cl
3sb, bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2and VCl O)
3abundant mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Sb content 0.60g/L, Bi content 1.10g/L, V content 1.40g/L.
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 79.23%, and selectivity is 92.53%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
[embodiment 18]
The preparation of hydroformylation Primary Catalysts: by containing 6.50gRh, containing 0.80gLa, containing 1.60gCe, containing 0.60gSb, containing 1.10gBi, containing 0.90gNb with containing the RhCl of 0.50gV
33H
2o, La (OAc)
35H
2o, CeCl
36H
2o, Cl
3sb, bismuth and ammonium citrate (Bi (NH
3)
2c
6h
7o
7h
2o), NbCl
5and VCl
3abundant mixed dissolution is in the aqueous acetic acid of 10wt% in concentration, obtains steeping fluid 400ml, is 168m by 1.0L specific surface
2/ g, pore volume is 0.94, and diameter is the spherical SiO of 5.6mm
2carrier impregnation, in above-mentioned steeping fluid, leaves standstill 3h in 100 DEG C of dryings, obtains described catalyzer.The Rh content measuring this catalyzer through ICP is 6.50g/L, La content 0.80g/L, Ce content 1.60g/L, Sb content 0.60g/L, Bi content 1.10g/L, Nb content 0.90g/L, V content 0.50g/L.。
The synthesis of 1,3-PD:
Step (1): 2.50mol toluene, 0.02mol hydroformylation Primary Catalysts, 0.20mol triphenyl phosphorus and 1.65mol vinyl acetate between to for plastic are added in 1L titanium material reactor; first discharge in still with argon gas and be pressurized to 1.0MPa after air; then carbon monoxide and hydrogen is passed into until pressure 5.3MPa; improve stirring velocity to 800rpm; stirring heating is warming up to temperature of reaction simultaneously; controlling temperature of reaction is 102 DEG C; the mol ratio of hydrogen and carbon monoxide is 2:1; after sustained reaction 4.5h, stopped reaction.Reactor is down to room temperature, and the products in water be obtained by reacting is washed 3 times, and organism enters oil phase, through rectification and purification except desolventizing, vinyl acetate between to for plastic and other by products, obtains 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 1.0MPa after air, then hydrogen is passed into until pressure 5.0MPa, improve stirring velocity to 600rpm, stirring heating is warming up to temperature of reaction simultaneously, controlling temperature of reaction is 70 DEG C, after sustained reaction 100min, stopped reaction.Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml methyl alcohol, 0.02mol sodium methylate (CH
3oNa) add 100ml titanium material reactor, first discharge in still with argon gas and be pressurized to 0.5MPa after air, be warming up to 65 DEG C, stir constant temperature 4h.
The above-mentioned reaction mixture be obtained by reacting is cooled, reduces pressure, is separated, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MASS) analysis.
As calculated 1, the yield of ammediol is 80.40%, and selectivity is 93.31%, for convenience of explanation and compare, the yield of the preparation condition of carrier physical property, catalyzer, reaction conditions, material feeding amount, 1,3-PD and selectivity are listed in table 1 and table 2 respectively.
Found out on year-on-year basis by embodiment 18 and embodiment 16 and embodiment 17, in raising 1, the selectivity of ammediol and yield aspect, in the catalyzer that the present invention uses, between VB metal V, Nb, there is synergy, describe between Rh, La, Ce, Sb, Bi, Nb and V seven kinds of active ingredients and there is well synergy.
Table 1
Table 2 (continued)
Table 2 (Continued)
Claims (10)
1. produce ammediol method used, comprise the following steps: (1) for raw material with vinyl acetate between to for plastic, carbon monoxide and hydrogen, is carried out hydroformylation reaction and obtained 3-acetoxyl group propionic aldehyde under hydroformylation catalyst and promotor exist; (2) in the presence of a hydrogenation catalyst, make hydrogen and 3-acetoxyl group propionic aldehyde react and obtain 3-acetoxyl group propyl alcohol; (3) alcoholysis of 3-acetoxyl group propyl alcohol obtains 1.3-propylene glycol; Wherein, described hydroformylation catalyst adopts SiO
2, Al
2o
3or its mixture is carrier, active ingredient comprises rhodium, lanthanide element and is selected from least one metallic element in VA and VB.
2. method according to claim 1, is characterized in that described lanthanide element is selected from least one in lanthanum, cerium, praseodymium, neodymium, samarium, europium, ytterbium and lutetium.
3. method according to claim 1, is characterized in that described VA metal is selected from least one in antimony and bismuth.
4. method according to claim 1, is characterized in that described VB metal is selected from least one in vanadium, niobium and tantalum.
5. method according to claim 1; it is characterized in that the content of rhodium in hydroformylation catalyst is: 3.00 ~ 15.00g/L; the content of lanthanide element is: 0.10 ~ 3.00g/L, and at least one content being selected from metal in VA and VB described in hydroformylation catalyst is 0.10 ~ 5.00g/L.
6. method according to claim 1, is characterized in that hydroformylation step (1) described promotor is selected from least one in pyridine and triphenyl phosphorus.
7. method according to claim 1, is characterized in that the temperature of step (1) hydroformylation reaction is 50 ~ 180 DEG C.
8. method according to claim 1, is characterized in that the preparation method of described hydroformylation catalyst, comprises the steps:
The solution of metallic compound in rhodium compound, lanthanide element compound, VA and VB mixes with carrier by the composition 1. pressing catalyzer;
2. dry.
9. method according to claim 1, is characterized in that step (3) alcoholysis catalysts is selected from least one in basic catalyst and an acidic catalyst.
10. method according to claim 1, is characterized in that the alcohol in step (3) alcoholysis reaction is selected from least one of the low-carbon (LC) saturated alcohol of C1 ~ C5.
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| CN111533767A (en) * | 2020-04-30 | 2020-08-14 | 卢海元 | Tetradentate phosphine ligand and preparation method thereof, hydroformylation catalyst and reaction method, and preparation method of 1, 3-propylene glycol |
| CN114522739A (en) * | 2020-11-23 | 2022-05-24 | 中国科学院大连化学物理研究所 | Method for preparing 1, 3-propylene glycol from vinyl acetate |
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