CN105585419A - 1,3-propanediol synthesis method - Google Patents
1,3-propanediol synthesis method Download PDFInfo
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Abstract
The invention relates to a 1,3-propanediol synthesis. The invention mainly aims at solving the problems of low activity and low selectivity of 1,3-propanediol catalyst in prior arts. The 1,3-propanediol synthesis method comprises the following steps: vinyl acetate is subjected to hydroformylation, such that 3-acetoxypropionaldehyde is obtained; 3-acetoxypropionaldehyde is hydrogenated, such that 3-acetoxypropanol is obtained; and 3-acetoxypropanol is is hydrolyzed, such that 1,3-propanediol is obtained. A hydroformylation catalyst adopts SiO2, Al2O3 or a mixture thereof as a carrier, and active components comprise rhodium, alkali metal and at least one metal element selected from IVA and IVB. With the above technical scheme, the technical problem is well solved. The method can be applied in 1,3-propanediol industrial production.
Description
Technical field
The present invention relates to the synthetic method of 1,3-PD.
Background technology
1,3-PD (1.3-PDO) is a kind of important industrial chemicals, be mainly used in plasticizer, washing agent, anticorrisive agent,Synthesizing of emulsifying agent, also for industries such as food, cosmetics and pharmacy. Because it is a kind of important polyester fiber monomer,Its topmost purposes is as monomer and terephthalic acid (TPA) synthesizing new polyester material one polytrimethylene terephthalate(PTT)。
The preparation method of 1,3-PD has oxirane one-step method, oxirane two-step method, acrolein hydration method, acetaldehydeStiasny method, acrylate method, bioanalysis, vinyl acetate hydroformylation etc. At present, the industrialization of 1.3-PDO is rawProduct method is chemical synthesis, and international market is mainly by German Degussa company, shell Shell company of the U.S. and the U.S.Three monopolizations of E.I.Du Pont Company. What Degussa company adopted is that acrolein hydration hydrogenation method (AC method), Shell Co. Ltd adoptWhat be that oxirane carbonyl method (EO method), E.I.Du Pont Company adopt is the own thorugh biologic engineering method (MF method) of innovating. WhereinOxirane two-step process and acrolein hydration method technique are current main flow technique.
It is former in the patents such as patent US4072709 (ProductionofLacticAcid), having told about and having utilized vinyl acetateMaterial, is catalyst by adopting homogeneous phase rhodium compound, by hydroformylation reaction, obtains 2 (or 3)-acetoxyl groups thirdAldehyde. Separate or do not separate, then 3-acetoxyl group propionic aldehyde obtains 1.3-PDO by hydrogenation and hydrolytic process. But above-mentioned sideIn preparation 1.3-PDO process, all there is the low and selective not high problem of 1.3-PDO yield in method.
Summary of the invention
Technical problem to be solved by this invention is yield and the selective low problem of 1,3-PD, provides a kind of newThe synthetic method of 1,3-PD, the method has 1,3-PD yield height and selective high feature.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: the synthetic method of 1,3-PD, bagDraw together following steps: (1) is taking vinyl acetate, carbon monoxide and hydrogen as raw material, hydroformylation catalyst and promoterUnder existence, carry out hydroformylation reaction and obtain 3-acetoxyl group propionic aldehyde; (2) hydrogenation catalyst exist under, make hydrogen withThe reaction of 3-acetoxyl group propionic aldehyde obtains 3-acetoxyl group propyl alcohol; (3) hydrolysis of 3-acetoxyl group propyl alcohol obtains 1,3-PD;Wherein, described hydroformylation catalyst adopts SiO2、Al2O3Or its mixture is carrier, active component comprise rhodium,Alkali metal and be selected from least one metallic element in IVA and IVB. Preferred described active component comprises rhodium, alkali simultaneouslyMetal, be selected from least one metallic element in IVA and be selected from least one metallic element in IVB. Now IVAMetallic element and the metallic element of IVB between there is collaborative work improving aspect the selective and yield of 1,3-PDWith.
In technique scheme, described alkali metal is at least one in lithium, sodium, potassium, rubidium and caesium preferably.
In technique scheme, preferably at least one in germanium, tin and lead of described IVA metal.
In technique scheme, preferably at least one in titanium, zirconium and hafnium of described IVB metal.
In technique scheme, as most preferred technical scheme, described active component comprises rhodium metal element, alkali simultaneouslyMetal, IVA metallic element and IVB metallic element; For example described active component is made up of rhodium, lithium, rubidium, tin and hafnium,Or formed by rhodium, lithium, rubidium, tin and zirconium, or formed by rhodium, lithium, rubidium, tin, zirconium and hafnium.
In technique scheme, in described hydroformylation catalyst, the content of rhodium is preferably 3.00～15.00g/L, more preferably5.00～10.00g/L; In described hydroformylation catalyst, alkali-metal content is preferably 0.10～3.00g/L, more preferably0.50～3.00g/L; In described hydroformylation catalyst, being selected from least one content of metal in IVA and IVB is preferably0.10～5.00g/L, more preferably 1.00～5.00g/L. Described hydroformylation catalyst carrier specific surface used is preferably50～300m2/g, more preferably 150～200m2/g, pore volume is preferably 0.80～1.20, and more preferably 0.90～1.00. DescribedAt least one in the preferred pyridine of promoter and triphenyl phosphorus.
Key of the present invention is the selection of hydroformylation catalyst, how really according to actual needs those skilled in the art will know thatThe proportioning of fixed suitable reaction temperature, reaction time, reaction pressure and material. But, hydrogen formyl in technique schemeThe temperature of changing reaction is preferably 50～180 DEG C; The pressure of reaction is preferably 1.0～15.0MPa; The time of reaction is preferably1.0～15.0h. The mol ratio of carbon monoxide and hydrogen is preferably 0.10～10.0.
In technique scheme, described hydroformylation catalyst, the optional production method comprising the steps obtains:
1. the composition of pressing catalyst by the solution of metallic compound in rhodium compound, alkali metal compound, IVA and IVB withCarrier mixes;
2. dry.
In technique scheme, step 1. described rhodium compound preferably in acetic acid rhodium, rhodium nitrate, radium chloride and rhodium sulfateAt least one; Step 1. described alkali metal compound preferably from alkali metal oxide, alkali metal chloride, alkali metal nitreAt least one in hydrochlorate, alkali metal sulfates and alkali metal acetate; Step is described IVA metallic compound preferably four 1.In the sub-tin of germanium chloride, stannous chloride, nitric acid, stannous oxide, lead acetate and plumbi nitras at least one; Step is described IVB 1.Middle metallic compound is preferably in titanium tetrachloride, ammonium titanium fluoride, hexafluoro metatitanic acid, zirconium chloride, acetic acid zirconium and the oxychloride hafniumAt least one; Step 2. described baking temperature is 80～120 DEG C, more preferably 100～120 DEG C.
The preparation key of catalyst of the present invention is the preparation of hydroformylation major catalyst, after obtaining major catalyst, logicalCross and make major catalyst can obtain catalyst of the present invention with described promoter contact. The side that major catalyst contacts with promoterFormula is not particularly limited, to be also not particularly limited the opportunity that both contact. For example catalyst of the present invention can usedBefore chemical reaction, make both contact and form described catalyst, can also make both applied anti-at catalyst of the present inventionAnswer contact in system that catalyst original position is generated.
In the method for the synthetic 1,3-PD of the present invention, after step (1) finishes, can be to the mixing of hydroformylation reactionThing separates acquisition target product 3-acetoxyl group propionic aldehyde and carries out step (2) again, also can step (1) generate 3-After acetoxyl group propionic aldehyde, do not separate and directly carry out step (2). Those skilled in the art know the suitable hydrogenation of selection and urgeAgent and definite suitable hydrogenation reaction temperature, time and material proportion. Conventional hydrogenation catalyst has transition metal unitThe metallic catalyst, metal oxide catalyst, metal sulfide catalyst, complex catalyst of element etc., for example platinum, palladium,Nickel, ruthenium carried catalyst, cupric oxide-copper chromite, aluminium oxide-zinc oxide-chromium oxide catalyst, nickel-molybdenum sulphide withAnd RhCl[P (C6H5)3]. In the present invention preferably Raney's nickel as hydrogenation catalyst, suitable hydrogenation temperature is preferably 30～100 DEG C; Preferably 0.5～8.0MPa of hydrogenation reaction pressure; The hydrogenation reaction time is preferably 10～200min; Aldehyde and hydrogenMol ratio preferably 0.10～2.0; Solvent preferred water, at least one in toluene.
After step (2) finishes, can separate and obtain target product 3-acetoxyl group third mixture of hydrogenation reactionAlcohol carries out step (3) again, also can step (2) generates after 3-acetoxyl group propyl alcohol and does not separate and directly carry out step(3). Those skilled in the art know select suitable hydrolyst and determine suitable hydrolysising reacting temperature, time andMaterial proportion. Conventional hydrolyst can be inorganic acid, inorganic base, organic acid and organic base. For example hydrochloric acid, nitreAcid, sulfuric acid, phosphoric acid, NaOH, potassium hydroxide, benzene sulfonic acid and ion exchange resin. Suitable hydrolysis temperatureDegree is preferably 50～100 DEG C; Preferably 0～2.0MPa of hydrolysis pressure; Solvent preferred water, benzene, cyclohexane, tolueneIn at least one.
End product of the present invention adopts gas chromatograph-mass spectrometer (GC-MS) (GC-MASS) point after cooling, decompression, separationAnalyse, calculate the conversion ratio of vinyl acetate and the yield of 1,3-PD and selective by following formula:
Compared with prior art, key of the present invention be the active component of hydroformylation catalyst comprise rhodium, alkali metal andBe selected from least one metallic element in IVA and IVB, be conducive to improve activity and the stability of hydroformylation catalyst,Thereby improve the yield of 1,3-PD with selective.
Experimental result shows, while adopting hydroformylation catalyst of the present invention, 1,3-PD yield 75.47%, selectively reachesTo 89.73%, obtain good technique effect, especially in catalyst, active component comprises rhodium, alkali metal, choosing simultaneouslyAt least one metallic element in IVA and while being selected from least one metallic element in IVB, has obtained more outstandingTechnique effect, can be used in the industrial production of 1,3-PD. Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.50gLi and the RhCl containing 3.50gSn3·3H2O、LiCl and SnCl2·2H2In the aqueous hydrochloric acid solution that the abundant mixed dissolution of O is 8wt% in concentration, obtain maceration extract 400ml,Be 168m by 1.0L specific surface2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation is above-mentionedIn maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is6.50g/L, Li content 1.50g/L, Sn content 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.47% as calculated, is selectively 89.73%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 2]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.50gLi and the RhCl containing 3.50gTi3·3H2O、LiCl and TiCl4In the aqueous hydrochloric acid solution that fully mixed dissolution is 8wt% in concentration, obtain maceration extract 400ml, by 1.0LSpecific surface is 168m2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract,Leave standstill 3h in 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L，Li content 1.50g/L, Ti content 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.56% as calculated, is selectively 89.64%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of hydroformylation catalyst: will fully mix containing 6.50Rh with containing RhCl33H2O and the LiCl of 1.50gLiBeing dissolved in pure water, obtaining maceration extract 400ml, is 168m by 1.0L specific surface2/ g, pore volume is 0.94, diameter isThe spherical SiO of 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst.The Rh content of measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 65.73% as calculated, is selectively 81.23%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
By finding out compared with embodiment 1～2, the present invention adopt hydroformylation catalyst, use simultaneously containing Rh,Li and Sn active component, simultaneously containing the catalyst performance of Rh, Li and Ti active component than only containing Rh and the active group of LiThe performance of divided catalyst is more excellent, and the selective and yield of 1,3-PD all wants high.
[embodiment 3]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.50gK and the Rh (OAc) containing 3.50gGe3、K2SO4And GeCl4Fully mixed dissolution is in 10wt% aqueous acetic acid in concentration, obtains maceration extract 400ml, by 1.0L ratioSurface is 200m2/ g, pore volume is 1.00, the spherical Al that diameter is 5.6mm2O3Carrier impregnation in above-mentioned maceration extract,Leave standstill 3h in 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L, KContent 1.50g/L, Ge content 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.28% as calculated, is selectively 89.77%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 4]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.50gRb and the RhCl containing 3.50gSn3·3H2O、RbNO3And SnCl2·2H2In the aqueous hydrochloric acid solution that the abundant mixed dissolution of O is 8wt% in concentration, obtain maceration extract 400ml,Be 150m by 1.0L specific surface2/ g, pore volume is 0.90, the spherical SiO that diameter is 5.6mm2Carrier impregnation is above-mentionedIn maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is6.50g/L, Rb content 1.50g/L, Sn content 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.34% as calculated, is selectively 89.57%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 5]
The preparation of hydroformylation catalyst: will contain 5.00gRh, contain 0.50gCs and the Rh containing 1.00gPb2(SO4)3·15H2O、CsOAc and Pb (OAc)2·3H2The abundant mixed dissolution of O, in pure water, obtains maceration extract 400ml, by 1.0L specific surfaceFor 168m2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill3h in 80 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 5.00g/L, Cs content0.50g/L, Pb content 1.00g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 70.07% as calculated, is selectively 85.28%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 6]
The preparation of hydroformylation catalyst: will contain 10.00gRh, contain 3.00gNa and the RhCl containing 5.00gPb3·3H2O、Na2O and Pb (NO3)2In the aqueous hydrochloric acid solution that fully mixed dissolution is 8wt% in concentration, obtain maceration extract 400ml, will1.0L specific surface is 168m2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation is at above-mentioned dippingIn liquid, leave standstill 3h in 120 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is10.00g/L, Na content 3.00g/L, Pb content 5.00g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 76.14% as calculated, is selectively 89.10%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 7]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.50gLi and the RhCl containing 3.50gTi3·3H2O、LiCl and ammonium titanium fluoride ((NH4)2TiF6) fully mixed dissolution in pure water, obtain maceration extract 400ml, by 1.0L than tableFace is 168m2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation is in above-mentioned maceration extract, quietPut 3h in 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L, LiContent 1.50g/L, Ti content 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 0.2MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 1.0MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 50 DEG C, the mol ratio of hydrogen and carbon monoxide is 1:10, after sustained response 1.0h, stopsReaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through rectifyingPurify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 71.64% as calculated, is selectively 88.51%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 8]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.50gLi and the RhCl containing 3.50gTi3·3H2O、LiCl and hexafluoro metatitanic acid (H2TiF6) fully mixed dissolution in pure water, obtain maceration extract 400ml, by 1.0L specific surfaceFor 168m2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill3h in 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L, and Li containsAmount 1.50g/L, Ti content 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 2.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 15.0MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 180 DEG C, the mol ratio of hydrogen and carbon monoxide is 10:1, after sustained response 15.0h, stopsOnly reaction. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, through essenceHeat up in a steamer and purify except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 76.11% as calculated, is selectively 89.06%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 9]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.50gLi and the RhCl containing 3.50gZr3·3H2O、LiCl and ZrCl4Fully mixed dissolution, in pure water, obtains maceration extract 400ml, is 168m by 1.0L specific surface2/g，Pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h dry in 100 DEG CDry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L, ZrContent 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.42% as calculated, is selectively 89.37%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 10]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.50gLi and the RhCl containing 3.50gZr3·3H2O、LiCl and Zr (OAC)4Fully mixed dissolution, in pure water, obtains maceration extract 400ml, is 168m by 1.0L specific surface2/g，Pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation, in above-mentioned maceration extract, leaves standstill 3h dry in 100 DEG CDry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L, Li content 1.50g/L, ZrContent 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.56% as calculated, is selectively 89.25%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 11]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.50gLi and the RhCl containing 3.50gHf3·3H2O、LiCl and oxychloride hafnium (HfOCl2·8H2O) fully mixed dissolution, in pure water, obtains maceration extract 400ml, by 1.0L ratioSurface is 168m2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract,Leave standstill 3h in 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L,Li content 1.50g/L, Hf content 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 75.45% as calculated, is selectively 89.33%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 12]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.00gLi, contain 0.50gRb and the RhCl containing 3.50gSn3·3H2O、LiCl、RbNO3And SnCl2·2H2In the aqueous hydrochloric acid solution that the abundant mixed dissolution of O is 8wt% in concentration,To maceration extract 400ml, be 168m by 1.0L specific surface2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2CarryBody is immersed in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Measure this catalysis through ICPThe Rh content of agent is 6.50g/L, Li content 1.00g/L, Rb content 0.50g/L, Sn content 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 76.78% as calculated, is selectively 90.12%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
Find out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 4, improving the selective of 1,3-PD and receivingRate aspect, has synergy between alkali metal Li, Rb and IVA metal Sn.
[embodiment 13]
The preparation of hydroformylation catalyst: will contain 6.50gRh, contain 1.00gLi, contain 0.50gRb and the RhCl containing 3.50gZr3·3H2O、LiCl、RbNO3And Zr (OAC)4Fully mixed dissolution, in water, obtains maceration extract 400ml, by 1.0L ratioSurface is 168m2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract,Leave standstill 3h in 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L,Li content 1.00g/L, Rb content 0.50g/L, Zr content 3.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 76.64% as calculated, is selectively 90.26%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 14]
The preparation of hydroformylation catalyst: will be containing 6.50gRh, containing 1.00gLi, containing 0.50gRb, containing 2.00gSn and containing1.50gZr RhCl3·3H2O、LiCl、RbNO3、SnCl2·2H2O and Zr (OAC)4Fully mixed dissolution is in concentrationIn aqueous hydrochloric acid solution for 8wt%, obtaining maceration extract 400ml, is 168m by 1.0L specific surface2/ g, pore volume is 0.94,Diameter is the spherical SiO of 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, described in obtainingCatalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L, Li content 1.00g/L, and Rb content 0.50g/L,Sn content 2.00g/L, Zr content 1.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 77.62% as calculated, is selectively 90.92%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
Find out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, improve the selective of 1,3-PD andYield aspect, has synergy between IVA metal Sn and IVB metallic Z r.
[embodiment 15]
The preparation of hydroformylation catalyst: will be containing 6.50gRh, containing 1.00gLi, containing 0.50gRb, containing 2.00gSn and containing1.50gHf RhCl3·3H2O、LiCl、RbNO3、SnCl2·2H2O and oxychloride hafnium (HfOCl2·8H2O) abundantIn the aqueous hydrochloric acid solution that mixed dissolution is 8wt% in concentration, obtaining maceration extract 400ml, is 168 by 1.0L specific surfacem2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in100 DEG C dry, obtains described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L, Li content 1.00G/L, Rb content 0.50g/L, Sn content 2.00g/L, Hf content 1.50g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 77.59% as calculated, is selectively 91.04%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
[embodiment 16]
The preparation of hydroformylation catalyst: will containing 6.50gRh, containing 1.00gLi, containing 0.50gRb, containing 2.00gSn, contain0.50gZr and containing the RhCl of 1.00gHf3·3H2O、LiCl、RbNO3、SnCl2·2H2O、Zr(OAC)4And oxychlorideHafnium (HfOCl2·8H2O), in the aqueous hydrochloric acid solution that fully mixed dissolution is 8wt% in concentration, obtain maceration extract 400ml,Be 168m by 1.0L specific surface2/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm2Carrier impregnation is above-mentionedIn maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is6.50g/L, Li content 1.00g/L, Rb content 0.50g/L, Sn content 2.00g/L, Zr content 0.50g/L, Hf containsAmount 1.00g/L.
Synthesizing of 1,3-PD:
Step (1): by 2.50mol toluene, 0.02mol hydroformylation major catalyst, 0.20mol triphenyl phosphorus and 1.65molVinyl acetate adds in 1L titanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into oneCarbonoxide and hydrogen are until pressure 5.2MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 98 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.0h, stops anti-Should. Reactor is down to room temperature, and the product that reaction is obtained washes with water 3 times, and organic matter enters oil phase, carries through rectifyingPure except desolventizing, vinyl acetate and other accessory substances, obtain 3-acetoxyl group propionic aldehyde.
Step (2): above-mentioned 3-acetoxyl group propionic aldehyde 15ml, toluene 30ml, 0.01mol Raney's nickel are added to 100mlTitanium material reactor, first discharges in still and is pressurized to 1.0MPa after air with argon gas, then passes into hydrogen until pressure 5.0MPa,Improve mixing speed to 600rpm, agitating heating is warming up to reaction temperature simultaneously, and controlling reaction temperature is 70 DEG C, continuesAfter reaction 100min, stop reaction. Reactor is down to room temperature, obtains 3-acetoxyl group propyl alcohol through purification removal of impurities.
Step (3): (10ml toluene and 20ml water are mixed by above-mentioned 3-acetoxyl group propyl alcohol 18ml, 30ml toluene-waterClose and form), 0.015molAmberliteIR120 ion exchange resin adds 100ml titanium material reactor, first uses argon gasDischarge in still and be pressurized to 0.5MPa after air, be warming up to 75 DEG C, stir constant temperature 7h.
Reactant mixture that above-mentioned reaction is obtained is cooling, decompression, separate, and liquid phase adopts gas chromatograph-mass spectrometer (GC-MS)(GC-MASS) analyze.
The yield of 1,3-PD is 78.41% as calculated, is selectively 91.65%, for convenience of explanation and relatively, and willYield and the selection of the preparation condition of support modification condition, catalyst, reaction condition, material feeding amount, 1,3-PDProperty is listed in respectively table 1 and table 2.
Find out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, improve the selective of 1,3-PD andYield aspect, in the catalyst that the present invention uses, has collaborative work between IVA metal Sn and IVB metallic Z r, HfWith, illustrate between Rh, Li, Rb, Sn, Zr and six kinds of active components of Hf and existed well and act synergistically.
Table 1
Table 2
Claims (10)
- The synthetic method of 1.3-propane diols, comprises the following steps: (1) taking vinyl acetate, carbon monoxide and hydrogen as raw material,Under hydroformylation catalyst and promoter existence, carry out hydroformylation reaction and obtain 3-acetoxyl group propionic aldehyde; (2) existUnder hydrogenation catalyst exists, hydrogen is reacted with 3-acetoxyl group propionic aldehyde and obtain 3-acetoxyl group propyl alcohol; (3) 3-The hydrolysis of acetoxyl group propyl alcohol obtains 1.3-propane diols; Wherein, described hydroformylation catalyst adopts SiO2、Al2O3OrIts mixture of person is carrier, active component comprise rhodium, alkali metal and be selected from IVA and IVB at least one metalElement.
- 2. method according to claim 1, is characterized in that described alkali metal is selected from lithium, sodium, potassium, rubidium and caesium extremelyFew a kind of.
- 3. method according to claim 1, is characterized in that described IVA metal is selected from least one in germanium, tin and lead.
- 4. method according to claim 1, is characterized in that described IVB metal is selected from least one in titanium, zirconium and hafnium.
- 5. method according to claim 1, is characterized in that the content of rhodium in hydroformylation catalyst is: 3.00～15.00g/L,Alkali-metal content is: 0.10～3.00g/L.
- 6. method according to claim 1, is characterized in that being selected from IVA and IVB described in hydroformylation catalyst goldenAt least one content belonging to is 0.10～5.00g/L.
- 7. method according to claim 1, is characterized in that the described promoter of step (1) is selected from pyridine and triphenyl phosphorusAt least one.
- 8. method according to claim 1, is characterized in that the temperature of step (1) hydroformylation reaction is 50～180 DEG C;The pressure of reaction is 1.0～15.0MPa; The time of reaction is 1.0～15.0h; Carbon monoxide and hydrogen volume ratio be 0.10～10.0。
- 9. method according to claim 1, is characterized in that the production method of described hydroformylation catalyst, comprise asLower step:1. the composition of pressing catalyst by the solution of metallic compound in rhodium compound, alkali metal compound, IVA and IVB withCarrier mixes;2. dry.
- 10. method according to claim 9, it is characterized in that step 1. described rhodium compound be selected from acetic acid rhodium, rhodium nitrate,At least one in radium chloride and rhodium sulfate.
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