CN105585444A

CN105585444A - 1,3-propanediol production method

Info

Publication number: CN105585444A
Application number: CN201410575060.6A
Authority: CN
Inventors: 查晓钟; 杨运信; 张丽斌
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2014-10-24
Filing date: 2014-10-24
Publication date: 2016-05-18
Anticipated expiration: 2034-10-24
Also published as: CN105585444B

Abstract

The invention relates to a 1,3-propanediol production method. 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 production 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 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, alkaline earth metal and at least one metal element selected from VA 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

The production method of 1,3-PD

Technical field

The present invention relates to the production 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 production 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,Alkaline-earth metal and be selected from least one metallic element in VA and IVB. Preferred described active component comprises rhodium, alkali simultaneouslyEarth metal, be selected from least one metallic element in VA and be selected from least one metallic element in IVB. Now VAMetallic element and the metallic element of IVB between there is synergy improving aspect the selective and yield of 1,3-PD.

In technique scheme, described alkaline-earth metal is at least one in beryllium, magnesium, calcium, strontium and barium preferably.

In technique scheme, preferably at least one in antimony and bismuth of described VA 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 simultaneouslyEarth metal, VA metallic element and IVB metallic element; For example described active component is made up of rhodium, strontium, antimony and hafnium, orPerson is made up of rhodium, strontium, antimony, bismuth and hafnium, or is made up of rhodium, strontium, antimony, bismuth, hafnium and titanium, or by rhodium, strontium,Beryllium, antimony, bismuth, hafnium and titanium composition.

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, the content of alkaline-earth metal is preferably 0.10～3.00g/L, more preferably0.50～3.00g/L; In described hydroformylation catalyst, be selected from VA and IVB at least one content of metal preferredBe 0.10～5.00g/L, more preferably 1.00～5.00g/L. Described hydroformylation catalyst carrier specific surface used is preferredBe 50～300m²/ g, more preferably 150～200m²/ g, pore volume is preferably 0.80～1.20, and more preferably 0.90～1.00.At least one in the preferred pyridine of described 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. press the composition of catalyst by the solution of metallic compound in rhodium compound, alkaline earth metal compound, VA and IVBMix with carrier;

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 alkaline earth metal compound preferably from alkaline earth oxide, alkaline earth metal chloride, alkaliAt least one in earth metal nitrate, alkali earth metal sulfate and Alkaline Earth Metal Acetate; Step is described VA metal 1.In the preferred basic bismuth carbonate of compound, bismuth sulfate, bismuth chloride, bismuth oxide, antimony oxide, antimony sulfate and antimony chloride at leastA kind of; Step 1. in described IVB metallic compound preferably from titanium tetrachloride, ammonium titanium fluoride, hexafluoro metatitanic acid, zirconium chloride,At least one in acetic acid zirconium and oxychloride hafnium; Step 2. described baking temperature is 80～120 DEG C, more preferably100～120℃。

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 is that the active component of hydroformylation catalyst comprises rhodium, alkaline-earth metalWith at least one metallic element being selected from VA 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, adopts hydroformylation catalyst of the present invention, and 1,3-PD yield 75.49%, selectively reachesTo 89.34%, obtain good technique effect, especially in hydroformylation catalyst, active component comprises rhodium, alkali simultaneouslyEarth metal, when being selected from least one metallic element in VA and being selected from least one metallic element in IVB, obtain moreAdd outstanding technique effect, can be used in the industrial production of 1,3-PD. Below by embodiment, the present invention is done into oneStep is set forth.

Detailed description of the invention

[embodiment 1]

The preparation of catalyst: will contain 6.50gRh, contain 2.00gSr and the RhCl containing 3.30gSb₃·3H₂O、Sr(OA_C)₂·0.5H₂O and Cl₃In the aqueous hydrochloric acid solution that the abundant mixed dissolution of Sb 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 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50G/L, Sr content 2.00g/L, Sb content 3.30g/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 4.5MPa improves mixing speed to 800rpm, and agitating heating is warming up to reaction temperature simultaneouslyDegree, controlling reaction temperature is 104 DEG C, the mol ratio of hydrogen and carbon monoxide is 2:1, after sustained response 4.5h, 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 75.49% as calculated, is selectively 89.34%, 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 catalyst: will contain 6.50gRh, contain 2.00gSr and the RhCl containing 3.30gHf₃·3H₂O、Sr(OA_C)₂·0.5H₂O and oxychloride hafnium (HfOCl₂·8H₂O) fully mixed dissolution, in water, obtains 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,Sr content 2.00g/L, Hf content 3.30g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 75.36% as calculated, is selectively 89.67%, 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 catalyst: will contain 6.50gRh and the RhCl containing 2.00gSr₃·3H₂O and Sr (OA_C)₂·0.5H₂O is abundantMixed dissolution, in water, obtains 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, Sr content 2.00g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 65.33% as calculated, is selectively 81.82%, 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,Sr and Sb active component, simultaneously containing the catalyst performance of Rh, Sr and Hf active component than only containing Rh and the active group of SrThe performance of divided catalyst is more excellent, and the selective and yield of 1,3-PD all wants high.

[embodiment 3]

The preparation of catalyst: will contain 6.50gRh, contain 2.00gMg and the Rh (OAc) containing 3.30gSb₃、MgSO₄WithSb₂O₃Fully mixed dissolution is in 8wt% aqueous solution of nitric acid in concentration, obtains maceration extract 400ml, by 1.0L specific surfaceFor 200m²/ g, pore volume is 1.00, the spherical Al that diameter is 5.6mm₂O₃Carrier 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 6.50g/L, Mg content2.00g/L, Sb content 3.30g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 75.44% as calculated, is selectively 89.53%, 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 catalyst: will contain 6.50gRh, contain 2.00gCa and the RhCl containing 3.30gSb₃·3H₂O、Ca(NO₃)₂· 4H₂O and Sb₂(SO₄)₃In the aqueous hydrochloric acid solution that fully mixed dissolution 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 120 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is6.50g/L, Ca content 2.00g/L, Sb content 3.30g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 75.51% as calculated, is selectively 89.26%, 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 5]

The preparation of catalyst: will contain 5.00gRh, contain 0.50gBe and the Rh containing 1.00gBi₂(SO₄)₃·15H₂O、BeCl₂(BiO)₂CO₃·0.5H₂The abundant mixed dissolution of O, in pure water, obtains 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 5.00g/L, Be content 0.50G/L, Bi content 1.00g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 70.63% as calculated, is selectively 85.20%, 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 catalyst: will contain 10.00gRh, contain 3.00gBa and the RhCl containing 5.00gBi₃·3H₂O, BaO andBiCl₃In the aqueous hydrochloric acid solution that fully mixed dissolution is 8wt% in concentration, obtain maceration extract 400ml, by 1.0L ratio 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 10.00g/L, BaContent 3.00g/L, Bi content 5.00g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 75.98% as calculated, is selectively 89.03%, 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 catalyst: will contain 6.50gRh, contain 2.00gSr and the RhCl containing 3.30gTi₃·3H₂O、Sr(OA_C)₂·0.5H₂O and ammonium titanium fluoride ((NH₄)₂TiF₆) fully mixed dissolution in pure water, obtain 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,Sr content 2.00g/L, Ti content 3.30g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 75.45% as calculated, is selectively 89.32%, 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 catalyst: will contain 6.50gRh, contain 2.00gSr and the RhCl containing 3.30gTi₃·3H₂O、Sr(OA_C)₂·0.5H₂O and hexafluoro metatitanic acid (H₂TiF₆) 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, SrContent 2.00g/L, Ti content 3.30g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 75.50% as calculated, is selectively 89.24%, 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 catalyst: will contain 6.50gRh, contain 2.00gSr and the RhCl containing 3.30gZr₃·3H₂O、Sr(OA_C)₂·0.5H₂O 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, Sr content 2.00g/L, ZrContent 3.30g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 75.51% as calculated, is selectively 89.23%, 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.

[embodiment 10]

The preparation of catalyst: will contain 6.50gRh, contain 2.00gSr and the RhCl containing 3.30gZr₃·3H₂O、Sr(OA_C)₂·0.5H₂O and Zr (OA_C)₄Fully mixed dissolution, in pure water, obtains 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, Sr content 2.00G/L, Zr content 3.30g/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.

The yield of 1,3-PD is 71.08% as calculated, is selectively 88.80%, 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 catalyst: will contain 6.50gRh, contain 2.00gSr and the RhCl containing 3.30gTi₃·3H₂O、Sr(OA_C)₂·0.5H₂O and TiCl₄In 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 100 DEG C dry, obtain described catalyst. The Rh content of measuring this catalyst through ICP is 6.50G/L, Sr content 2.00g/L, Ti content 3.30g/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 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.

The yield of 1,3-PD is 75.83% as calculated, is selectively 89.02%, 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 catalyst: will contain 6.50gRh, contain 2.00gSr, contain 1.50gSb and the RhCl containing 1.80gHf₃·3H₂O、Sr(OA_C)₂·0.5H₂O、Cl₃Sb and oxychloride hafnium (HfOCl₂·8H₂O) abundant mixed dissolution is 8wt% in concentrationIn aqueous hydrochloric acid solution, 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, Sr content 2.00g/L, Sb content 1.50g/L, Hf contentFor 1.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 76.70% as calculated, is selectively 90.86%, 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 2, improving the selective of 1,3-PD and receivingRate aspect, in the catalyst that the present invention uses, has synergy between VA metal Sb and IVB metal Hf.

[embodiment 13]

The preparation of catalyst: will contain 6.50gRh, contain 2.00gSr, contain 1.50gBi and the RhCl containing 1.80gHf₃·3H₂O、Sr(OA_C)₂·0.5H₂O、BiCl₃With oxychloride hafnium (HfOCl₂·8H₂O) abundant mixed dissolution is 8wt% in concentrationIn aqueous hydrochloric acid solution, 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, Sr content 2.00g/L, Bi content 1.50g/L, Hf contentFor 1.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 76.84% as calculated, is selectively 90.65%, 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.

[embodiment 14]

The preparation of catalyst: will be containing 6.50gRh, containing 2.00gSr, containing 0.50gSb, containing 1.00gBi with containing 1.80gHfRhCl₃·3H₂O、Sr(OA_C)₂·0.5H₂O、Cl₃Sb、BiCl₃With oxychloride hafnium (HfOCl₂·8H₂O) fully mixedClosing and be dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtain 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, Sr content 2.00g/L, SbContent 0.50g/L, Bi content 1.00g/L, Hf content is 1.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 78.05% as calculated, is selectively 91.42%, 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, in the catalyst that the present invention uses, has synergy between Sb and Bi in VA metal.

[embodiment 15]

The preparation of catalyst: will contain 6.50gRh, contain 2.00gSr, contain 0.50gSb, contain 1.00gBi and contain 1.80gTi'sRhCl₃·3H₂O、Sr(OA_C)₂·0.5H₂O、Cl₃Sb、BiCl₃And ammonium titanium fluoride ((NH₄)₂TiF₆) fully mixed dissolution inConcentration is in the aqueous hydrochloric acid solution of 8wt%, obtains maceration extract 400ml, is 168m by 1.0L specific surface²/ g, pore volume is0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry,To described catalyst. The Rh content of measuring this catalyst through ICP is 6.50g/L, Sr content 2.00g/L, Sb content0.50g/L, Bi content 1.00g/L, Ti content is 1.80g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 77.93% as calculated, is selectively 91.60%, 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 catalyst: will containing 6.50gRh, containing 2.00gSr, containing 0.50gSb, containing 1.00gBi, containing 1.20gHf andContaining the RhCl of 0.60gTi₃·3H₂O、Sr(OA_C)₂·0.5H₂O、Cl₃Sb、BiCl₃, oxychloride hafnium (HfOCl₂·8H₂O)And ammonium titanium fluoride ((NH₄)₂TiF₆) in aqueous hydrochloric acid solution that fully mixed dissolution is 8wt% in concentration, obtain maceration extract400ml is 168m by 1.0L specific surface²/ g, pore volume is 0.94, the spherical SiO that diameter is 5.6mm₂Carrier impregnationIn above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Measure the Rh of this catalyst through ICPContent is 6.50g/L, Sr content 2.00g/L, and Sb content 0.50g/L, Bi content 1.00g/L, Hf content is 1.20g/L,Ti content is 0.60g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 79.31% as calculated, is selectively 92.38%, 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, the present invention use catalyst in, between IVB metal Ti, Hf, there is synergy, illustrated Rh,Between Sr, Sb, Bi, Ti and six kinds of active components of Hf, there is well synergy.

[embodiment 17]

The preparation of catalyst: will be containing 6.50gRh, containing 2.00gBe, containing 0.50gSb, containing 1.00gBi, containing 1.20gHfWith the RhCl containing 0.60gTi₃·3H₂O、BeCl₂、Cl₃Sb、BiCl₃, oxychloride hafnium (HfOCl₂·8H₂And fluotitanic acid O)Ammonium ((NH₄)₂TiF₆) in 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,Be content 2.00g/L, Sb content 0.50g/L, Bi content 1.00g/L, Hf content is 1.20g/L, Ti content is 0.60g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 79.25% as calculated, is selectively 92.53%, 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 18]

The preparation of catalyst: will containing 6.50gRh, containing 1.60gSr, containing 0.40gBe, containing 0.50gSb, containing 1.00gBi,Contain 1.20gHf and the RhCl containing 0.60gTi₃·3H₂O、Sr(OA_C)₂·0.5H₂O、BeCl₂、Cl₃Sb、BiCl₃, chlorine oxygenChange hafnium (HfOCl₂·8H₂And ammonium titanium fluoride ((NH O)₄)₂TiF₆) hydrochloric acid that fully mixed dissolution is 8wt% in concentration is water-solubleIn liquid, obtaining maceration extract 400ml, is 168m by 1.0L specific surface²/ g, pore volume is 0.94, diameter is 5.6mmSpherical SiO₂Carrier impregnation in above-mentioned maceration extract, leave standstill 3h in 100 DEG C dry, obtain described catalyst. Through ICPThe Rh content of measuring this catalyst is 6.50g/L, Sr content 1.60g/L, and Be content 0.40g/L, Sb content 0.50g/L,Bi content 1.00g/L, Hf content is 1.20g/L, Ti content is 0.60g/L.

Synthesizing of 1,3-PD:

The yield of 1,3-PD is 80.29% as calculated, is selectively 93.40%, 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 18 and embodiment 16 and embodiment 17, improve the selective of 1,3-PD andYield aspect, the present invention use catalyst in, between alkaline-earth metal Sr, Be, there is synergy, illustrated Rh,Between Sr, Be, Sb, Bi, Ti and seven kinds of active components of Hf, there is well synergy.

Table 1

Table 2

Claims

The production 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, alkaline-earth metal and be selected from VA and IVB at least one goldBelong to element.
2. production method according to claim 1, is characterized in that described alkaline-earth metal is selected from beryllium, magnesium, calcium, strontium and bariumIn at least one.
3. production method according to claim 1, is characterized in that described VA metal is selected from least one in antimony and bismuth.
4. production method according to claim 1, is characterized in that described IVB metal is selected from titanium, zirconium and hafnium at leastA kind of.
5. production method according to claim 1, is characterized in that the content of rhodium in hydroformylation catalyst is:3.00～15.00g/L, the content of alkaline-earth metal is: 0.10～3.00g/L.
6. production method according to claim 1, is characterized in that being selected from described in hydroformylation catalyst VA and IVBAt least one content of middle metal is 0.10～5.00g/L.
7. production method according to claim 1, is characterized in that the described promoter of step (1) is selected from pyridine and triphenylAt least one in phosphorus.
8. production method according to claim 1, the temperature that it is characterized in that 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 volumeThan being 0.10～10.0.
9. production method according to claim 1, is characterized in that the preparation of the described hydroformylation catalyst of step (1)Method, comprises the steps:

1. press the composition of catalyst by the solution of metallic compound in rhodium compound, alkaline earth metal compound, VA and IVBMix with carrier;

2. dry.
10. production method according to claim 9, it is characterized in that step 1. described rhodium compound be selected from acetic acid rhodium, nitric acidAt least one in rhodium, radium chloride and rhodium sulfate.