CN101570523B - Method for catalyzing and oxidizing allyl alcohol to produce epoxy propanol - Google Patents

Abstract

The invention discloses a method for producing glycidyl alcohol by catalytically oxidizing allyl alcohol, which is characterized in that allyl alcohol, oxygen, hydrogen, diluted Mixed contact reaction of gas, solvent and catalyst, the molar ratio of allyl alcohol to oxygen, hydrogen, and diluent gas is 1: (0.1～10): (0.1～10): (0～100), the mass of allyl alcohol and catalyst The ratio is (0.5-50): 1, the mass ratio of the solvent to the catalyst is (0-1000): 1, and the catalyst is a microporous titanium-silicon material or a composition containing the microporous titanium-silicon material. The composition of the porous titanium silicon material is expressed in the form of oxide as xTiO ₂ ·100SiO ₂ ·yE _m O _n ·zE, where the value of x is 0.001-50.0, the value of (y+z) is 0.005-20.0 and y/z<5 , E represents one or several noble metals selected from Ru, Rh, Pd, Re, Os, Ir, Ag, Pt and Au, m and n are the numbers required to satisfy the oxidation state of E, and the material grains contain hollow or concave-convex structure. The method has high conversion rate of allyl alcohol, good product selectivity and good activity stability.

Description

A kind of method of catalytic oxidation allyl alcohol to produce glycidyl alcohol

technical field

The invention relates to a method for catalyzing the oxidation of allyl alcohol, and more particularly relates to a method for catalyzing the oxidation of allyl alcohol by using a titanium-silicon material containing noble metal as a catalyst.

Background technique

Glycidyl alcohol is an important fine chemical raw material and intermediate, which is used to synthesize a series of glycerol derivatives, and is widely used in the fields of surface coatings, textiles, food, chemical synthesis and pharmaceutical chemicals. The industrial production of glycidyl alcohol is mainly obtained by epoxidizing allyl alcohol with an oxidizing agent (such as hypochlorous acid or perchloric acid) using tungstate as a catalyst. This process is highly polluting to the environment, and the catalyst used is low in activity and non-renewable.

Therefore, it is of great practical significance to explore a new method for catalytic oxidation of allyl alcohol with high conversion rate of allyl alcohol, good selectivity of glycidol, especially low pollution, environmental friendliness and simplicity. Titanium-silicon molecular sieves, which began to appear in the early 1980s, have a good selective oxidation effect on olefins, alcohols, phenols, etc. (such as EP0230949, US4480135, US4396783). Compared with other types of catalysts, titanium-silicon molecular sieves are used as catalysts The oxidation system has the following significant advantages: (1) The reaction conditions are mild and can be carried out at normal pressure and low temperature (20-100°C); (2) The oxidation target product has a high yield and good selectivity; (3) The process is simple , Environmentally friendly.

There are research reports on catalyzing the oxidation of allyl alcohol to glycidyl alcohol on titanium-silicon molecular sieves (such as J Catal, 1993, 140 (1): 71-83; Catal Lett, 1996, 39: 83-87; J Catal, 2003 , 214(2): 317-326; Acta Catalytica Sinica, 2006, 27(3): 285-290), but due to the high price of the oxidant H ₂ O ₂ used in the system, and H ₂ O ₂ is extremely unstable and corrosive Special safety measures should be taken in packaging, storage and transportation. However, the preparation of H ₂ O ₂ requires separate equipment and a circulation system, which costs a lot, and the on-site production cost is very high. Therefore, before the introduction of more stringent environmental protection regulations, the titanium silicon molecule/H ₂ O ₂ system using H ₂ O ₂ as the oxidant has certain economic obstacles in the industrialization of allyl alcohol epoxidation.

Molecular oxygen is cheap, easy to obtain and non-polluting, and is the most ideal oxygen source. Using H ₂ and O ₂ to directly synthesize H ₂ O ₂ can greatly reduce the preparation cost of H ₂ O ₂ , which is beneficial to the industrialization of titanium silicon molecular sieve/H ₂ O ₂ system. Pt and Pd are effective components for the synthesis of H ₂ O ₂ from H ₂ and O ₂ . It has been reported in the literature that they are supported on titanium-silicon molecular sieve materials to generate H ₂ O ₂ in situ for the study of gas-phase epoxidation of propylene. For example, Meiers R. et al. (J.Catal., 1998, 176:376-386) studied the preparation of propylene oxide by epoxidation of propylene with Pt-Pd/titanium silicate molecular sieve as catalyst. But so far there is no report on the preparation of glycidol by catalytic oxidation of allyl alcohol.

Contents of the invention

The purpose of the present invention is to provide a method for catalyzing the epoxidation of allyl alcohol with a unique microporous titanium-silicon material as a catalyst.

The method for producing propylene oxide by catalytically oxidizing allyl alcohol provided by the invention is characterized in that allyl alcohol, oxygen, hydrogen, diluent gas, and solvent are Mixed contact reaction with catalyst, the molar ratio of allyl alcohol to oxygen, hydrogen, diluent gas is 1: (0.1～10): (0.1～10): (0～100), the mass ratio of allyl alcohol to catalyst is ( 0.5-50): 1, the mass ratio of solvent to catalyst is (0-1000): 1, said catalyst is a microporous titanium-silicon material or a composition containing the microporous titanium-silicon material, microporous titanium-silicon The composition of the material is expressed in the form of oxide as xTiO ₂ ·100SiO ₂ ·yE _m O _n ·zE, where the value of x is 0.001-50.0, the value of (y+z) is 0.005-20.0 and y/z<1, and E represents One or more noble metals selected from Ru, Rh, Pd, Re, Os, Ir, Ag, Pt and Au, m and n are the numbers required to satisfy the oxidation state of E, and the material grains contain hollow or concave-convex structures .

In the method provided by the present invention, said microporous titanium-silicon material is disclosed in Chinese patent application No. 200710064981.6. In the expression form of oxides, the x value is preferably 0.005-25, and the (y+z) value is preferably 0.01. -10, the noble metal E is preferably one or more of Pd, Pt and Au, more preferably Pd and/or Pt, when there are two or more noble metals, the value of y mentioned is the y value of each noble metal The said z value is the sum of the z values of each noble metal. For example, when the selected noble metals are Pt and Pd, the composition of the material is expressed as xTiO ₂ ·100SiO ₂ ·y ₁ PtO in the form of oxides ·y ₂ PdO·z ₁ Pt·z ₂ Pd, that is, y=y ₁ +y ₂ , z=z ₁ +z ₂ . All or part of the crystal grains of the material are hollow structures, and the radial length of the cavity part of the hollow crystal grains is 2 to 300 nanometers, preferably 10 to 200 nanometers; the material is at 25°C, P/P ₀ =0.10, adsorption The amount of benzene adsorption measured under the condition of time 1 hour is at least 50 mg/g, preferably at least 70 mg/g; there is a hysteresis loop between the adsorption isotherm and the desorption isotherm of its low-temperature nitrogen adsorption; the cavity part The shape is not fixed, and can be various shapes such as rectangle, circle, irregular circle, irregular polygon, or one or a combination of several of these shapes; its grain can be a single grain or Aggregated grains formed by agglomeration of multiple grains.

The microporous titanium-silicon material has a hollow structure in whole or in part, which is beneficial to the diffusion of reactants and product molecules, improves the synergy between noble metals and titanium-silicon molecular sieves, and overcomes the disadvantages of noble metal aggregation.

In the Chinese patent application with the application number 200710064981.6, the two preparation methods of the above-mentioned microporous titanium-silicon material are disclosed at the same time.

One of the methods is to add titanium-silicon molecular sieve, protective agent, precious metal source and reducing agent to the solution containing alkali source and mix them evenly, then transfer them to the reaction kettle for hydrothermal treatment, filter, wash and dry, and more specifically include :

(1) First, titanium-silicon molecular sieve, protective agent, precious metal source and reducing agent are added to the solution containing alkali source and mixed evenly, which is composed of titanium-silicon molecular sieve (gram): protective agent (mol): alkali source (mol): Reducing agent (mole): precious metal source (gram, in precious metal elemental basis): water (mole)=100: (0.0001-5.0): (0.005-5.0): (0.005-15.0): (0.005-10.0): (200 -10000);

(2) Transfer the mixture obtained in step (1) into a reactor to react under hydrothermal treatment conditions, and recover the product to obtain the microporous titanium-silicon material of the present invention.

Wherein, the composition in step (1) is preferably titanium-silicon molecular sieve (gram): protective agent (mole): alkali source (mole): reducing agent (mole): precious metal source (gram, in precious metal simple substance): water (mole) =100:(0.005-1.0):(0.01-2.0):(0.01-10.0):(0.01-5.0):(500-5000).

The titanium-silicon molecular sieves mentioned in the step (1) include titanium-silicon molecular sieves of various structures, such as TS-1, TS-2, Ti-BETA, Ti-MCM-22, etc., preferably TS-1.

The said protecting agent of step (1) refers to polymer or tensio-active agent, and wherein polymer can be polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene etc. and derivant thereof, tensio-active agent There may be anionic surfactants, cationic surfactants and nonionic surfactants.

The said reducing agent of step (1) can be hydrazine, borohydride, sodium citrate etc., wherein hydrazine can be hydrazine hydrate, hydrazine hydrochloride, hydrazine sulfate etc., borohydride can be sodium borohydride, potassium borohydride etc.

The precious metal source in step (1) is selected from the inorganic or organic substances of the above-mentioned precious metals, which can be oxides, halides, carbonates, nitrates, ammonium nitrate salts, ammonium chloride salts, hydroxides or other precious metals. complexes, etc. Taking palladium as an example, the palladium source can be an inorganic palladium source and/or an organic palladium source. Wherein the inorganic palladium source can be palladium oxide, palladium carbonate, palladium chloride, palladium nitrate, ammonium palladium nitrate, ammonia palladium chloride, palladium hydroxide or other complexes of palladium, etc., and the organic palladium source can be palladium acetate, acetylacetone palladium etc.

The alkali source in step (1) is an inorganic alkali source or an organic alkali source. The inorganic alkali source is ammonia water, sodium hydroxide, potassium hydroxide, barium hydroxide, etc.; the organic alkali source is urea, quaternary ammonium compound, fatty amine compound, alcohol amine compound or a mixture thereof.

The general formula of said quaternary ammonium base compound is (R ¹ ) ₄ NOH, wherein R ¹ is an alkyl group with 1-4 carbon atoms, preferably propyl group.

The general formula of the fatty amine compounds is R ² (NH ₂ ) _n , wherein R ² is selected from alkyl or alkylene groups with 1-6 carbon atoms, n=1 or 2; the fatty amine compounds The compound is ethylamine, n-butylamine, butylenediamine or hexamethylenediamine.

The general formula of said alcohol amine compound is (HOR ³ ) _m NH _(3-m) ; wherein R ³ is selected from an alkyl group with 1-4 carbon atoms; m=1, 2 or 3; said alcohol The amine compound is monoethanolamine, diethanolamine or triethanolamine.

The hydrothermal treatment conditions in step (2) are hydrothermal treatment at a temperature of 80-200°C and autogenous pressure for 2-360 hours, and the process of recovering the product is well known to those skilled in the art and has no special features, usually including The process of washing and drying the crystallized product.

The second method includes the following steps:

(1) After mixing titanium source, silicon source, alkali source, protective agent, precious metal source and water, hydrothermal crystallization at 120-200 ° C for 6 hours to 10 days, taking out and filtering, drying and roasting to obtain intermediate crystalline materials, the mixture The molar composition is silicon source: titanium source: alkali source: precious metal source: protective agent: water=100: (0.005-50.0): (0.005-20.0): (0.005-10.0): (0.005-5.0): (200- 10000), wherein the silicon source is in SiO ₂ , the titanium source is in TiO ₂ , and the noble metal source is in simple substance;

(2) Transfer the intermediate crystalline material obtained in step (1) to the remaining filtrate of step (1), and add a reducing agent having a molar ratio of 0.1-10 to the precious metal source added in step (1), The microporous titanium-silicon material of the present invention is obtained by hydrothermal treatment in a reactor at a temperature of 80-200° C. and autogenous pressure for 2-360 hours, and recovering the product.

Wherein, the molar composition of the mixture in step (1) is preferably silicon source: titanium source: alkali source: precious metal source: protective agent: water=100: (0.01-10.0): (0.01-10.0): (0.01-5.0): ( 0.01-1.0): (500-5000).

The silicon source in step (1) is silica gel, silica sol or organosilicate, preferably organosilicate; the general formula of said organosilicate is R ⁴ ₄ SiO ₄ , wherein R ⁴ preferably has 1 - an alkyl group of 4 carbon atoms, more preferably ethyl.

In step (1), said titanium source is inorganic titanium salt or organic titanate, preferably organic titanate; said inorganic titanium salt can be TiCl ₄ , Ti(SO ₄ ) ₂ or TiOCl ₂ ; said The general formula of organic titanate is Ti(OR ⁵ ) ₄ , wherein R ⁵ is an alkyl group with 1-6 carbon atoms, more preferably an alkyl group with 2-4 carbon atoms.

The alkali source mentioned in the step (1) is a quaternary ammonium base compound or a mixture of a quaternary ammonium base compound, an aliphatic amine compound, and an alcohol amine compound. Wherein, the general formula of the quaternary ammonium base compound is (R ⁶ ) ₄ NOH, and R ⁶ is an alkyl group with 1-4 carbon atoms, preferably a propyl group. The general formula of the fatty amine compound is R ⁷ (NH ₂ ) _n , wherein R ⁷ is selected from an alkyl or alkylene group with 1-6 carbon atoms, n=1 or 2, such as ethylamine, normal Butylamine, Butylenediamine, Hexamethylenediamine, etc. The general formula of said alcohol amine compounds is (HOR ⁸ ) _m NH _(3-m) ; wherein R ⁸ is selected from alkyl groups with 1-4 carbon atoms; m=1, 2 or 3, such as monoethanolamine , diethanolamine, triethanolamine, etc.

The said protecting agent of step (1) refers to polymer or tensio-active agent, and wherein polymer can be polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene etc. and derivant thereof, tensio-active agent There may be anionic surfactants, cationic surfactants and nonionic surfactants.

The said noble metal source of step (1) is selected from the organic matter or inorganic matter of noble metal, can be their oxide compound, halide, carbonate, nitrate, ammonium nitrate salt, ammonium chloride salt, hydroxide or noble metal other complexes etc. Taking the palladium source as an example, it can be an inorganic palladium source and/or an organic palladium source, wherein the inorganic palladium source can be palladium oxide, palladium carbonate, palladium chloride, palladium nitrate, ammonium palladium nitrate, ammonia palladium chloride, palladium hydroxide or Other complexes of palladium, etc., the source of organic palladium can be palladium acetate, palladium acetylacetonate, etc.

Said reducing agent in step (1) can be hydroxylamine, hydrazine, borohydride, sodium citrate etc., and wherein hydrazine can be hydrazine hydrate, hydrazine hydrochloride, hydrazine sulfate etc., and borohydride can be sodium borohydride, borohydride Potassium etc.

The method for catalytically oxidizing allyl alcohol provided by the present invention can adopt batch operation or continuous operation mode. When the batch operation mode is carried out, after adding allyl alcohol, solvent, and catalyst to the reactor, oxygen, hydrogen, and diluent gas are continuously added; while in continuous mode, a fixed-bed reactor can be used, and after the catalyst is loaded, the solvent, allyl Alcohol, oxygen, hydrogen, and dilution gas are continuously added; a slurry bed reactor can also be used to continuously add oxygen, hydrogen, and dilution gas after beating the catalyst, allyl alcohol, and solvent, while continuously separating products. In the case of batch operation or continuous operation, the total reaction gas space velocity is 10-10000h ^-1 , preferably 100-5000h ^-1 .

The method provided by the present invention can also adopt a closed tank reaction, that is, the catalyst, solvent, allyl alcohol, oxygen, hydrogen, and diluent gas are simultaneously added into the tank and mixed for reaction.

In the method provided by the invention, the preferred ratio of raw materials is as follows: the molar ratio of allyl alcohol to oxygen is preferably 1: (0.2～5.0), the molar ratio of allyl alcohol to hydrogen is preferably 1: (0.2～5.0), The mass ratio of solvent to catalyst is preferably (0-500):1.

In the method provided by the present invention, the reaction temperature is preferably 20-120° C., and the reaction pressure is preferably 0.3-2.5 MPa.

In the method provided by the present invention, diluent gas and solvent may be added according to actual conditions, or no diluent gas or solvent may be added.

Said diluting gas may be inert gases such as nitrogen, argon, helium, neon, or carbon dioxide, methane, ethane, propane, etc.

Said solvent is selected from one or more mixtures of water, alcohol, ketone and nitrile, and said alcohol is alcohols such as methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, etc. Or ketones such as acetone and butanone, or nitriles such as acetonitrile. Among said solvents, a mixture of one or more of methanol, tert-butanol and water is more preferred.

In the method provided by the invention, the catalyst is a microporous titanium-silicon material or a composition containing a microporous titanium-silicon material, wherein said composition is composed of a microporous titanium-silicon material and other materials selected from titanium-containing materials, silicon dioxide and oxide One or more components of aluminum.

The method for producing glycidyl alcohol by catalytically oxidizing allyl alcohol provided by the present invention uses molecular oxygen as an oxidizing agent in the presence of hydrogen, without adding any inhibitor or initiator in the raw material gas, and adopts a noble metal-containing, especially palladium-containing hollow As a catalytic active component, the microporous titanium-silicon material increases the diffusion rate of reactants and products, reduces the occurrence of side reactions such as ring opening and over-oxidation, and has high conversion rate of allyl alcohol, good product selectivity, and good activity stability. .

Description of drawings

Fig. 1 is the adsorption-desorption isotherm graph of the low-temperature nitrogen adsorption of sample A in Example 1.

Fig. 2 is the adsorption-desorption isotherm curve of the low-temperature nitrogen adsorption of sample B in Example 2.

Fig. 3 is the adsorption-desorption isotherm curve of the low-temperature nitrogen adsorption of sample C in Example 3.

Fig. 4 is the adsorption-desorption isotherm curve of the low-temperature nitrogen adsorption of sample D in Example 4.

Fig. 5 is an adsorption-desorption isotherm curve of low-temperature nitrogen adsorption of sample E in Example 5.

Fig. 6 is an adsorption-desorption isotherm curve of low-temperature nitrogen adsorption of sample F in Example 6.

Fig. 7 is the adsorption-desorption isotherm curve of the low-temperature nitrogen adsorption of sample G in Example 7.

Fig. 8 is an adsorption-desorption isotherm curve of low-temperature nitrogen adsorption of sample H in Example 8.

FIG. 9 is a transmission electron microscope (TEM) photograph of sample A of Example 1. FIG.

Fig. 10 is a transmission electron microscope (TEM) photo of sample B in Example 2.

Fig. 11 is a transmission electron microscope (TEM) photograph of sample C of Example 3.

Fig. 12 is a transmission electron microscope (TEM) photo of sample D in Example 4.

Fig. 13 is a transmission electron microscope (TEM) photograph of sample E of Example 5.

Fig. 14 is a transmission electron microscope (TEM) photograph of sample F in Example 6.

Fig. 15 is a transmission electron microscope (TEM) photograph of sample G in Example 7.

Fig. 16 is a transmission electron microscope (TEM) photograph of sample H of Example 8.

Detailed ways

The following examples and comparative examples will further illustrate the present invention, but do not limit the contents of the present invention.

In comparative examples and examples, all reagents used are commercially available chemically pure reagents.

The titanium silicate molecular sieves used in the comparative examples and examples are TS-1 molecular sieve samples prepared according to the method described in the prior art Zeolites, 1992, Vol.12 pages 943-950.

The adsorption-desorption isotherm curve of the low-temperature nitrogen adsorption of the sample was measured on the ASAP2405 static nitrogen adsorption instrument of Micromeritics Company in the United States according to the ASTM D4222-98 standard method.

The benzene adsorption capacity of the sample was measured by conventional static adsorption method, the measurement conditions were 25°C, P/P ₀ =0.10, and the adsorption time was 1 hour.

The transmission electron micrograph (TEM) of the sample was obtained on a Tecnai G ² F20S-TWIN transmission electron microscope of FEI Company in the Netherlands, with an accelerating voltage of 20kV.

In the comparative example: before the reaction, the comparative catalyst needs to be reduced and activated for 3 hours in a nitrogen-hydrogen mixed atmosphere at a temperature of 300°C.

Examples 1-8 illustrate the preparation process of the microporous titanium-silicon materials A, B, C, D, E, F, G, and H used in the method provided by the present invention.

Example 1

Get 20 grams of titanium-silicon molecular sieve TS-1, concentration is 0.01g/ml (as palladium atom) ammonium nitrate palladium complex solution and appropriate amount of hydrazine hydrate and cetyltrimethylammonium bromide are added to tetrapropyl Aqueous solution of ammonium hydroxide (mass percentage concentration 10%) stirs and mixes evenly, wherein titanium silicon molecular sieve (gram): hexadecyltrimethylammonium bromide (mole): tetrapropyl ammonium hydroxide (mole): hydrated Hydrazine (mol): ammonium nitrate palladium complex (g, calculated as palladium): water (mol) = 100: 0.005: 0.5: 3.0: 2.0: 1000. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at a temperature of 150°C and autogenous pressure for 48 hours, filter the resultant, wash with water, dry it naturally, and continue drying at 180°C for 3 hours to obtain the novel compound containing Noble metal microporous titanium silicon material A. After characterization, its composition can be expressed as 4TiO ₂ · 100SiO ₂ · 0.01PdO · 0.09Pd in the form of oxides. The adsorption-desorption isotherm curve of its low-temperature nitrogen adsorption has a hysteresis loop (Figure 1), and the benzene adsorption capacity is 65mg /g, transmission electron micrographs show that it is a hollow structure (Figure 9).

Example 2

Get 20 grams of titanium-silicon molecular sieve TS-1, a palladium chloride solution with a concentration of 0.01 g/ml (in terms of palladium atoms), and an appropriate amount of hydrazine hydrochloride and polypropylene to join in an aqueous solution of sodium hydroxide (mass percentage concentration 15%) and stir Mix well, wherein titanium silicon molecular sieve (gram): polypropylene (mol): sodium hydroxide (mol): hydrazine hydrochloride (mol): palladium chloride (gram, in palladium): water (mol) = 100: 0.9: 1.8:0.15:0.1:4600. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at a temperature of 180°C and autogenous pressure for 24 hours, filter the resultant, wash with water, dry naturally, and continue to dry at 110°C for 3 hours to obtain the novel compound containing Noble metal microporous titanium silicon material B. After characterization, its composition can be expressed as 8TiO ₂ · 100SiO ₂ · 0.006PdO · 0.008Pd in the form of oxides. The adsorption-desorption isotherm curve of its low-temperature nitrogen adsorption has a hysteresis loop (Figure 2), and the benzene adsorption capacity is 68mg /g, transmission electron micrographs show that it is a hollow structure (Figure 10).

Example 3

Tetraethyl orthosilicate, tetrabutyl titanate, palladium acetate solution and Tween 80 with a concentration of 0.01 g/ml (in terms of palladium atoms) were added to the aqueous solution of tetrapropylammonium hydroxide and butylenediamine (mass The percentage concentration is 10%) and stir and mix evenly, wherein the molar composition silicon source: titanium source: tetrapropylammonium hydroxide: butylenediamine: palladium source: protective agent: water = 100: 0.03: 0.5: 0.1: 0.05: 0.02:550, the silicon source is counted as _SiO2 , the titanium source is counted as _TiO2 , and the palladium source is counted as Pd. Then put it into a sealed reactor, hydrothermally treat it at a temperature of 120°C and autogenous pressure for 120 hours, take out the resultant, filter it, dry it, and roast it to obtain an intermediate crystalline material. Transfer the intermediate crystalline material to the above remaining filtrate, add an appropriate amount of hydrazine hydrate, and then conduct a hydrothermal treatment at a temperature of 170°C and an autogenous pressure for 36 hours, filter the resultant, wash with water, dry naturally, and continue at 150°C After drying for 3 hours, the novel noble metal-containing microporous titanium-silicon material C of the present invention is obtained. After characterization, its composition can be expressed as 0.008TiO ₂ · 100SiO ₂ · 0.01PdO · 0.2Pd in the form of oxides. The adsorption-desorption isotherm curve of its low-temperature nitrogen adsorption has a hysteresis loop (Fig. 3), and the adsorption capacity of benzene is 56mg/g, transmission electron micrographs show that it is a hollow structure (Figure 11).

Example 4

Add tetraethyl orthosilicate, tetrabutyl titanate, ammonium chloride palladium solution and sodium dodecylbenzenesulfonate to the tetrapropylammonium hydroxide Stir and mix evenly in an aqueous solution (mass percentage concentration 15%), add in batches under vigorous stirring, and continue to stir for a period of time, wherein the molar composition silicon source: titanium source: alkali source: palladium source: protective agent: water = 100: 2.0: 5.2 : 2.0:0.5:2500, the silicon source is counted as SiO ₂ , the titanium source is counted as TiO ₂ , and the palladium source is counted as Pd. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at a temperature of 150°C and autogenous pressure for 96 hours, take out the resultant, filter it, dry it, and roast it to obtain an intermediate crystalline material. Transfer the intermediate crystalline material to the above remaining filtrate, add an appropriate amount of hydrazine hydrochloride, and then perform hydrothermal treatment at a temperature of 120°C and autogenous pressure for 48 hours, filter the resultant, wash with water, dry naturally, and continue at 120°C After drying for 3 hours, the novel noble metal-containing microporous titanium-silicon material D of the present invention is obtained. After characterization, its composition can be expressed as 19TiO ₂ · 100SiO ₂ · 0.5PdO · 1.3Pd in the form of oxides. The adsorption-desorption isotherm curve of its low-temperature nitrogen adsorption has a hysteresis loop (Figure 4), and the benzene adsorption capacity is 74mg /g, transmission electron micrographs show that it is a hollow structure (Figure 12).

Example 5

Take 20 grams of titanium-silicon molecular sieve TS-1, a palladium acetate solution with a concentration of 0.01 g/ml (as palladium atoms), and an appropriate amount of sodium borohydride and Tween 80, and add them to an aqueous solution of butanediamine (10% concentration by mass percentage) Stir and mix evenly, wherein titanium-silicon molecular sieve (gram): Tween 80 (mol): butylenediamine (mol): sodium borohydride (mol): palladium acetate (gram, in palladium): water (mol)=100: 0.1:0.02:0.05:0.03:520. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at a temperature of 120°C and autogenous pressure for 120 hours, filter the resultant, wash with water, dry it naturally, and continue to dry it at 150°C for 3 hours to obtain the novel containing Noble metal microporous titanium silicon material E. After characterization, its composition can be expressed as 0.1TiO ₂ · 100SiO ₂ · 0.1PdO · 0.75Pd in the form of oxides. The adsorption-desorption isotherm curve of its low-temperature nitrogen adsorption has a hysteresis loop (Fig. 5), and the adsorption capacity of benzene is 78mg/g, transmission electron micrographs show that it is a hollow structure (Figure 13).

Example 6

Get 20 grams of titanium-silicon molecular sieves TS-1, the concentration is the ammonium chloride palladium solution of 0.01g/ml (in terms of palladium atoms) and an appropriate amount of hydrazine sulfate and sodium dodecylbenzenesulfonate are added to the tetrapropylammonium hydroxide Aqueous solution (mass percentage concentration 10%) was stirred and mixed evenly, added in batches under vigorous stirring, and continued to stir for a period of time, wherein titanium silicon molecular sieve (gram): sodium dodecylbenzenesulfonate (mole): tetrapropyl hydroxide Ammonium (mol): hydrazine sulfate (mol): ammonium chloride palladium (gram, calculated as palladium): water (mol) = 100: 0.5: 0.1: 8.5: 4.8: 2000. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at a temperature of 90°C and autogenous pressure for 240 hours, filter the resultant, wash with water, dry it naturally, and continue to dry it at 120°C for 3 hours to obtain the novel compound containing Noble metal microporous titanium silicon material F. After characterization, its composition can be expressed as 0.04TiO ₂ · 100SiO ₂ · 0.6PdO · 5.1Pd in the form of oxides. The adsorption-desorption isotherm curve of its low-temperature nitrogen adsorption has a hysteresis loop (Figure 6), and the benzene adsorption capacity is 73mg/g, transmission electron micrographs show that it is a hollow structure (Figure 14).

Example 7

Tetraethyl orthosilicate, tetraethyl titanate, palladium acetate solution with a concentration of 0.01 g/ml (calculated as palladium atoms) and hexadecyltrimethylammonium bromide were added to tetrapropylammonium hydroxide ( mass percent concentration 13%), stirring and mixing evenly, wherein silicon source: titanium source: alkali source: palladium source: protective agent: water=100: 8.2: 7.5: 0.1: 0.05: 800, silicon source is calculated as _SiO2 , titanium source Calculated as _TiO2 , palladium source as Pd. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at a temperature of 160°C and autogenous pressure for 96 hours, take out the resultant, filter it, dry it, and roast it to obtain an intermediate crystalline material. Transfer the intermediate crystalline material to the remaining filtrate, add an appropriate amount of hydrazine hydrochloride, and then perform hydrothermal treatment at a temperature of 170°C and autogenous pressure for 36 hours, filter the resultant, wash with water, dry naturally, and continue at 150°C After drying for 3 hours, the novel noble metal-containing microporous titanium-silicon material G of the present invention is obtained. After characterization, its composition can be expressed as 23TiO ₂ · 100SiO ₂ · 0.04PdO · 0.8Pd in the form of oxides. The adsorption-desorption isotherm curve of its low-temperature nitrogen adsorption has a hysteresis loop (Figure 7), and the benzene adsorption capacity is 62mg /g, transmission electron micrographs show that it is a hollow structure (Figure 15).

Example 8

Get 20 grams of titanium-silicon molecular sieves TS-1, concentration is that the ammonium palladium nitrate and ammonium nitrate platinum complex solution and hydrazine hydrate and cetyltrimethylammonium bromide of 0.01g/ml (in terms of palladium atom) join in In the aqueous solution (mass percentage concentration 14%) of tetrapropyl ammonium hydroxide, stir and mix uniformly, wherein titanium silicon molecular sieve (gram): hexadecyl trimethyl ammonium bromide (mol): tetrapropyl ammonium hydroxide (mol ): hydrazine hydrate (mole): platinum ammonium nitrate (gram, in platinum): palladium ammonium nitrate (gram, in palladium): water (mole)=100: 0.1: 1.2: 2.0: 0.8: 1.2: 1800. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at a temperature of 180°C and autogenous pressure for 72 hours, filter the resultant, wash with water, dry it naturally, and continue drying at 180°C for 3 hours to obtain the novel compound containing Double noble metal microporous titanium silicon material H. After characterization, its composition can be expressed as 4TiO ₂ · 100SiO ₂ · 0.3PdO · 0.9Pd · 0.1PtO · 0.7Pt in the form of oxides, and the adsorption-desorption isotherm curve of its low-temperature nitrogen adsorption has a hysteresis loop (Figure 8) , the benzene adsorption amount is 77 mg/g, and the transmission electron micrograph shows that it is a hollow structure (Figure 16).

Comparative example 1

In this comparative example, a supported palladium/titanium silicate molecular sieve (0.5% Pd/TS-1) catalyst is prepared by impregnating palladium.

Take 10 grams of titanium-silicon molecular sieve TS-1 sample and add 15mL of water to 5mL of _PdCl2 aqueous solution with a concentration of 0.01g/mL, stir at 40°C for 24 hours, seal it properly during the period, and then dry it naturally at room temperature for 48 hours. A supported palladium/titanium silicate molecular sieve (0.5% Pd/TS-1) catalyst was obtained.

Comparative example 2

In this comparative example, a supported palladium/titanium silicate molecular sieve (2%Pd/TS-1) catalyst was prepared by impregnating palladium.

Take 10 grams of titanium-silicon molecular sieve TS-1 sample and add it to 20 mL of PdCl ₂ aqueous solution with a concentration of 0.01 g/mL, stir for 24 hours at a temperature of 40 ° C, seal it properly during the period, and then dry it naturally at room temperature for 48 hours to obtain the supported Palladium/titanium silicate (2% Pd/TS-1) catalyst.

Examples 9-18 illustrate the process of producing glycidyl alcohol by the catalytic oxidation of allyl alcohol provided by the present invention using the microporous titanium-silicon materials A-H prepared in Examples 1-8 as catalysts.

Example 9

Allyl alcohol, oxygen (4% volume, all the other being nitrogen), hydrogen, solvent and sample A are 1: 1: 1 according to the mol ratio of allyl alcohol and oxygen, hydrogen, the mass ratio of solvent tert-butyl alcohol and catalyst is 200, the reaction is carried out at a temperature of 60°C and a pressure of 0.5 MPa, and a total gas volume space velocity of 1000 h ^-1 .

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 23%; the selectivity of glycidyl alcohol was 98%.

The results of the reaction for 20 hours were as follows: the conversion rate of allyl alcohol was 19%; the selectivity of glycidyl alcohol was 97%.

Example 10

Allyl alcohol, oxygen, hydrogen (10% by volume, all the other being argon), solvent and sample B are 1:2:1 according to the molar ratio of allyl alcohol, oxygen, hydrogen, and the mass ratio of solvent methanol to catalyst is 20 , at a temperature of 30°C and a pressure of 1.5 MPa, the reaction was carried out at a total gas volume space velocity of 150 h ^-1 .

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 31%; the selectivity of glycidyl alcohol was 97%.

The result of reaction for 20 hours is as follows: the conversion rate of allyl alcohol is 25%; the selectivity of glycidyl alcohol is 94%.

Example 11

Allyl alcohol, oxygen (80% volume, all the other being carbon dioxide), hydrogen, solvent and sample C are 1:5:2 according to the mol ratio of allyl alcohol and oxygen, hydrogen, the mass ratio of solvent tert-butyl alcohol and catalyst is 80, the reaction is carried out at a temperature of 40°C and a pressure of 0.8 MPa, and a total gas volume space velocity of 2000h ^-1 .

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 22%; the selectivity of glycidyl alcohol was 97%.

The result of reaction for 20 hours is as follows: the conversion rate of allyl alcohol is 17%; the selectivity of glycidyl alcohol is 95%.

Example 12

Allyl alcohol, oxygen, hydrogen (4% by volume, all the other being methane), solvent and sample D are 1:2:5 according to the mol ratio of allyl alcohol and oxygen, hydrogen, the mass ratio of solvent methanol and catalyst is 400, The reaction is carried out at a temperature of 50°C, a pressure of 0.5 MPa, and a total gas volume space velocity of 4000 h ^-1 .

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 20%; the selectivity of glycidyl alcohol was 95%.

The result of reaction for 20 hours is as follows: the conversion rate of allyl alcohol is 16%; the selectivity of glycidyl alcohol is 91%.

Example 13

Allyl alcohol, oxygen, hydrogen, solvent and sample E are 1:0.5:3 according to the molar ratio of allyl alcohol to oxygen and hydrogen, the mass ratio of solvent water to catalyst is 100, and the temperature is 80°C and the pressure is 2.5MPa The reaction was carried out at a total gas volume space velocity of 3000h ^-1 .

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 19%; the selectivity of glycidyl alcohol was 93%.

The result of reaction for 20 hours is as follows: the conversion rate of allyl alcohol is 16%; the selectivity of glycidyl alcohol is 92%.

Example 14

Allyl alcohol, oxygen, hydrogen, solvent and sample F are 1:3:0.5 according to the molar ratio of allyl alcohol to oxygen and hydrogen, the mass ratio of solvent methanol to catalyst is 300, and the temperature is 30°C and the pressure is 1.2MPa The reaction was carried out at a total gas volume space velocity of 1500h ^-1 .

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 28%; the selectivity of glycidyl alcohol was 94%.

The result of reaction for 20 hours is as follows: the conversion rate of allyl alcohol is 24%; the selectivity of glycidyl alcohol is 91%.

Example 15

Allyl alcohol, oxygen, hydrogen, solvent and sample G are 1:2:1 according to the molar ratio of allyl alcohol to oxygen and hydrogen, the mass ratio of solvent methanol to catalyst is 20, and the temperature is 70°C and the pressure is 1.5MPa The reaction was carried out at a total gas volume space velocity of 600h ^-1 .

The result of the reaction for 2 hours was as follows: the conversion rate of allyl alcohol was 21%; the selectivity of glycidyl alcohol was 93%.

The result of reaction for 20 hours is as follows: the conversion rate of allyl alcohol is 17%; the selectivity of glycidyl alcohol is 90%.

Example 16

Allyl alcohol, oxygen, hydrogen, solvent and sample H are 1:2:2 according to the molar ratio of allyl alcohol to oxygen and hydrogen, the mass ratio of solvent methanol to catalyst is 50, and the temperature is 40°C and the pressure is 0.5MPa , the reaction was carried out at a total gas volume space velocity of 2000h ^-1 .

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 34%; the selectivity of glycidyl alcohol was 98%.

The results of the reaction for 20 hours were as follows: the conversion rate of allyl alcohol was 27%; the selectivity of glycidyl alcohol was 93%.

Examples 17 and 18 illustrate carrying out the process provided by the present invention in a closed tank reactor.

Example 17

Allyl alcohol, oxygen, hydrogen, solvent tert-butanol and sample A are 1:5:1:1 according to the molar ratio of allyl alcohol to tert-butanol, oxygen and hydrogen, and the mass ratio of solvent tert-butanol to catalyst is 50 , at a temperature of 60°C and a pressure of 0.8 MPa.

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 23%; the selectivity of glycidyl alcohol was 97%.

The result of reacting for 8 hours is as follows: the conversion rate of allyl alcohol is 65%; the selectivity of glycidyl alcohol is 92%.

Example 18

Allyl alcohol, oxygen, hydrogen, solvent methanol and sample B are 1:20:2:2 according to the molar ratio of allyl alcohol to methanol, oxygen, and hydrogen, and the mass ratio of methanol to catalyst is 200 at a temperature of 30°C. The reaction was carried out at a pressure of 1.8 MPa.

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 25%; the selectivity of glycidyl alcohol was 96%.

The results of the 8-hour reaction were as follows: the conversion rate of allyl alcohol was 62%; the selectivity of glycidyl alcohol was 94%.

Comparative example 3

This comparative example illustrates the process and result of using the supported palladium/titanium silicate molecular sieve (0.5% Pd/TS-1) prepared in comparative example 1 as a catalyst to catalyze the oxidation of allyl alcohol.

Allyl alcohol, oxygen, hydrogen, solvent and catalyst are 1:1:1 according to the molar ratio of allyl alcohol to oxygen and hydrogen, the mass ratio of solvent tert-butanol to catalyst is 200, and the temperature is 60°C and the pressure is 0.5 Under MPa, the reaction was carried out at a total gas volume space velocity of 1000 h ⁻¹ .

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 15%; the selectivity of glycidyl alcohol was 88%.

The result of reaction for 20 hours is as follows: the conversion rate of allyl alcohol is 7%; the selectivity of glycidyl alcohol is 82%.

Comparative example 4

This comparative example illustrates the process and result of using the supported palladium/titanium silicate molecular sieve (2%Pd/TS-1) prepared in comparative example 2 as a catalyst to catalyze the oxidation of allyl alcohol.

With allyl alcohol, oxygen, hydrogen, solvent and catalyst according to the molar ratio of allyl alcohol to oxygen and hydrogen as 1:1:1, the mass ratio of solvent methanol to catalyst is 200, at a temperature of 60°C and a pressure of 0.5MPa , the reaction was carried out at a total gas volume space velocity of 1000h ^-1 .

The results of the reaction for 2 hours were as follows: the conversion rate of allyl alcohol was 18%; the selectivity of glycidyl alcohol was 87%.

The result of reaction for 20 hours is as follows: the conversion rate of allyl alcohol is 9%; the selectivity of glycidyl alcohol is 80%.

From the reaction results of Examples 9-18 and Comparative Examples 3 and 4, it can be seen that the method of the present invention has a high conversion rate of allyl alcohol, good selectivity of the product glycidyl alcohol, and good activity stability.

Claims (6)

1. the method for a catalyzing and oxidizing allyl alcohol to produce epoxy propanol, it is characterized in that being 0～180 ℃ in temperature is under the condition of 0.1～3.0MPa with pressure, with vinyl carbinol, oxygen, hydrogen, diluent gas, solvent and catalyst mix contact reacts, vinyl carbinol and oxygen, hydrogen, the mol ratio of diluent gas is 1: (0.1～10): (0.1～10): (0～100), the mass ratio of vinyl carbinol and catalyzer is (0.5-50): 1, the mass ratio of solvent and catalyzer is (0～1000): 1, said catalyzer is a kind of micropore titanium-silicon material or the composition that contains this micropore titanium-silicon material, and the composition of micropore titanium-silicon material is expressed as xTiO with the form of oxide compound ₂100SiO ₂YE _mO _nZE, wherein the x value is 0.001～50.0, (y+z) value is 0.005～20.0 and y/z＜1, and E is Pt and/or Pd precious metal, and m and n satisfy the required number of E oxidation state, and this material grains contains hollow or concaveconvex structure; Said diluent gas is selected from nitrogen, argon gas, helium, neon, perhaps is selected from carbonic acid gas, methane, ethane, propane; Said solvent is selected from one or more the mixture in methyl alcohol, the trimethyl carbinol and the water.

2. according to the method for claim 1, it is characterized in that said x value is 0.005～25.0, (y+z) value is 0.01～10.0.

3. according to the method for claim 1, it is characterized in that the said composition that contains micropore titanium-silicon material is selected from titanium-containing materials, silicon-dioxide and the aluminum oxide one or more by micropore titanium-silicon material and other and forms.

4. according to the method for claim 1, the mol ratio that it is characterized in that said vinyl carbinol and oxygen is 1: (0.2～5.0), the mol ratio of vinyl carbinol and hydrogen are 1: (0.2～5.0), the mass ratio of solvent and catalyzer are (0～500): 1.

5. according to the method for claim 1, it is characterized in that temperature of reaction is 20～120 ℃, reaction pressure is 0.3～2.5MPa.

6. according to the method for claim 1, it is characterized in that adopting periodical operation or operate continuously mode, reacting total gas space velocity is 10～10000h ^-1

Images