TWI698398B - Method and application of synthesizing titanium-containing silicon oxide material using biopolymer - Google Patents

Abstract

A method and application for synthesizing titanium-containing silicon oxide materials from biopolymers. The aqueous solution prepared from the titanium source, silicon source, acid source, alkali source, biopolymer and solvent is directly subjected to solid-liquid separation after maturation. After drying, and then undergoing a calcination process or an extraction process, a titanium-containing silicon oxide material with a high specific surface area can be obtained; because the present invention uses a biopolymer as a template, the titanium-containing silicon oxide material is more environmentally friendly in the manufacturing process. And its product still has outstanding catalytic activity after calcination process or extraction process, and can be used to catalyze the epoxidation reaction of olefin compounds and contribute to the production of epoxides.

Description

Method and application for synthesizing titanium-containing silicon oxide material by biopolymer

The present invention relates to a method and application for synthesizing titanium-containing silicon oxide material by template method, and in particular to a method for synthesizing titanium-containing silicon oxide material by using biopolymer as a template, and the titanium-containing oxide material Silicon material is used as a catalyst to produce epoxides through direct oxidation reaction of olefins.

Titanium-containing silicon oxide materials often have a high surface area pore structure, which can be used as an excellent adsorbent, catalyst or catalyst carrier. At present, the most common synthesis of titanium-containing silicon oxide materials is prepared by using surfactants as templates and combined with hydrothermal reaction methods. The most famous example is the use of positively charged quaternary ammonium salt interfaces. The active agent is used as a template; for example, US patents US 7018950, US 688782 and US 6512128 all disclose methods for preparing titanium-containing silica catalysts. The steps are mainly to use silicon source, titanium source and quaternary ammonium as a template The ions are mixed and stirred in the solvent to obtain a solid containing the catalyst component and the template agent, and then the template agent is removed from the obtained solid, so as to obtain a specific pore size, specific pore size distribution and specific volume ratio containing Titanium silica catalyst.

Using the template method to prepare titanium-containing silicon oxide material is to introduce titanium into a silicon dioxide material with a high surface area, which can make the material's catalytic activity more diverse. During the preparation process, the templating agent will form micelles in the aqueous solution, and the added silicon compound will gather around the micelles and form a silicon oxide substrate on them. The templating agent (ie, surfactant) can pass high temperature The calcination process or the extraction process removes it, thereby creating a porous structure material with a size and shape similar to the template agent. The advantage of this preparation process is that the pore volume of the synthesized material can be controlled by the molecular size of the template, and the pore size can be controlled by the microcell size of the template. However, the use of surfactants as templates is not only costly and may cause toxicity, but also causes environmental pollution.

In order to overcome the various deficiencies of the above-mentioned prior art, the applicant of the present invention specially developed a relatively low-cost and non-toxic green material as a template to prepare titanium-containing silicon oxide materials to reduce the environmental pollution caused by the process. Therefore, the prepared titanium-containing silicon oxide material can have high catalytic activity in the epoxidation reaction.

The main purpose of the present invention is to provide a method and application for synthesizing titanium-containing silicon oxide materials using biopolymers. The aqueous solution prepared by using titanium sources, silicon sources, acid sources, alkali sources, biopolymers and solvents is matured ( After aging), after filtration, drying and calcination procedures or extraction procedures, a titanium-containing silicon oxide material with high specific surface area and high catalytic activity can be obtained, which can be further used as a catalyst to catalyze the epoxidation reaction of olefin compounds to produce Epoxide.

In order to achieve the above purpose, the present invention provides a method for preparing titanium-containing silicon oxide material. The aqueous solution prepared by the titanium source, silicon source, acid source, alkali source, biopolymer and solvent is stirred uniformly, and then the aqueous solution is placed React at a temperature of -20-200°C and continue stirring for 0.5-5 hours. Then, it undergoes an aging treatment at 60-200°C for 6-48 hours. Then, solid-liquid separation is performed, and the solid obtained through the solid-liquid separation is dried. Finally, the dried solid is subjected to a calcination process or an extraction process to obtain a titanium-containing silicon oxide material with a high specific surface area.

The titanium-containing silicon oxide material prepared by the present invention meets the following conditions: 1. The average pore diameter of the titanium-containing silicon oxide material is greater than 10 angstroms (Å). 2. The pore diameter of more than 90% of the total pore volume of the titanium-containing silicon oxide material is 5-200 angstroms. 3. The specific pore volume of the titanium-containing silicon oxide material is 0.2 cubic centimeters/gram (cm ³ /g) or more.

The titanium source in the foregoing method can be derived from titanate, an inorganic titanium source, or a combination thereof; the silicon source can be derived from amorphous silicon dioxide, alkoxysilane, silicate, or a combination thereof ; The acid source can be derived from any substance that can lower the pH of the system, such as organic acid, inorganic acid or a combination thereof; the alkali source can be derived from any substance that can increase the pH of the system, such as organic bases, inorganic bases, and relative ions (Counter ion) is an organic molecule or a combination of hydroxyl anions; biopolymers can be derived from polymers produced by organisms; solvents can be derived from alcoholic solvents; the extractant used in the extraction process can be derived from solvents and Mixed aqueous solutions of acid sources.

In addition, the present invention also provides a method for preparing epoxides, the steps of which are to first provide the titanium-containing silicon oxide material prepared by the foregoing method as a catalyst to react olefin compounds and oxides to form epoxides.

In addition, silylation can be used to increase the catalytic activity of the catalyst before the catalytic reaction.

In the foregoing method, the amount of catalyst used is not strictly limited, and the amount of catalyst only needs to be able to complete the epoxidation reaction in the shortest time. The molar ratio of the olefin compound to the oxide used during the reaction is between 1:100-100:1, preferably between 1:10-10:1. The reaction temperature is not particularly limited, and is usually 0-200°C, preferably 25-150°C. The reaction pressure may be a pressure sufficient to make all the reactants liquid or above, preferably between 1-100 atmospheric pressure. The reaction residence time is 1 minute to 48 hours, preferably 5 minutes to 8 hours. This procedure is applicable to any reactor or instrument, such as fixed bed, conveying bed, fluid bed, slurry stirring, or continuous flow stirring reactor in batch, continuous or semi-continuous mode.

The method of the present invention has simple procedures and low cost, and the organic substances used are environmentally friendly and non-polluting, which is practical for industrial applications.

Detailed descriptions are given below by specific embodiments, so that it will be easier to understand the purpose, technical content, features and effects of the present invention.

Please refer to Figure 1 to illustrate the process steps of a method for preparing a titanium-containing silicon oxide material provided by the present invention. The figure shows five steps S100-S140. Steps S100 to S120 illustrate a method for preparing a titanium-containing silicon oxide material. It is defined in steps S130 and S140 that two possible steps in the preparation process of the titanium-containing silicon oxide material can be added to provide a titanium-containing silicon oxide material with a high specific surface area. In practice, one or more of steps S130 and S140 can be used in a single production process, but for the sake of brevity, these steps are presented together (the dotted box indicates that these features are optional), Put it in a single flowchart.

First, in step S100, prepare the titanium source, silicon source, acid source, alkali source, biopolymer and solvent into an aqueous solution, and stir uniformly; then in step S110, place the aqueous solution at a temperature of -20-200°C. The reaction is continuously stirred for 0.5-5 hours, followed by a 60-200°C maturation treatment for 6-48 hours, and then solid-liquid separation is carried out to separate the solid from the reaction solution, and then the solid obtained through the solid-liquid separation is Continuous drying at 30-120°C for 0.5-6 hours; finally, in step S120, the dried solid is subjected to a calcination procedure or an extraction procedure with an extractant prepared by a mixed aqueous solution of a solvent and an acid source to obtain high Titanium-containing silicon oxide material with specific surface area.

The titanium-containing silicon oxide material prepared by the present invention meets the following conditions: 1. The average pore diameter of the titanium-containing silicon oxide material is greater than 10 angstroms (Å). 2. The pore diameter of more than 90% of the total pore volume of the titanium-containing silicon oxide material is 5-200 angstroms. 3. The specific pore volume of the titanium-containing silicon oxide material is 0.2 cubic centimeters/gram (cm ³ /g) or more

The titanium source used in the present invention includes, but is not limited to: titanate, inorganic titanium source or a combination thereof. Specifically, the titanate may be tetramethyl titanate, tetraethyl titanate, n-tetrapropyl titanate, tetraisopropyl titanate, n-tetrabutyl titanate, and tetrabutyl titanate. Ester, iso-tetrabutyl titanate, tetra-tertiary butyl titanate, tetra(2-ethylhexanol) titanate, tetra(octadecyl)ortho titanate or a combination thereof; the inorganic titanium source can be It is a titanium halide and includes titanium trichloride, titanium tetrachloride, titanium tribromide, titanium tetrabromide, titanium triiodide, titanium tetraiodide, titanium sulfate or a combination thereof. The above titanium sources can be used alone or in a mixture of multiple titanium sources.

The silicon source used in the present invention includes, but is not limited to: amorphous silicon dioxide, alkoxysilane, silicate or a combination thereof. Specifically, the general formula of amorphous silicon dioxide is SiO ₂ , including, but not limited to: smoked silica, white smoke, silica gel, silica sol and other silica powders or bulk materials ; Alkoxysilane can be a silane containing four alkoxy groups, including tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate and similar substances. Furthermore, alkoxysilanes containing different organic functional groups can also be used as silicon sources, such as monoalkyltrialkoxysilanes, dialkyldialkoxysilanes, trialkyl Trialkylmonoalkoxysilanes and similar substances; silicate can be sodium silicate, potassium silicate, magnesium silicate, calcium silicate and similar substances. The above silicon sources can be used alone or in a mixture of multiple silicon sources.

The acid source used in the present invention includes, but is not limited to: organic acid, inorganic acid or any substance that can lower the pH of the system; specifically, the organic acid can be a substance containing carboxyl or sulfonic acid groups, such as formic acid , Acetic acid, propionic acid, sulfonic acid, sulfinic acid, thiocarboxylic acid, citric acid, malic acid, tartaric acid, oxalic acid, succinic acid, lactic acid and similar substances; inorganic acids can release hydrogen ions and co- Substances of conjugate alkali ions, such as hydrochloric acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, nitric acid, hydrazoic acid, hyponitric acid, hyponitric acid, nitrous acid, peroxynitric acid, sulfuric acid, hydrogen sulfuric acid, Hydrogen disulfide, thiosulfuric acid, hyposulfuric acid, persulfuric acid, phosphoric acid, hypophosphorous acid, phosphorous acid, metaphosphoric acid, metaphosphorous acid, diphosphoric acid, hypophosphoric acid, pyrophosphoric acid, boric acid, metaboric acid, tetraboric acid, fluoroboric acid, Perboric acid, carbonic acid, hydrocyanic acid, cyanic acid, fulvic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid, selenocyanic acid, trithiocarbonic acid, hydrogen peroxide, hydrofluoric acid, hypofluoric acid, bromine Acid, hydrobromic acid, chromic acid, dichromic acid, permanganic acid and similar substances. The above acid sources can be used alone or in a mixture of multiple acid sources.

The alkali source used in the present invention includes, but is not limited to: organic bases, inorganic bases, organic molecules with hydroxyl anions as the counter ion, or any substance that can increase the pH; specifically, the organic base may contain Alkali metal alcohols, organometallic compounds or substances containing nitrogen atoms, such as sodium methoxide, potassium ethoxide, potassium tertiary butoxide, butyl lithium, phenyl lithium, lithium diisopropylamide, six Lithium hexamethyldisilazide (lithium hexamethyldisilazide), pyridine, imidazole, benzimidazole, histidine and similar substances; inorganic bases can be hydroxides or carbonates containing metal ions, such as lithium hydroxide, sodium hydroxide , Potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, ammonium hydroxide, zinc hydroxide, copper hydroxide, nickel hydroxide, chromium hydroxide, sodium carbonate, bicarbonate Sodium, potassium carbonate, potassium bicarbonate and similar substances; organic molecules whose opposite ions are hydroxide anions can be trimethyloctadecylammonium hydroxide (trimethyloctadecylammonium hydroxide), cetyltrimethylammonium hydroxide ( cetyltrimethylammonium hydroxide, dodecyl trimethyl ammonium hydroxide and similar substances. The above alkali sources can be used alone or in a mixture of multiple alkali sources.

The biopolymer used in the present invention is a polymer produced from living organisms; for example, chitosan, collagen, gelatin, agarose, chitin ), polyhydroxyalkanoates (polyhydroxyalkanoates), pullulan, starch (starch), cellulose (hyaluronic acid) and similar substances. Among them, starch includes amylose (amylose) and amylopectin (amylopectin). The above biopolymers can be used alone or in a mixture of multiple biopolymers.

The solvents used in the present invention include, but are not limited to: alcoholic solvents; specifically, alcoholic solvents include alcohols with 1-10 carbons, for example, methanol, ethanol, n-propanol, isopropanol Alcohol, vinyl butanol, allyl butanol, n-butanol, second butanol, tertiary butanol, pentanol, cyclohexanol, benzyl alcohol and diol compounds, etc. or A combination of multiple alcohols mixed with each other.

In addition, the molar ratio of the titanium source to the silicon source in the aqueous solution is in the range of 0.00001-0.5, preferably 0.0001 to 0.1; the weight ratio of the biopolymer to the silicon source is in the range of 0.005-5; the acid source and the silicon The molar ratio of the source ranges from 0.01-6, preferably 0.1-3; the molar ratio of the alkali source to the silicon source ranges from 0.01-6, preferably 0.1-3; the ratio of the biopolymer to water The weight ratio is in the range of 0.0001 to 1; the solvent to water weight ratio is in the range of 0-5, preferably 0.01-3. The calcination temperature range is 300-800°C, preferably 450-750°C; the calcination time range is 1-9 hours, preferably 3-6 hours; the weight ratio of solvent, acid source and water in the extractant composition is in the range of 3. -10:0.01-5:0-10, preferably 5-8:0.05-3:0-3; extraction temperature range is 25-150℃, preferably 40-90℃; extraction time range is 0.5-6 Hour, preferably 1-3 hours; the ratio of the weight ratio of the extractant to the dried solid is in the range of 1000-10.

The titanium-containing silicon oxide material prepared by the present invention can be used as a catalyst. The catalyst can be treated by silylation before the catalytic reaction, such as step S130, to reduce the content of silanol groups to reduce the nature of the catalyst. The acidity of the catalyst changes the surface characteristics of the catalyst, thereby increasing the catalytic activity of the catalyst.

The method for silylation treatment can be a gas phase method in which a titanium-containing silicon oxide material reacts with a gas phase silylation reagent, or a liquid phase method in which a titanium-containing silicon oxide material reacts with a liquid phase silylation reagent. Silylation can use one or more organosilanes in a general way, and the organosilanes used for silylation can be halosilanes (general formula R ¹ R ² R ³ SiX), silazanes (general formula [R ⁴ R ⁵ R ⁶ Si] ₂ NH), silyl imidazole (general formula R ⁷ R ⁸ R ⁹ Si[N ₂ C ₃ H ₃ ]) or silylamine (general formula (R ¹⁰ ) ₃ SiN ( R ¹¹ ) ₂ ), wherein R ¹ , R ² and R ^{3 are the} same or different, and are each a saturated alkyl group of 1-6 carbons or a phenyl group; R ⁴ , R ⁵ and R ^{6 are the} same or different, and are each 1-6 alkyl groups, haloalkyl groups or phenyl groups; R ⁷ -R ¹¹ are each saturated alkyl groups of 1-3 carbons. The preferred organosilanes are one or more combinations of hexamethyldisilazane, silylamine, trimethylchlorosilane, and N-trimethylsilylimidazole. The solvent required for silylation can be one or more aromatic hydrocarbons composed of 6-16 carbons or saturated alkanes composed of 6-16 carbons. The preferred solvents are toluene, benzene and cyclohexane isopropyl One or more combinations of benzene.

When performing silylation, the weight ratio of organosilane to titanium-containing silicon oxide material is 0.01-1, preferably 0.1-0.8; the weight ratio of solvent to titanium-containing silicon oxide material is 1-200, preferably 1-100. And the reaction temperature of silylation is 25-200°C, preferably 50-150°C; the reaction time is 0.5-3 hours, preferably 1-2 hours.

In addition, there is an alternative method, such as step S140, incorporating the transition metal into the titanium-containing silicon oxide material to enhance the catalytic activity of the material.

In the titanium-containing silicon oxide material prepared by the present invention, other transition metals can be incorporated by impregnation, precipitation, blending or other similar methods as needed. Among them, the impregnation method is to disperse the transition metal solution in a suitable solvent and mix it with the titanium-containing silicon oxide material to form the titanium-containing silicon oxide material impregnated with the transition metal, and optionally use the titanium-containing silicon oxide material impregnated with the transition metal as the material. Further drying and calcination procedures. Wherein, the concentration range of the transition metal accounts for 0.001-10 weight percent (wt%) of the total amount of the titanium-containing silicon oxide material, preferably 0.005-5 wt%. The titanium-containing silicon oxide material impregnated with transition metal prepared by this method, the transition metal is located in or outside the framework of the titanium-containing silicon oxide material.

The titanium-containing silicon oxide material prepared by the present invention can be shaped and granulated at any stage before the calcination process, after the calcination process, before the extraction process, after the extraction process, before silylation, and after silylation. The method of molding and granulation can be selected according to needs such as compression molding process or extrusion molding process to make titanium-containing silicon oxide material into particles with a specific particle size range.

The titanium-containing silicon oxide material prepared by the invention has a high specific surface area and a high degree of dispersion of titanium active sites, so it can be used as a catalyst for the oxidation or selective oxidation of many organic compounds. On the other hand, if a third component (for example, aluminum... etc.) is added to the titanium-containing silicon oxide material prepared by the present invention to increase the acid site, it can catalyze alkylation, reforming, etc.

The titanium-containing silicon oxide material prepared by the invention can be used as a catalyst to prepare epoxides. Please refer to FIG. 2 to illustrate the process steps of the method for applying the titanium-containing silicon oxide material prepared by the present invention to the preparation method of epoxide. The figure shows three steps S200-S220. In step S220, an epoxide preparation method is described. In steps S200 and S210, it is defined that two possible steps in the preparation process of the epoxide can be added to improve the high catalytic activity of the catalyst. In practice, one or more of steps S200 and S210 can be used in a single production process, but for the sake of brevity, these steps are presented together (the dotted box indicates that these features are optional), Put it in a single flowchart.

As in steps S200 and S210, before the catalytic reaction, silylation and/or incorporation of transition metals into the titanium-containing silicon oxide material can be selected to increase the catalytic activity of the catalyst. The rest of the details of these steps are the same as the aforementioned steps S130 and S140, and they can also be combined with the processing steps of molding and granulation, which will not be repeated here.

In step S220, the titanium-containing silicon oxide material obtained by the foregoing method is used as a catalyst to catalyze the epoxidation reaction of olefins and oxides to form epoxides.

The titanium-containing silicon oxide material used in the epoxidation reaction can be in the form of powder, agglomerates, microspheres, monoliths, and can also be extrusion molding, compression molding or any other form. The olefin compounds used in the epoxidation reaction include, but are not limited to: aliphatic, cyclic, monocyclic, bicyclic or polycyclic compounds; it can also be mono-olefin, diolefin (diolefin) -olefin) or poly-olefin compounds. When the number of double bonds of the olefin compound is greater than 2, the type of the double bond may be a conjugated double bond or a non-conjugated double bond. Among them, monoolefin compounds include, but are not limited to: olefin compounds composed of 2-60 carbons. The olefin compound may have a substituent, and the substituent is preferably a relatively stable substituent. These monoolefin compounds include, but are not limited to: ethylene, propylene, 1-butene, isobutene, 1-hexene, 2-hexene, 3-hexene, 1-octene, 1-decene, Styrene or cyclohexene. Diolefin compounds, including, but not limited to: butadiene or isoprene.

In addition, the oxide used in the epoxidation reaction can be an organic peroxide whose general formula is ROOH (R represents a hydrocarbon group); a hydrocarbon group is a group composed of 3-20 carbons (preferably, the carbon number is 3- 10), including, but not limited to: second or third alkyl group or aralkyl group, for example, tertiary butyl, tertiary pentyl, cyclopentyl or 2- Phenyl-2-propyl. These organic peroxides include, but are not limited to: ethylbenzene hydroperoxide, cumene hydroperoxide, tertiary butyl hydroperoxide or cyclohexyl hydroperoxide; when cumene hydroperoxide is used as Organic peroxide, the product after the reaction is alpha-Cumyl alcohol. α-Cumene alcohol can be converted into α-methyl styrene (alpha-methyl styrene) through dehydration. In addition to many industrial applications, this compound can be converted into cumene after hydrogenation. Benzene can become cumene hydrogen peroxide after oxidation; other types of organic peroxides also have similar characteristics that can be recycled and reused.

The oxide used in the epoxidation reaction can also be hydrogen peroxide, and its general formula is H-O-O-H. Hydrogen peroxide can be obtained in the form of an aqueous solution, and can produce epoxide and water after reacting with olefin compounds.

The oxide as a reactant may be a pure or impure substance that has been concentrated or diluted.

During the epoxidation reaction to produce epoxide, a solvent or diluent can be added to make the reaction proceed in a liquid state. The solvent and diluent become liquid under the conditions of the epoxidation reaction and are inert to each reactant and product. These solvents include, but are not limited to: methanol, acetone, ethylbenzene, cumene, isobutane or cyclohexane, etc., or a mixture of them. The solvent can be a substance that exists in the oxide solution to be used. For example, when a mixed solution of cumene hydrogen peroxide and cumene is selected as the oxide, cumene can be used for the epoxidation reaction. The required solvent does not need to add an additional solvent.

In the aforementioned method, the amount of catalyst used is not strictly limited, as long as the epoxidation reaction can be completed in the shortest time. The molar ratio of the olefin compound to the oxide used during the reaction is between 1:100-100:1, preferably between 1:10-10:1. The reaction temperature is not particularly limited, and is usually 0-200°C, preferably 25-150°C. The reaction pressure is sufficient to ensure that all the reactants have a liquid composition or more, preferably between 1-100 atmospheric pressure. The reaction residence time is the shortest time for obtaining the highest yield of epoxide, generally 1 minute to 48 hours, preferably 5 minutes to 8 hours. This procedure is applicable to any reactor or instrument, for example, fixed bed, conveying bed, fluid bed, slurry stirring, or continuous flow stirring reactor in batch, continuous or semi-continuous mode.

Next, by presenting several specific examples below, we will further illustrate how the present invention effectively prepares titanium-containing silicon oxide materials, and this material can be used as a catalyst to catalyze the epoxidation reaction of olefin compounds and oxides to produce epoxy化物.

Example one

Preparation of titanium-containing silicon oxide material: add 2.9 kg of ammonia (28%) to 0.26 kg of tetraisopropyl orthotitanate, 3.6 kg of sodium silicate, 0.54 kg of gelatin, and 2.7 kg of sulfuric acid (98%). , 3 kilograms of isopropanol and 45 kilograms of water, stir at room temperature for 2 hours, and then mature at 100°C for 16 hours. Then, after filtering and removing the solution, the powder is dried at 70°C. The dried powder is subjected to a calcination process, the calcination temperature is 750°C, the heating rate is 5°C per minute, and the temperature is naturally cooled after holding the temperature for 6 hours to obtain a titanium-containing silicon oxide material with a high specific surface area. In this embodiment, the organic matter removal rate after the calcination process is higher than 97%.

Example two

Preparation of titanium-containing silicon oxide material: The preparation method is the same as in Example 1, but the calcination procedure is replaced with an extraction procedure. An aqueous solution of 10 kg of sulfuric acid, 70 kg of ethanol, and 20 kg of water was used as the extract. 1 kg of the powder and 100 kg of the extract were taken after maturation treatment and filtered and dried, stirred at 80°C for 2 hours, and filtered. And repeat this extraction procedure 2 more times. After the solution is removed, the powder is dried at 70°C to obtain a titanium-containing silicon oxide material with a high specific surface area. In this embodiment, the organic matter removal rate after the extraction process is higher than 90%.

Example three

Preparation of propylene oxide: 15 grams of titanium-containing silicon oxide material prepared in Example 1 was used as a catalyst, and 225 grams of 25 weight percent (wt%) cumene hydrogen peroxide solution (the solvent was cumene) and 125 grams of propylene was mixed uniformly in a 1 liter closed autoclave and heated at 95°C for reaction. The reaction time was less than 1.5 hours. The reaction results are shown in Table 1.

Example four

Preparation of titanium-containing silicon oxide material: The preparation method is the same as in Example 1, but the high specific surface area titanium-containing silicon oxide material obtained after the calcination process is taken 16.5 g for silylation. This titanium-containing silicon oxide material was uniformly mixed with 165 g of toluene and 11.2 g of hexamethyldisilazane, stirred at 120°C for 1 hour, and then filtered and dried. The titanium-containing silicon oxide material obtained in this embodiment has a specific surface area of 353 m ² /g, a pore volume of 0.752 ml/g, and an average pore diameter of 5.5 nm.

Preparation of propylene oxide: The preparation method is the same as in Example 3, but the catalyst used is changed to the titanium-containing silicon oxide material prepared in Example 4. The reaction results are shown in Table 1.

Table I Example three Example four Conversion rate of cumene hydrogen peroxide (%) (Note ¹ ) 83 98 Propylene oxide selectivity (%) (Note ² ) 77 95 Note ^1. Conversion rate of cumene hydroperoxide = consumption of cumene hydroperoxide/addition of cumene hydroperoxide x 100% Note ^2. Selectivity of propylene oxide = propylene oxide generation/hydrogen peroxide Cumene consumption x 100%

Example 1 and Example 2 show that the titanium-containing silicon oxide material prepared by the biopolymer of the present invention can be removed from the material by a calcination process or an extraction process. Table 1 shows that Example 3 shows that the titanium-containing silicon oxide material prepared by using biopolymers of the present invention has outstanding catalytic activity for catalyzing the epoxidation reaction of olefin compounds; Example 4 shows that the present invention is prepared by using biopolymers. After the titanium-containing silicon oxide material is silanized, its catalytic activity for catalyzing the epoxidation of olefin compounds can be greatly improved.

In general, according to the preparation method and application of the titanium-containing silicon oxide material of the present invention, an environmentally friendly biopolymer can be used as a template, and a generally simple template method can be used to prepare a titanium-containing material with a high specific surface area. Silicon oxide material, and the prepared titanium-containing silicon oxide material has high catalytic activity and can be further used as a catalyst to successfully catalyze the epoxidation reaction of olefin compounds.

Only the above are only preferred embodiments of the present invention, and are not used to limit the scope of implementation of the present invention. Therefore, all equivalent changes or modifications made in accordance with the characteristics and spirit of the application scope of the present invention shall be included in the patent application scope of the present invention.

no

Figure 1 is a flow chart of a method for preparing a titanium-containing silicon oxide material provided by the present invention. Figure 2 is a flow chart of an epoxide preparation method provided by the present invention.

Claims (22)

A method for preparing a titanium-containing silicon oxide material includes the following steps: mixing a titanium source, a silicon source, an acid source, an alkali source, a biopolymer, and a solvent to prepare an aqueous solution; Solid-liquid separation, and then drying the solid obtained from the solid-liquid separation; and subjecting the dried solid to a calcination process or an extraction process with an extractant to obtain the titanium-containing silica material, which satisfies the following conditions : The average pore diameter of the titanium-containing silicon oxide material is greater than 10 angstroms (Å); 90% or more of the total pore volume of the titanium-containing silicon oxide material has a pore diameter of 5-200 angstroms; and the specific pore volume of the titanium-containing silicon oxide material It is 0.2 cubic centimeters/gram (cm ³ /g) or more. The method for preparing a titanium-containing silicon oxide material according to claim 1, wherein the titanium source is a titanate, an inorganic titanium source or a combination thereof, and the silicon source is amorphous silicon dioxide, alkane Alkoxysilane, silicate, or a combination thereof, the acid source is an organic acid, an inorganic acid, or a combination thereof, the alkali source is an organic base, an inorganic base, and the counter ion is an organic hydroxide anion. A molecule or a combination thereof, the biopolymer is a polymer produced by an organism, the solvent is an alcohol solvent, and the extractant is a solution of a mixture of the acid source and the solvent. The method for preparing a titanium-containing silicon oxide material according to claim 2, wherein the titanate is selected from the group consisting of tetramethyl titanate, tetraethyl titanate, n-tetrapropyl titanate, and tetraiso titanate. Propyl ester, n-tetrabutyl titanate, tetrabutyl titanate, tetrabutyl iso-titanate, tetrabutyl titanate, tetra(2-ethylhexanol) titanate, tetra( The group consisting of octadecyl) orthotitanate and combinations thereof. The inorganic titanium source is selected from the group consisting of titanium trichloride, titanium tetrachloride, titanium tribromide, titanium tetrabromide, titanium triiodide, A group consisting of titanium tetraiodide, titanium sulfate and combinations thereof. The method for preparing a titanium-containing silicon oxide material according to claim 2, wherein the amorphous silicon dioxide is selected from the group consisting of smoked silica, white smoke, silica gel, silica sol, and combinations thereof The alkoxysilane is selected from the group consisting of tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, monoalkyltrialkoxysilanes (alkyltrialkoxysilanes) , Dialkyldialkoxysilanes, trialkylmonoalkoxysilanes and combinations thereof. The silicate is selected from the group consisting of sodium silicate and potassium silicate Salt, magnesium silicate, calcium silicate and combinations thereof. The method for preparing a titanium-containing silicon oxide material according to claim 2, wherein the organic acid is selected from formic acid, acetic acid, propionic acid, sulfonic acid, sulfinic acid, thiocarboxylic acid, citric acid, malic acid, and tartaric acid , Oxalic acid, succinic acid, lactic acid and combinations thereof. The inorganic acid is selected from hydrochloric acid, hypochlorous acid, chlorous acid, chloric acid, perchloric acid, nitric acid, hydrazoic acid, double nitric acid, Hyponitrous acid, nitrous acid, peroxynitric acid, sulfuric acid, hydrogen sulfuric acid, hydrogen disulfide, thiosulfuric acid, hyposulfuric acid, persulfuric acid, phosphoric acid, hypophosphorous acid, phosphorous acid, metaphosphoric acid, metaphosphorous acid, diphosphoric acid, hypophosphoric acid , Pyrophosphoric acid, boric acid, metaboric acid, tetraboric acid, fluoroboric acid, perboric acid, carbonic acid, hydrocyanic acid, cyanic acid, fulvic acid, isocyanic acid, thiocyanic acid, isothiocyanic acid, selenocyanic acid, trithio Carbonic acid, hydrogen peroxide, hydrofluoric acid, hypofluoric acid, bromic acid, hydrobromic acid, chromic acid, dichromic acid, permanganic acid and combinations thereof. The method for preparing titanium-containing silicon oxide material according to claim 2, wherein the organic base is selected from the group consisting of sodium methoxide, potassium ethoxide, potassium tert-butoxide, butyl lithium, phenyl lithium, and diisophenylamine Lithium diisopropylamide, lithium hexamethyldisilazide, pyridine, imidazole, benzimidazole, histidine and combinations thereof. The inorganic base is selected from lithium hydroxide, Sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, aluminum hydroxide, ammonium hydroxide, zinc hydroxide, copper hydroxide, nickel hydroxide, chromium hydroxide, sodium carbonate , Sodium bicarbonate, potassium carbonate, potassium bicarbonate and combinations thereof. The organic molecule whose counter ion is a hydroxide anion is selected from the group consisting of trimethyloctadecylammonium hydroxide (trimethyloctadecylammonium hydroxide), ten Cetyltrimethylammonium hydroxide (cetyltrimethylammonium hydroxide), dodecyl trimethylammonium hydroxide (dodecyl trimethyl ammonium hydroxide) and the combination of the group. The method for preparing a titanium-containing silicon oxide material according to claim 2, wherein the biopolymer is selected from the group consisting of chitosan, collagen, gelatin, and agarose , Chitin, polyhydroxyalkanoates, pullulan, starch, cellulose, hyaluronic acid and similar substances. The method for preparing titanium-containing silicon oxide material according to claim 2, wherein the alcohol solvent is selected from methanol, ethanol, n-propanol, isopropanol, vinyl butanol, allyl butanol, n-butanol Alcohol, second butanol, tertiary butanol, pentanol, cyclohexanol, benzyl alcohol, diol compounds and combinations thereof. The method for preparing a titanium-containing silicon oxide material according to claim 1, wherein the molar ratio of the titanium source to the silicon source in the aqueous solution ranges from 0.00001 to 0.5, and the biopolymer and the silicon source The ratio range of the weight ratio is 0.005-5, the molar ratio of the acid source to the silicon source is 0.01-6, and the molar ratio of the alkali source to the silicon source is 0.01-6. The ratio of the weight ratio of biopolymer to water is in the range of 0.0001 to 1 and the ratio of the weight ratio of solvent to water is in the range of 0-5. The method for preparing a titanium-containing silicon oxide material according to claim 9, wherein the molar ratio of the titanium source to the silicon source in the aqueous solution ranges from 0.0001 to 0.1, and the ratio of the acid source to the silicon source The molar ratio ranges from 0.1 to 3, the molar ratio of the alkali source to the silicon source ranges from 0.1 to 3, and the solvent to water weight ratio ranges from 0.01 to 3. The method for preparing a titanium-containing silicon oxide material as described in claim 1, wherein the aqueous solution is reacted at -20-200°C for 0.5-5 hours, and aged at 60-200°C for 6-48 hours. The solid obtained by solid-liquid separation is continuously dried at 30-120°C for 0.5-6 hours. The method for preparing titanium-containing silicon oxide material according to claim 1, wherein the calcination temperature of the calcination process is 300-800°C, the calcination time is 1-9 hours, and the extractant used in the extraction process is composed of The weight ratio of solvent, acid source and water is in the range of 3-10:0.01-5:0-10, the temperature is in the range of 25-150℃, and the extraction time is in the range of 0.5-6 hours. The weight of the extractant and the dried solid The ratio range is 1000-10. The method for preparing titanium-containing silicon oxide material according to claim 12, wherein the calcination temperature of the calcination process is 450-750°C, the calcination time is 3-6 hours, and the extractant used in the extraction process is composed of The weight ratio of solvent, acid source and water is in the range of 5-8:0.05-3:0-3, the temperature range is 40-90°C, and the extraction time range is 1-3 hours. The preparation method of the titanium-containing silicon oxide material described in claim 1 further comprises at least one of the following steps: Silylation is performed on the titanium-containing silicon oxide material, the reaction temperature is 25-200°C, and the reaction time is 0.5-3 hours; and A transition metal is incorporated into the titanium-containing silicon oxide material, and the concentration range of the transition metal accounts for 0.001-10 weight percent of the total amount of the titanium-containing silicon oxide material. The method for preparing a titanium-containing silicon oxide material according to claim 14, wherein the concentration range of the transition metal accounts for 0.005 to 5 weight percent of the total amount of the titanium-containing silicon oxide material. A preparation method of epoxide, characterized in that it comprises the following steps: A titanium-containing silicon oxide material obtained by the method described in claim 1 is provided as a catalyst to react olefin compounds and oxides to form the epoxide. The method for preparing an epoxide according to claim 16, wherein the olefin compound is a monoolefin, diolefin or multiolefin compound, and the oxide is an organic peroxide or hydroperoxide. The method for preparing an epoxide according to claim 17, wherein the monoolefin compound is selected from the group consisting of ethylene, propylene, 1-butene, isobutene, 1-hexene, 2-hexene, and 3-hexene , 1-octene, 1-decene, styrene and cyclohexene, the diolefin compound is butadiene or isoprene, the organic peroxide is ethylbenzene hydrogen peroxide, Cumene hydroperoxide, tertiary butyl hydroperoxide or cyclohexyl hydroperoxide. The method for preparing an epoxide according to claim 16, wherein the molar ratio of the olefin compound to the oxide is 1:100-100:1. The method for preparing an epoxide according to claim 19, wherein the molar ratio of the olefin compound to the oxide is 1:10-10:1. The method for preparing an epoxide according to claim 16, wherein the reaction temperature of the olefin compound and the oxide is 0-200°C, and the reaction pressure is a pressure sufficient to make all the reactants liquid or higher, and the reaction stays The time is 1 minute-48 hours. The method for preparing an epoxide according to claim 21, wherein the reaction temperature of the olefin compound and the oxide is 25-150°C, the reaction pressure is 1-100 atmospheric pressure, and the reaction residence time is 5 minutes- 8 hours.

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