CN101537371B - Modification method for titanium-silicon molecular sieve - Google Patents

Abstract

A modification method for a titanium-silicon molecular sieve comprises the following steps of mixing the titanium-silicon molecular sieve, a protective agent, an alkali source, a noble metal source and water according to the proportion of 100:(0.0001-5):(0.005-5):(0.005-10):(500-10,000), hydro-thermal treatment and recycling, wherein the titanium-silicon molecular sieve is calculated by the gram; the noble metal source is calculated by the gram of a noble metal simple substance; the protective agent, the alkali source and the water are calculated by the mol; and the protective agent is selected from one or more of polypropylene, polyethyleneglycol, polystyrene, polyvinyl chloride, polyethylene and derivatives thereof, glucose, cyclodextrin, an anionic surfactant, a cationic surfactant and a non-ionic surfactant. The titanium-silicon molecular sieve prepared by the method has high content of framework titanium, is used for oxidation reaction of organic matters and has high activity, selectivity and stability.

Description

A kind of modification method of titanium silicon molecular sieve

technical field

The invention relates to a method for modifying a titanium-silicon molecular sieve.

Background technique

Titanium silicate molecular sieve is a new type of heteroatom molecular sieve developed in the early 1980s. At present, TS-1 with MFI structure, TS-2 with MEL structure, MCM-22 with MWW structure and TS-48 with larger pore structure have been synthesized. Titanium-silicon molecular sieves can be used to catalyze various organic oxidation reactions, such as olefin epoxidation, alkane partial oxidation, alcohol oxidation, phenol hydroxylation, cyclic ketone ammoxidation, etc. As an oxidant, hydrogen oxide has high reaction selectivity and relatively simple process, and has the incomparable advantages of energy saving, economy and environmental friendliness compared with traditional oxidation systems. As a catalyst for the selective oxidation of organic matter, titanium-silicon molecular sieves are considered to be a milestone in the field of molecular sieve catalysis.

H ₂ O ₂ is a recognized green oxidant, and its oxidation by-product is only water, but H ₂ O ₂ is extremely unstable and will decompose when exposed to heat, light, rough surfaces, heavy metals and other impurities, and is corrosive. 1. Special safety measures should be taken during transportation. Therefore, consider the application _{of H2O2} on site, or combine the production process _{of H2O2} with _the downstream process of using _H2O2 .

Using H ₂ and O ₂ to directly synthesize H ₂ O ₂ , the atomic utilization rate reaches 100%, and then people consider using H ₂ and O ₂ to synthesize H ₂ O ₂ in situ and then oxidize organic raw materials to solve the problem of directly using H ₂ O ₂ oxidation costs and safety issues. Noble metals such as Pt, Pd, and Au are effective catalytic components for the synthesis of H ₂ O ₂ from H ₂ and O ₂ , and many literatures have reported using them to modify titanium-silicon materials to catalyze the in situ generation of H 2 from H ₂ and _{O 2} Selective Oxidation of Organics with _O2 . For example, Meiers R. et al. (J.Catal., 1998,176:376-386) used Pt-Pd/TS-1 as a catalyst to study the gas-phase epoxidation of propylene; US6867312B1 and US6884898B1 disclosed noble metal modified TS- 1 Method for propylene oxidation on molecular sieves. The reaction conditions of the process are mild, but the problems of the catalyst are low catalyst activity and poor stability.

CN 1245090A discloses a method for modifying titanium-silicon molecular sieve (TS-1), which comprises mixing the synthesized TS-1 molecular sieve, acidic compound and water, and reacting at 5-95°C for 5 minutes to After 6 hours, the acid-treated TS-1 molecular sieve was obtained; the obtained acid-treated TS-1 molecular sieve, organic base and water were mixed evenly, and reacted in a sealed reaction kettle at a temperature of 120-200°C and autogenous pressure for 2 hours to 8 days, then the resulting product is filtered, washed and dried; the TS-1 molecular sieve obtained by this method reduces the invalid decomposition of the oxidant due to the removal of part of the titanium in the pores of the molecular sieve, so that its catalytic oxidation activity is comparable to that of the prior art It is significantly improved compared with that, and has better stability of catalytic activity at the same time.

Contents of the invention

The purpose of the present invention is to provide a new method for modifying titanium-silicon molecular sieve materials.

The invention provides a method for modifying a titanium-silicon molecular sieve, comprising the following steps:

(1) Mix titanium-silicon molecular sieve, protective agent, alkali source, precious metal source, and water according to the ratio of 100: (0.0001-5): (0.005-5): (0.005-10): (500-10000), wherein titanium The silicon molecular sieve is calculated in grams, the noble metal source is calculated in grams of precious metal simple substance, and the protective agent, alkali source, and water are calculated in moles, and the protective agent is selected from polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, One or more of polyethylene and its derivatives, glucose, cyclodextrin, anionic surfactant, cationic surfactant and nonionic surfactant;

(2) hydrothermally treating the mixture obtained in step (1), and then recovering molecular sieves.

The titanium-silicon molecular sieve modification method provided by the present invention can make the titanium outside the framework of the molecular sieve enter the framework, thereby reducing the titanium outside the framework and increasing the titanium in the framework (usually using the absorption peak intensity at 960cm ^- 1 and 550cm ^-1 in the infrared spectrum Ratio I ₉₆₀ /I ₅₅₀ to characterize the relative titanium content in the framework of the titanium-silicon molecular sieve, judge the relative titanium content in the framework according to the size of this value, the larger the value is, the higher the relative titanium content in the framework); Modified titanium-silicon molecular sieve grains with a hollow structure, which is conducive to the diffusion of reactant and product molecules. The method of the invention is simple and easy to operate, and the process is easy to control. Compared with the modified titanium-silicon molecular sieve prepared by the existing method, the modified titanium-silicon molecular sieve prepared by the method of the present invention is used for the oxidation reaction of organic matter, and the activity, selectivity and stability are improved.

Description of drawings

Figure 1 is a transmission electron microscope (TEM) photo of the sample obtained in Example 1.

Detailed ways

In the modification method provided by the present invention, the ratio of titanium silicon molecular sieve, protective agent, alkali, precious metal source, and water in step (1) is preferably 100: (0.005～1): (0.01～2): (0.01～5) : (500-5000), wherein the titanium-silicon molecular sieve is measured in grams, the noble metal source noble metal is measured in grams, and the protective agent, alkali source, and water are measured in moles.

In the modification method provided by the present invention, the derivatives of polyethylene, polyethylene glycol, polystyrene, polyvinyl chloride, and polypropylene are their pyrrolidone, vinyl alcohol, ether, and pyrimidine derivatives, preferably Polypropylene alcohol, polypropylene ether, polyacrylpyrimidine, polyethylene glycol pyrrolidone, polyethylene glycol ether, polyethylene glycol pyrimidine, polystyrene pyrrolidone, polystyrene alcohol, polystyrene ether, polystyrene pyrimidine, Polyvinyl chloride pyrrolidone, polyvinyl chloride alcohol, polyvinyl chloride ethyl ether, polyvinyl chloride pyrimidine, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl ether, polyvinyl pyrimidine.

In the modification method provided by the present invention, the anionic surfactant such as fatty acid salt, sulfate ester salt, phosphate ester salt, alkylbenzene sulfonate, α-olefin sulfonate, alkyl sulfonate, α -Sulfomonocarboxylates, fatty acid sulfoalkyl esters, succinate sulfonates, alkylnaphthalene sulfonates, petroleum sulfonates, lignosulfonates, alkyl glyceryl ether sulfonates; cationic surfactants Agents such as fatty amine quaternary ammonium salt cationic surfactants, cyclic cationic surfactants, cetyltrimethylammonium bromide, dodecyldimethylamine oxide, trioctyl (nonyl) methyl chloride (Bromium) ammonium; non-ionic surfactants such as fatty alcohol polyoxyethylene ether, block polyoxyethylene-polyoxypropylene ether, alkyl alcohol amides, polyol esters, Tween series, Span series, fluorocarbon Surfactant series.

In the modification method provided by the present invention, the noble metal source described in step (1) is selected from oxides, halides, carbonates, nitrates, ammonium nitrate salts, acetates, ammonium chloride salts, hydrogen One or more of oxides and other complexes of noble metals. The other complexes are, for example, complexes of noble metals with acetylacetone, complexes of noble metals with cyclooctadiene and cyclooctatriene. For example, when the noble metal is palladium, it can be one or more of palladium oxide, palladium carbonate, palladium chloride, palladium nitrate, palladium ammonium nitrate, palladium ammonium chloride, palladium hydroxide, palladium acetate, palladium acetylacetonate . Preferred noble metals are palladium and/or platinum.

In the modification method provided by the present invention, the base in step (1) is an inorganic base or an organic base. Among them, the inorganic alkali is one or more of ammonia water, sodium hydroxide, potassium hydroxide, and barium hydroxide; the organic alkali source is one of urea, quaternary ammonium base compounds, fatty amine compounds, and alcohol amine compounds. or several.

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

The general formula of the aliphatic amine compound is R ² (NH ₂ ) _n , wherein R ² is selected from an alkyl group or an alkylene group with 1-6 carbon atoms, and n=1 or 2. Preference is given to ethylamine, n-butylamine, butylenediamine or hexamethylenediamine.

The general formula of the 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. The alcohol amine compound such as monoethanolamine, diethanolamine or triethanolamine.

In the modification method provided by the present invention, the order of adding titanium-silicon molecular sieve, protective agent, noble metal source, alkali source and water in step (1) is to add titanium-silicon molecular sieve, protective agent and noble metal source to the mixture containing alkali source in the solution.

In the modification method provided by the present invention, the hydrothermal treatment and recovery in step (2) can be carried out according to the existing methods of hydrothermal treatment and recovery in the synthesis or modification of titanium silicon molecular sieves. The hydrothermal treatment includes keeping at a temperature of 80-200° C. and autogenous pressure for 2-360 hours. The recovery includes the steps of filtering, washing, drying and roasting. Washing can be done with distilled water or deionized water; drying conditions include: temperature is room temperature to 200°C, time is 3 to 24 hours, in an air atmosphere; roasting conditions include: temperature is 300 to 600°C, time is 3 to 24 hours, nitrogen or air atmosphere middle.

The modification method provided by the present invention can be used for the modification of titanium-silicon molecular sieves, such as TS-1, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41, Ti-MCM-48 , especially suitable for TS-1 molecular sieve modification. The described titanium-silicon molecular sieves can be molecular sieves synthesized according to various methods in the prior art, or modified titanium-silicon molecular sieves prepared by existing methods. They can be processed or not roasted, that is, can contain or not Contains organic templating agent. The modified titanium-silicon molecular sieve recovered in step (2) can be further modified by the method of the present invention.

The following examples will further illustrate the present invention, but do not limit the present invention thereby. The reagents used in the examples are commercially available chemically pure reagents. The titanium-silicon molecular sieve TS-1 used in the comparative examples and examples was prepared according to the method described in Zeolites, 1992, Vol.12, pages 943-950. The transmission electron micrograph (TEM) of the sample was obtained on a Tecnai G2F20S-TWIN transmission electron microscope of the Netherlands FEI company, with an accelerating voltage of 20kV. The infrared spectrum of the molecular sieve sample skeleton was measured on a Nicolet 8210 Fourier transform infrared spectrometer, KBr pellets, and the test range was 400-4000cm ^-1 . The I ₉₆₀ /I ₅₅₀ data of the samples prepared by TS-1, Comparative Examples and Examples are listed in Table 1.

Comparative example 1

This comparative example illustrates the process of preparing supported palladium/titanium silicate molecular sieve catalyst (0.5%Pd/TS-1) by conventional method.

Take 20 grams of titanium-silicon molecular sieve TS-1 and 2.0 mL of ammonium nitrate palladium complex solution with a concentration of 0.05 g/mL (calculated as palladium atoms), add it to 20 mL of deionized water, stir evenly, seal it, and soak it at a temperature of 40 ° C 24h, then dried naturally, and reduced activation at 300°C in a hydrogen atmosphere for 5h to obtain the traditional supported palladium/titanium silicate molecular sieve catalyst (0.5%Pd/TS-1) DB-1.

Example 1

Get 20 grams of titanium-silicon molecular sieves TS-1, concentration is the ammonium nitrate palladium complex solution of 0.05g/mL (in terms of palladium atoms) and hexadecyltrimethylammonium bromide to join the tetrapropylammonium hydroxide In the aqueous solution (mass percentage concentration 16%), stir evenly, wherein titanium silicon molecular sieve (gram): hexadecyltrimethylammonium bromide (mole): tetrapropyl ammonium hydroxide (mole): ammonium nitrate palladium complex Matter (gram, calculated as palladium): water (mol)=100:0.005:0.5:2.0:1000. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at 150°C and autogenous pressure for 48h, then filter, wash, dry at room temperature for 8 hours, and roast at 500°C for 5h to obtain the modified microporous titanium-silicon material A. Its transmission electron microscope The photographs show that it is a hollow structure (Fig. 1).

Example 2

20 grams of titanium-silicon molecular sieve TS-1, palladium chloride solution and polyvinylpyrrolidone (relative molecular weight is 30000) with a concentration of 0.05g/mL (as palladium atoms) were added to the aqueous solution of sodium hydroxide (mass percentage concentration 15%) ), stir evenly, wherein titanium silicon molecular sieve (gram): polyvinylpyrrolidone (mol): sodium hydroxide (mol): palladium chloride (gram, calculated as palladium): water (mol) = 100: 0.9: 1.8: 0.1:4600. Then put it into a sealed stainless steel reaction kettle, hydrothermally treat it at 180°C and autogenous pressure for 24h, filter, wash, dry at room temperature, and roast at 500°C for 5h to obtain the modified microporous titanium-silicon material B.

Example 3

Get 20 grams of titanium silicon molecular sieve TS-1, concentration is the palladium acetate solution of 0.05g/mL (as palladium atom) and Tween 80 joins the aqueous solution (mass percentage concentration 20% of tetrapropyl ammonium hydroxide and butanediamine) ) and stir and mix evenly, wherein titanium-silicon molecular sieve (gram): alkali source (mole): palladium source (gram, calculated as palladium): protective agent (mole): water (mole) = 100: 0.5: 0.05: 0.02: 550 , and then placed in a sealed reactor, hydrothermally treated at 120°C and autogenous pressure for 120h, then filtered, washed, dried naturally at room temperature, and calcined at 500°C for 5h to obtain the modified microporous titanium-silicon material C.

Example 4

20 grams of titanium-silicon molecular sieve TS-1, a concentration of 0.05g/mL (as palladium atoms) ammonium chloride palladium solution and polyvinylpyrrolidone (relative molecular mass is 15000) were added to the aqueous solution of tetrapropylammonium hydroxide ( Concentration of 15% by mass percentage) stirring and mixing uniformly, wherein titanium silicon molecular sieve (gram): protective agent (mole): alkali source (mole): palladium source (gram, in palladium): water (mole)=100: 0.01: 2.0:0.5:2500, then put it into a sealed stainless steel reaction kettle, hydrothermally treat it at a temperature of 150°C and an autogenous pressure for 96 hours, filter and wash the resultant, dry it naturally at room temperature, and roast it at 600°C for 3 hours to obtain the modified micro Porous titanium silicon material D.

Example 5

Take 20 grams of titanium-silicon molecular sieve TS-1, a palladium acetate solution with a concentration of 0.05 g/mL (calculated as palladium atoms), and glucose, and add it to an aqueous solution of butanediamine (10% by mass concentration) and stir and mix evenly, wherein the titanium-silicon Molecular sieve (gram): glucose (mol): butylenediamine (mol): palladium acetate (gram, calculated as palladium): water (mol) = 100: 0.1: 0.02: 4.0: 3500. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at 120°C and autogenous pressure for 120h, filter, wash, dry naturally at room temperature, and bake at 400°C for 8h to obtain the modified microporous titanium-silicon material E.

Example 6

Get 20 grams of titanium-silicon molecular sieves TS-1, concentration is 0.02g/mL (in terms of palladium atoms) ammonium chloride palladium solution and sodium dodecylbenzenesulfonate join the aqueous solution of tetrapropyl ammonium hydroxide (mass percent Concentration 10%), stirring and mixing uniformly, wherein titanium silicon molecular sieve (gram): sodium dodecylbenzenesulfonate (mole): tetrapropyl ammonium hydroxide (mole): ammonium chloride palladium (gram, in palladium) : water (mol)=100:0.5:1.1:4.8:2000. Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at 90°C and autogenous pressure for 240h, filter, wash, dry naturally at room temperature, and roast at 500°C for 5h to obtain the modified microporous titanium-silicon material F.

Example 7

Add 20 grams of titanium-silicon molecular sieve TS-1, palladium acetate solution with a concentration of 0.01 g/mL (calculated as palladium atoms) and cetyltrimethylammonium bromide to tetrapropylammonium hydroxide (mass percentage concentration 13 %), stirring and mixing evenly, wherein titanium silicon molecular sieve (gram): protective agent (mol): alkali source (mol): palladium source (gram, calculated as palladium): water (mol)=100: 0.2: 0.1: 0.02: 800, then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at a temperature of 160°C and an autogenous pressure for 120h, take out the resultant, filter it, wash it, then dry it at room temperature, and roast it at 500°C for 5h to obtain a modified microporous titanium-silicon material g.

Example 8

20 grams of titanium-silicon molecular sieve TS-1, a concentration of 0.02g/mL (in terms of palladium atoms) ammonium palladium nitrate solution and β-cyclodextrin were added to the aqueous solution of tetrapropylammonium hydroxide (mass percentage concentration 15%) Stir and mix evenly in medium, wherein titanium-silicon molecular sieve (gram): protective agent (mol): alkali source (mol): palladium source (gram, calculated as palladium): water (mol) = 100: 0.1: 0.9: 4.5: 4800, Then put it into a sealed stainless steel reactor, hydrothermally treat it at 150°C and autogenous pressure for 96 hours, filter, wash, dry at 110°C for 3 hours, and roast at 550°C for 5 hours to obtain the modified microporous titanium-silicon material H.

Example 9

Get 20 grams of titanium-silicon molecular sieves, a concentration of 0.05g/mL (in terms of palladium atoms) in ethanol solution of palladium acetate and polyethylene glycol (relative molecular mass is 20000) to the aqueous solution of triethanolamine (mass percentage concentration 18%) Stir and mix evenly in medium, wherein titanium silicon molecular sieve (gram): polyethylene glycol (mol): triethanolamine (mol): palladium acetate (gram, calculated as palladium): water (mol) = 100: 0.02: 1.2: 1.0: 1500. Then put it into a reaction kettle, hydrothermally treat it at 130°C and autogenous pressure for 320h, filter, wash, dry at 120°C for 3 hours, and roast at 500°C for 5h to obtain the modified microporous titanium-silicon material I.

Example 10

20 grams of titanium-silicon molecular sieve TS-1, palladium acetate solution and hexadecyltrimethylammonium chloride with a concentration of 0.01g/mL (as palladium atoms) were added to tetrapropylammonium hydroxide (mass percentage concentration 13 %), stir to make it evenly mixed, wherein titanium silicon molecular sieve (gram): protective agent (mole): alkali source (mole): palladium source (gram, calculated as palladium): water (mole) = 100: 0.12: 0.1 : 5.0: 3000, then put into a stainless steel sealed reactor, hydrothermally treat at 160°C and autogenous pressure for 120h, then filter, wash, dry at 110°C for 4 hours, and roast at 500°C for 5h to obtain modified microporous titanium Silicon Materials J.

Comparative example 2

This comparative example illustrates the process of preparing supported palladium-platinum/titanium silicate molecular sieve (0.5%Pd, 0.5%Pt/TS-1) by conventional impregnation modification method.

Take 20 grams of titanium-silicon molecular sieve TS-1 and a concentration of 0.05g/mL (calculated by palladium atoms) of ammonium palladium nitrate and a concentration of 0.05g/mL (calculated by platinum atoms) ammonium nitrate-platinum complex solution, add 2.0mL each Stir evenly in 20mL deionized water, seal, soak at 40°C for 24h, dry naturally, and perform reduction activation in 300°C hydrogen atmosphere for 5h to obtain the traditional supported palladium-platinum/titanium silicon molecular sieve catalyst (0.5%Pd , 0.5% Pt/TS-1) DB-2.

Example 11

Get 20 grams of titanium-silicon molecular sieve TS-1, a concentration of 0.01g/mL (in terms of palladium atoms) of ammonium nitrate palladium and a concentration of 0.01g/mL (in terms of platinum atoms) of ammonium nitrate-platinum complex solution and hexadecane Trimethylammonium bromide is added to the aqueous solution of tetrapropylammonium hydroxide (mass percentage concentration 16%) and stirred and mixed evenly, wherein titanium silicon molecular sieve (gram): hexadecyltrimethylammonium bromide (mol) : tetrapropylammonium hydroxide (mole): ammonium ammonium nitrate (gram, in platinum): ammonium palladium nitrate (gram, in palladium): water (mole)=100: 0.1: 1.2: 0.5: 0.5: 1800, Then put it into a stainless steel sealed reaction kettle, hydrothermally treat it at 160°C and autogenous pressure for 72h, filter the obtained product, wash it, dry it naturally, and roast it at 500°C for 5h to obtain the modified microporous titanium-silicon material K.

Table 1

source of samples sample name I ₉₆₀ /I ₅₅₀ Synthesized according to the literature TS-1 0.685 Example 1 A 0.706 Example 2 B 0.711 Example 3 C 0.710 Example 4 D 0.702 Example 5 E 0.707 Example 6 F 0.698 Example 7 G 0.701 Example 8 h 0.702 Example 9 I 0.694 Example 10 J 0.696 Example 11 K 0.702 Comparative example 1 DB-1 0.678 Comparative example 2 DB-2 0.672

It can be seen from _Table 1 that the value of I ₉₆₀ /I _{550 of} the sample prepared by the method of the present invention is larger than that of TS-1 and the comparative example, indicating that the content of titanium in the skeleton of the sample prepared by the method of the present invention is high.

Example 12

This example illustrates the effect of the example sample and the comparative sample provided by the present invention for the reaction of propylene oxide to prepare propylene oxide (PO).

Get the sample 0.5g prepared by above-mentioned embodiment or comparative example respectively and join in the epoxidation reaction container that contains methanol 80mL, pass into propylene, oxygen, hydrogen and nitrogen, wherein the mol ratio of propylene, oxygen, hydrogen, nitrogen is 1 : 1:1:7, under the conditions of temperature 60°C, pressure 1.0MPa, propylene space velocity 10h ^-1 , carry out epoxidation reaction to generate PO.

Table 2 shows the data of propylene conversion and PO selectivity for reaction 2h and 12h.

Table 2

As can be seen from Table 2, the activity and selectivity of the sample obtained by the method of the present invention are high, and have good stability.

Claims (15)

1. the method for modifying of a micropore titanium silicon molecular sieve comprises the following steps:

(1) with HTS, protective agent, alkali source, noble metal source, water according to 100: (0.0001～5): (0.005～5): (0.005～10): the ratio of (500～10000) is mixed, wherein HTS is in gram, noble metal source is in the gram number of precious metal simple substance, protective agent, alkali source, water are in mole, and described protective agent is selected from one or more in glucose, anion surfactant, cationic surfactant and the non-ionic surface active agent;

(2) the mixture hydrothermal treatment consists that step (1) is obtained reclaims then.

2. in accordance with the method for claim 1, it is characterized in that the ratio of HTS, protective agent, alkali source, noble metal source, water is 100: (0.005～1): (0.01～2): (0.01～5): (500～5000).

3. in accordance with the method for claim 1, wherein the described noble metal source of step (1) is selected from oxide, halide, carbonate, acetate, nitrate, ammonium salt, chlorination ammonium salt, hydroxide, acetylacetonate complex, cyclo-octadiene complex compound and the cyclo-octatriene complex compound of noble metal one or more.

4. according to claim 1 or 3 described methods, it is characterized in that described noble metal is palladium and/or platinum.

5. in accordance with the method for claim 1, it is characterized in that alkali source described in the step (1) is one or more in ammoniacal liquor, NaOH, potassium hydroxide, barium hydroxide, urea, quaternary ammonium base compound, amine compound and the alcohol amine compound.

6. in accordance with the method for claim 5, it is characterized in that described its general formula of quaternary ammonium base compound is (R ¹) ₄NOH is characterized in that, R ¹For having the alkyl of 1～4 carbon atom.

7. in accordance with the method for claim 6, it is characterized in that described R ¹Be propyl group.

8. in accordance with the method for claim 5, it is characterized in that its general formula of described amine compound is R ²(NH ₂) _n, R wherein ²Be selected from alkyl or alkylidene, n=1 or 2 with 1～6 carbon atom.

9. in accordance with the method for claim 8, it is characterized in that described amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.

10. in accordance with the method for claim 5, its general formula of wherein said alcohol amine compound is (HOR ³) _mNH _(3-m)R wherein ³Be selected from alkyl with 1～4 carbon atom; M=1,2 or 3.

11. in accordance with the method for claim 10, it is characterized in that described alcohol amine compound is MEA, diethanol amine or triethanolamine.

12. in accordance with the method for claim 1; it is characterized in that the charging sequence that HTS, protective agent, noble metal source, alkali source and water are mixed in the step (1) is for to join HTS, protective agent and noble metal source in the solution that contains alkali source.

13. in accordance with the method for claim 1, it is characterized in that the temperature of the hydrothermal treatment consists described in the step (2) is 80～200 ℃, the time is 2～360h, under the self-generated pressure.

14. in accordance with the method for claim 1, it is characterized in that the described HTS of step (1) is TS-1, TS-2, Ti-MCM-41, Ti-MCM-48, Ti-BETA or Ti-MCM-22.

15. a metal-modified HTS is characterized in that, described molecular sieve is according to each described method preparation of claim 1～14.

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