CN101618338A - Method for modifying titanium-silicon molecular sieve - Google Patents
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- CN101618338A CN101618338A CN200810115865A CN200810115865A CN101618338A CN 101618338 A CN101618338 A CN 101618338A CN 200810115865 A CN200810115865 A CN 200810115865A CN 200810115865 A CN200810115865 A CN 200810115865A CN 101618338 A CN101618338 A CN 101618338A
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Abstract
The invention provides a method for modifying a titanium-silicon molecular sieve, and belongs to the technical field of inorganic chemicals and the synthesis of inorganic chemicals. The method comprises the following steps of: adding the titanium-silicon molecular sieve, a protective agent and a noble metal source in a solution containing organic amine, evenly mixing the mixture, adding a hydrating solution of silicon in the mixing solution and evenly mixing the mixed solution, putting the mixedsolution in a reaction kettle for hydro-thermal treatment, and recycling the sieve. The titanium-silicon molecular sieve modified by the method has obviously high catalytic oxidation activity, selectivity and stability.
Description
Technical field
The present invention relates to a kind of method of modifying titanium-silicon molecular sieve.
Background technology
HTS is the novel hetero-atom molecular-sieve of early eighties exploitation in last century.The MCM-22 of the at present synthetic TS-1 that MFI type structure is arranged, the TS-2 of MEL type structure, MWW type structure and have than the TS-48 of macroporous structure etc.HTS can be used for the multiple organic oxidizing reaction of catalysis, for example alkene epoxidation, partial oxidation of alkanes, oxidation of alcohols, phenols hydroxylating, cyclic ketones ammoxidation, and in the reaction, can adopt free of contamination low concentration hydrogen peroxide as oxidant, the selectivity height of reaction has unrivaled energy-conservation, economy of conventional oxidation system and environmental friendliness advantage.HTS is considered to a milestone in molecular sieve catalytic field as the organic matter catalyst for selective oxidation.
H
2O
2Be the green oxidation agent of generally acknowledging, its oxidized byproduct has only water, but H
2O
2Extremely unstable, meet heat, light, rough surface, heavy metal and other impurity and can decompose, and have corrosivity so H
2O
2In packing, storage, transportation, to take special safety measure.People consider H for this reason
2O
2Use on the spot, or with H
2O
2Production technology with use H
2O
2Downstream process combine.
Utilize H
2And O
2Can directly synthesize H
2O
2, and atom utilization reaches 100%, and then people expect utilizing H
2And O
2Come original position to synthesize H
2O
2Reoxidize Organic Ingredients and directly utilize H to solve
2O
2Cost and safety problem.This technological reaction mild condition, selectivity are good, and present subject matter is that catalyst activity is low, poor stability, H
2Effective rate of utilization is low.
Pt, Pd, Au etc. are catalysis H
2And O
2Synthetic H
2O
2Active principle, many bibliographical informations utilize it that titanium silicalite material is carried out modification to come original position to generate H
2O
2Be used for the organic matter selective oxidation reaction.For example, and Meiers R. etc. (J.Catal., 1998, be that catalyst is studied propylene gas-phase epoxidation with Pt-Pd/TS-1 176:376-386); US 6867312B1 and US 6884898B1 etc. have also carried out the research of this respect.
CN1421389A discloses a kind of method of modifying of HTS, this method comprises the aqueous solution of silicon and the TS-1 molecular sieve that has synthesized according to molecular sieve (gram): Si (mole)=(70～1500): 1 ratio mixes, the gained mixture was reacted under 80～190 ℃ temperature 0.1～150 hour in reactor, filter, wash and drying, obtain modification TS-1 molecular sieve.
CN1245090A discloses the method for modifying of a kind of HTS (TS-1), and this method comprises that TS-1 molecular sieve, acid compound and the water that will synthesize mix, and reacts 5 minutes down to 6h at 5～95 ℃, obtains acid-treated TS-1 molecular sieve; Gained is mixed through acid-treated TS-1 molecular sieve, organic base and water, and in sealed reactor under 120～200 ℃ temperature and self-generated pressure 2h to the 8 day time of reaction, then products therefrom is filtered, washing and drying obtain modifying titanium-silicon molecular sieve.
Summary of the invention
The method that the purpose of this invention is to provide a kind of new modifying titanium-silicon molecular sieve material.
The invention provides a kind of method of modifying titanium-silicon molecular sieve, may further comprise the steps:
(1) HTS, protective agent and noble metal source are joined mixing in the aqueous solution of organic amine, its proportioning is a HTS: protective agent: organic amine: noble metal source: water=100: (0.0001～5): (0.005～5): (0.005～10): (500～10000); Wherein HTS is in gram, and noble metal source is in the gram number of precious metal simple substance, and protective agent, organic amine, water are in mole; Described protective agent is selected from one or more in polybenzimidazoles, polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene and their derivative, anion surfactant, cationic surfactant, non-ionic surface active agent, glucose and the cyclodextrin;
(2) with silicon source, organic amine and water according to 1: (0.5～10): the mixed in molar ratio of (100～500) obtains the hydrolyzate of silicon;
(3) hydrolyzate of the silicon that the mixture and the step (2) of step (1) gained obtained restrains according to molecular sieve: Si=(200～1500): 1 mole ratio is mixed, and hydrothermal treatment consists reclaims modifying titanium-silicon molecular sieve.
The method of modifying titanium-silicon molecular sieve of the present invention, operation is simple, and modifying process is controlled easily.Overcome the drawback that the activation of conventional method high temperature reduction causes Metal Palladium to be assembled, and, because when in the presence of organic amine compound, HTS being carried out high temperature high pressure process, introduce noble metal, strengthened in the synergy that makes precious metal palladium and titanium-silicon molecular screen material, make gained TS-1 molecular sieve have better catalytic oxidation activity.Method gained molecular sieve provided by the invention is owing to be coated with inertia component silicon at outer surface and place, aperture, catalytic oxidation is mainly carried out in the duct of molecular sieve and be unlikely to make the materials such as coke of formation to stop up the aperture, and suppress the carrying out of side reaction, thereby improve selectivity and the activity stability and the life of catalyst of its catalytic oxidation.
The specific embodiment
In the HTS method of modifying provided by the invention; HTS in the step (1): protective agent: organic amine: noble metal source: water is preferably 100: (0.005～1): (0.01～2): (0.01～5): (500～5000); wherein HTS is in the gram number; noble metal source is in the gram number of precious metal simple substance, and protective agent, organic amine, water are in molal quantity.
In the HTS method of modifying provided by the invention; described polybenzimidazoles; polypropylene; polyethylene glycol; polystyrene; polyvinyl chloride; poly derivative is preferably their pyrrolidones; vinyl alcohol; ether or pyrimidine derivatives, promptly described protective agent can be selected from the polybenzimidazoles pyrrolidones; polybenzimidazoles alcohol; the polybenzimidazoles ether; the polybenzimidazoles pyrimidine; the polypropylene pyrrolidones; POLYPROPYLENE GLYCOL; the polypropylene ether; the polypropylene pyrimidine; the polyethylene glycol pyrrolidones; the polyethylene glycol ether; the polyethylene glycol pyrimidine; the polystyrene pyrrolidones; polystyrene alcohol; the polystyrene ether; the polystyrene pyrimidine; the polyvinyl chloride pyrrolidones; polyvinyl chloride alcohol; the polyvinyl chloride ether; the polyvinyl chloride pyrimidine; polyvinylpyrrolidone; polyvinyl alcohol; polyvinyl ethyl ether and polyethylene pyrimidine.
In the HTS method of modifying provided by the invention, described anion surfactant is soap for example, sulfuric acid, phosphate ester salt, alkylbenzenesulfonate, alpha-alkene sulfonate, alkylsulfonate, the alpha-sulfo monocarboxylate, aliphatic acid sulfoalkyl ester, sulphosuccinates, alkylnaphthalene sulfonate, petroleum sulfonate, lignosulfonates, alkyl glyceryl ether sulfonate etc., cationic surfactant is for example: fatty amine quaternary cationics, the ring-type cationic surfactant, softex kw, DDAO, three sufferings (ninth of the ten Heavenly Stems) ylmethyl chlorine (bromine) are changed ammonium, and non-ionic surface active agent is AEO for example, the block polyoxyethylene polyoxypropylene ether, alkylolamides, the polyol ester class, tween series, sapn series, fluorocarbon surfactant series.
In the method for modifying provided by the present invention, the described noble metal source of step (1) is selected from one or more in the organic complex of oxide, halide, carbonate, nitrate, acetate, ammonium salt, sal-ammoniac salt, hydroxide and noble metal of noble metal, and described organic complex is noble metal and complex compound, noble metal and the cyclo-octadiene of acetylacetone,2,4-pentanedione and the complex compound that cyclo-octatriene forms for example.For example when described noble metal was palladium, noble metal source can be one or more in palladium oxide, carbonate palladium, palladium bichloride, palladium nitrate, nitric acid ammonia palladium, sal-ammoniac palladium, palladium dydroxide, palladium, the palladium acetylacetonate.Preferred palladium of described noble metal and/or platinum.
In the method for modifying provided by the invention, step (1) and the described organic amine of step (2) are one or more in quaternary amine alkali compounds, fat amine compound, the alcamine compound, are preferably the quaternary amine alkali compounds.
Described its general formula of quaternary ammonium base compounds is (R
1)
4NOH, wherein R
1For having the alkyl of 1～4 carbon atom, be preferably propyl group.
Its general formula of described fat amine compound is R
2(NH
2)
n, R wherein
2Be selected from alkyl or alkylidene with 1～6 carbon atom, n=1 or 2 is preferably ethamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of described alcamine compound is (HOR
3)
mNH
(3-m)R wherein
3Be selected from alkyl with 1～4 carbon atom; M=1,2 or 3.Described alcamine compound is MEA, diethanol amine or triethanolamine for example.
In the method provided by the present invention, the described silicon of step (2) source is inorganic silicon colloidal sol or organosilicon acid esters Si (OR
4)
4, R wherein
4For having the alkyl of 1～4 carbon atom, be preferably ethyl.
In the method provided by the present invention, the mol ratio of the said silicon of step (2) source, organic amine and water is preferably 1: (0.8～5): (200～500).
In the method provided by the present invention, the time of said hydrolysis is 2～180 minutes in the step (2), and preferred 5～90 minutes, the temperature during hydrolysis had no particular limits, and is generally room temperature.
In the method for modifying provided by the invention, the hydro-thermal treatment method in the synthetic or HTS modification carries out the described hydrothermal treatment consists of step (3) according to existing HTS, is included in hydrothermal treatment consists 2～360h under 80～200 ℃ of temperature and the self-generated pressure.
In the method for modifying that provides of invention, described recovery comprises the step of filtrations, washing, drying, roasting, can according to HTS in the prior art synthesize or modification in recovery method carry out, the present invention does not have specific (special) requirements.Described washing can be adopted distilled water or deionized water washing; The condition of described drying is room temperature～200 ℃, air atmosphere, drying time 3～24h; Described roasting condition is 300～800 ℃, nitrogen or air atmosphere, roasting time 3～24h.
Method of modifying provided by the invention can be used for the HTS modification, described HTS is TS-1 for example, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41 or Ti-MCM-48 also can be the modifying titanium-silicon molecular sieves of these molecular sieves through having method modification (for example introducing noble metal by the method for dipping) now or obtaining according to the inventive method modification.Be preferably the TS-1 molecular sieve, described TS-1 molecular sieve can be according to the synthetic TS-1 molecular sieve of any method of the prior art, can through or without calcination process, contain or do not contain organic formwork agent.
Following embodiment will the present invention is further illustrated, but therefore do not limit the present invention.Used reagent is commercially available chemically pure reagent among the embodiment.Used HTS is by Zeolites among Comparative Examples and the embodiment, 1992, and the TS-1 molecular sieve of the method preparation described in the 943rd～950 page of the Vol.12.
Comparative Examples 1
This Comparative Examples explanation conventional method prepares the process of load type palladium/titanium-silicon molecular sieve catalyst (0.5%Pd/TS-1).
Get 10 gram titanium-silicon molecular sieve TS-1s and concentration and be 10mL deionized water for stirring that the nitric acid ammonia palladium complex solution 1.0mL of 0.05g/mL (in the palladium atom) joins evenly after, sealing, under 40 ℃ of temperature, flood 24h, drying at room temperature is 12 hours then, reduction activation 5h under 300 ℃, in the hydrogen atmosphere promptly gets conventional load type palladium/titanium-silicon molecular sieve catalyst (0.5%Pd/TS-1) DB-1.
Embodiment 1
Get 10 gram titanium-silicon molecular sieve TS-1s, concentration and be stir in the nitric acid ammonia palladium complex solution of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 10%) that softex kw joins TPAOH mixed liquor 1, HTS (gram) wherein: softex kw (mole): TPAOH (mole): nitric acid ammonia palladium complex (gram is in palladium): water (mole)=100: 0.2: 0.005: 0.5: 1000.Under the room temperature, with ethyl orthosilicate, butanediamine and water according to ethyl orthosilicate (mole): butanediamine (mole): the ratio of water (mole)=1: 4.5: 200 stirred 50 minutes, get mixed liquor 2, to put into stainless steel cauldron behind mixed liquor 1 and mixed liquor 2 the ratio mixing according to molecular sieve (gram): Si (mole)=200: 1, sealing, hydrothermal treatment consists 48h under 150 ℃ temperature and self-generated pressure, filter, washing, drying at room temperature, roasting 5h in 550 ℃ nitrogen atmosphere promptly gets modifying titanium-silicon molecular sieve again, is designated as A.
Embodiment 2
Get 10 gram titanium-silicon molecular sieve TS-1s, concentration and be stir in the palladium chloride solution of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that polyacrylate joins hexamethylene diamine mixed liquor 1, HTS (gram) wherein: polyacrylate (mole): NaOH (mole): palladium bichloride (gram is in palladium): water (mole)=100: 0.9: 1.0: 0.15: 1600.Under 45 ℃ with methyl silicate, TPAOH and water according to methyl silicate (mole): TPAOH (mole): the ratio of water (mole)=1: 1.8: 300 stirred 30 minutes, get mixed liquor 2, seal putting into stainless steel cauldron behind mixed liquor 1 and mixed liquor 2 the ratio mixing again according to molecular sieve (gram): Si (mole)=500: 1, hydrothermal treatment consists 24h under 180 ℃ temperature and self-generated pressure, filter, wash, dry 3h under 110 ℃, roasting 5h in 450 ℃ of following nitrogen atmospheres promptly gets modifying titanium-silicon molecular sieve B.
Embodiment 3
Get 10 gram titanium-silicon molecular sieve TS-1s, concentration and be stir in the palladium nitrate solution of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 10%) that Tween 80 joins TPAOH and n-butylamine mixed liquor 1, HTS (gram) wherein: protective agent (mole): organic amine (mole): palladium source (gram is in palladium): water (mole)=100: 0.03: 0.1: 0.05: 550; (mole is with SiO according to Ludox with Ludox, butanediamine and water under the room temperature
2Meter): butanediamine (mole): the ratio stirring of water (mole)=1: 1.2: 450 80 minutes must mixed liquor 2; Also seal putting into stainless steel cauldron behind mixed liquor 1 and mixed liquor 2 the ratio mixing according to molecular sieve (gram): Si (mole)=800: 1, hydrothermal treatment consists 120h under 120 ℃ temperature and self-generated pressure, filter, wash, then at 150 ℃ of following dry 3h, roasting 5h in 350 ℃ of following nitrogen atmospheres gets modifying titanium-silicon molecular sieve C.
Embodiment 4
Get 10 gram titanium-silicon molecular sieve TS-1s, concentration and be stir in the sal-ammoniac palladium solution of 0.02g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that neopelex joins TPAOH mixed liquor 1, HTS (gram) wherein: protective agent (mole): organic amine (mole): palladium source (gram is in palladium): water (mole)=100: 2.0: 0.8: 1.0: 2500; Under the room temperature with silicic acid four butyl esters, ethamine and water according to silicic acid four butyl esters (mole): ethamine (mole): the ratio of water (mole)=1: 2.5: 320 stirred 30 minutes mixed liquor 2, to put into stainless steel cauldron behind mixed liquor 1 and mixed liquor 2 the ratio mixing again according to molecular sieve (gram): Si (mole)=1000: 1, hydrothermal treatment consists 96h under 150 ℃ temperature and self-generated pressure, filter, wash, dry 3h under 120 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modifying titanium-silicon molecular sieve D.
Embodiment 4
Get 10 gram titanium-silicon molecular sieve TS-1s; concentration be stir in the sal-ammoniac palladium solution of 0.02g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that neopelex joins TPAOH mixed liquor 1; HTS (gram) wherein: protective agent (mole): organic amine (mole): palladium source (gram; in palladium): water (mole)=100: 2.0: 0.8: 1.0: 2500; then under normal temperature with silicic acid four butyl esters; ethamine and water are according to silicic acid four butyl esters (mole): ethamine (mole): the ratio of water (mole)=1: 2.5: 320 stirred 30 minutes mixed liquor 2; to put into stainless steel cauldron behind mixed liquor 1 and mixed liquor 2 the ratio mixing again according to molecular sieve (gram): Si (mole)=1000: 1; hydrothermal treatment consists 96h under 150 ℃ temperature and self-generated pressure; filter; washing; dry 3h under 120 ℃; roasting 5h in 550 ℃ of following nitrogen atmospheres gets modifying titanium-silicon molecular sieve D.
Embodiment 5
Get 10 gram titanium-silicon molecular sieve TS-1s, concentration and be stir in the ammonium nitrate palladium solution of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 10%) that polyvinylpyrrolidone joins butanediamine mixed liquor 1, HTS (gram) wherein: polyvinylpyrrolidone (mole): butanediamine (mole): acid chloride (gram is in palladium): water (mole)=100: 0.001: 0.05: 0.02: 800.Under room temperature with tetraethyl orthosilicate, TPAOH and water according to tetraethyl orthosilicate (mole): TPAOH (mole): the ratio of water (mole)=1: 2: 260 stirred 15 minutes mixed liquor 2; To put into stainless steel cauldron behind mixed liquor 1 and mixed liquor 2 the ratio mixing according to molecular sieve (gram): Si (mole)=1200: 1, hydrothermal treatment consists 120h under 120 ℃ temperature and self-generated pressure, filter, washing, dry 3h under 150 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modifying titanium-silicon molecular sieve E.
Embodiment 6
Get 10 gram titanium-silicon molecular sieve TS-1s, concentration and be stir in the sal-ammoniac palladium solution of 0.05g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that neopelex joins TPAOH mixed liquor 1, HTS (gram) wherein: neopelex (mole): TPAOH (mole): sal-ammoniac palladium (gram is in palladium): water (mole)=100: 0.1: 2.0: 5.0: 4800; Under the room temperature with silicic acid orthocarbonate, diethanol amine and water according to silicic acid orthocarbonate (mole): diethanol amine (mole): the ratio of water (mole)=1: 3: 300 stirred 20 minutes mixed liquor 2, again mixed liquor 1 and mixed liquor 2 are mixed according to the ratio of molecular sieve (gram): Si (mole)=1500: 1, put into stainless steel cauldron, hydrothermal treatment consists 240h under 90 ℃ temperature and self-generated pressure, filter, washing, dry 3h under 120 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modifying titanium-silicon molecular sieve F.
Embodiment 7
Get 10 gram titanium-silicon molecular sieve TS-1, palladium dydroxide and polybenzimidazoles (density 1.2g/cm
3) join stir in the TPAOH (mass percent concentration 15%) mixed liquor 1, HTS (gram) wherein: protective agent (mole): organic amine (mole): palladium source (gram is in palladium): water (mole)=100: 5.0: 0.01: 0.5: 2000; Under the room temperature with silicic acid four butyl esters, ethamine and water according to silicic acid four butyl esters (mole): ethamine (mole): the ratio of water (mole)=1: 4: 120 stirred 120 minutes mixed liquor 2, to put into the stainless steel sealed reactor behind mixed liquor 1 and mixed liquor 2 the ratio mixing again according to molecular sieve (gram): Si (mole)=600: 1, hydrothermal treatment consists 120h under 160 ℃ temperature and self-generated pressure, filter, washing, at 150 ℃ of dry 3h, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modifying titanium-silicon molecular sieve G.
Embodiment 8
Get 10 gram titanium-silicon molecular sieve TS-1s, concentration and be stir in the nitric acid ammonia palladium solution of 0.05g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that cyclodextrin joins TPAOH mixed liquor 1, HTS (gram) wherein: protective agent (mole): organic amine (mole): palladium source (gram is in palladium): water (mole)=100: 3.2: 1.5: 3.0: 3500; Under the room temperature with tetraethyl orthosilicate, n-butylamine and water according to tetraethyl orthosilicate (mole): n-butylamine (mole): the ratio of water (mole)=1: 2: 420 stirred 60 minutes mixed liquor 2, to put into the stainless steel sealed reactor behind mixed liquor 1 and mixed liquor 2 the ratio mixing again according to molecular sieve (gram): Si (mole)=300: 1, hydrothermal treatment consists 48h under 120 ℃ temperature and self-generated pressure, filter, wash, dry 3h under 120 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modifying titanium-silicon molecular sieve H.
Embodiment 9
Get stir in the aqueous solution (mass percent concentration 18%) that 10 gram titanium-silicon molecular sieve TS-1s, palladium oxides and glucose joins triethanolamine mixed liquor 1, HTS (gram) wherein: glucose (mole): triethanolamine (mole): palladium oxide (gram is in palladium): water (mole)=100: 0.02: 1.2: 4.0: 1200; Under the room temperature with tetraethyl orthosilicate, TPAOH and water according to tetraethyl orthosilicate (mole): TPAOH (mole): the ratio of water (mole)=1: 5: 150 stirred 15 minutes mixed liquor 2; To put into the stainless steel sealed reactor behind mixed liquor 1 and mixed liquor 2 the ratio mixing according to molecular sieve (gram): Si (mole)=700: 1, hydrothermal treatment consists 320h under 130 ℃ temperature and self-generated pressure, filter, wash, dry 3h under 120 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modifying titanium-silicon molecular sieve I.
Embodiment 10
With 10 gram titanium-silicon molecular sieve TS-1s, palladium acetylacetonates, potassium borohydride and softex kw join mix in the TPAOH (mass percent concentration 13%) mixed liquor 1, HTS (gram) wherein: protective agent (mole): organic amine (mole): palladium source (gram is in palladium): water (mole)=100: 0.5: 1.8: 0.8: 4000; Under the room temperature with tetraethyl orthosilicate, MEA and water according to tetraethyl orthosilicate (mole): MEA (mole): the ratio of water (mole)=1: 0.8: 250 stirred 30 minutes mixed liquor 2, to put into the stainless steel sealed reactor behind mixed liquor 1 and mixed liquor 2 the ratio mixing again according to molecular sieve (gram): Si (mole)=900: 1, hydrothermal treatment consists 120h under 160 ℃ temperature and self-generated pressure, filter, wash, dry 3h under 150 ℃, roasting 5h in 550 ℃ of following nitrogen atmospheres promptly gets the HTS J of modification.
Comparative Examples 2
The conventional dipping of this Comparative Examples explanation method of modifying prepares load type palladium-platinum/HTS (0.5%Pd, process 0.5%Pt/TS-1).
The 10mL deionized water for stirring of getting 10 gram titanium-silicon molecular sieve TS-1s and joining for the nitric acid ammonia palladium of 0.05g/mL (in palladium or pt atom) and each 1.0mL of nitric acid ammonia platinum complex solution evenly after, seal, under 40 ℃ of temperature, flood 24h.Air dry then, and in 300 ℃ of following hydrogen atmospheres, carry out reduction activation 5h, promptly get conventional load type palladium-platinum/titanium-silicon molecular sieve catalyst (0.5%Pd, 0.5%Pt/TS-1) DB-2.
Embodiment 11
Get stir in the aqueous solution (mass percent concentration 16%) that nitric acid ammonia palladium that 10 gram titanium-silicon molecular sieve TS-1s, concentration are 0.01g/mL (in precious metal atom) and nitric acid ammonia platinum complex solution and softex kw join TPAOH mixed liquor 1, HTS (gram) wherein: softex kw (mole): TPAOH (mole): nitric acid ammonia platinum (gram, in platinum): nitric acid ammonia palladium (gram is in palladium): water (mole)=100: 0.02: 1.6: 0.1: 0.05: 1800.Under the room temperature with tetraethyl orthosilicate, TPAOH and water according to tetraethyl orthosilicate (mole): TPAOH (mole): the ratio of water (mole)=1: 1: 250 stirred 150 minutes mixed liquor 2, to put into the stainless steel sealed reactor behind mixed liquor 1 and mixed liquor 2 the ratio mixing again according to molecular sieve (gram): Si (mole)=1100: 1, hydrothermal treatment consists 72h under 160 ℃ temperature and self-generated pressure, filter, wash, air dry under the room temperature, roasting 5h in 550 ℃ of following nitrogen atmospheres gets modifying titanium-silicon molecular sieve K.
Embodiment 12
The sample of present embodiment explanation embodiment 1～11 preparation and the sample of Comparative Examples 1～2 preparation are used for hydrogen, the oxygen existence effect of preparing epoxypropane by epoxidation of propene reaction down.
Reaction condition is as follows: each 0.5g of sample is joined in the epoxidation reaction container that contains methyl alcohol 60mL, feed propylene, oxygen, hydrogen and nitrogen, and formation propylene-oxygen-hydrogen-nitrogen mixture atmosphere (mol ratio is 1: 1: 1: 7), and 40 ℃ of temperature, pressure 2.0MPa, the propylene air speed is 10h
-1Condition under, carry out epoxidation reaction and generate expoxy propane (PO).
Propylene conversion and the PO selectivity of reaction 2h and 12h the results are shown in Table 1.
By table 1 as seen, the sample of the inventive method preparation is used for propylene ring oxidation reaction, active height, PO selectivity height, good stability.
Table 1
Claims (18)
1. the method for a modifying titanium-silicon molecular sieve comprises the following steps:
(1) HTS, protective agent and noble metal source are joined mixing in the aqueous solution that contains organic amine, its proportioning is a HTS: protective agent: organic amine: noble metal source: water=100: (0.0001～5): (0.005～5): (0.005～10): (500～10000); Wherein HTS is in gram, and noble metal source is in the gram number of precious metal simple substance, and protective agent, organic amine, water are in mole; Described protective agent is selected from one or more in polybenzimidazoles, polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene and their derivative, anion surfactant, cationic surfactant, non-ionic surface active agent, glucose and the cyclodextrin;
(2) with silicon source, organic amine and water according to 1: (0.5～10): the mixed in molar ratio of (100～500) obtains the hydrolyzate of silicon;
(3) hydrolyzate of the silicon that the mixture and the step (2) of step (1) gained obtained restrains according to molecular sieve: Si=(200～1500): 1 mole ratio is mixed, and hydrothermal treatment consists reclaims modifying titanium-silicon molecular sieve.
2. in accordance with the method for claim 1, it is characterized in that HTS in the step (1): protective agent: organic amine: noble metal source: water=100: (0.005～1): (0.01～2): (0.01～5): (500～5000).
3. in accordance with the method for claim 1, it is characterized in that described polybenzimidazoles, polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, poly derivative is the polybenzimidazoles pyrrolidones, polybenzimidazoles alcohol, the polybenzimidazoles ether, the polybenzimidazoles pyrimidine, the polypropylene pyrrolidones, POLYPROPYLENE GLYCOL, the polypropylene ether, the polypropylene pyrimidine, the polyethylene glycol pyrrolidones, the polyethylene glycol ether, the polyethylene glycol pyrimidine, the polystyrene pyrrolidones, polystyrene alcohol, the polystyrene ether, the polystyrene pyrimidine, the polyvinyl chloride pyrrolidones, polyvinyl chloride alcohol, the polyvinyl chloride ether, the polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether, the polyethylene pyrimidine.
4. in accordance with the method for claim 1, wherein the described noble metal source of step (1) is selected from oxide, halide, carbonate, nitrate, ammonium salt, chlorination ammonium salt, hydroxide and the organic complex of noble metal one or more.
5. according to claim 1 or 4 described methods, it is characterized in that described noble metal is palladium and/or platinum.
6. in accordance with the method for claim 1, it is characterized in that organic amine is selected from one or more in quaternary amine alkali compounds, fat amine compound, the alcamine compound respectively described in step (1) and the step (2).
7. in accordance with the method for claim 6, it is characterized in that described its general formula of quaternary ammonium base compounds is (R
1)
4NOH, wherein R
1For having the alkyl of 1～4 carbon atom.
8. in accordance with the method for claim 7, it is characterized in that described R
1Be propyl group.
9. in accordance with the method for claim 6, it is characterized in that its general formula of described fat 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.
10. in accordance with the method for claim 9, it is characterized in that described fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
11. in accordance with the method for claim 6, its general formula of wherein said alcamine compound is (HOR
3)
mNH
(3-m)R wherein
3Be selected from alkyl, m=1,2 or 3 with 1～4 carbon atom.
12. in accordance with the method for claim 11, it is characterized in that described alcamine compound is MEA, diethanol amine or triethanolamine.
13. 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.
14. in accordance with the method for claim 13, it is characterized in that described HTS is TS-1.
15. in accordance with the method for claim 1, it is characterized in that the described silicon of step (2) source is inorganic silicon colloidal sol or organosilicon acid esters Si (OR
4)
4In one or more, R wherein
4For having the alkyl of 1～4 carbon atom.
16. the method according to claim 1 is characterized in that, the mol ratio of the described silicon of step (2) source, organic amine and water is 1: (0.8～5): (200～500).
17. in accordance with the method for claim 1, it is characterized in that the temperature of the described hydrothermal treatment consists of step (3) is 80～200 ℃, pressure is self-generated pressure, and the time is 2～360h.
18. a modified with noble metals HTS is characterized in that, described molecular sieve is according to each described method preparation of claim 1～17.
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