CN101850266B - Method for preparing precious metal-containing titanium silicalite - Google Patents
Method for preparing precious metal-containing titanium silicalite Download PDFInfo
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- CN101850266B CN101850266B CN2009101319901A CN200910131990A CN101850266B CN 101850266 B CN101850266 B CN 101850266B CN 2009101319901 A CN2009101319901 A CN 2009101319901A CN 200910131990 A CN200910131990 A CN 200910131990A CN 101850266 B CN101850266 B CN 101850266B
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Abstract
The invention discloses a method for preparing precious metal-containing titanium silicalite. The method comprises the following processes of: adding a titanium silicalite and a precious metal source into alkali source aqueous solution which contains a protective agent and a reducing agent for mixing uniformly; performing hydro-thermal treatment, and naturally drying, washing and filtering a product; and afterdrying and roasting the product. Compared with the prior art, the catalytic oxidative activity and the activity stability of the precious metal-containing titanium silicalite prepared by the method are both improved obviously in an oxidizing reaction.
Description
Technical field
The present invention relates to a kind of method of modifying of HTS, with precious metal chemical complex HTS is carried out the method that the modification Processing of Preparation contains the noble metal Ti-Si zeolite more specifically to a kind of.
Background technology
HTS is the novel hetero-atom molecular-sieve that last century, early eighties began to develop.The TS-1 that MFI type structure is arranged that has synthesized at present, the TS-2 of MEL type structure, the MCM-22 of MWW type structure and have than the TS-48 of macroporous structure etc.The synthetic titanium-silicon molecular sieve TS-1 of wherein Italian Enichem company's exploitation is that the transition metal titanium is introduced formed a kind of new titanium-silicone molecular sieve with good catalytic selectivity oxidation susceptibility in the framework of molecular sieve with ZSM-5 structure.TS-1 not only has the catalysed oxidn of titanium, but also has the shape effect selected and the advantages of excellent stability of ZSM-5 molecular sieve.Adopt this HTS as catalyst, can the polytype organic oxidizing reaction of catalysis, like the epoxidation of alkene, the partial oxidation of alkane, the oxidation of alcohols, the hydroxylating of phenols, the ammoxidation of cyclic ketones etc.Because the TS-1 molecular sieve is in organic oxidation reaction; Can adopt free of contamination low concentration hydrogen peroxide as oxidant; Oxidizing process complex process and problem of environment pollution caused have been avoided; Have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, and have good reaction selectivity, therefore have great prospects for commercial application.HTS is considered to a milestone in molecular sieve catalytic field as the organic matter catalyst for selective oxidation.
Hydrogen peroxide (H
2O
2) be the green oxidation agent of generally acknowledging, its oxidized byproduct has only water.Because H
2O
2Extremely unstable, meet heat, light, rough surface, heavy metal and other impurity can decompose, and have corrosivity, in packing, storage, transportation, will take special safety measure, therefore, with H
2O
2Production technology and use H
2O
2Downstream process combines, but these chemical products of ability more efficient use.
Utilize H
2And O
2Can directly synthesize H
2O
2, and atom utilization reaches 100%, and then people want to utilize H
2And O
2Come original position to synthesize H
2O
2Reoxidize Organic Ingredients and directly utilize H to solve
2O
2Cost and safety problem.Because Pt, Pd, Au etc. are H
2And O
2Synthetic H
2O
2Active principle, have many document patent reports that it is loaded on the titanium silicalite material original position and generate H
2O
2Be used for the research of organic matter selective oxidation reaction.As, MeiersR. etc. (J.Catal., 1998,176:376～386) are that catalyst is studied propylene gas-phase epoxidation with Pt-Pd/TS-1; US 6867312B1 and US 6884898B1 etc. have also carried out the research of this respect.Noble metal is loaded on original position generation H on the titanium silicalite material
2O
2Though be used for method mild condition, the selectivity of organic matter selective oxidation good (can reach more than 95%), the titanium silicalite material catalyst activity of carried noble metal is lower, poor stability.
CN1387948A discloses propylene to prepare epoxy propane catalyst in a kind of hydrogen-oxygen atmosphere, is with infusion process the compound loaded of palladium and platinum to be prepared difunctional palladium-platinum-titanium-silicon molecular sieve catalyst to HTS; Then the nano grade transition metal compound is mixed with the palladium-platinum-titanium-silicon molecular sieve catalyst of above-mentioned preparation, obtain palladium-platinum-transition metal-titanium-silicon molecular sieve catalyst system.
CN101274765A discloses a kind of micropore titanium-silicon material that contains noble metal and preparation method thereof; The preparation method who wherein mentions joins HTS, protective agent, noble metal source and reducing agent earlier to change hydrothermal treatment consists in the agitated reactor in the solution that contains alkali source behind the mixing over to; Filter, wash, be drying to obtain; More particularly this method comprises: (1) joins mixing in the solution that contains alkali source with HTS, protective agent, noble metal source and reducing agent earlier; It consists of HTS (gram): protective agent (mole): alkali (mole): reducing agent (mole): noble metal source (gram is in precious metal simple substance): water (mole)=100: (0.0001～5.0): (0.005～5.0): (0.005～15.0): (0.005～10.0): (200～10000); (2) mixture of step (1) gained is changed in the agitated reactor under the hydrothermal treatment consists condition, react again, and reclaim product and promptly get micropore titanium-silicon material.But it is being still waiting improvement aspect activity and the activity stability.
Summary of the invention
The present invention is directed to the titanium-silicon zeolite material that contains noble metals such as Pt, Pd, Au that existing preparation method obtains and generate H in position
2O
2Be used for the deficiency that organic matter selective oxidation reaction technology exists, a kind of preparation method who contains the noble metal Ti-Si zeolite is provided.
Method provided by the invention is HTS and noble metal source to be joined change hydrothermal treatment consists in the agitated reactor in the alkaline aqueous solution that contains protective agent and reducing agent behind the mixing over to; Air dry, washing, filtration and then dry also roasting promptly get, and more particularly this method comprises:
(1) HTS and noble metal source are joined in the alkali source aqueous solution that contains protective agent and reducing agent mixes; Obtain consisting of HTS: protective agent: alkali source: reducing agent: noble metal source: water=100: (0.0001～5): (0.005～5): (0.005～15): (0.005～10): the mixture of (200～10000); Wherein HTS and water are in gram; Protective agent, alkali source and reducing agent are in mole, and noble metal source restrains in precious metal simple substance;
(2) mixture with step (1) gained reacts under the hydrothermal treatment consists condition; Again the product after the hydrothermal treatment consists earlier be not higher than air dry under 60 ℃, the environment of normal pressure; Water content is less than 10 weight % after making air dry; Warp washs, filters, and then dry and roasting, obtains containing the Ti-Si zeolite of noble metal.
In the method provided by the invention, said HTS can comprise the HTS of all kinds structure, like TS-1, TS-2, Ti-BETA, Ti-MOR, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15, Ti-MCM-48 etc., is preferably TS-1.
In the method provided by the invention, said protective agent is meant polymer or surfactant.Described polymer is the derivative of polymer such as glucose, cyclodextrin, polybenzimidazoles and polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene for example, like derivatives such as the pyrrolidones of polymer, vinyl alcohol, ether, pyrimidines.With the polyethylene is example, as: polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether, polyethylene pyrimidine etc.Described polybenzimidazoles, polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, poly derivative are preferably their pyrrolidones, vinyl alcohol, ether or pyrimidine derivatives, and promptly described protective agent can be selected from polybenzimidazoles pyrrolidones, polybenzimidazoles alcohol, polybenzimidazoles ether, polybenzimidazoles pyrimidine, polypropylene pyrrolidones, POLYPROPYLENE GLYCOL, polypropylene ether, polypropylene pyrimidine, polyethylene glycol pyrrolidones, polyethylene glycol ether, polyethylene glycol pyrimidine, polystyrene pyrrolidones, polystyrene alcohol, polystyrene ether, polystyrene pyrimidine, polyvinyl chloride pyrrolidones, polyvinyl chloride alcohol, polyvinyl chloride ether, polyvinyl chloride pyrimidine, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether and polyethylene pyrimidine or the like.
In the method provided by the invention, said surfactant can be anion surfactant, cationic surfactant and non-ionic surface active agent.Anion surfactant such as soap, sulfuric acid, phosphate ester salt, alkylbenzenesulfonate, alpha-alkene sulfonate, alkylsulfonate, alpha-sulfo monocarboxylate, aliphatic acid sulfoalkyl ester, sulphosuccinates, alkylnaphthalene sulfonate, petroleum sulfonate, lignosulfonates, alkyl glyceryl ether sulfonate etc.Cationic surfactant such as fatty amine quaternary cationics, ring-type cationic surfactant, softex kw, DDAO, three sufferings (ninth of the ten Heavenly Stems) ylmethyl chlorine (bromine) are changed ammonium.Non-ionic surface active agent for example AEO, block polyoxyethylene polyoxypropylene ether, alkylolamides, polyol ester class, tween series, sapn is serial, fluorocarbon surfactant is serial.
In the method provided by the invention, said alkali source is inorganic alkali source and/or organic alkali source.Wherein, inorganic alkali source is ammoniacal liquor, NaOH, potassium hydroxide, barium hydroxide etc.; Organic alkali source is urea, quaternary ammonium base compounds, fat amine compound, alcamine compound or the mixture be made up of them.
Said its general formula of quaternary ammonium base compounds is (R
1)
4NOH, R
1For having the alkyl of 1～4 carbon atom, preferred alkyl is a propyl group.
Its general formula of said fat amine compound is R
2(NH
2)
n, R
2Be selected from alkyl or alkylidene, n=1 or 2 with 1～6 carbon atom; Preferred fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of said alcamine compound is (HOR
3)
mNH
(3-m), R
3Be selected from alkyl, m=1,2 or 3 with 1～4 carbon atom; Preferred alcamine compound is MEA, diethanol amine or triethanolamine.
In the method provided by the invention, said reducing agent can be hydrazine, boron hydride, natrium citricum, azanol, formaldehyde etc., and wherein hydrazine can be hydrazine hydrate, hydrazine hydrochloride, hydrazine sulfate etc., and boron hydride can be sodium borohydride, potassium borohydride etc.
In the method provided by the invention; Said noble metal source is selected from one or more in the noble metals such as Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au; The organic matter or the inorganic matter of preferred palladium and/or platinum can be other complex compounds etc. of oxide, halide, carbonate, nitrate, ammonium salt, sal-ammoniac salt, hydroxide or noble metal.With the palladium is example, and the palladium source can be inorganic palladium source and/or organic palladium source.Inorganic palladium source is other complex compound etc. of palladium oxide, carbonate palladium, palladium bichloride, palladium nitrate, nitric acid ammonia palladium, sal-ammoniac palladium, palladium dydroxide or palladium for example, and the organic palladium source can be palladium, palladium acetylacetonate etc.
In the method provided by the invention; Said mixture composition is preferably HTS (gram): protective agent (mole): alkali source (mole): reducing agent (mole): noble metal source (gram is in precious metal simple substance): water (gram)=100: (0.005～1): (0.01～2): (0.01～10): (0.01～5): (500～5000).
In the method provided by the invention, said hydrothermal treatment consists condition is a hydrothermal treatment consists 2～360 hours under 80～200 ℃ of temperature and self-generated pressure.
In the method provided by the invention; Said air dry; Be meant that under the smooth conditions that is not higher than 60 ℃ and normal pressure, preferred room temperature to 50 ℃ and normal pressure natural evaporation moisture makes the water content of air dry afterproduct zeolitic material be not more than 10% weight, preferably be not more than the process of 5% weight.Its decision method is the thermal weight loss value of sample after the measurement air dry, and the sample after the air dry soon carries out thermal weight loss under 200 ℃ measures, if the thermal weight loss value promptly meets the demands less than 10 weight % of sole mass, preferred 5 weight %.
The process of said washing and filtration does not have special feature, is well known to those skilled in the art, and generally includes washing or alcohol and washes, the process of filtering then; Said dry once more and roasting refers to it is that roasting was at least 1 hour in 300～800 ℃ of temperature ranges 100～250 ℃ of temperature range inner dryings at least 2 hours.
Method provided by the invention is improved the synergy of noble metal and HTS; And the inventive method has overcome the drawback that traditional preparation process method (like the impregnating preparation method) causes noble metal to be assembled, the dispersiveness of noble metal and good stability.
Method provided by the invention reduces the outer titanium amount of skeleton of molecular sieve, and effectively skeleton titanium amount increases.We adopt 960cm through investigating the infrared spectrum of HTS
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550The relative Ti content that characterizes in the HTS skeleton is effective skeleton titanium amount; Can judge the relative Ti content in the skeleton according to the size of this value, value shows that more greatly Ti content is high more relatively in the skeleton, and is visible by the data of table 1; The sample that the inventive method obtains, its I
960/ I
550Value is than the I of TS-1 and Comparative Examples
960/ I
550Value is big, explains that relative Ti content is high.
In addition, the titanium-silicon zeolite material that the present invention provides method to obtain, its catalytic oxidation activity compared with prior art obviously improve, and have stability of catalytic activity (seeing test case) preferably simultaneously.
The specific embodiment
Below the present invention is done explanation further, but therefore do not limit the present invention through embodiment.
Used reagent is commercially available AR among the embodiment.Used HTS is by prior art Zeolites among Comparative Examples and the embodiment, 1992, and the TS-1 sieve sample of the method preparation described in the 943rd～950 page of the Vol.12.Sieve sample skeleton infrared spectrum is measured on Nicolet 8210 type Fourier infrared spectrographs, KBr compressing tablet, test specification 400～4000cm
-1
Comparative Examples 1
The process of the conventional preparation of this Comparative Examples explanation load type palladium/titanium-silicon molecular sieve catalyst.
With 20 gram titanium-silicon molecular sieve TS-1s and concentration be the 20mL deionized water for stirring that joins of the nitric acid ammonia palladium complex solution 20mL of 0.01g/mL (in the palladium atom) evenly after, proper seal, temperature is at 40 ℃ of dippings 24 hours down.Air dry then, and in 300 ℃ of following hydrogen atmospheres, carried out reduction activation 5 hours, promptly get conventional load type palladium/titanium-silicon molecular sieve catalyst, be designated as DB-1.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Comparative Examples 2
The explanation of this Comparative Examples contains the process of the micropore titanium-silicon material of noble metal according to CN101274765A embodiment 1 preparation.
Get in the aqueous solution (mass percent concentration 10%) that nitric acid ammonia palladium complex solution that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.05g/ml (in the palladium atom) and an amount of hydrazine hydrate and softex kw join TPAOH and mix; HTS (gram) wherein: softex kw (mole): TPAOH (mole): hydrazine hydrate (mole): nitric acid ammonia palladium complex (gram is in palladium): water (mole)=100: 0.005: 0.5: 3.0: 2.0: 1000.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 48 hours under 150 ℃ temperature and self-generated pressure, and gains are filtered, use water washing; After the air dry; And under 180 ℃, continued dry 3 hours, promptly get the micropore titanium-silicon material that contains noble metal, be designated as DB-2.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 1
20 gram titanium-silicon molecular sieve TS-1s and nitric acid ammonia palladium complexs are joined in the TPAOH aqueous solution that contains softex kw and hydrazine hydrate mix; HTS (gram) wherein: softex kw (mole): TPAOH (mole): hydrazine hydrate (mole): nitric acid ammonia palladium complex (gram is in palladium): water (gram)=100: 0.2: 0.05: 0.05: 0.02: 650.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 48 hours under 150 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; 450 ℃ of roasting temperatures 3 hours, promptly get and contain noble metal titanium-silicon zeolite material A.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 2
20 gram titanium-silicon molecular sieve TS-1s and palladium bichlorides are joined in the sodium hydrate aqueous solution that contains polyvinylpyrrolidone and hydrazine hydrochloride mix; HTS (gram) wherein: polyvinylpyrrolidone (mole): NaOH (mole): hydrazine hydrochloride (mole): palladium bichloride (gram is in palladium): water (gram)=100: 0.01: 1.5: 0.5: 4.0: 3500.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 24 hours under 180 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; 550 ℃ roasting temperatures 3 hours, promptly get and contain noble metal titanium-silicon zeolite material B.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 3
20 gram titanium-silicon molecular sieve TS-1s and sal-ammoniac palladium complexs are joined in the aqueous solution of urea that contains TTAB and hydrazine hydrate mix; HTS (gram) wherein: TTAB (mole): urea (mole): hydrazine hydrate (mole): sal-ammoniac palladium complex (gram is in palladium): water (gram)=100: 0.04: 1.0: 0.5: 1.0: 1200.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 144 hours under 120 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; And, promptly get and contain noble metal titanium-silicon zeolite material C 580 ℃ of following roastings 3 hours.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 4
20 gram titanium-silicon molecular sieve TS-1s and palladium acetylacetonates are joined in the potassium hydroxide aqueous solution that contains glucose and natrium citricum mix; HTS (gram) wherein: glucose (mole): potassium hydroxide (mole): natrium citricum (mole): palladium acetylacetonate (gram is in palladium): water (gram)=100: 0.9: 1.8: 0.15: 0.1: 4600.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 24 hours under 180 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; 650 ℃ roasting temperatures 2 hours, promptly get and contain noble metal titanium-silicon zeolite material D.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 5
20 gram titanium-silicon molecular sieve TS-1s and acid chlorides are joined in the butanediamine aqueous solution that contains Tween 80 and azanol mix; HTS (gram) wherein: Tween 80 (mole): butanediamine (mole): azanol (mole): acid chloride (gram is in palladium): water (gram)=100: 0.08: 0.4: 2.0: 3.0: 2500.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 120 hours under 120 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; 750 ℃ roasting temperatures 0.5 hour, promptly get and contain noble metal titanium-silicon zeolite material E.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 6
20 gram titanium-silicon molecular sieve TS-1s and palladium oxides are joined in the hexamethylene diamine aqueous solution that contains neopelex and formaldehyde mix; HTS (gram) wherein: neopelex (mole): hexamethylene diamine (mole): formaldehyde (mole): palladium oxide (gram is in palladium): water (gram)=100: 0.5: 0.1: 8.5: 4.8: 2000.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 240 hours under 90 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; 700 ℃ roasting temperatures 1 hour, promptly get and contain noble metal titanium-silicon zeolite material F.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 7
20 gram titanium-silicon molecular sieve TS-1s and palladium nitrates are joined in the n-butylamine aqueous solution that contains cyclodextrin and sodium borohydride mix; HTS (gram) wherein: cyclodextrin (mole): n-butylamine (mole): sodium borohydride (mole): palladium nitrate (gram is in palladium): water (gram)=100: 0.005: 0.5: 3.0: 2.0: 1000.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 320 hours under 120 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; And, promptly get and contain noble metal titanium-silicon zeolite material G 550 ℃ of following roastings 3 hours.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 8
20 gram titanium-silicon molecular sieve TS-1s and nitric acid ammonia palladiums are joined in the ammonia spirit that contains polyvinyl ethyl ether and hydrazine sulfate mix; HTS (gram) wherein: polyvinyl ethyl ether (mole): ammoniacal liquor (mole): hydrazine sulfate (mole): nitric acid ammonia palladium (gram is in palladium): water (gram)=100: 0.1: 0.1: 4.5: 2.8: 1500.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 360 hours under 80 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; 550 ℃ roasting temperatures 5 hours, promptly get and contain noble metal titanium-silicon zeolite material H.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 9
20 gram titanium-silicon molecular sieve TS-1s and palladium dydroxides are joined in the triethanolamine aqueous solution that contains polyethylene glycol and natrium citricum mix; HTS (gram) wherein: polyethylene glycol (mole): triethanolamine (mole): natrium citricum (mole): acid chloride (gram is in palladium): water (gram)=100: 0.05: 1.5: 0.5: 0.2: 800.Put into agitated reactor then; Hydrothermal treatment consists is 36 hours under 170 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; 650 ℃ roasting temperatures 3 hours, promptly get and contain noble metal titanium-silicon zeolite material I.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 10
20 gram titanium-silicon molecular sieve TS-1s and carbonate palladiums are joined in the diethanol amine aqueous solution that contains sorbester p18 and potassium borohydride mix; HTS (gram) wherein: sorbester p18 (mole): diethanol amine (mole): potassium borohydride (mole): carbonate palladium (gram is in palladium): water (gram)=100: 0.1: 0.2: 0.5: 0.3: 520.Put into agitated reactor then; Hydrothermal treatment consists is 120 hours under 150 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; 550 ℃ roasting temperatures 6 hours, promptly get and contain noble metal titanium-silicon zeolite material J.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Comparative Examples 3
The process of the conventional preparation of this Comparative Examples explanation load type palladium-platinum/titanium-silicon molecular sieve catalyst.
With 20 gram titanium-silicon molecular sieve TS-1s and concentration are the nitric acid ammonia palladium of 0.01g/mL (in the palladium atom) with each 10mL of nitric acid ammonia platinum complex solution joins 20ml deionized water for stirring evenly after, proper seal, temperature was flooded 24 hours down at 40 ℃.Air dry then, and in 300 ℃ of following hydrogen atmospheres, carried out reduction activation 5 hours, promptly get conventional load type palladium-platinum/titanium-silicon molecular sieve catalyst DB-3.Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Comparative Examples 4
The explanation of this Comparative Examples contains the process of the micropore titanium-silicon material of two noble metals according to CN101274765A embodiment 12 preparations.
Get in the aqueous solution (mass percent concentration 16%) that nitric acid ammonia palladium that 20 gram titanium-silicon molecular sieve TS-1s, concentration are 0.05g/ml (in the palladium atom) and nitric acid ammonia platinum complex solution and hydrazine hydrate and softex kw join TPAOH and mix; HTS (gram) wherein: softex kw (mole): TPAOH (mole): hydrazine hydrate (mole): nitric acid ammonia platinum (gram; In platinum): nitric acid ammonia palladium (gram is in palladium): water (mole)=100: 0.1: 1.2: 2.0: 1.2: 0.8: 1800.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 72 hours under 160 ℃ temperature and self-generated pressure, and gains are filtered, use water washing, after the air dry, and under 180 ℃, continues dry 3 hours, promptly gets the micropore titanium-silicon material DB-4 that contains two noble metals.
Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Embodiment 11
20 gram titanium-silicon molecular sieve TS-1s and nitric acid ammonia palladium, nitric acid ammonia platinum are joined in the TPAOH aqueous solution that contains softex kw and hydrazine hydrate and mix; HTS (gram) wherein: softex kw (mole): TPAOH (mole): hydrazine hydrate (mole): nitric acid ammonia platinum (gram; In platinum): nitric acid ammonia palladium (gram is in palladium): water (gram)=100: 0.1: 1.2: 2.0: 0.8: 1.2: 1800.Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 72 hours under 180 ℃ temperature and self-generated pressure; Gains are taken out, and air dry to water content is less than 10% weight, with water washing, filtration, and then after 150 ℃ of dryings under the room temperature; 550 ℃ roasting temperatures 3 hours, promptly get the titanium-silicon zeolite material K that contains two noble metals.
Its 960cm
-1Place's absworption peak and 550cm
-1Place's absorption peak strength ratio I
960/ I
550Data are listed in table 1.
Table 1
| Sample source | Sample number into spectrum | I 960/I 550 |
| It is synthetic to press document | TS-1 | 0.685 |
| Embodiment 1 | A | 0.732 |
| Embodiment 2 | B | 0.725 |
| Embodiment 3 | C | 0.731 |
| Embodiment 4 | D | 0.724 |
| Embodiment 5 | E | 0.727 |
| Embodiment 6 | F | 0.713 |
| Embodiment 7 | G | 0.717 |
| Embodiment 8 | H | 0.714 |
| Embodiment 9 | I | 0.722 |
| Embodiment 10 | J | 0.715 |
| Embodiment 11 | K | 0.730 |
| Comparative Examples 1 | DB-1 | 0.678 |
| Comparative Examples 2 | DB-2 | 0.698 |
| Comparative Examples 3 | DB-3 | 0.671 |
| Comparative Examples 4 | DB-4 | 0.711 |
Visible by table 1, the sample I of the inventive method preparation
960/ I
550Value is than the I of TS-1 and Comparative Examples
960/ I
550Value is big, explains that the relative Ti content of sample of the inventive method preparation is high.
Test case
This test case explains that the sample of embodiment sample provided by the invention and Comparative Examples preparation is used for hydrogen and exists following propylone direct opoxidation to prepare the effect of propylene oxide reaction.
Getting the foregoing description 1～11 prepared sample A～K and Comparative Examples 1～4 prepared each 0.5g of sample DB-1～DB-4 respectively joins in the epoxidation reaction container that contains 80mL methyl alcohol; Feed propylene, oxygen, hydrogen and nitrogen; (mol ratio is 1: 1: 1: 7) to form propylene-oxygen-hydrogen-nitrogen mixture atmosphere; 60 ℃ of temperature, pressure 1.0MPa, the propylene air speed is 10h
-1Condition under, carry out the reaction that epoxidation generates expoxy propane (PO).
Table 2 and table 3 provide respectively is propylene conversion and the PO data optionally of reaction 2 hours and 24 hours.Wherein:
Propylene conversion (%)=(mole-unreacted propylene mole of propylene in feeding intake)/mole * 100 of propylene in feeding intake;
Total mole * 100 that transform of the mole/propylene of expoxy propane PO selectivity (%)=propylene oxide in products.
Table 2
| Sample source | Sample number into spectrum | Propylene conversion % | PO selectivity % |
| Embodiment 1 | A | 7.5 | 93 |
| Embodiment 2 | B | 7.2 | 94 |
| Embodiment 3 | C | 6.8 | 93 |
| Embodiment 4 | D | 7.3 | 92 |
| Embodiment 5 | E | 6.5 | 91 |
| Embodiment 6 | F | 7.0 | 93 |
| Embodiment 7 | G | 6.7 | 91 |
| Embodiment 8 | H | 7.2 | 93 |
| Embodiment 9 | I | 7.0 | 92 |
| Embodiment 10 | J | 6.9 | 92 |
| Comparative Examples 1 | DB-1 | 2.6 | 89 |
| Comparative Examples 2 | DB-2 | 5.2 | 92 |
| Embodiment 11 | K | 7.4 | 93 |
| Comparative Examples 3 | DB-3 | 2.7 | 89 |
| Comparative Examples 4 | DB-4 | 5.5 | 92 |
Table 3
| Sample source | Sample number into spectrum | Propylene conversion % | PO selectivity % |
| Embodiment 1 | A | 7.2 | 92 |
| Embodiment 2 | B | 6.8 | 93 |
| Embodiment 3 | C | 6.5 | 92 |
| Embodiment 4 | D | 7.1 | 90 |
| Embodiment 5 | E | 6.4 | 91 |
| Embodiment 6 | F | 6.8 | 93 |
| Embodiment 7 | G | 6.5 | 92 |
| Embodiment 8 | H | 6.9 | 92 |
| Embodiment 9 | I | 6.8 | 91 |
| Embodiment 10 | J | 6.8 | 93 |
| Comparative Examples 1 | DB-1 | 0.4 | 80 |
| Comparative Examples 2 | DB-2 | 3.6 | 89 |
| Embodiment 11 | K | 7.2 | 92 |
| Comparative Examples 3 | DB-3 | 1.2 | 76 |
| Comparative Examples 4 | DB-4 | 4.1 | 91 |
Can find out that from table 2 activity of the sample that its catalytic oxidation activity of zeolitic material sample (propylene conversion) that the inventive method obtains obtains apparently higher than control methods explains that its catalytic oxidation activity compared with prior art obviously improves; Simultaneously, table 3 illustrates further it and has catalytic activity and activity stability preferably.
Claims (19)
1. one kind prepares the method that contains the noble metal Ti-Si zeolite, it is characterized in that this method comprises the following steps:
(1) HTS and noble metal source are joined in the alkali source aqueous solution that contains protective agent and reducing agent mixes; Obtain consisting of HTS: protective agent: alkali source: reducing agent: noble metal source: water=100: (0.0001～5): (0.005～5): (0.005～15): (0.005～10): the mixture of (200～10000); Wherein HTS and water are in gram; Protective agent, alkali source and reducing agent are in mole; Noble metal source restrains in precious metal simple substance; Said protective agent is selected from a kind of in glucose, cyclodextrin, polybenzimidazoles and polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride and the polyethylene or their mixture, perhaps is selected from anion surfactant, cationic surfactant or non-ionic surface active agent, and said alkali source is inorganic alkali source and/or organic alkali source; Wherein, Inorganic alkali source is ammoniacal liquor, NaOH, potassium hydroxide, barium hydroxide, and organic alkali source is urea, quaternary ammonium base compound, amine compound, alcohol amine compound or the mixture be made up of them, and said reducing agent is hydrazine, azanol, formaldehyde, boron hydride or natrium citricum;
(2) mixture with step (1) gained reacts under the hydrothermal treatment consists condition; Again the product after the hydrothermal treatment consists earlier be not higher than air dry under 60 ℃, the environment of normal pressure; Water content is less than 10 weight % after making air dry; Warp washs, filters, and then dry and roasting, obtains containing the Ti-Si zeolite of noble metal.
2. according to the process of claim 1 wherein that said HTS is selected from one or more the mixture among TS-1, TS-2, Ti-BETA, Ti-MOR, Ti-MCM-22, Ti-MCM-41, Ti-SBA-15 and the Ti-MCM-48.
3. according to the process of claim 1 wherein that said HTS is TS-1.
4. according to the process of claim 1 wherein that said its general formula of quaternary ammonium base compound is (R
1)
4NOH, wherein R
1For having the alkyl of 1～4 carbon atom.
5. according to the method for claim 4, wherein said R
1Be propyl group.
6. according to the process of claim 1 wherein that its general formula of said 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.
7. according to the method for claim 6, wherein said amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
8. according to the process of claim 1 wherein that its general formula of said alcohol amine compound is (HOR
3)
mNH
(3-m), R wherein
3Be selected from alkylidene, m=1,2 or 3 with 1～4 carbon atom.
9. according to the method for claim 8, wherein said alcohol amine compound is MEA, diethanol amine or triethanolamine.
10. according to the method for claim 1, said hydrazine is hydrazine hydrate, hydrazine hydrochloride or hydrazine sulfate.
11. according to the method for claim 1, said boron hydride is sodium borohydride or potassium borohydride.
12. according to the process of claim 1 wherein that said noble metal source is selected from the oxide of noble metal, halide, carbonate, nitrate, nitric acid ammonia salt, sal-ammoniac salt, hydroxide.
13. according to the process of claim 1 wherein that said noble metal source is the palladium source.
14. according to the method for claim 13, said palladium source is inorganic palladium source and/or organic palladium source.
15. according to the method for claim 14, wherein said inorganic palladium source is selected from palladium oxide, carbonate palladium, palladium bichloride, palladium nitrate, nitric acid ammonia palladium, sal-ammoniac palladium, palladium dydroxide.
16. according to the method for claim 14, said organic palladium source is selected from palladium or palladium acetylacetonate.
17. according to the process of claim 1 wherein that said mixture consists of HTS: protective agent: alkali source: reducing agent: noble metal source: water=100: (0.005～1.0): (0.01～2.0): (0.01～10.0): (0.01～5.0): (500～5000).
18. according to the process of claim 1 wherein that said hydrothermal treatment consists condition is a hydrothermal treatment consists 2～360 hours under 80～200 ℃ of temperature and self-generated pressure.
19., be that roasting was at least 1 hour in 300～800 ℃ of temperature ranges 100～250 ℃ of temperature range inner dryings at least 2 hours according to the process of claim 1 wherein said dry once more and roasting.
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