CN101654255B - Method for synthesizing titanium-silicon material containing noble metal - Google Patents
Method for synthesizing titanium-silicon material containing noble metal Download PDFInfo
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Abstract
The invention provides a method for synthesizing a titanium-silicon material containing a noble metal. The method comprises the following steps of: evenly mixing a titanium source and a silicon source; evenly mixing the mixture and a protectant; adding the mixing solution to an aqueous solution of an alkali source containing a noble metal source and evenly mixing; adding a reducer to the mixed solution; putting the mixed solution to a closed reaction kettle for hydrothermal treatment; obtaining the intermediate product by recovery; and evenly mixing the intermediate product and an aqueous solution of organic alkali, and performing the hydrothermal treatment of the mixed solution in the closed reaction kettle to recover the product. In the titanium-silicon material obtained by the method, the synergetic effect of the noble metal and the titanium-silicon molecular sieves is improved; and when the titanium-silicon material is used for selective oxidation of organic matters in situ synthesis of H2O2, the activity is high, and the stability is good.
Description
Technical field
The present invention relates to a kind of method of synthesis of titanium silicon material, relate in particular to a kind of method of original position synthesizing titanium-silicon material containing noble metal.
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.Wherein Italian Enichem company exploitation synthetic titanium-silicon molecular sieve TS-1 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 the TS-1 molecular sieve as catalyzer, can the polytype organic oxidizing reaction of catalysis, as the epoxidation of alkene, the partial oxidation of alkane, the oxidation of alcohols, the hydroxylation of phenols, the ammonia oxidation of cyclic ketones etc.Because the TS-1 molecular sieve is in organic oxidizing reaction, can adopt free of contamination lower concentration hydrogen peroxide as oxygenant, oxidising 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 preference.
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, uneven surface, heavy metal and other impurity can decompose, and have corrodibility, will take special security measures in packing, storage, transportation, therefore, with H
2O
2Use on the spot, or with H
2O
2Production technique and use H
2O
2Downstream process combines, but these Chemicals 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 raw material 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 organism selective oxidation reaction.As, MeiersR. etc. (J.Catal., 1998, be that catalyzer is studied propylene gas-phase epoxidation with Pt-Pd/TS-1 176:376-386); US6867312B1 and US6884898B1 etc. have also carried out the research of this respect.Noble metal support original position on titanium silicalite material is generated H
2O
2Though be used for method mild condition, the selectivity of organism selective oxidation good (can reach more than 95%), the titanium silicalite material catalyst activity of carried noble metal is lower, poor stability, H in the reaction in
2Effective rate of utilization is low.
CN1387948A discloses propylene to prepare epoxy propane catalyst in a kind of hydrogen-oxygen atmosphere, is with pickling process the compound loaded of palladium and platinum to be prepared difunctional palladium-platinum-titanium-silicon molecular sieve catalyst on 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.
Summary of the invention
The purpose of this invention is to provide a kind of method that is different from the synthesizing titanium-silicon material containing noble metal of prior art, gained contains the precious metal titanium silicalite material and is used for the synthetic H of original position
2O
2The organism selective oxidation time, active high, good stability.
Method provided by the invention specifically comprises the steps:
(1) titanium source and silicon source a kind of protective material of mixing back adding are obtained mixed solution; then mixed solution is joined in the alkali source aqueous solution that contains noble metal source; mix; the mole that obtains mixture consists of the silicon source: titanium source: alkali source: noble metal source: protective material: water=100:(0.005-50.0): (0.005-20.0): (0.005-10.0): (0.005-5.0): (200-10000), wherein the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, noble metal source is in simple substance; The mol ratio that adds then with noble metal source is the reductive agent of 0.1-10, in closed reactor under temperature 80-200 ℃ and the autogenous pressure hydrothermal treatment consists 2-360 hour, reclaims and obtains intermediate product;
(2) intermediate product that step (1) is obtained and the aqueous solution of organic bases, wherein, intermediate product: organic bases: water=100:(0.01-2): (500-5000), intermediate product is in gram, organic bases, water are in mole, in closed reactor under temperature 120-200 ℃ and the autogenous pressure hydrothermal treatment consists 5-120 hour then, and reclaim product.
In the method provided by the invention, the mole of step (1) mixture is formed the silicon source that is preferably: titanium source: alkali source: noble metal source: protective material: water=100:(0.01～10.0): (0.01～10.0): (0.01～5.0): (0.01～1.0): (500～5000).
Said silicon source is silica gel, silicon sol or organosilicon acid esters, preferably organosilicon acid esters; Said its general formula of organosilicon acid esters is R
1 4SiO
4, R wherein
1Preferably have the alkyl of 1～4 carbon atom, be more preferably ethyl.
Said titanium source is inorganic titanium salt or organic titanate, preferably organic titanate; Said inorganic titanium salt can be TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2Its general formula of said organic titanate is Ti (OR
2)
4, R wherein
2For having the alkyl of 1～6 carbon atom, more preferably has the alkyl of 2～4 carbon atoms.
In the method provided by the invention, in the step (1) in said alkali source and the step (2) said organic bases can be the mixture that quaternary amine alkali compounds or quaternary amine alkali compounds and fat amine compound, alcamine compound are formed.
Said its general formula of quaternary ammonium hydroxide compounds is (R
3)
4NOH, R
3For having the alkyl of 1～4 carbon atom, preferably propyl group.Its general formula of said fat amine compound is R
4(NH
2)
n, R wherein
4Be selected from alkyl or alkylidene group, n=1 or 2, for example ethamine, n-Butyl Amine 99, butanediamine, diamines etc. with 1～6 carbon atom.Its general formula of said alcamine compound is (HOR
5)
mNH
(3-m)R wherein
5Be selected from alkyl with 1～4 carbon atom; M=1,2 or 3, for example monoethanolamine, diethanolamine, trolamine etc.
In the method provided by the invention, said protective material is meant polymkeric substance or tensio-active agent in the step (1).
Described polymkeric substance is the derivative of polymkeric substance such as glucose, cyclodextrin, polybenzimidazole and polypropylene, polyoxyethylene glycol, polystyrene, polyvinyl chloride, polyethylene for example, as derivatives such as the pyrrolidone of polymkeric substance, vinyl alcohol, ether, pyrimidines.With the polyethylene is example, as: polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl ethyl ether, polyethylene pyrimidine etc.Described polybenzimidazole; polypropylene; polyoxyethylene glycol; polystyrene; polyvinyl chloride; poly derivative is preferably their pyrrolidone; vinyl alcohol; ether or pyrimidine derivatives, promptly described protective material can be selected from the polybenzimidazole pyrrolidone; polybenzimidazole alcohol; the polybenzimidazole ether; the polybenzimidazole pyrimidine; the polypropylene pyrrolidone; POLYPROPYLENE GLYCOL; the polypropylene ether; the polypropylene pyrimidine; the polyoxyethylene glycol pyrrolidone; the polyoxyethylene glycol ether; the polyoxyethylene glycol pyrimidine; the polystyrene pyrrolidone; polystyrene alcohol; the polystyrene ether; the polystyrene pyrimidine; the polyvinyl chloride pyrrolidone; polyvinyl chloride alcohol; the polyvinyl chloride ether; the polyvinyl chloride pyrimidine; polyvinylpyrrolidone; polyvinyl alcohol; polyvinyl ethyl ether and polyethylene pyrimidine or the like.
Described tensio-active agent can be anion surfactant, cats product and nonionogenic tenside.
Anion surfactant such as soap, sulfuric acid, phosphate ester salt, alkylbenzene sulfonate, sulfonated, alkylsulfonate, alpha-sulfo monocarboxylate, lipid acid sulfoalkyl ester, sulphosuccinates, sulfonated alkyl naphathalene, sulfonated petro-leum, sulfonated lignin, alkyl glyceryl ether sulfonate etc.
Cats product such as fatty amine quaternary cationics, ring-type cats product, cetyl trimethylammonium bromide, dimethyl dodecyl amine oxide, three sufferings (ninth of the ten Heavenly Stems) ylmethyl chlorine (bromine) are changed ammonium.
Nonionogenic tenside is fatty alcohol-polyoxyethylene ether, block polyoxyethylene polyoxypropylene ether, alkylol amide, polyol ester class, tween series, sapn series, fluorocarbon surfactant series for example.
In the method provided by the invention, said noble metal source is selected from the organism or the inorganics of one or more precious metals in the precious metals such as Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, can be other complex compound etc. of their oxide compound, halogenide, carbonate, nitrate, ammonium salt, chlorination ammonium salt, oxyhydroxide or precious metal.With the palladium source is example, can be inorganic palladium source and/or organic palladium source, wherein inorganic palladium source can be other complex compound of palladous oxide, carbonate palladium, Palladous chloride, Palladous nitrate, nitric acid ammonia palladium, ammonia chloride palladium, palladium hydroxide or palladium etc., and the organic palladium source can be palladium, palladium acetylacetonate etc.Preferred palladium of said precious metal and/or platinum.
In the synthetic method provided by the invention, said reductive agent can be azanol, hydrazine, hydroborate, Trisodium Citrate etc., and wherein hydrazine can be hydrazine hydrate, hydrazine hydrochloride, hydrazonium sulfate etc., and hydroborate can be sodium borohydride, POTASSIUM BOROHYDRIDE etc.
In the synthetic method provided by the invention, the process of the said recovery intermediate product of step (1) comprises filtration, washing, drying and roasting, and the process of the said recovery product of step (2) comprises processes such as product filtration, washing, drying, roastings.
Synthetic method provided by the invention; protective material and reductive agent have been used; synergy between precious metal and the HTS is improved; overcome prior synthesizing method (as the impregnating synthetic method) and caused precious metal accumulative drawback; the dispersiveness of precious metal is good especially, and this has guaranteed its activity.Compare with prior art (as traditional dip loading technology), in oxidizing reaction, for example in the reaction of preparing epoxypropane by epoxidation of propene, the selectivity of reaction product and catalytic activity and stability obviously improve (seeing embodiment 12).
Embodiment
Following embodiment will the invention will be further described, but therefore do not limit the present invention.
Used reagent is commercially available chemically pure reagent 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.
Comparative Examples 1
The process of the conventional preparation of this Comparative Examples explanation load type palladium/titanium-silicon molecular sieve catalyst.
Get 20 gram titanium-silicon molecular sieve TS-1s and concentration and be 20ml deionized water for stirring that the nitric acid ammonia palladium complex solution 20ml of 0.01g/ml (in the palladium atom) joins evenly after, suitably sealing, temperature is at 40 ℃ of dippings 24 hours down.Seasoning 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 DB-1.
Embodiment 1
Mix joining in the TPAOH aqueous solution that contains acid chloride behind positive tetraethyl orthosilicate, tetrabutyl titanate and the tween 80 mixing; wherein mole is formed the silicon source: titanium source: alkali source: palladium source: protective material: water=100:0.03:0.5:0.5:0.02:550, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, add then with the equimolar hydrazine hydrate in above-mentioned palladium source after changed in the sealed reactor under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists over to 36 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 150 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and water according to middle crystalline material (gram): organic bases (mole): the mixed of water (mole)=100:0.5:550, hydrothermal treatment consists is 36 hours under 170 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the titanium silicalite material A that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 2
Mix joining behind positive tetraethyl orthosilicate, tetrabutyl titanate and the Sodium dodecylbenzene sulfonate mixing in the mixed aqueous solution of the TPAOH that contains the ammonia chloride palladium and butanediamine; wherein mole is formed the silicon source: titanium source: TPAOH: butanediamine: palladium source: protective material: water=100:2.0:5.2:1.2:0.2:0.5:2500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, add then and changed in the sealed reactor under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists behind 2 times of hydrazine hydrochlorides with above-mentioned palladium source (mole) over to 48 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 120 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and water according to middle crystalline material (gram): organic bases (mole): the mixed of water (mole)=100:0.1:1500, hydrothermal treatment consists is 36 hours under 170 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material B that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 3
Mix joining in the TPAOH aqueous solution that contains acid chloride behind positive tetraethyl orthosilicate, metatitanic acid orthocarbonate and the polybenzimidazole pyrrolidone mixing; wherein mole is formed the silicon source: titanium source: alkali source: palladium source: protective material: water=100:0.1:0.2:0.02:0.1:600, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, add 5 times then and behind the hydrazine hydrate of above-mentioned palladium source mole, changed in the sealed reactor under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists over to 36 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 150 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and diamines and water according to middle crystalline material (gram): TPAOH (mole): diamines (mole): the mixed of water (mole)=100:0.5:0.5:850, hydrothermal treatment consists is 36 hours under 170 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material C that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 4
Mix joining behind silicon sol, tetrabutyl titanate and the Sodium dodecylbenzene sulfonate mixing in the mixed aqueous solution of the TPAOH that contains the ammonia chloride palladium and diethanolamine; wherein mole is formed the silicon source: titanium source: TPAOH: diethanolamine: palladium source: protective material: water=100:1.0:2.2:7.3:1.0:0.2:1500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, add 7 times then and behind the hydrazine hydrochloride in above-mentioned palladium source (mole), changed in the sealed reactor under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists over to 48 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 180 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and water according to middle crystalline material (gram): organic bases (mole): the mixed of water (mole)=100:1.5:2500, hydrothermal treatment consists is 106 hours under 120 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material D that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 5
With positive tetraethyl orthosilicate, TiCl
4Mix with joining behind the cetyl trimethylammonium bromide mixing in the TPAOH aqueous solution that contains palladium acetylacetonate, wherein the silicon source: titanium source: alkali source: palladium source: protective material: water=100:8.2:2.5:0.1:0.05:800, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, add then with the equimolar Trisodium Citrate in above-mentioned palladium source after changed in the sealed reactor under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists over to 36 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 150 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and n-Butyl Amine 99 and water according to middle crystalline material (gram): TPAOH (mole): n-Butyl Amine 99 (mole): the mixed of water (mole)=100:1.5:0.5:3500, hydrothermal treatment consists is 72 hours under 160 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material E that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 6
Mix joining in the TPAOH aqueous solution that contains the ammonia chloride palladium behind 40 order silica gel, tetrabutyl titanate and the Sodium dodecylbenzene sulfonate mixing; silicon source wherein: titanium source: alkali source: palladium source: protective material: water=100:5.0:0.02:4.5:0.9:4800, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, add 10 times then and behind the sodium borohydride of above-mentioned palladium source mole, changed in the sealed reactor under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists over to 48 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 120 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and water according to middle crystalline material (gram): organic bases (mole): the mixed of water (mole)=100:0.2:1150, hydrothermal treatment consists is 84 hours under 130 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material F that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 7
Mix joining behind positive tetraethyl orthosilicate, tetraethyl titanate and the polyvinyl chloride pyrimidine mixing in the mixed aqueous solution of the TPAOH that contains carbonate palladium and ethamine; silicon source wherein: titanium source: TPAOH: ethamine: palladium source: protective material: water=100:1.2:2.5:2.5:1.5:0.7:1200, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, add then with the equimolar POTASSIUM BOROHYDRIDE in above-mentioned palladium source after changed in the sealed reactor under 150 ℃ temperature and autogenous pressure hydrothermal treatment consists over to 56 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 150 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and water according to middle crystalline material (gram): organic bases (mole): the mixed of water (mole)=100:2.5:3000, hydrothermal treatment consists is 6 hours under 170 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material G that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 8
With positive quanmethyl silicate, Ti (SO
4)
2Mix with joining in the TPAOH aqueous solution that contains nitric acid ammonia palladium behind the dodecyl glyceryl ether sodium sulfonate mixing, wherein the silicon source: titanium source: alkali source: palladium source: protective material: water=100:6.0:0.1:4.0:0.3:4500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, add then with the equimolar sodium borohydride in above-mentioned palladium source after changed in the sealed reactor under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists over to 48 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 160 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and monoethanolamine and water according to middle crystalline material (gram): TPAOH (mole): monoethanolamine (mole): the mixed of water (mole)=100:7.5:0.5:4500, hydrothermal treatment consists is 36 hours under 170 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material H that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 9
With positive tetraethyl orthosilicate, TiOCl
2Mix with joining in the TPAOH that contains acid chloride behind the Tetradecyl Trimethyl Ammonium Bromide mixing, wherein the silicon source: titanium source: alkali source: palladium source: protective material: water=100:0.5:0.5:1.5:0.8:3500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, add then with the equimolar azanol in above-mentioned palladium source after changed in the sealed reactor under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists over to 6 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 150 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and trolamine and water according to middle crystalline material (gram): TPAOH (mole): trolamine (mole): the mixed of water (mole)=100:0.05:0.01:500, hydrothermal treatment consists is 96 hours under 120 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material I that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 10
Mix joining in the TPAOH that contains palladous oxide behind positive tetraethyl orthosilicate, tetraethyl titanate and polyoxyethylene glycol (relative molecular mass the is about 20000) mixing; silicon source wherein: titanium source: alkali source: palladium source: protective material: water=100:0.15:0.15:0.05:0.12:1500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.In mixture, be incorporated in then and changed in the sealed reactor under 130 ℃ temperature and autogenous pressure hydrothermal treatment consists behind the hydrazine hydrochloride of 0.2 times of above-mentioned palladium source mole over to 68 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 150 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and water according to middle crystalline material (gram): organic bases (mole): the mixed of water (mole)=100:0.3:4000, hydrothermal treatment consists is 36 hours under 150 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material J that contains precious metal, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Embodiment 11
Mix joining behind positive tetraethyl orthosilicate, tetrabutyl titanate and the cetyl trimethylammonium bromide mixing in the TPAOH that contains Palladous chloride and nitric acid ammonia platinum; silicon source wherein: titanium source: alkali source: palladium source: platinum source: protective material: water=100:9.5:1.0:0.33:0.18:0.08:1000, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd, and the platinum source is in Pt.In mixture, add then with the equimolar hydrazine hydrochloride in above-mentioned palladium source and platinum source after changed in the sealed reactor under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists over to 12 hours, gains are filtered, wash with water, after the seasoning, and continued down dry 3 hours at 150 ℃, then 550 ℃ roasting temperature 3 hours in the middle of crystalline material.With middle crystalline material and organic bases TPAOH and water according to middle crystalline material (gram): organic bases (mole): the mixed of water (mole)=100:2.0:1000, hydrothermal treatment consists is 16 hours under 180 ℃ temperature and autogenous pressure, gains are filtered, wash with water, after the seasoning, and under 150 ℃, continued dry 3 hours, then 550 ℃ roasting temperature 3 hours, promptly get the micropore titanium-silicon material K that contains two precious metals, the x-ray diffraction spectra of this material has the chromatogram characteristic of TS-1 molecular sieve.
Comparative Examples 2
The process of the conventional preparation of this Comparative Examples explanation load type palladium-platinum/titanium-silicon molecular sieve catalyst.
Get 20 gram titanium-silicon molecular sieve TS-1s and concentration and be the nitric acid ammonia palladium of 0.01g/ml (in the palladium atom) and 20ml deionized water for stirring that each 10ml of nitric acid ammonia platinum complex solution joins evenly after, suitably sealing, temperature is at 40 ℃ of dippings 24 hours down.Seasoning 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-2.
Embodiment 12
Present embodiment illustrates that the sample of embodiment sample A provided by the invention, B, K and Comparative Examples preparation is used for hydrogen and exists following propylene gas-phase epoxidation to prepare the effect of propylene oxide reaction.
Get the foregoing description 1,2,11 respectively and Comparative Examples 1,2 prepared each 0.5g of sample join in the epoxidation reaction container that contains 80ml methyl alcohol, feed propylene, oxygen, hydrogen and nitrogen, form propylene-oxygen-hydrogen-nitrogen mixture atmosphere (mol ratio is 1:1:1:7), 60 ℃ of temperature, pressure 1.0MPa, the propylene air speed is 10h
-1Condition under, carry out the reaction that epoxidation generates propylene oxide (P0).
Table 1 and table 2 provide respectively is optionally data of the propylene conversion of reaction 2 hours and 12 hours and P0.
Table 1
| Sample source | Sample number into spectrum | Propylene conversion % | P0 selectivity % |
| Embodiment 1 | A | 6.5 | 93 |
| Embodiment 2 | B | 4.7 | 92 |
| Comparative Examples 1 | DB-1 | 2.6 | 89 |
| Embodiment 11 | K | 5.4 | 91 |
| Comparative Examples 2 | DB-2 | 2.7 | 88 |
Table 2
| Sample source | Sample number into spectrum | Propylene conversion % | P0 selectivity % |
| Embodiment 1 | A | 6.2 | 92 |
| Embodiment 2 | B | 4.4 | 91 |
| Comparative Examples 1 | DB-1 | 0.4 | 80 |
| Embodiment 11 | K | 5.3 | 92 |
| Comparative Examples 2 | DB-2 | 1.2 | 81 |
From table 1 and table 2 as can be seen, the titanium silicalite material that contains precious metal that synthetic method provided by the invention obtains is used for hydrogen and exists when propylene gas-phase epoxidation prepares propylene oxide reaction down, active comparative sample apparently higher than loading type, selectivity also increases to some extent, has stability of catalytic activity preferably simultaneously.
Claims (21)
1. the method for a synthesizing titanium-silicon material containing noble metal is characterized in that this method comprises the following steps:
(1) titanium source and silicon source a kind of protective material of mixing back adding are obtained mixed solution; then mixed solution is joined in the alkali source aqueous solution that contains noble metal source; mix; the mole that obtains mixture consists of the silicon source: titanium source: alkali source: noble metal source: protective material: water=100: (0.005-50.0): (0.005-20.0): (0.005-10.0): (0.005-5.0): (200-10000), wherein the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, noble metal source is in simple substance; The mol ratio that adds then with noble metal source is the reductive agent of 0.1-10, in closed reactor under temperature 80-200 ℃ and the autogenous pressure hydrothermal treatment consists 2-360 hour, reclaims and obtains intermediate product; Said protective material is a tensio-active agent, is selected from anion surfactant, cats product or nonionogenic tenside; Said reductive agent is selected from one or more the mixture in azanol, hydrazine, hydroborate and the Trisodium Citrate;
(2) intermediate product that step (1) is obtained and the aqueous solution of organic bases, wherein, intermediate product: organic bases: water=100: (0.01-2): (500-5000), intermediate product is in gram, organic bases, water are in mole, in closed reactor under temperature 120-200 ℃ and the autogenous pressure hydrothermal treatment consists 5-120 hour then, and reclaim product.
2. according to the process of claim 1 wherein that the said silicon of step (1) source is silica gel, silicon sol or organosilicon acid esters.
3. according to the method for claim 2, wherein said organosilicon acid esters general formula is R
1 4SiO
4, R wherein
1Be selected from alkyl with 1-4 carbon atom.
4. according to the method for claim 3, it is characterized in that said R
1Be ethyl.
5. according to the process of claim 1 wherein that the said titanium of step (1) source is inorganic titanium salt or organic titanate.
6. according to the method for claim 5, wherein said inorganic titanium salt is TiCl
4, Ti (SO
4)
2Perhaps TiOCl
2
7. according to the method for claim 5, wherein said its general formula of organic titanate is Ti (OR
2)
4, R wherein
2Be selected from alkyl with 1-6 carbon atom.
8. according to the method for claim 7, R wherein
2Be selected from alkyl with 2-4 carbon atom.
9. according to the process of claim 1 wherein in the step (1) mixture that to be quaternary ammonium hydroxide compound or quaternary ammonium hydroxide compound form with amine compound or alcohol amine compound of said organic bases in the said alkali source and step (2).
10. according to the method for claim 9, wherein said its general formula of quaternary ammonium hydroxide compound is (R
3)
4NOH, wherein R
3For having the alkyl of 1-4 carbon atom.
11. according to the method for claim 10, wherein said R
3Be propyl group.
12. according to the method for claim 9, wherein said its general formula of amine compound is R
4(NH
2)
n, R wherein
4Be selected from alkyl or alkylidene group, n=1 or 2 with 1-6 carbon atom.
13. according to the method for claim 9, wherein said amine compound is ethamine, n-Butyl Amine 99, butanediamine or hexanediamine.
14. according to the method for claim 9, wherein said its general formula of alcohol amine compound is (HOR
5)
mNH
(3-m)R wherein
5Be selected from alkyl, m=1,2 or 3 with 1-4 carbon atom.
15. according to the method for claim 9, wherein said alcohol amine compound is monoethanolamine, diethanolamine or trolamine.
16. according to the process of claim 1 wherein inorganics or the organism of the said noble metal source of step (1) for this precious metal.
17. according to the method for claim 16, said noble metal source is inorganic palladium source or organic palladium source.
18. according to the method for claim 17, said inorganic palladium source is selected from other complex compound of palladous oxide, carbonate palladium, Palladous chloride, Palladous nitrate, ammonium nitrate palladium, ammonia chloride palladium, palladium hydroxide or palladium.
19. according to the method for claim 17, said organic palladium source is palladium or palladium acetylacetonate.
20., it is characterized in that the mole of step (1) mixture consists of the silicon source: titanium source: alkali source: palladium source: protective material: water=100: (0.01-10.0): (0.01-10.0): (0.01-5.0): (0.01-1.0): (500-5000) according to the method for claim 1.
21. according to the method for claim 1, said hydrazine is selected from hydrazine hydrate, hydrazine hydrochloride or hydrazonium sulfate, said hydroborate is selected from sodium borohydride or POTASSIUM BOROHYDRIDE.
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Citations (4)
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|---|---|---|---|---|
| US5082641A (en) * | 1987-05-22 | 1992-01-21 | Rhone-Poulenc Chimie | Silicon/titanium oxide mfi zeolites |
| US5859265A (en) * | 1994-07-20 | 1999-01-12 | Basf Aktiengesellschaft | Oxidation catalyst, its preparation and oxidation using the oxidation catalyst |
| CN1245090A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for modifying Ti-Si molecular sieve |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5082641A (en) * | 1987-05-22 | 1992-01-21 | Rhone-Poulenc Chimie | Silicon/titanium oxide mfi zeolites |
| US5859265A (en) * | 1994-07-20 | 1999-01-12 | Basf Aktiengesellschaft | Oxidation catalyst, its preparation and oxidation using the oxidation catalyst |
| CN1245090A (en) * | 1998-08-18 | 2000-02-23 | 中国石油化工集团公司 | Process for modifying Ti-Si molecular sieve |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
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