CN101654256B - Method for in situ synthesis of titanium-silicon molecular sieve material containing noble metal - Google Patents
Method for in situ synthesis of titanium-silicon molecular sieve material containing noble metal Download PDFInfo
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Abstract
The invention provides a method for in situ synthesis of a titanium-silicon molecular sieve material containing a noble metal. The method is characterized by comprising: adding a titanium source, a silicon source and a protectant to an aqueous solution of an alkali source containing a noble metal source and evenly mixing; putting the mixed solution in a closed reactor for reaction at a temperature of between 120 and 200 DEG C and at a self elevating pressure for at least half an hour; filtering, drying and roasting the product to obtain an intermediate crystalline state material; mixing the intermediate crystalline state material and the filtrate obtained after the product is filtered, and adding a reducer to the mixed solution; and putting the mixed solution in a closed reaction kettle for treatment at a temperature of between 80 and 200 DEG C and under a self elevating pressure for 2 to 360 hours, and recovering the product. By the method, the synergetic effect of the noble metal and the titanium-silicon molecular sieves is improved; and compared with the prior art, when the titanium-silicon molecular sieve material synthesized by the method is used for oxidizing reactions such as a reaction of preparing propylene oxide by epoxidation of propylene, the selectivity, the catalytic activity and the stability of the reaction product are obviously improved.
Description
Technical field
The present invention relates to a kind of micropore titanium-silicon material preparation method, specifically about a kind of micropore titanium-silicon material preparation method who contains precious 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, like the epoxidation of alkene, the partially 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, in packing, storage, transportation, will take special security measures, 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-problems.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 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.
Summary of the invention
The deficiency that the titanium silicalite material that the present invention is directed to noble metal supports such as Pt, Pd exists during as organism selective oxidation reaction catalyzer; A kind of synthetic method that contains the precious metal titanium-silicon molecular screen material that is different from prior art is provided, and gained contains the precious metal titanium-silicon molecular screen 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; It is characterized in that titanium source, silicon source and protective material joined in the alkali source aqueous solution that contains noble metal source and mix; Obtain mole and consist 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): mixture (200-10000), the silicon source is with SiO in the formula
2Meter, the titanium source is with TiO
2Meter, noble metal source is in precious metal simple substance, with mixture reaction at least 0.5 hour under 120～200 ℃ and the power of boosting certainly in closed reactor; With product filtration, drying; Crystalline material in the middle of roasting gets is mixed middle crystalline material again with the filtrating that obtains after above-mentioned product filters, the mol ratio of adding and above-mentioned noble metal source is (0.1-10): 1 reductive agent; In closed reactor, handled 2-360 hour under 80-200 ℃ and the autogenous pressure then, and reclaim product.
In the method provided by the invention, silicon source: titanium source: alkali source: noble metal source: protective material: the preferred mole of water consists of 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 atom.
Said alkali source is the mixture that quaternary amine alkali compounds or quaternary amine alkali compounds and fat amine compound, alcamine compound are formed.Wherein, 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, tetramethylenediamine, hexanediamine etc. with 1-4 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, diethylolamine, trolamine etc.
In the method provided by the invention, said protective material is meant polymkeric substance or tensio-active agent.
Described polymkeric substance is the verivate of polymkeric substance such as glucose, Schardinger dextrins, polybenzimidazole and Vestolen PP 7052, polyoxyethylene glycol, PS, SE, Vilaterm for example, like verivates such as the pyrrolidone of polymkeric substance, vinyl alcohol, ether, pyrimidines.With the Vilaterm is example, as: Vinylpyrrolidone polymer, Z 150PH, polyvinyl ethyl ether, Vilaterm pyrimidine etc.Described polybenzimidazole, Vestolen PP 7052, polyoxyethylene glycol, PS, SE, poly verivate are preferably their pyrrolidone, vinyl alcohol, ether or pyrimidine derivatives, and promptly described protective material can be selected from polybenzimidazole pyrrolidone, polybenzimidazole alcohol, polybenzimidazole ether, polybenzimidazole pyrimidine, Vestolen PP 7052 pyrrolidone, POLYPROPYLENE GLYCOL, Vestolen PP 7052 ether, Vestolen PP 7052 pyrimidine, polyoxyethylene glycol pyrrolidone, polyoxyethylene glycol ether, polyoxyethylene glycol pyrimidine, PS pyrrolidone, PS alcohol, PS ether, PS pyrimidine, SE pyrrolidone, SE alcohol, SE ether, SE pyrimidine, Vinylpyrrolidone polymer, Z 150PH, polyvinyl ethyl ether and Vilaterm pyrimidine or the like.
Described tensio-active agent can be AS, cats product and nonionogenic tenside.
AS such as soap, sulfuric acid, phosphate ester salt, sulfonated alkylbenzene, sulfonated, AS, 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 for example AEO, block polyoxyethylene polyoxypropylene ether, alkylol amide, polyol ester class, tween series, sapn is serial, fluorocarbon surfactant is serial.
In the method that invention provides; 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 salt, 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 method provided by the invention, said reductive agent can be azanol, hydrazine, hydroborate, Trisodium Citrate etc., and wherein hydrazine can be Hydrazine Hydrate 80, hydrazine hydrogen chloride, hydrazonium sulfate etc., and hydroborate can be Peng Qinghuana, POTASSIUM BOROHYDRIDE 97MIN etc.
In the method provided by the invention, the process of said recovery intermediate product comprises filtration, washing, drying and roasting, and the process of said recovery product comprises processes such as product filtration, washing, drying, roastings.
The synthetic method that contains the titanium-silicon molecular screen material of precious metal provided by the invention; Protective material and reductive agent have been used; Synergy between precious metal and the HTS is improved; Overcome traditional dip loading method and made precious metal accumulative drawback, the dispersiveness of precious metal is good especially, and this has guaranteed its activity.With prior art, like traditional dip loading compared with techniques, 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 do explanation further to the present invention, but therefore 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 Vol.12 943-950 page or leaf.
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, proper seal, 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
Positive tetraethyl orthosilicate, tetrabutyl titanate and tween 80 joined in the TPAOH aqueous solution that contains acid chloride mix; Wherein mole is formed the silicon source: titanium source: alkali source: palladium source: protective material: water=100:0.03:0.5:0.2:0.02:550, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into sealed reactor then, hydrothermal treatment consists is 120 hours under 120 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add with the equimolar Hydrazine Hydrate 80 in above-mentioned palladium source after under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours; Gains are filtered, use water washing, after the seasoning, and under 150 ℃, continued dry 3 hours; Promptly get the micropore titanium-silicon 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
Positive tetraethyl orthosilicate, tetrabutyl titanate and X 2073 joined in the TPAOH aqueous solution that contains the ammonia chloride palladium mix; Wherein mole is formed the silicon source: titanium source: alkali source: palladium source: protective material: water=100:2.0:5.2:0.5:0.6:2500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 96 hours under 150 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add 2 times to behind the hydrazine hydrogen chloride in above-mentioned palladium source (mole) under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists 48 hours; Gains are filtered, use water washing, after the seasoning, and under 120 ℃, continued dry 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
Positive tetraethyl orthosilicate, tetrabutyl titanate and tween 80 joined in the TPAOH aqueous solution that contains acid chloride mix; 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.Put into sealed reactor then, hydrothermal treatment consists is 120 hours under 120 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add 5 times to behind the Hydrazine Hydrate 80 of above-mentioned palladium source mole under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours; Gains are filtered, use water washing, after the seasoning, and under 150 ℃, continued dry 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
Positive tetraethyl orthosilicate, metatitanic acid orthocarbonate and dodecyl glyceryl ether sodium sulfonate joined in the TPAOH aqueous solution that contains the ammonia chloride palladium mix; Wherein mole is formed the silicon source: titanium source: alkali source: palladium source: protective material: water=100:1.0:2.2:1.0:0.2:1500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 96 hours under 140 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add 0.2 times to behind the hydrazine hydrogen chloride in above-mentioned palladium source (mole) under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists 48 hours; Gains are filtered, use water washing, after the seasoning, and under 180 ℃, continued dry 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, Ti (SO
4)
2Join in the TPAOH that contains carbonate palladium and the ethamine mixed aqueous solution with cetyl trimethylammonium bromide and to mix; Silicon source wherein: titanium source: TPAOH: ethamine: palladium source: protective material: water=100:8.2:2.5:5.0:0.1:0.05:800, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 96 hours under 160 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add 0.1 times to behind the hydrazonium sulfate of above-mentioned palladium source mole under 175 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours; Gains are filtered, use water washing, after the seasoning, and under 150 ℃, continued dry 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
Silicon sol, tetrabutyl titanate and SE pyrimidine joined in the TPAOH that contains nitric acid ammonia palladium and the monoethanolamine mixed aqueous solution mix; Silicon source wherein: titanium source: TPAOH: monoethanolamine: palladium source: protective material: water=100:5.0:0.02:0.01:4.5:0.9:4800, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 36 hours under 150 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add with the equimolar Peng Qinghuana in above-mentioned palladium source after under 120 ℃ temperature and autogenous pressure hydrothermal treatment consists 48 hours; Gains are filtered, use water washing, after the seasoning, and under 120 ℃, continued dry 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
With positive tetraethyl orthosilicate, TiOCl
2Join in the TPAOH that contains acid chloride and the trolamine mixed aqueous solution with cetyl trimethylammonium bromide and to mix; Silicon source wherein: titanium source: TPAOH: trolamine: palladium source: protective material: water=100:1.2:2.5:0.2:0.05:0.2:1200, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 56 hours under 160 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add 7 times to behind the hydrazine hydrogen chloride of above-mentioned palladium source mole under 100 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours; Gains are filtered, use water washing, after the seasoning, and under 150 ℃, continued dry 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
Positive tetraethyl orthosilicate, tetrabutyl titanate and polybenzimidazole pyrrolidone are joined in the mixed aqueous solution of the TPAOH that contains nitric acid ammonia palladium and tetramethylenediamine and mix; Silicon source wherein: titanium source: TPAOH: tetramethylenediamine: palladium source: protective material: water=100:6.0:0.1:0.1:2.0:0.7:4500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 12 hours under 180 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add 0.8 times under 80 ℃ temperature and autogenous pressure, handling 48 hours behind the Peng Qinghuana of above-mentioned palladium source mole; Gains are filtered, use water washing, after the seasoning, and under 160 ℃, continued dry 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
Positive tetraethyl orthosilicate, tetraethyl titanate and TTAB joined in the TPAOH that contains palladium acetylacetonate mix; Silicon source wherein: titanium source: alkali source: palladium source: protective material: water=100:0.5:0.5:1.5:0.5:2500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 72 hours under 160 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add 3 times to behind the hydrazine hydrogen chloride of above-mentioned palladium source mole under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours; Gains are filtered, use water washing, after the seasoning, and under 150 ℃, continued dry 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
40 order silica gel, tetraethyl titanate and polyoxyethylene glycol (relative molecular mass is about 20000) join in the mixed aqueous solution of the TPAOH that contains acid chloride and hexanediamine and mix; Silicon source wherein: titanium source: TPAOH: hexanediamine: palladium source: protective material: water=100:0.1:0.1:0.1:1.1:0.12:3500, the silicon source is with SiO
2Meter, the titanium source is with TiO
2Meter, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 6 hours under 180 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add with the equimolar Trisodium Citrate in above-mentioned palladium source after under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 36 hours; Gains are filtered, use water washing, after the seasoning, and under 150 ℃, continued dry 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
Positive tetraethyl orthosilicate, tetrabutyl titanate and cetyl trimethylammonium bromide joined in the TPAOH aqueous solution that contains Palladous chloride and nitric acid ammonia platinum mix; Silicon source wherein: titanium source: alkali source: palladium source: platinum source: protective material: water=100:1.0:1.0:0.3:0.17:0.02:1000, 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.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 72 hours under 160 ℃ temperature and autogenous pressure, crystalline material in the middle of gains taking-up filtration after drying, roasting are got.Middle crystalline material is changed in the above-mentioned last filtrating; Add with the equimolar Hydrazine Hydrate 80 in above-mentioned palladium source and platinum source after under 170 ℃ temperature and autogenous pressure hydrothermal treatment consists 18 hours; Gains are filtered, use water washing, after the seasoning, and under 150 ℃, continued dry 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, proper seal, temperature was flooded 24 hours down at 40 ℃.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 explains 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, table 2 provide respectively is reaction 2 and and the propylene conversion of 12h and P0 data optionally.
Table 1
| Sample source | Sample number into spectrum | Propylene conversion % | P0 selectivity % |
| Embodiment 1 | A | 6.2 | 91.6 |
| Embodiment 2 | B | 7.5 | 92.2 |
| Comparative Examples 1 | DB-1 | 2.6 | 89.0 |
| Embodiment 11 | K | 8.4 | 92.1 |
| Comparative Examples 2 | DB-2 | 2.7 | 88.5 |
Table 2
| Sample source | Sample number into spectrum | Propylene conversion % | P0 selectivity % |
| Embodiment 1 | A | 5.9 | 91.2 |
| Embodiment 2 | B | 7.2 | 91.8 |
| Comparative Examples 1 | DB-1 | 0.4 | 80.3 |
| Embodiment 11 | K | 8.2 | 92.3 |
| Comparative Examples 2 | DB-2 | 1.2 | 81.2 |
Can find out from table 1; The synthetic titanium-silicon molecular screen material that contains precious metal that obtains of method provided by the invention is used for hydrogen and exists when propylene gas-phase epoxidation prepares propylene oxide reaction down; Active comparative sample apparently higher than noble metal support type; Selectivity also increases to some extent, can find out also have stability of catalytic activity preferably from table 2 simultaneously.
Claims (21)
1. the synthetic method that contains the titanium-silicon molecular screen material of precious metal of an original position; It is characterized in that titanium source, silicon source and protective material joined in the alkali source aqueous solution that contains noble metal source and mix; Obtain mole and consist 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): mixture (200-10000), the silicon source is with SiO in the formula
2Meter, the titanium source is with TiO
2Meter, noble metal source is in precious metal simple substance, with mixture in closed reactor 120～200 ℃ with autogenous pressure reaction at least 0.5 hour down; With product filter, drying, crystalline material in the middle of roasting gets is mixed the filtrating that obtains after middle crystalline material and the above-mentioned product filtration again; Adding is (0.1-10) with the mol ratio of above-mentioned noble metal source: 1 reductive agent; In closed reactor, handled 2-360 hour under 80-200 ℃ and the autogenous pressure then, and reclaim product, wherein; Said protective material is a tensio-active agent, and tensio-active agent is selected from AS, 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. according to the process of claim 1 wherein that said silicon 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 said titanium 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 the said alkali source mixture that to be quaternary ammonium hydroxide compound or quaternary ammonium hydroxide compound form with amine compound or alcohol amine compound.
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 1-4 carbon atom.
13. according to the method for claim 9, wherein said amine compound is ethamine, n-Butyl Amine 99, tetramethylenediamine 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, diethylolamine or trolamine.
16. according to the process of claim 1 wherein inorganics or the organism of said noble metal source 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, an 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 80, hydrazine hydrogen chloride or hydrazonium sulfate, said hydroborate is selected from Peng Qinghuana or POTASSIUM BOROHYDRIDE 97MIN.
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| CN105413742B (en) * | 2015-11-27 | 2017-11-03 | 中国石油大学(北京) | The application of synthesis and its light paraffins isomerization of zeolite cladding noble metal |
| CN107879357B (en) * | 2016-09-30 | 2019-11-15 | 中国石油化工股份有限公司 | The method of a kind of HTS and its synthetic method and application and a kind of oxidation of cyclic ketones |
| CN109999902B (en) * | 2019-04-11 | 2022-04-19 | 浙江工业大学 | Packaged platinum group sub-nanometer metal loaded porous titanium-silicon molecular sieve catalyst and preparation and application thereof |
| CN112604711A (en) * | 2020-11-24 | 2021-04-06 | 兰州理工大学 | Preparation method and application of novel titanium silicalite molecular sieve |
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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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| 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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