CN101623653B - Method for modifying titanium-silicon molecular sieve material - Google Patents
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- CN101623653B CN101623653B CN200810116447XA CN200810116447A CN101623653B CN 101623653 B CN101623653 B CN 101623653B CN 200810116447X A CN200810116447X A CN 200810116447XA CN 200810116447 A CN200810116447 A CN 200810116447A CN 101623653 B CN101623653 B CN 101623653B
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Abstract
The invention discloses a method for modifying a titanium-silicon molecular sieve material, which is characterized by comprising the following steps: adding titanium-silicon molecular sieve, silicon-containing compound, protective agent, reducing agent and noble metal source into solution containing alkali source, evenly mixing the mixture, then carrying out hydro-thermal treatment for the mixture in a closed reaction kettle, and reclaiming a product. The method improves the content of framework titanium, relatively reduces the content of the titanium on the outside surface and orifices of the molecular sieve by covering inert component silicon on the outside surface and the orifices of the titanium-silicon molecular sieve, and reduces the occurrence of side reaction on the outside surface and orifices of a molecular sieve catalyst so as to improve the oxidation activity, stability and target product selectivity of the modified titanium-silicon molecular sieve material at the same time of improving the synergistic action of noble metals and titanium-silicon molecular sieve materials.
Description
Technical field
The invention relates to a kind of method of modifying of titanium-silicon molecular screen material, specifically titanium-silicon molecular screen material is carried out the method for modification with noble metal source.
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.
Many bibliographical informations have been arranged to load on Pt, Pd, Au and is used for original position on the titanium silicalite material and generates H
2O
2The research (US 6867312B1, US 6884898B1 and " J.Catal., 1998,176:376-386 " etc.) of organic matter selective oxidation reaction.Appl.Catal.A:Gen., 2001,213:163-171 has reported that epoxidation propylene generates the research of expoxy propane (PO), H
2And O
2The reaction original position generates H on noble metal active positions such as Pd
2O
2Intermediate, the H that generates then
2O
2Intermediate is at contiguous Ti
4+Epoxidation propylene generates expoxy propane on the position, though reaction condition is gentle, selectivity is good, has defectives such as the lower and poor catalyst stability of catalyst activity.
Method of modifying for titanium-silicon molecular screen material; Report is also arranged in the prior art; The disclosed method of modifying of CN1421389A for example, comprise the aqueous solution of silicon and the TS-1 molecular sieve that has synthesized according to molecular sieve (gram): Si (mole)=(70-1500): 1 mixed is even, and the gained mixture was reacted 0.1-150 hour under 80-190 ℃ temperature in agitated reactor; Filter, wash and drying, the TS-1 molecular sieve that obtains with the silicon modification.The method of modifying that CN1245090A is disclosed comprises the TS-1 molecular sieve, acid compound and the water that have synthesized are mixed, and reacts 5 minutes to 6 hours down at 5-95 ℃, obtains acid-treated TS-1 molecular sieve; Gained is mixed through acid-treated TS-1 molecular sieve, organic base and water, and in sealed reactor under 120-200 ℃ temperature and self-generated pressure 2 hours to the 8 day time of reaction, then with products therefrom filter, washing and dry; This method has reduced the invalid decomposition of oxidant, thereby the molecular sieve catalytic oxidation activity is compared with prior art obviously improved owing to removed the outer titanium of skeleton in the part molecular sieve pore passage, has stability of catalytic activity preferably simultaneously.
Summary of the invention
Technical problem to be solved by this invention is to generate H to original position
2O
2Be used for the deficiency that there is the titanium-silicon molecular screen material catalyst in organic matter selective oxidation reaction technology; A kind of method of titanium-silicon molecular screen material being carried out modification with noble metal is provided, makes that oxidation activity, stability and the purpose selectivity of product through the titanium-silicon molecular screen material of modification is improved.
The method of modifying of titanium-silicon molecular screen material provided by the invention is HTS, silicon-containing compound, protective agent, noble metal source and reducing agent to be joined in the solution that contains alkali source mixedly change hydrothermal treatment consists in the agitated reactor over to after evenly, reclaims product.
More particularly; Method of modifying provided by the invention; It is characterized in that it being: silicon-containing compound: protective agent: alkali source: reducing agent: noble metal source: water=100: (0.005-1.0): (0.0001-5.0): (0.005-5.0): (0.005-10.0): (0.005-10.0): ingredient proportion (500-10000) according to HTS; HTS, silicon-containing compound, protective agent, reducing agent and noble metal source joined in the solution that contains alkali source mix,, and reclaim product then with mixture hydrothermal treatment consists in closed reactor; Wherein said HTS restrains in precious metal simple substance in gram, noble metal source; Protective agent, alkali source, reducing agent and water is in mole, when silicon-containing compound is inorganic matter in the silica mole, when silicon-containing compound is organic matter in the silicon-containing compound mole.
In the method provided by the present invention, said ingredient proportion is preferably HTS: silicon-containing compound: protective agent: alkali: reducing agent: noble metal source: water=100: (0.005-1.0): (0.005-1.0): (0.01-2.0): (0.01-10.0): (0.01-5.0): (500-5000).
Can also comprise the said process of repetition one or many in the method provided by the present invention,, thereby improve its catalytic oxidation activity with silicon content in the further raising framework of molecular sieve and noble metal introducing amount.
In the method for modifying provided by the invention, said HTS comprises the HTS of all kinds structure in feeding intake, like TS-1, and TS-2, Ti-BETA, Ti-MCM-22 etc. wherein are preferably TS-1.
In the method provided by the invention, preferred inorganic silicon colloidal sol of said silicon-containing compound or organosilicon acid esters.The organosilicon acid esters that said organosilicon acid esters more preferably is made up of the alkyl with 1-4 carbon atom, wherein most preferred organosilicon acid esters is the silicon tetraethyl acid esters.
In the method provided by the invention; Said protective agent is meant polymer or surfactant; Wherein polymer can be polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride, polyethylene etc. and derivative thereof, and surfactant can be anion surfactant, cationic surfactant, zwitterionic surfactant or non-ionic surface active agent.
In the method provided by the invention, said reducing agent can be hydrazine, boron hydride, natrium citricum 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 can be selected from the compound of noble metals such as ruthenium, rhodium, palladium, silver, gold, platinum, rhenium.With the palladium source is example, can be inorganic palladium source or organic palladium source or their mixing.Wherein inorganic palladium source can be palladium oxide, carbonate palladium, palladium bichloride, palladium nitrate, nitric acid ammonia palladium, sal-ammoniac palladium etc.; The organic palladium source can be palladium, palladium acetylacetonate etc.
In the method provided by the invention, said alkali source is inorganic alkali source or organic alkali source.Wherein inorganic alkali source can be ammoniacal liquor, NaOH, potassium hydroxide, barium hydroxide etc.; Organic alkali source can be for urea, quaternary amine alkali compounds, fat amine compound, alcamine compound or by several kinds of mixtures of being formed in them.
Said its general formula of quaternary ammonium base compounds is (R
1)
4NOH, wherein R
1For having the alkyl of 1-4 carbon atom, R
1Propyl group preferably.
Its general formula of said fat amine compound is R
2(NH
2)
n, R wherein
2Be selected from alkyl or alkylidene, n=1 or 2 with 1-6 carbon atom.Fat amine compound is preferably ethamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of said alcamine compound is (HOR
3)
mNH
(3-m)R wherein
3Be selected from alkyl with 1-4 carbon atom; M=1,2 or 3.Alcamine compound is preferably MEA, diethanol amine or triethanolamine.
In the method provided by the invention, said is under temperature 80-200 ℃ and self-generated pressure, to handle 2-360 hour with mixture condition of hydrothermal treatment consists in closed reactor.
Method of modifying provided by the invention at first, makes the outer titanium of HTS skeleton get into skeleton once more, and the skeleton Ti content improves; Secondly, make to be coated with a certain amount of inertia component silicon, relatively reduced the Ti content at molecular sieve outer surface and aperture place, reduced the generation of side reaction at molecular sieve catalyst outer surface and place, aperture at HTS outer surface and place, aperture; In addition; This method of modifying is introduced noble metal source, the traditional load of comparing technology, and operation is simple; Process is controlled easily; Overcome the drawback that traditional method of modifying (like the impregnating method) causes noble metal to be assembled, the good dispersion of noble metal, thus the synergy of noble metal and titanium-silicon molecular screen material is improved.
Comprehensive These characteristics; The titanium-silicon molecular screen material and the prior art that obtain through method of modifying of the present invention; Like comparing of traditional dip loading technology modification; In oxidation reaction, for example in the reaction of preparing epoxypropane by epoxidation of propene, oxidation activity, stability and purpose selectivity of product are improved.
The specific embodiment
Through embodiment the present invention is done explanation further below, but therefore do not limit content of 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 explanation of this Comparative Examples utilizes the process of conventional infusion process modifying titanium-silicon molecular sieve material.
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.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 DB-1.
Embodiment 1
Get 20 gram titanium-silicon molecular sieve TS-1s, concentration and be in nitric acid ammonia palladium complex solution, ethyl orthosilicate and the hydrazine hydrate of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 10%) that softex kw joins TPAOH and mix; HTS (gram) wherein: ethyl orthosilicate (mole): softex kw (mole): TPAOH (mole): hydrazine hydrate (mole): nitric acid ammonia palladium complex (gram is in palladium): water (mole)=100: 0.1: 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 ℃, continues dry 3 hours, promptly gets the titanium-silicon molecular screen material A of modification.
Embodiment 2
Get 20 gram titanium-silicon molecular sieve TS-1s, concentration and be in palladium chloride solution, Ludox and the hydrazine hydrochloride of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that polypropylene joins NaOH and mix; HTS (gram) wherein: (mole is with SiO for Ludox
2Meter): polypropylene (mole): NaOH (mole): hydrazine hydrochloride (mole): palladium bichloride (gram is in palladium): water (mole)=100: 0.5: 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, and gains are filtered, use water washing, after the air dry, and under 110 ℃, continues dry 3 hours, promptly gets the titanium-silicon molecular screen material B of modification.
Embodiment 3
Get 20 gram titanium-silicon molecular sieve TS-1s, concentration and be in acid chloride solution, methyl silicate and the right amount of boron sodium hydride of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 10%) that Tween 80 joins TPAOH and butanediamine and mix; HTS (gram) wherein: methyl silicate (mole): alkali source (mole): palladium source (mole): protective agent (mole): water (mole)=100: 0.01: 0.03: 0.5: 0.05: 0.02: 550; Put into sealed reactor then; Hydrothermal treatment consists is 120 hours under 120 ℃ temperature and self-generated pressure; Gains are filtered, use water washing; After the air dry, and under 150 ℃, continued dry 3 hours, promptly get the titanium-silicon molecular screen material C that passes through modification.
Embodiment 4
Get 20 gram titanium-silicon molecular sieve TS-1s, positive silicic acid isopropyl ester, concentration and be in sal-ammoniac palladium solution and an amount of hydrazine sulfate of 0.02g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that neopelex joins TPAOH and mix; Continue to stir a period of time; HTS (gram) wherein: positive silicic acid isopropyl ester (mole): alkali source (mole): palladium source (mole): protective agent (mole): water (mole)=100: 0.2: 1.0: 1.2: 2.0: 0.5: 2500; Put into the stainless steel sealed reactor then; Hydrothermal treatment consists is 96 hours under 150 ℃ temperature and self-generated pressure, and gains are filtered, use water washing, after the air dry; And under 120 ℃, continued dry 3 hours, promptly get the titanium-silicon molecular screen material D of modification.
Embodiment 5
Get 20 gram titanium-silicon molecular sieve TS-1s, butyl silicates, concentration and be in acid chloride solution and the right amount of boron sodium hydride of 0.01g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 10%) that Tween 80 joins butanediamine and mix; HTS (gram) wherein: butyl silicate (mole): Tween 80 (mole): butanediamine (mole): sodium borohydride (mole): acid chloride (gram is in palladium): water (mole)=100: 0.05: 0.1: 0.02: 0.05: 0.03: 520.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 120 hours under 120 ℃ temperature and self-generated pressure, and gains are filtered, use water washing, after the air dry, and under 150 ℃, continues dry 3 hours, promptly gets the titanium-silicon molecular screen material E of modification.
Embodiment 6
Get 20 gram titanium-silicon molecular sieve TS-1s, ethyl orthosilicates, concentration and be in sal-ammoniac palladium solution and the hydrazine sulfate of 0.05g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 10%) that neopelex joins TPAOH and mix; Add under the high degree of agitation in batches; Continue to stir a period of time; HTS (gram) wherein: ethyl orthosilicate (mole): neopelex (mole): TPAOH (mole): hydrazine sulfate (mole): sal-ammoniac palladium (gram is in palladium): water (mole)=100: 0.8: 0.5: 1.1: 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, and gains are filtered, use water washing, after the air dry, and under 120 ℃, continues dry 3 hours, promptly gets the titanium-silicon molecular screen material F of modification.
Embodiment 7
Acid chloride solution and hydrazine hydrate and the softex kw of getting 20 gram titanium-silicon molecular sieve TS-1s, ethyl orthosilicates, concentration and be 0.01g/mL (in the palladium atom) join in the TPAOH (mass percent concentration 13%) and mix; HTS (gram) wherein: ethyl orthosilicate (mole): protective agent (mole): alkali source (mole): hydrazine hydrate (mole): palladium source (mole): water (mole)=100: 0.3: 0.01: 1.5: 5.0: 3.2: 800, the palladium source is in Pd.Put into the stainless steel sealed reactor then, hydrothermal treatment consists is 120 hours under 160 ℃ temperature and self-generated pressure, and gains are filtered, use water washing, after the air dry, and under 150 ℃, continues dry 3 hours, promptly gets the titanium-silicon molecular screen material G of modification.
Embodiment 8
Get 20 gram HTSs, ethyl orthosilicates, concentration and be in nitric acid ammonia palladium solution and the potassium borohydride of 0.05g/mL (in the palladium atom) and the aqueous solution (mass percent concentration 15%) that neopelex joins TPAOH and mix; Add under the high degree of agitation in batches; Continue to stir a period of time; HTS (gram) wherein: ethyl orthosilicate (mole): protective agent (mole): alkali source (mole): potassium borohydride (mole): palladium source (mole): water (mole)=100: 1.0: 0.005: 0.2: 0.5: 0.2: 4800, put into the stainless steel sealed reactor then, hydrothermal treatment consists is 96 hours under 150 ℃ temperature and self-generated pressure; Gains are filtered, use water washing; After the air dry, and under 120 ℃, continued dry 3 hours, promptly get the titanium-silicon molecular screen material H of modification.
Embodiment 9
Get 20 gram HTSs, ethyl orthosilicates, concentration and be in ethanolic solution 10ml and an amount of natrium citricum and the aqueous solution (mass percent concentration 18%) that polyethylene glycol joins triethanolamine of acid chloride of 0.05g/mL (in the palladium atom) and mix; HTS (gram) wherein: ethyl orthosilicate (mole): polyethylene glycol (mole): triethanolamine (mole): natrium citricum (mole): acid chloride (gram is in palladium): water (mole)=100: 0.02: 0.02: 0.8: 10.0: 0.01: 1500.Put into agitated reactor then, hydrothermal treatment consists is 320 hours under 130 ℃ temperature and self-generated pressure, and gains are filtered, use water washing, after the air dry, and under 120 ℃, continues dry 3 hours, promptly gets the titanium-silicon molecular screen material I of modification.
Embodiment 10
With 20 gram HTSs, positive tetraethyl orthosilicate, concentration is that acid chloride solution and hydrazine hydrate and the softex kw of 0.05g/mL (in the palladium atom) joins in the TPAOH (mass percent concentration 13%) and mix; HTS (gram) wherein: ethyl orthosilicate (mole): protective agent (mole): alkali source (mole): hydrazine hydrate (mole): palladium source (mole): water (mole)=100: 0.6: 0.2: 0.01: 0.12: 1.0: 3500; Put into sealed reactor then; Hydrothermal treatment consists is 120 hours under 160 ℃ temperature and self-generated pressure; Gains are filtered, use water washing; After the air dry, and under 150 ℃, continued dry 3 hours, promptly get the titanium-silicon molecular screen material J of modification.
Comparative Examples 2
The conventional dipping of this Comparative Examples explanation method of modifying prepares the process of 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 ℃.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-2.
Embodiment 11
Present embodiment explanation is with palladium, the platinum process as noble metal source modifying titanium-silicon molecular sieve material.
Getting 20 gram titanium-silicon molecular sieve TS-1s, ethyl orthosilicates, concentration is in nitric acid ammonia palladium and nitric acid ammonia platinum complex solution and the hydrazine hydrate of 0.01g/mL (in palladium, pt atom) and the aqueous solution (mass percent concentration 16%) that softex kw joins TPAOH and mixes; HTS (gram) wherein: ethyl orthosilicate (mole): 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: 0.6: 0.4: 2.0: 1.0: 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 titanium-silicon molecular screen material K of modification.
Embodiment 12
The present embodiment explanation is used for hydrogen through the titanium-silicon molecular screen material sample A-K of modification of the present invention with comparative example DB-1 and DB-2 and has the effect of preparing epoxypropane by epoxidation of propene reaction down.
Get respectively that embodiment 1 and CN1245090A embodiment 2 each 0.5g join in the epoxidation reaction container that contains methyl alcohol 50ml among the foregoing description sample A-K and comparative example DB-1, DB-2 and the CN1421389A; 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 epoxidation reaction and generate expoxy propane.
Table 1 and table 2 provide respectively is propylene conversion and the PO data optionally of reaction 2 hours and 16 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 selectivity (%)=propylene oxide in products.
Table 1
| Sample source | Sample number into spectrum | Propylene conversion % | Expoxy propane selectivity % |
| CN1421389A | Embodiment 1 | 0 | 0 |
| CN1245090A | Embodiment 2 | 0 | 0 |
| Comparative Examples 1 | DB-1 | 2.77 | 89.4 |
| Embodiment 1 | A | 4.86 | 94.5 |
| Embodiment 2 | B | 5.35 | 96.2 |
| Embodiment 3 | C | 4.84 | 93.5 |
| Embodiment 4 | D | 4.87 | 94.3 |
| Embodiment 5 | E | 4.62 | 95.6 |
| Embodiment 6 | F | 5.32 | 95.4 |
| Embodiment 7 | G | 5.36 | 94.6 |
| Embodiment 8 | H | 4.97 | 94.3 |
Continuous table 1
| Sample source | Sample number into spectrum | Propylene conversion % | Expoxy propane selectivity % |
| Embodiment 9 | I | 4.85 | 94.6 |
| Embodiment 10 | J | 5.26 | 93.8 |
| Comparative Examples 2 | DB-2 | 2.94 | 88.7 |
| Embodiment 11 | K | 5.75 | 96.6 |
Table 2
| Sample source | Sample number into spectrum | Propylene conversion % | Expoxy propane selectivity % |
| CN1421389A | Embodiment 1 | 0 | 0 |
| CN1245090A | Embodiment 2 | 0 | 0 |
| Comparative Examples 1 | DB-1 | 0.72 | 82.2 |
| Embodiment 1 | A | 4.84 | 94.2 |
| Embodiment 2 | B | 5.32 | 95.6 |
| Embodiment 3 | C | 4.75 | 93.1 |
| Embodiment 4 | D | 4.77 | 94.1 |
| Embodiment 5 | E | 4.55 | 94.4 |
| Embodiment 6 | F | 5.30 | 94.8 |
| Embodiment 7 | G | 5.32 | 94.3 |
| Embodiment 8 | H | 4.88 | 93.5 |
| Embodiment 9 | I | 4.76 | 93.3 |
| Embodiment 10 | J | 5.07 | 93.0 |
| Comparative Examples 2 | DB-2 | 1.63 | 84.9 |
| Embodiment 11 | K | 5.56 | 95.4 |
Can find out from the data of table 1 and table 2; Embodiment 1 does not have reactivity with the modifying titanium-silicon molecular sieve that CN1245090A embodiment 2 obtains among the CN1421389A; The oxidation activity of the inventive method gained sample is apparently higher than comparative sample; The expoxy propane selectivity also increases to some extent, explains that its catalytic oxidation activity of sample of preparation method's gained of the present invention and selectivity compared with prior art obviously improve.Can find out that from the data of table 2 the inventive method gained sample has activity stability preferably simultaneously.
Claims (22)
1. the method for modifying of a titanium-silicon molecular screen material; It is characterized in that it being: silicon-containing compound: protective agent: alkali source: reducing agent: noble metal source: water=100: (0.005-1.0): (0.0001-5.0): (0.005-5.0): (0.005-10.0): (0.005-10.0): ingredient proportion (500-10000) according to HTS; HTS, silicon-containing compound, protective agent, reducing agent and noble metal source joined in the solution that contains alkali source mix; Then with mixture hydrothermal treatment consists in closed reactor; And the recovery product, in the precious metal simple substance gram, protective agent, alkali source, reducing agent and water are in mole in gram, noble metal source for wherein said HTS; When silicon-containing compound is inorganic matter in the silica mole, when silicon-containing compound is organic matter in the silicon-containing compound mole; Said protective agent is selected from one or more the mixture in polypropylene, polyethylene glycol, polystyrene, polyvinyl chloride and polyethylene and the derivative thereof, perhaps is selected from anion surfactant, cationic surfactant, zwitterionic surfactant or non-ionic surface active agent.
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 and the Ti-MCM-22.
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 silicon-containing compound is inorganic silicon colloidal sol or organosilicon acid esters.
5. according to the method for claim 4, wherein said organosilicon acid esters is the organosilicon acid esters with alkyl of 1-4 carbon atom.
6. according to the method for claim 5, alkyl wherein is an ethyl.
7. according to the process of claim 1 wherein that said reducing agent is hydrazine, boron hydride or natrium citricum.
8. according to the method for claim 7, said hydrazine is hydrazine hydrate, hydrazine hydrochloride or hydrazine sulfate.
9. according to the method for claim 7, said boron hydride is sodium borohydride or potassium borohydride.
10. according to the process of claim 1 wherein that said noble metal source is selected from other complex compound of the oxide of noble metal, halide, carbonate, nitrate, ammonium salt, chlorination ammonium salt, hydroxide or noble metal.
11. according to the process of claim 1 wherein that said noble metal source is the palladium source.
12. according to the method for claim 11, said palladium source is inorganic palladium source and/or organic palladium source.
13. according to the method for claim 12, wherein said inorganic palladium source is selected from other complex compound of palladium oxide, carbonate palladium, palladium bichloride, palladium nitrate, ammonium nitrate palladium, sal-ammoniac palladium, palladium dydroxide or palladium.
14. according to the method for claim 12, said organic palladium source is selected from palladium or palladium acetylacetonate.
15. according to the process of claim 1 wherein that said alkali source is inorganic alkali source or organic alkali source.
16. according to the method for claim 15, wherein inorganic alkali source is ammoniacal liquor, NaOH, potassium hydroxide, barium hydroxide; Organic alkali source is urea, quaternary ammonium base compounds, fat amine compound, alcamine compound or the mixture be made up of them.
17. according to the method for claim 16, wherein said its general formula of quaternary ammonium base compounds is (R
1)
4NOH, wherein R
1For having the alkyl of 1-4 carbon atom.
18. according to the method for claim 17, wherein said R
1Be propyl group.
19. according to the method for claim 16, wherein said its general formula of fat amine compound is R
2(NH
2)
n, R wherein
2Be selected from alkyl or alkylidene, n=1 or 2 with 1-6 carbon atom.
20. according to the method for claim 19, wherein said fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
21. according to the method for claim 16, wherein said its general formula of alcamine compound is (HOR
3)
mNH
(3-m)R wherein
3Be selected from alkyl with 1-4 carbon atom; M=1,2 or 3.
22. according to the method for claim 21, wherein said alcamine compound is MEA, diethanol amine or triethanolamine.
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| CN102502690A (en) | 2011-10-31 | 2012-06-20 | 大连理工大学 | Method for modifying TS (Titanium silicalite)-1 based on mixed liquor of quaternary ammonium salt and inorganic base |
| CN103508845B (en) * | 2012-06-27 | 2015-09-23 | 中国石油化工股份有限公司 | A kind of method of cyclohexane oxidation |
| CN107879356B (en) * | 2016-09-30 | 2020-10-27 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, synthesis method and application thereof, and method for oxidizing cyclic ketone |
| CN107879354B (en) * | 2016-09-30 | 2020-09-22 | 中国石油化工股份有限公司 | Titanium-silicon molecular sieve, synthesis method and application thereof, and method for oxidizing cyclic ketone |
| 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 |
| CN106824264B (en) * | 2016-12-30 | 2019-01-18 | 中催技术有限公司 | A kind of Titanium Sieve Molecular Sieve and its method of modifying and application |
| CN111099614B (en) * | 2018-10-29 | 2021-12-17 | 中国石油化工股份有限公司 | Noble metal titanium silicon molecular sieve, synthesis method and application thereof, and cyclohexene oxidation method |
| CN111747451A (en) * | 2020-07-09 | 2020-10-09 | 复旦大学 | Ferroferric oxide/mesoporous silica magnetic composite particle and super-assembly method thereof |
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