CN103183356B - Method for modifying titanium silicalite molecular sieve by precious metal source - Google Patents
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Abstract
A method for modifying a titanium silicalite molecular sieve by a precious metal source is characterized in that a mixture of modification liquid and a titanium silicalite molecular sieve is treated in a closed reaction vessel at 120-200 DEG C for at least 2 hours, and then the product is dried and roasted, wherein the water contained in the reaction vessel can form saturated water steam under the reaction condition, and has a weight ratio to the titanium silicalite molecular sieve being less than 1.2; the modification liquid comprises a silicone source, a titanium source, water, organic base, a precious metal source, and a reducing agent; the weight ratio of the titanium silicalite molecular sieve to the modification liquid is 100:(1-150); and the treating capacity of the titanium silicalite molecular sieve is at least 10 g per liter of the reaction vessel volume. The method needs no mother liquor separation, omits procedures of filtration or washing, greatly reduces environment pollution, improves volume utilization efficiency of high pressure equipment, increases productivity, reduces preparation cost, and improves the environmental protection and economic benefits of the synthesis.
Description
Technical field
The present invention relates to the method for modified with noble metals HTS under a kind of water vapour.
Background technology
HTS be last century early eighties start develop novel hetero-atom molecular-sieve.The TS-1 having MFI type structure synthesized at present, the TS-2 of MEL type structure, the MCM-22 of MWW type structure and the TS-48 etc. had compared with macroporous structure.Adopt HTS as catalyzer, free of contamination lower concentration hydrogen peroxide can be adopted as oxygenant, 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 etc. of cyclic ketones, avoid the problem of oxidising process complex process and contaminate environment, there is unrivaled energy-conservation, the advantage such as economy and environment is friendly of conventional oxidation system, and there is good reaction preference.
Although hydrogen peroxide (H
2o
2) be generally acknowledged Green Oxidant, its oxidized byproduct only has water.But due to H
2o
2extremely unstable, heat, light, uneven surface, heavy metal and other impurity can decompose, and have corrodibility, will take special security measures in packaging, storage, transport.Therefore, by H
2o
2apply on the spot, or by H
2o
2production technique and use H
2o
2downstream process combines, and just more effectively can utilize this Chemicals.Utilize H
2and O
2directly can synthesize H
2o
2, and atom utilization reaches 100%, and then people want to utilize H
2and O
2carry out fabricated in situ 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
2synthesis H
2o
2active principle, have many document patent reports by its load in-situ preparation H on titanium silicalite material
2o
2for the research of organism selective oxidation reaction.As, Meiers R. etc. (J.Catal., 1998,176:376 ~ 386) are that catalyzer is studied propylene gas-phase epoxidation with Pt-Pd/TS-1; US 6867312B1 and US 6884898B1 etc. have also carried out the research of this respect.By noble metal support in-situ preparation H on titanium silicalite material
2o
2although for method mild condition, the selectivity good (can reach more than 95%) of organism selective oxidation, the titanium silicalite material catalyst activity of carried noble metal is lower, poor stability.
Summary of the invention
The present invention seeks on prior art basis, a kind of method of modified with noble metals HTS is provided.
The method of modified with noble metals HTS provided by the invention, the mixture of a kind of modification liquid and HTS is placed in closed reactor at 120 ~ 200 DEG C, processes at least 2h, then product drying, roasting obtains product, wherein, containing forming saturated steam at reaction conditions and the water yield being less than 1.2 with the weight ratio of HTS in reactor, in mole composition of described modification liquid, silicon source: titanium source: organic bases: water: noble metal source: reductive agent=1: (0 ~ 0.1): (0.05 ~ 5): (15 ~ 100): (0.001 ~ 0.1): (0.001 ~ 0.5), silicon is with SiO
2meter, titanium is with TiO
2meter, noble metal source is in precious metal simple substance, and the weight ratio of HTS and modification liquid is 100: (1 ~ 150), and the treatment capacity of HTS is at least 10g/L reactor volume.
The method of modified with noble metals HTS provided by the invention has following advantage:
1, the consumption for the treatment of processes organic bases and precious metal is low, and without mother liquor filtering separation, also without washes discharge, the environmental protection efficiency of production process significantly improves.
2, high-tension apparatus capacity utilization improves, and expands production capacity, improves production efficiency, reduce production cost.
Embodiment
Method provided by the invention is applicable to various types of HTS, common HTS has TS-1, TS-2, Ti-Beta, Ti-MWW, Ti-MCM-41 molecular sieve etc., its oxidation activity of HTS obtained through modified with noble metals method of the present invention can effectively improve, preferred TS-1 molecular sieve.
In method provided by the invention, in mole composition of described modification liquid, silicon source: titanium source: organic bases: water: noble metal source: reductive agent=1: (0.01 ~ 0.05): (0.3 ~ 3.0): (20 ~ 50): (0.005 ~ 0.1): (0.001 ~ 0.2).
In method provided by the invention, described silicon source comprises silicon oxide, silica gel, silicon sol and organosilicon acid esters, and preferred silicon source is organosilicon acid esters; Described its general formula of organosilicon acid esters is R
1 4siO
4, wherein R
1preferably have the alkyl of 1-4 carbon atom, preferred alkyl is ethyl.
In method provided by the invention, described titanium source comprises inorganic titanium salt or organic titanate, and preferred titanium source is organic titanate; Described inorganic titanium salt can be TiCl
4, Ti (SO
4)
2or TiOCl
2; Its general formula of described organic titanate is Ti (OR
2)
4, wherein R
2preferably have the alkyl of 1-6 carbon atom, preferred alkyl is ethyl, propyl group or butyl.
In method provided by the invention, described organic bases can be selected from as organo-alkali compounds such as quaternary ammonium hydroxide compounds, fat amine compound and alcamine compounds.Described quaternary ammonium hydroxide compounds can be selected from 4-propyl bromide, TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH etc., described fat amine compound can be ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine or hexanediamine etc., and described alcamine compound can be monoethanolamine, diethanolamine or trolamine.Described organic bases also can be selected from TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine, one or more in trolamine, such as, the mixture of tetraethyl ammonium hydroxide and n-Butyl Amine 99, the mixture of tetraethyl ammonium hydroxide and n-Butyl Amine 99, the mixture of quadrol and TPAOH, the mixture of di-n-propylamine and TPAOH, the mixture of tetraethyl ammonium hydroxide and TPAOH, the mixture of hexanediamine and TPAOH all may be used for the present invention, and particular requirement is not had for the ratio of above-mentioned mixing yet, as long as can the present invention be realized.
In method provided by the invention, the weight ratio of HTS and modification liquid is 100: (10 ~ 150), and the weight ratio of preferred HTS and modification liquid is 100: (30 ~ 120).
Described noble metal source is selected from one or more in simple substance Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, or the compound be selected from containing one or more in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, or be selected from several mixture in above-mentioned precious metal simple substance or compound.Being preferably palladium, platinum, the organism of gold and silver or inorganics, can be other complex compound etc. of oxide compound, halogenide, carbonate, nitrate, ammonium salt, ammonia chloride salt, oxyhydroxide or precious metal.One of the present invention preferred embodiment in, described noble metal source is halogenide, the ammonia chloride salt of precious metal.For palladium, palladium source can be inorganic palladium source and/or organic palladium source.Wherein inorganic palladium source can be other complex compound etc. of palladous oxide, carbonate palladium, Palladous chloride, Palladous nitrate, nitric acid ammonia palladium, ammonia chloride palladium, palladium hydroxide or palladium, and organic palladium source can be palladium, palladium acetylacetonate etc.The present inventor is surprised to find that especially, when using the halogenide of precious metal as noble metal source, compare the HTS adopting other noble metal source modifications to obtain, its propylene conversion and object product propene oxide (PO) selectivity all have better effect, therefore, noble metal source of the present invention is preferably the halogenide of precious metal, the muriate of such as precious metal or ammonia chloride salt, is such as Palladous chloride or ammonia chloride palladium with palladium.
In method provided by the invention, described reductive agent can be selected from but be not limited to the mixture of one or more in azanol, formaldehyde, hydrazine, hydroborate and Trisodium Citrate, wherein hydrazine can be hydrazine hydrate, hydrazine hydrochloride, hydrazonium sulfate etc., and hydroborate can be sodium borohydride, POTASSIUM BOROHYDRIDE etc.
In method provided by the invention, preferably containing forming saturated steam at reaction conditions and the water yield being less than 1.0 with the weight ratio of HTS in reactor, the water yield of described formation saturated steam can be provided by reaction kettle for reaction thing material, also can realize through adding outside water vapour.
In method provided by the invention, reaction mixture treatment temp in closed reactor is 120 ~ 200 DEG C, and be preferably 140 ~ 180 DEG C, the treatment time is 2 ~ 72h, is preferably 6 ~ 72h.
In method provided by the invention, after temperature and pressure in reactor returns under close to normal temperature and pressure, without the need to after filtration and washing step, product in drying process and roasting process and recyclable reactor.Described drying process DEG C can be carried out in room temperature ~ 200, described roasting can 300 DEG C ~ 800 DEG C in air atmosphere 2 ~ 12h carry out, these processes are familiar with by those skilled in the art, have no special requirements at this.
Below by embodiment, the present invention is further described, but does not therefore limit content of the present invention.
In embodiment, used reagent is commercially available chemically pure reagent.In comparative example and embodiment, HTS used is by prior art Zeolites, the TS-1 sieve sample of the method synthesis described in 1992, Vol.12 943rd ~ 950 pages.
Comparative example 1
This comparative example illustrates the process of conventional synthesis load type palladium/titanium-silicon molecular sieve catalyst.
By 20g titanium-silicon molecular sieve TS-1 and concentration be the 20mL deionized water for stirring that joins of the nitric acid ammonia palladium solution 20mL of 0.01g/mL (in palladium atom) evenly after, suitably seal, temperature floods 24h at 40 DEG C.Then seasoning, and reduction activation 5h is carried out in hydrogen atmosphere at 300 DEG C, obtain conventional load type palladium/titanium-silicon molecular sieve catalyst DB.
Embodiment 1
The tetraethyl orthosilicate of metering, Palladous chloride, Trisodium Citrate are mixed with tetraethyl ammonium hydroxide, and add appropriate distilled water, in stirring at normal temperature 1.0h after mixing, at 75 DEG C, stir 3h again and obtain modification liquid, its mole consists of silicon: titanium: organic bases: water: noble metal source: reductive agent=1: 0: 0.85: 20: 0.05: 0.05 (wherein silicon and titanium are with SiO
2and TiO
2meter, precious metal is in simple substance).Get TS-1 molecular sieve 12g to mix with modification liquid 10g obtained above.Said mixture loaded 50mL polytetrafluoroethyllining lining and be placed on 100mL polytetrafluoroethyllining lining, then in sealing autoclave, reacting 12h in 175 DEG C.Products therefrom is dried 120 minutes in 150 DEG C, then roasting 5h at 580 DEG C, obtain modified with noble metals TS-1 molecular sieve-4 A.
Embodiment 2
The amorphous silica gel of metering, acid chloride, hydrazine hydrate are mixed with TPAOH, and add appropriate distilled water, in stirring at normal temperature 1.5h after mixing, add tetrabutyl titanate again and stir 0.5h, then at 70 DEG C, stir 3h and obtain modification liquid, its mole consists of silicon: titanium: organic bases: water: noble metal source: reductive agent=1: 0.02: 0.75: 25: 0.025: 0.15 (wherein silicon and titanium are with SiO
2and TiO
2meter, precious metal is in simple substance).Get 10g TS-1 molecular sieve to mix with 8.5g modification liquid obtained above.Mixture is loaded 50mL polytetrafluoroethyllining lining, then be placed on 100mL polytetrafluoroethyllining lining, then in sealing autoclave, react 24h in 180 DEG C.Products therefrom is dried 120 minutes in 150 DEG C, then roasting 2h at 650 DEG C, obtain modified with noble metals TS-1 molecular sieve B.
Embodiment 3
The tetraethyl orthosilicate of metering, tetraethyl titanate, carbonate palladium, formaldehyde are mixed with TPAOH, and add appropriate distilled water, in stirring at normal temperature 1.0h after mixing, at 80 DEG C, stir 3h again and obtain modification liquid, its mole consists of silicon: titanium: organic bases: water: noble metal source: reductive agent=1: 0.02: 0.75: 35: 0.02: 0.025 (wherein silicon and titanium are with SiO
2and TiO
2meter, precious metal is in simple substance).Get 15g TS-1 molecular sieve to mix with 13g modification liquid obtained above.Mixture loaded 50mL polytetrafluoroethyllining lining and be placed on 100mL polytetrafluoroethyllining lining, then in sealing autoclave, reacting 62h in 160 DEG C.Products therefrom is dried 240 minutes in 135 DEG C, then roasting 3h at 560 DEG C, obtain modified with noble metals TS-1 molecular sieve C.
Embodiment 4
By the mixing of the tetraethyl orthosilicate of metering, tetrabutyl titanate, platinum nitrate, sodium borohydride, trolamine and 4-propyl bromide, and add appropriate distilled water, in stirring at normal temperature 1.0h after mixing, at 75 DEG C, stir 3h again and obtain modification liquid, its mole consists of silicon: titanium: trolamine: 4-propyl bromide: water: noble metal source: reductive agent=1: 0.015: 0.35: 0.3: 20: 0.01: 0.2 (wherein silicon and titanium are with SiO
2and TiO
2meter, precious metal is in simple substance).Get 12g TS-1 molecular sieve to mix with 9.5g modification liquid obtained above.Mixture is loaded 50mL polytetrafluoroethyllining lining, then be placed in the added support of 100mL polytetrafluoroethyllining lining, then in sealing autoclave, react 48h in 165 DEG C.Products therefrom is dried 360 minutes in 100 DEG C, then roasting 6h at 540 DEG C, obtain modified with noble metals TS-1 molecular sieve D.
Embodiment 5
The white carbon black silicon-dioxide of metering, hydrochloro-auric acid, hydrazine hydrochloride are mixed with 4-propyl bromide, n-Butyl Amine 99, and add appropriate distilled water, in stirring at normal temperature 2.0h, add tetrabutyl titanate again and stir 0.5h, then at 75 DEG C, stir 3h and obtain modification liquid, its mole consists of silicon: titanium: 4-propyl bromide: n-Butyl Amine 99: water: noble metal source: reductive agent=1: 0.025: 0.85: 1: 25: 0.1: 0.12 (wherein silicon and titanium are with SiO
2and TiO
2meter, precious metal is in simple substance).Get 12g TS-1 molecular sieve to mix with 5g modification liquid obtained above.Mixture is loaded 50mL polytetrafluoroethyllining lining and be placed on added by 100mL polytetrafluoroethyllining lining and support, and the 5mL that adds water under it, then in sealing autoclave, react 36h in 155 DEG C.Products therefrom is dried 180 minutes in 175 DEG C, then roasting 5h at 500 DEG C, obtain modified with noble metals TS-1 molecular sieve E.
Embodiment 6
By the mixing of the silicon sol of metering, Silver Nitrate, hydrazine hydrate, di-n-propylamine and TPAOH, and add appropriate distilled water, in stirring at normal temperature 1.5h after mixing, add tetraethyl titanate again and stir 0.5h, then at 65 DEG C, stir 5h and obtain modification liquid, its mole consists of silicon: titanium: di-n-propylamine: TPAOH: water: noble metal source: reductive agent=1: 0.02: 0.35: 1.2: 30: 0.03: 0.1 (wherein silicon and titanium are with SiO
2and TiO
2meter, precious metal is in simple substance).Get 10g TS-1 molecular sieve to mix with 5g modification liquid obtained above.Mixture is loaded 100mL polytetrafluoroethyllining lining, then in sealing autoclave, process 65h in 150 DEG C.Products therefrom is dried 120 minutes in 160 DEG C, then roasting 3h at 700 DEG C, obtain modified with noble metals TS-1 molecular sieve F.
Embodiment 7
By the Z-type silica gel of metering, nitric acid ammonia palladium, azanol, n-Butyl Amine 99,4-propyl bromide mixing, and add appropriate distilled water, in stirring at normal temperature 1.5h, then tetraethyl titanate is added, at 75 DEG C, stir 3h again and obtain modification liquid, its mole consists of silicon: titanium: n-Butyl Amine 99: 4-propyl bromide: water: noble metal source: reductive agent=1: 0.02: 0.95: 0.8: 45: 0.06: 0.18 (wherein silicon and titanium are with SiO
2and TiO
2meter, precious metal is in simple substance).Get 12g TS-1 molecular sieve to mix with 6g modification liquid obtained above.Said mixture is loaded 50mL polytetrafluoroethyllining lining and be placed on added by 100mL polytetrafluoroethyllining lining and support, then in sealing autoclave, react 18h in 180 DEG C.Products therefrom is dried 270 minutes in 130 DEG C, then roasting 3h at 550 DEG C, obtain modified with noble metals TS-1 molecular sieve G.
Embodiment 8
The present embodiment is used for the method for according to the present invention, HTS being carried out to modified with noble metals is described.
The method identical with embodiment 1 is adopted to carry out modified with noble metals to HTS, unlike, during Kaolinite Preparation of Catalyst, use acid chloride to substitute Palladous chloride, obtain the HTS H of modified with noble metals.
Embodiment 9
The present embodiment is used for the method for according to the present invention, HTS being carried out to modified with noble metals is described.
The method identical with embodiment 2 is adopted to carry out modified with noble metals to HTS, unlike, during Kaolinite Preparation of Catalyst, use Palladous chloride to substitute acid chloride, obtain the HTS I of modified with noble metals.
Embodiment 10
The present embodiment is used for the method for according to the present invention, HTS being carried out to modified with noble metals is described.
The method identical with embodiment 3 is adopted to carry out modified with noble metals to HTS, unlike, during Kaolinite Preparation of Catalyst, use ammonia chloride palladium to substitute carbonate palladium, obtain the HTS J of modified with noble metals.
Test case
This test case illustrates that sample that embodiment sample provided by the invention and comparative example synthesize exists for hydrogen the effect that lower propylene gas-phase epoxidation synthesizing epoxypropane reacts.
The each 0.5g of sample getting above-described embodiment 1 ~ 10 and comparative example 1 respectively joins in the epoxidation reaction container containing 50mL methyl alcohol, pass into propylene, oxygen, hydrogen and nitrogen, form propylene-oxygen-hydrogen-nitrogen mixture atmosphere (mol ratio is 1: 1: 1: 7), at temperature 60 C, pressure 1.0MPa, propylene air speed is under the condition of 10h-1, carries out the reaction that epoxidation generates propylene oxide (PO).
What table 1 provided is propylene conversion and the PO optionally data of reacting 2h.
Wherein optionally calculation formula is as follows for propylene conversion and PO:
As can be seen from Table 1, treatment process gained molecular sieve of the present invention catalytic performance compared with comparative example gained molecular sieve DB is more superior.Illustrate that the inventive method is compared with normal load method of modifying, not only maintains the advantage in performance, can also production cost be reduced, alleviate environmental pollution.
Table 1
| Sample source | Sample number into spectrum | Propylene conversion % | PO selectivity % |
| Embodiment 1 | A | 5.8 | 93 |
| Embodiment 2 | B | 5.1 | 92 |
| Embodiment 3 | C | 5.3 | 94 |
| Embodiment 4 | D | 5.6 | 93 |
| Embodiment 5 | E | 5.2 | 91 |
| Embodiment 6 | F | 4.9 | 90 |
| Embodiment 7 | G | 4.7 | 93 |
| Embodiment 8 | H | 5.2 | 91 |
| Embodiment 9 | I | 5.9 | 95 |
| Embodiment 10 | J | 5.6 | 96 |
| Comparative example 1 | DB | 2.6 | 89 |
It can also be seen that from the data of table 1, when using the halogenide of palladium as noble metal source, compare the HTS (embodiment 2,3,8 and embodiment 1,9,10) that other noble metal source modifications obtain, its propylene conversion and PO selectivity all have better effect.
Claims (10)
1. the method with noble metal source modifying titanium-silicon molecular sieve, it is characterized in that the mixture of a kind of modification liquid and HTS to be placed in closed reactor to process at least 2h at 120 ~ 200 DEG C, then product drying and roasting, wherein, modification liquid is by silicon source, titanium source, water, organic bases, noble metal source and reductive agent composition, its molar ratio is silicon source: titanium source: organic bases: water: noble metal source: reductive agent=1: (0 ~ 0.1): (0.05 ~ 5): (15 ~ 100): (0.001 ~ 0.1): (0.001 ~ 0.5), silicon source is with SiO
2meter, titanium source is with TiO
2meter, noble metal source is in precious metal simple substance, containing forming saturated steam at reaction conditions and the water yield being less than 1.2 with the weight ratio of HTS in said reactor, the part by weight of HTS and modification liquid is 100: (1 ~ 150), and the treatment capacity of HTS is at least 10g/L reactor volume.
2., according to the process of claim 1 wherein, described HTS is TS-1, TS-2, Ti-Beta, Ti-MWW, Ti-MCM-41 molecular sieve.
3. according to the method for claim 1, wherein, in mole composition of described modification liquid, silicon source: titanium source: organic bases: water: noble metal source: reductive agent=1: (0.01 ~ 0.05): (0.3 ~ 3.0): (20 ~ 50): (0.005 ~ 0.1): (0.001 ~ 0.2).
4., according to the process of claim 1 wherein, described HTS and the part by weight of modification liquid are 100: (30 ~ 120).
5., according to the process of claim 1 wherein, it is R that described silicon source is selected from silicon oxide, silica gel, silicon sol or general formula
1 4siO
4organosilicon acid esters, R
1be selected from the alkyl of 1 ~ 4 carbon atom.
6., according to the process of claim 1 wherein, described titanium source is selected from TiCl
4, Ti (SO
4)
2or TiOCl
2, or general formula is Ti (OR
2)
4organic titanate, R
2be selected from the alkyl of 2 ~ 4 carbon atoms.
7. according to the process of claim 1 wherein, described organic bases be selected from quaternary ammonium hydroxide compound, amine compound or alcohol amine compound one or more.
8. according to the method for claim 1, wherein, described organic bases be selected from TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine and trolamine one or more.
9. according to the method for claim 1, wherein, described noble metal source is selected from one or more in simple substance Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, or the compound be selected from containing one or more in Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, or be selected from several mixture in above-mentioned precious metal simple substance or compound.
10., according to the process of claim 1 wherein, described reductive agent is selected from the mixture of one or more in azanol, formaldehyde, hydrazine, hydroborate and Trisodium Citrate.
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