CN103183355A - Precious metal modification method of titanium silicalite molecular sieve - Google Patents
Precious metal modification method of titanium silicalite molecular sieve Download PDFInfo
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Abstract
A precious metal modification method of a titanium silicalite molecular sieve is characterized in that the method comprises the following steps: mixing a titanium silicalite molecular sieve, a precious metal source, and an organic alkali solution, treating the mixture in a closed reaction vessel at 100-200 DEG C for at least 2 hours, taking the product out at normal temperature and normal pressure, drying, and roasting to obtain the precious metal modified titanium silicalite molecular sieve product, 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, and the treating capacity of the titanium silicalite molecular sieve is at least 10 g per liter of the reaction vessel volume. The method is low in cost, few in three-wastes, and high in efficiency, and the molecular sieve has good catalytic performance.
Description
Technical field
The present invention relates to a kind of method of modifying of HTS, more specifically to a kind of method of HTS synthetic under the prior art condition being utilized modified with noble metals.
Background technology
Si molecular sieves 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.Adopt HTS as catalyzer, can adopt free of contamination lower concentration hydrogen peroxide 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 of cyclic ketones etc., oxidising process complex process and problem of environment pollution caused have been avoided, have unrivaled energy-conservation, the economy of conventional oxidation system and advantages of environment protection, and have good reaction preference.
Though hydrogen peroxide (H
2O
2) be the green oxidation agent of generally acknowledging, its oxidized byproduct has only water.But because H
2O
2Extremely unstable, meet heat, light, uneven surface, heavy metal and other impurity can decompose, and have corrodibility, will take special security measures in packing, storage, transportation.Therefore, with H
2O
2Use on the spot, or with H
2O
2Production technique and use H
2O
2Downstream process combines, but these Chemicals of ability more efficient use.Utilize H
2And O
2Can directly synthesize H
2O
2, and atom utilization reaches 100%, and then people want to utilize H
2And O
2Come original position to synthesize H
2O
2Reoxidize organic raw material and directly utilize H to solve
2O
2Cost and safety problem.Because Pt, Pd, Au etc. are H
2And O
2Synthetic H
2O
2Active principle, have many document patent reports that it is loaded on the titanium silicalite material original position and generate H
2O
2Be used for the research of organism selective oxidation reaction.As, Meiers R. etc. (J.Catal., 1998, be that catalyzer is studied propylene gas-phase epoxidation with Pt-Pd/TS-1 176:376-386); US 6867312B1 and US 6884898B1 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 good (can reach more than 95%) of organism selective oxidation, conventional load method activity is lower, poor stability, H in the reaction in
2Effective rate of utilization is low.The more important thing is and often use big water gaging in the preparation process, wastewater discharge is big, and environmental pressure is heavy.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology the modified with noble metals method of the HTS that a kind of cost is low, the three wastes are few, efficient is high.
The modified with noble metals method of HTS provided by the present invention, it is characterized in that HTS, noble metal source, organic bases solution mixes the back to be handled 2 hours under 100～200 ℃ in closed reaction kettle at least, take out the product drying at normal temperatures and pressures, roasting gets the HTS product of modified with noble metals, wherein, contain in the reactor under reaction conditions form saturated steam and with the weight ratio of HTS less than 1.2 the water yield, the treatment capacity of HTS is 10g/L reactor volume at least, HTS and noble metal source, the blending ratio of organic bases is 100: (0.005～0.2): (0.005～0.2), HTS restrains in quality, organic bases is in mole, and noble metal source is in the precious metal simple substance mole.
The modified with noble metals method of HTS provided by the invention has following advantage:
(1) because water vapor modification treating processes does not have the mother liquor filtering separation, also there is not the washes discharging, the consumption of organic bases reduces simultaneously, and the environmental benefit of production process and remarkable in economical benefits improve.
(2) because water vapor modification treating processes Central Plains material usage reduces, and operation shortens, and product yield improves, the high-tension apparatus capacity utilization improves, and has improved production efficiency, has reduced production cost.
Embodiment
The modified with noble metals method of HTS provided by the present invention, it is characterized in that HTS, noble metal source, organic bases solution mixes the back to be handled 2 hours under 100～200 ℃ in closed reaction kettle at least, take out the product drying at normal temperatures and pressures, roasting gets the HTS product of modified with noble metals, wherein, contain in the reactor under reaction conditions form saturated steam and with the weight ratio of HTS less than 1.2 the water yield, the treatment capacity of HTS is 10g/L reactor volume at least, HTS and noble metal source, the blending ratio of organic bases is 100: (0.005～0.2): (0.005～0.2), HTS restrains in quality, organic bases is in mole, and noble metal source is in the precious metal simple substance mole.
In the method for modifying provided by the invention, described HTS refers to HTS synthetic through hydro-thermal and that other existing methods are synthetic, be well known to those skilled in the art, the example of described HTS can for but be not limited to: the HTS of MFI structure (as TS-1), the HTS of MEL structure (as TS-2), the HTS of BEA structure (as Ti-Beta), the HTS of MWW structure (as Ti-MCM-22), the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS of MOR structure (as Ti-MOR), at least a in the HTS (as Ti-ZSM-48) of the HTS of TUN structure (as Ti-TUN) and other structure.Of the present invention a kind of preferred embodiment in, described HTS is the HTS of MFI structure.
In the method for modifying provided by the invention, described organic bases can be selected from and be organo-alkali compounds such as quaternary ammonium hydroxide compound, amine compound and alcohol amine compound.Described quaternary ammonium hydroxide compound can be selected from TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH etc., described amine compound can be ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine or hexanediamine etc., and described alcohol amine compound can be monoethanolamine, diethanolamine or trolamine.The example of described organic bases can for but be not limited to one or more mixture in TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine, the trolamine.The example of the mixture of described multiple organic bases can for but be not limited to 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.
In the method for modifying provided by the invention, described noble metal source is selected from one or more precious metals, the organism that is preferably palladium and/or platinum or the inorganics in the precious metals such as Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, can be other complex compound of oxide compound, halogenide, carbonate, nitrate, ammonium salt, ammonia chloride salt, oxyhydroxide or precious metal etc.Of the present invention a kind of preferred embodiment in, described noble metal source is halogenide, the ammonia chloride salt of precious metal.Be example with the palladium, the palladium source can be inorganic palladium source and/or organic palladium source.Wherein the example in inorganic palladium source can be but be not limited to 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 example in organic palladium source can be but be not limited to palladium, palladium acetylacetonate etc.
In the method provided by the invention, the blending ratio of HTS and precious metal, organic bases is 100: (0.005～0.2): (0.005～0.2), preferred 100: (0.01～0.15): (0.01～0.15), HTS restrains in quality, organic bases is in mole, and noble metal source is in the precious metal simple substance mole.
In the method provided by the invention, carry out the exchange of matter and energy by the mode that similar gas phase shifts.Contain in the reactor under reaction conditions form saturated steam and with the weight ratio of HTS less than 1.2 the water yield, the treatment capacity of HTS is 10g/L reactor volume at least.The described water yield is provided by mixture contained humidity in the closed reactor, or realizes through adding outside water vapour.In the method for modifying provided by the invention, particularly in reactor, contain under reaction conditions form saturated steam and with the weight ratio of HTS less than satisfying requirement of the present invention under 1.0 the situation, can be used as preferred.
In the method provided by the invention, the described process that HTS, noble metal source, organic bases solution are handled in closed reaction kettle after mixing, preferred implementation condition is to carry out 6～72h in 120～180 ℃.
In the method provided by the invention, when through after the steam treatment, with reaction system cooling, pressure release, reclaim product.Described recovery need not to filter and washing, directly takes out the product drying, calcination process obtains modified product.Described drying process and roasting process are familiar with by those skilled in the art, and at this and have no special requirements, for example drying can be in room temperature～200 ℃ be carried out, described roasting can 300 ℃～800 ℃ in air atmosphere 2～12h carry out.Modified product does not need reduction activation namely to can be used for reaction after super-dry, calcination process.
The invention will be further described below by embodiment, but content not thereby limiting the invention.
Among Comparative Examples and the embodiment, agents useful for same is commercially available chemically pure reagent, and used HTS is by prior art Zeolites, the synthetic TS-1 sieve sample of method described in the 943rd～950 page of 1992, the Vol.12.
Comparative Examples 1
The process of the conventional synthetic load type palladium/titanium-silicon molecular sieve catalyst of this Comparative Examples explanation.
With 20g titanium-silicon molecular sieve TS-1 and concentration be the 20mL deionized water for stirring that joins of the nitric acid ammonia palladium complex solution 20mL of 0.01g/mL (in the palladium atom) evenly after, suitably sealing, temperature is at 40 ℃ of dipping 24h down.Seasoning then, and in 300 ℃ of following hydrogen atmospheres, carry out reduction activation 5h, namely get conventional load type palladium/titanium-silicon molecular sieve catalyst DB-1.
Embodiment 1
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 10g TS-1 molecular sieve, the 4.8g mass concentration is that 28% tetraethyl ammonium hydroxide solution (containing the 0.05g Palladous chloride) mixes.With pack into 50mL polytetrafluoroethyllining lining and place the 100mL polytetrafluoroethyllining lining to add in the support of said mixture, under supporting, add water 2mL simultaneously, then in sealing autoclave in 145 ℃ of reaction 12h.With gained through the molecular sieve of modified with noble metals in 100 ℃ of oven dry 180 minutes, then at 650 ℃ of roasting temperature 3h, obtain the TS-1 molecular sieve-4 A of modified with noble metals.
Embodiment 2
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 12g TS-1 molecular sieve, with 1g trolamine and 5g mass concentration be that 16.3% TPAOH solution (containing the 0.1g platinum nitrate) mixes.With pack into 50mL polytetrafluoroethyllining lining and place the 100mL polytetrafluoroethyllining lining to add in the support of said mixture, under supporting, add water 3mL simultaneously, then in sealing autoclave in 160 ℃ of reaction 56h.With gained through the molecular sieve of modified with noble metals in 150 ℃ of oven dry 120 minutes, then at 540 ℃ of roasting temperature 6h, obtain the TS-1 molecular sieve B of modified with noble metals.
Embodiment 3
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 12g TS-1 molecular sieve, with 0.5g Tri N-Propyl Amine and 7.5g mass concentration be that 16.3% TPAOH solution (containing the 0.02g acid chloride) mixes.With the said mixture 50mL polytetrafluoroethyllining lining of packing into, be placed on the 100mL polytetrafluoroethyllining lining again and add in the support, then in sealing autoclave in 175 ℃ of reaction 48h.With gained through the molecular sieve of modified with noble metals in 90 ℃ of oven dry 240 minutes, then at 700 ℃ of roasting temperature 2h, obtain the TS-1 molecular sieve C of modified with noble metals.
Embodiment 4
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 12g TS-1 molecular sieve, with Tetramethylammonium hydroxide and the 3.5g mass concentration of 3g 12% be that 16.3% TPAOH solution (containing 0.005g ammonia chloride palladium) mixes, said mixture is placed in the 100mL polytetrafluoroethyllining lining, in sealing autoclave, react 36h in 150 ℃ then.With gained through the molecular sieve of modified with noble metals in 150 ℃ of oven dry 180 minutes, then at 530 ℃ of roasting temperature 5h, obtain the TS-1 molecular sieve D of modified with noble metals.
Embodiment 5
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 14g TS-1 molecular sieve, with 0.5g di-n-propylamine and 6.5g mass concentration be that 28% tetramethyl ammonium hydroxide solution (containing the 0.2g carbonate palladium) mixes.With pack into 50mL polytetrafluoroethyllining lining and place the 100mL polytetrafluoroethyllining lining to add in the support of said mixture, at it under, add water 2mL simultaneously, in sealing autoclave, react 56h in 150 ℃ then.With gained through the molecular sieve of modified with noble metals in 150 ℃ of oven dry 180 minutes, then at 550 ℃ of roasting temperature 3h, obtain the TS-1 molecular sieve E of modified with noble metals.
Embodiment 6
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 10g TS-1 molecular sieve, with the 2.5g mass concentration be that 20% the trolamine aqueous solution (containing the 0.01g palladium hydroxide) mixes, with pack into 50mL polytetrafluoroethyllining lining and place the 100mL tetrafluoroethylene to add in the support of said mixture, under it, add simultaneously water 3mL, in sealing autoclave, react 24h in 135 ℃ then.With gained through the molecular sieve of modified with noble metals in 160 ℃ of oven dry 120 minutes, then at 650 ℃ of roasting temperature 4h, obtain the TS-1 molecular sieve F of modified with noble metals.
Embodiment 7
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 10g TS-1 molecular sieve, with 0.5g quadrol and 4.0g mass concentration be that 16.3% TPAOH solution (containing the 0.08g hydrochloro-auric acid) mixes.With the said mixture 50mL polytetrafluoroethyllining lining of packing into, be placed on the 100mL polytetrafluoroethyllining lining again and add in the support, at it under, add water 5mL simultaneously, in sealing autoclave, react 54h in 160 ℃ then.With gained through the molecular sieve of modified with noble metals in 140 ℃ of oven dry 120 minutes, then at 600 ℃ of roasting temperature 6h, obtain the TS-1 molecular sieve G of modified with noble metals.
Embodiment 8
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 10g TS-1 molecular sieve, with the 4.0g mass concentration be that 16.3% TPAOH solution (containing 0.05g ammonia chloride ruthenium) mixes.With the said mixture 50mL polytetrafluoroethyllining lining of packing into, be placed on the 100mL polytetrafluoroethyllining lining again and add in the support, at it under, add water 5mL simultaneously, in sealing autoclave, react 54h in 160 ℃ then.With gained through the molecular sieve of modified with noble metals in 120 ℃ of oven dry 120 minutes, then at 600 ℃ of roasting temperature 4h, obtain the TS-1 molecular sieve H of modified with noble metals.
Embodiment 9
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 10g TS-1 molecular sieve, with the 6.0g mass concentration be that 16.3% TPAOH solution (containing 0.09g nitric acid ammonia iridium) mixes.With the said mixture 50mL polytetrafluoroethyllining lining of packing into, be placed on the 100mL polytetrafluoroethyllining lining again and add in the support, at it under, add water 5mL simultaneously, in sealing autoclave, react 54h in 160 ℃ then.With gained through the molecular sieve of modified with noble metals in 110 ℃ of oven dry 120 minutes, then at 550 ℃ of roasting temperature 5h, obtain the TS-1 molecular sieve I of modified with noble metals.
Embodiment 10
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Get 10g TS-1 molecular sieve, with the 5.0g mass concentration be that 14.6% TPAOH solution (containing the 0.06g Silver Nitrate) mixes.With the said mixture 50mL polytetrafluoroethyllining lining of packing into, be placed on the 100mL polytetrafluoroethyllining lining again and add in the support, at it under, add water 5mL simultaneously, in sealing autoclave, react 54h in 160 ℃ then.With gained through the molecular sieve of modified with noble metals in 120 ℃ of oven dry 120 minutes, then at 500 ℃ of roasting temperature 6h, obtain the TS-1 molecular sieve J of modified with noble metals.
Embodiment 11
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Adopt the method identical with embodiment 3 that HTS is carried out modified with noble metals, different is, during the preparation catalyzer, uses the alternative acid chloride of Palladous chloride, gets the HTS K of modified with noble metals.
Embodiment 12
Present embodiment is used for illustrating the method for HTS being carried out modified with noble metals according to the present invention.
Adopt the method identical with embodiment 5 that HTS is carried out modified with noble metals, different is, during the preparation catalyzer, uses the alternative carbonate palladium of ammonia chloride palladium, gets the HTS L of modified with noble metals.
Test case
This test case illustrates that the sample that embodiment sample provided by the invention and Comparative Examples are synthesized is used for the hydrogen existence effect of propylene gas-phase epoxidation synthesizing epoxypropane reaction down.
Each 0.5g of sample that gets above-described embodiment 1～10 and Comparative Examples 1 respectively joins in the epoxidation reaction container that contains 50mL methyl alcohol, feed propylene, oxygen, hydrogen and nitrogen, (mol ratio is 1: 1: 1: 7) to form propylene-oxygen-hydrogen-nitrogen mixture atmosphere, 60 ℃ of temperature, pressure 1.0MPa, the propylene air speed is under the condition of 10h-1, carries out the reaction that epoxidation generates propylene oxide (PO).
Table 1 provides is optionally data of the propylene conversion of reaction 2h and PO.
Wherein optionally calculation formula is as follows for propylene conversion and PO:
Table 1
| Sample source | Sample number into spectrum | Propylene conversion % | PO selectivity % |
| Embodiment 1 | A | 4.9 | 92 |
| Embodiment 2 | B | 5.1 | 93 |
| Embodiment 3 | C | 4.4 | 90 |
| Embodiment 4 | D | 5.1 | 91 |
| Embodiment 5 | E | 4.6 | 90 |
| Embodiment 6 | F | 5.0 | 92 |
| Embodiment 7 | G | 5.4 | 93 |
| Embodiment 8 | H | 5.9 | 96 |
| Embodiment 9 | I | 4.7 | 92 |
| Embodiment 10 | J | 3.8 | 98 |
| Embodiment 11 | K | 5.6 | 94 |
| Embodiment 12 | L | 5.3 | 96 |
| Comparative Examples 1 | DB-1 | 2.6 | 89 |
From table 1 data as can be seen, to compare catalytic performance more superior for method of modifying gained molecular sieve of the present invention and Comparative Examples gained molecular sieve DB-1.So the inventive method has not only kept the superiority on the performance, and can also reduce production costs, and alleviates environmental pollution.
Claims (8)
1. the modified with noble metals method of a HTS, it is characterized in that HTS, noble metal source, organic bases solution are mixed the back to be handled 2 hours under 100～200 ℃ at least in closed reaction kettle, take out the HTS product that product drying, roasting get modified with noble metals at normal temperatures and pressures, wherein, contain in the reactor under reaction conditions form saturated steam and with the weight ratio of HTS less than 1.2 the water yield, the treatment capacity of HTS is 10g/L reactor volume at least.
2. according to the process of claim 1 wherein, described HTS is selected from TS-1, TS-2, Ti-Beta, Ti-MWW, Ti-MCM-41, Ti-SBA-15 molecular sieve.
3. according to the method for claim 1, wherein, described organic bases is selected from one or more in TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine and the trolamine.
4. according to the process of claim 1 wherein, described noble metal source is selected from the simple substance of Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Ag or one or more the mixture in the compound.
5. according to the method for claim 1, wherein, the blending ratio of HTS and noble metal source, organic bases is 100: (0.005～0.2): (0.005～0.2), and HTS restrains in quality, organic bases is in mole, and noble metal source is in the precious metal simple substance mole.
6. according to the method for claim 5, wherein, the blending ratio of HTS and noble metal source, organic bases is 100: (0.01～0.15): (0.01～0.15), and HTS restrains in quality, organic bases is in mole, and noble metal source is in the precious metal simple substance mole.
7. according to the process of claim 1 wherein, treatment condition be in the closed reactor 120～180 ℃ carried out 6～72 hours.
8. according to the process of claim 1 wherein, contain in the reactor under reaction conditions, form saturated steam and with the weight ratio of HTS less than 1.0 the water yield.
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