CN103183355B - Precious metal modification method of titanium silicalite molecular sieve - Google Patents
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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 HTS of having synthesized under prior art condition being utilized modified with noble metals.
Background technology
Si molecular sieves 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 to be loaded to 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, conventional load method activity is lower, poor stability, H in reaction in－situ
2effective rate of utilization is low.The more important thing is in preparation process and often use large water gaging, wastewater discharge is large, environmental pressure weight.
Summary of the invention
The object 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, efficiency is high.
The modified with noble metals method of HTS provided by the present invention, it is characterized in that HTS, noble metal source, in airtight reactor, at least 2 hours are processed at 100 ~ 200 DEG C after organic alkali solution mixing, take out product drying at normal temperatures and pressures, roasting obtains the HTS product of modified with noble metals, 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, the treatment capacity of HTS is at least 10g/L reactor volume, HTS and noble metal source, the blending ratio of organic bases is 100: (0.005 ~ 0.2): (0.005 ~ 0.2), HTS is in quality gram, organic bases in mole, noble metal source is in 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 process is without mother liquor filtering separation, also without washes discharge, the consumption of organic bases reduces simultaneously, and the environmental benefit of production process and remarkable in economical benefits improve.
(2) because raw material usage in water vapor modification process reduces, operation shortens, and product yield improves, and high-tension apparatus capacity utilization improves, and improves production efficiency, reduces 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, in airtight reactor, at least 2 hours are processed at 100 ~ 200 DEG C after organic alkali solution mixing, take out product drying at normal temperatures and pressures, roasting obtains the HTS product of modified with noble metals, 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, the treatment capacity of HTS is at least 10g/L reactor volume, HTS and noble metal source, the blending ratio of organic bases is 100: (0.005 ~ 0.2): (0.005 ~ 0.2), HTS is in quality gram, organic bases in mole, noble metal source is in precious metal simple substance mole.
In method of modifying provided by the invention, described HTS refers to the HTS through Hydrothermal Synthesis and other existing method synthesis, be well known to those skilled in the art, the example of described HTS can be but be not limited to: the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS of hexagonal structure is (as Ti-MCM-41, Ti-SBA-15), the HTS (as Ti-MOR) of MOR structure, at least one in the HTS (as Ti-TUN) of TUN structure and the HTS (as Ti-ZSM-48) of other structure.One of the present invention preferred embodiment in, described HTS is the HTS of MFI structure.
In method of modifying provided by the invention, described organic bases can be selected from as organo-alkali compounds such as quaternary ammonium hydroxide compound, amine compound and alcohol amine compounds.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 be but one or more the mixture be not limited in TPAOH, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, TBAH, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine, 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 method of modifying provided by the invention, described noble metal source is selected from one or more precious metals in the precious metals such as Ru, Rh, Pd, Re, Os, Ir, Pt, Ag and Au, the organism being preferably palladium and/or platinum 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 the example in inorganic palladium source can be but be not limited to 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 the example in organic palladium source can be but be not limited to palladium, palladium acetylacetonate etc.
In 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), preferably 100: (0.01 ~ 0.15): (0.01 ~ 0.15), HTS is in quality gram, organic bases in mole, noble metal source is in precious metal simple substance mole.
In method provided by the invention, the mode shifted by similar gas phase carries out the exchange of matter and energy.Containing forming saturated steam at reaction conditions and the water yield being less than 1.2 with the weight ratio of HTS in reactor, the treatment capacity of HTS is at least 10g/L reactor volume.The described water yield is provided by mixture contained humidity in closed reactor, or realizes through adding outside water vapour.In method of modifying provided by the invention, particularly in a kettle. containing forming saturated steam and requirement of the present invention can be met when being less than 1.0 with the weight ratio of HTS at reaction conditions, can as preferably.
In method provided by the invention, the described process will processed in airtight reactor after HTS, noble metal source, organic alkali solution mixing, preferred implementation condition carries out 6 ~ 72h in 120 ~ 180 DEG C.
In method provided by the invention, when after steam treatment, by reaction system cooling, pressure release, reclaim product.Described recovery is without the need to filtering and washing, and directly taking-up product drying, calcination process obtain modified product.Described drying process and roasting process be familiar with by those skilled in the art, has no special requirements at this, and such as drying 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.Modified product, after super-dry, calcination process, does not need reduction activation namely to can be used for reaction.
Below by embodiment, the invention will be further described, but content not thereby limiting the invention.
In comparative example and embodiment, agents useful for same is commercially available chemically pure reagent, and 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 complex 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-1.
Embodiment 1
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.
Get 10g TS-1 molecular sieve, 4.8g mass concentration is 28% tetraethyl ammonium hydroxide solution (containing 0.05g Palladous chloride) mixing.Said mixture is loaded 50mL polytetrafluoroethyllining lining and be placed in added by 100mL polytetrafluoroethyllining lining and support, add water 2mL simultaneously under support, then in sealing autoclave, reacts 12h in 145 DEG C.The molecular sieve through modified with noble metals of gained is dried 180 minutes in 100 DEG C, then at 650 DEG C of roasting temperature 3h, obtains the TS-1 molecular sieve-4 A of modified with noble metals.
Embodiment 2
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.
Getting 12g TS-1 molecular sieve, is that 16.3% TPAOH solution (containing 0.1g platinum nitrate) mixes with 1g trolamine and 5g mass concentration.Said mixture is loaded 50mL polytetrafluoroethyllining lining and be placed in added by 100mL polytetrafluoroethyllining lining and support, add water 3mL simultaneously under support, then in sealing autoclave, reacts 56h in 160 DEG C.The molecular sieve through modified with noble metals of gained is dried 120 minutes in 150 DEG C, then at 540 DEG C of roasting temperature 6h, obtains the TS-1 molecular sieve B of modified with noble metals.
Embodiment 3
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.
Getting 12g TS-1 molecular sieve, is that 16.3% TPAOH solution (containing 0.02g acid chloride) mixes with 0.5g Tri N-Propyl Amine and 7.5g mass concentration.Said mixture is loaded 50mL polytetrafluoroethyllining lining, then be placed in the added support of 100mL polytetrafluoroethyllining lining, then in sealing autoclave, react 48h in 175 DEG C.The molecular sieve through modified with noble metals of gained is dried 240 minutes in 90 DEG C, then at 700 DEG C of roasting temperature 2h, obtains the TS-1 molecular sieve C of modified with noble metals.
Embodiment 4
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.
Get 12g TS-1 molecular sieve, be that 16.3% TPAOH solution (containing 0.005g ammonia chloride palladium) mixes with the Tetramethylammonium hydroxide of 3g 12% with 3.5g mass concentration, said mixture is placed in 100mL polytetrafluoroethyllining lining, then in sealing autoclave, reacts 36h in 150 DEG C.The molecular sieve through modified with noble metals of gained is dried 180 minutes in 150 DEG C, then at 530 DEG C of roasting temperature 5h, obtains the TS-1 molecular sieve D of modified with noble metals.
Embodiment 5
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.
Getting 14g TS-1 molecular sieve, is that 28% tetramethyl ammonium hydroxide solution (containing 0.2g carbonate palladium) mixes with 0.5g di-n-propylamine and 6.5g mass concentration.Said mixture is loaded 50mL polytetrafluoroethyllining lining and be placed in added by 100mL polytetrafluoroethyllining lining and support, add water 2mL simultaneously under it, then in sealing autoclave, reacts 56h in 150 DEG C.The molecular sieve through modified with noble metals of gained is dried 180 minutes in 150 DEG C, then at 550 DEG C of roasting temperature 3h, obtains the TS-1 molecular sieve E of modified with noble metals.
Embodiment 6
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.
Get 10g TS-1 molecular sieve, the trolamine aqueous solution (containing 0.01g palladium hydroxide) being 20% with 2.5g mass concentration mixes, said mixture is loaded 50mL polytetrafluoroethyllining lining and be placed in added by 100mL tetrafluoroethylene and support, add water 3mL simultaneously under it, then in sealing autoclave, reacts 24h in 135 DEG C.The molecular sieve through modified with noble metals of gained is dried 120 minutes in 160 DEG C, then at 650 DEG C of roasting temperature 4h, obtains the TS-1 molecular sieve F of modified with noble metals.
Embodiment 7
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.
Getting 10g TS-1 molecular sieve, is that 16.3% TPAOH solution (containing 0.08g hydrochloro-auric acid) mixes with 0.5g quadrol and 4.0g mass concentration.Said mixture is loaded 50mL polytetrafluoroethyllining lining, then be placed in the added support of 100mL polytetrafluoroethyllining lining, add water 5mL simultaneously under it, then in sealing autoclave, reacts 54h in 160 DEG C.The molecular sieve through modified with noble metals of gained is dried 120 minutes in 140 DEG C, then at 600 DEG C of roasting temperature 6h, obtains the TS-1 molecular sieve G of modified with noble metals.
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.
Getting 10g TS-1 molecular sieve, is that 16.3% TPAOH solution (containing 0.05g ammonia chloride ruthenium) mixes with 4.0g mass concentration.Said mixture is loaded 50mL polytetrafluoroethyllining lining, then be placed in the added support of 100mL polytetrafluoroethyllining lining, add water 5mL simultaneously under it, then in sealing autoclave, reacts 54h in 160 DEG C.The molecular sieve through modified with noble metals of gained is dried 120 minutes in 120 DEG C, then at 600 DEG C of roasting temperature 4h, obtains the TS-1 molecular sieve 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.
Getting 10g TS-1 molecular sieve, is that 16.3% TPAOH solution (containing 0.09g nitric acid ammonia iridium) mixes with 6.0g mass concentration.Said mixture is loaded 50mL polytetrafluoroethyllining lining, then be placed in the added support of 100mL polytetrafluoroethyllining lining, add water 5mL simultaneously under it, then in sealing autoclave, reacts 54h in 160 DEG C.The molecular sieve through modified with noble metals of gained is dried 120 minutes in 110 DEG C, then at 550 DEG C of roasting temperature 5h, obtains the TS-1 molecular sieve 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.
Getting 10g TS-1 molecular sieve, is that 14.6% TPAOH solution (containing 0.06g Silver Nitrate) mixes with 5.0g mass concentration.Said mixture is loaded 50mL polytetrafluoroethyllining lining, then be placed in the added support of 100mL polytetrafluoroethyllining lining, add water 5mL simultaneously under it, then in sealing autoclave, reacts 54h in 160 DEG C.The molecular sieve through modified with noble metals of gained is dried 120 minutes in 120 DEG C, then at 500 DEG C of roasting temperature 6h, obtains the TS-1 molecular sieve J of modified with noble metals.
Embodiment 11
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 Palladous chloride to substitute acid chloride, obtain the HTS K of modified with noble metals.
Embodiment 12
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 5 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 L 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:
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 example 1 | DB-1 | 2.6 | 89 |
As can be seen from Table 1, method of modifying gained molecular sieve of the present invention catalytic performance compared with comparative example gained molecular sieve DB-1 is more superior.So the inventive method not only maintains the superiority in performance, and can also production cost be reduced, alleviate environmental pollution.
Claims (8)
1. the modified with noble metals method of a HTS, it is characterized in that in airtight reactor, processing at least 2 hour at 100 ~ 200 DEG C by after HTS, noble metal source, organic alkali solution mixing, take out product drying at normal temperatures and pressures, HTS product that roasting obtains modified with noble metals, 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, the treatment capacity of HTS is at least 10g/L reactor volume.
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 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.
4., according to the process of claim 1 wherein, described noble metal source is selected from one or more the mixture in the simple substance of Ru, Rh, Pd, Re, Os, Ir, Pt, Au, Ag or 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), HTS is in quality gram, organic bases in mole, noble metal source is in 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), HTS is in quality gram, organic bases in mole, noble metal source is in precious metal simple substance mole.
7. according to the process of claim 1 wherein, treatment condition be in closed reactor 120 ~ 180 DEG C carry out 6 ~ 72 hours.
8. according to the process of claim 1 wherein, containing forming saturated steam at reaction conditions and the water yield being less than 1.0 with the weight ratio of HTS in reactor.
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| CN105293517B (en) * | 2014-06-24 | 2017-07-21 | 中国石油化工股份有限公司 | HTS and its preparation method and application and a kind of method of alkene direct oxidation |
| CN106031882A (en) * | 2015-03-10 | 2016-10-19 | 中国石油化工股份有限公司 | Molecular sieve containing precious metals, preparation method and applications thereof, and alkene direct oxidation method |
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| CN109574033A (en) * | 2017-09-28 | 2019-04-05 | 中国石油化工股份有限公司 | Molding Titanium Sieve Molecular Sieve containing noble metal and its preparation method and application and the method for producing hydrogen peroxide |
| WO2023116315A1 (en) * | 2021-12-22 | 2023-06-29 | 中国石油化工股份有限公司 | Titanium silicate molecular sieve, and nano-gold-loaded titanium silicate molecular sieve catalyst and preparation method therefor and use thereof |
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