CN108067294A - The catalyst and preparation method of package gold nano grain in molecular sieve crystal - Google Patents
The catalyst and preparation method of package gold nano grain in molecular sieve crystal Download PDFInfo
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- CN108067294A CN108067294A CN201711402248.0A CN201711402248A CN108067294A CN 108067294 A CN108067294 A CN 108067294A CN 201711402248 A CN201711402248 A CN 201711402248A CN 108067294 A CN108067294 A CN 108067294A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B01D53/34—Chemical or biological purification of waste gases
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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Abstract
The present invention discloses the catalyst and preparation method of package gold nano grain in a kind of molecular sieve crystal, belongs to metallic molecule sieve catalyst preparation field.The catalyst is prepared by Direct Hydrothermal method, can be used in the reaction of high temperature Oxidation of Carbon Monoxide.The preparation process of the catalyst is：Silicon source sour water solution is taken, adds silicon source, sodium hydroxide and metal precursor, Dynamic Hydrothermal kettle is placed it in after stirring evenly and carries out crystallization, the product that crystallization obtains, which is washed, filtered and dried, is made 5 molecular sieve catalysts of Au@ZSM.Using dynamic crystallization gold nano grain self assembly is promoted to enter inside molecular sieve crystal in the method for the present invention, organic formwork agent need not be used in building-up process, without addition crystal seed, and generated time greatly shortens.In 5 catalyst of Au@ZSM prepared by the present invention, gold nano grain is wrapped in inside 5 molecular sieve crystals of ZSM, and successive reaction remains to that original dimension is kept to inactivate without agglomeration for 8 days in high temperature reaction of carbon monoxide.
Description
Technical field：
The invention belongs to metallic molecule sieve catalyst preparation fields, are related to package in a kind of molecular sieve crystal of high stability
Au@ZSM-5 catalyst, preparation method and its application in the reaction of high temperature Oxidation of Carbon Monoxide of gold nano grain.
Background technology：
Since Japanese Scientists Haruta etc. (Chem.Lett., 1987,16,405；J.Catal.,1989,115,301)
It was found that since gold nano grain has mirable activity in the low-temperature oxidation reaction of carbon monoxide, gold nano catalyst
Research now has spread over the weights such as epoxidation of propylene, selective oxidation, selection hydrogenation and C-C couplings as the hot spot of catalytic field
In reacting.Numerous studies show the size of gold grain be an important factor for influencing golden catalytic activity (Science, 2008,
321,1331).The reduction of gold grain size can promote the objects such as the atomic ratio of its electronic structure, crystalline structure, surface and body phase
Great variety occurs for Physicochemical property, and then generates unique catalytic performance.But gold grain extremely easily aggregation at high temperature
It grows up and limits its application with critical defects such as reaction stability differences, become urgent problem to be solved in Au catalyst application.
Molecular sieve has regular pore passage structure and hole cage, big specific surface area, high thermal stability etc., thus as extensive
The metal particle catalyst carrier of accreditation.Drawn using conventional post treatment method (infusion process, ion-exchange etc.) into molecular sieve
The gold nanoparticle entered be it is simple be attached in molecular sieve surface or duct, therefore prepare the high-temperature process needed for molecular sieve
Hot conditions in step or reaction still result in the migration of gold nanoparticle, aggregation, and then substantially reduce catalyst
Activity and reusability.To solve the problems, such as this, researchers are directed to metal nanoparticle being assembled into molecular sieve crystal
Portion makes metal nanoparticle be subject to the limitation of framework of molecular sieve and improve anti-sintering property.However metal nanoparticle is introduced
Synthesis inside to molecular sieve crystal is extremely difficult.In the recent period, Egeblad etc. is used by metal dispersion into silicon source, and organic
Gold is directly assembled to inside Silicalite-1 molecular sieve crystals under the guiding of template (Angew.Chem.Int.Ed.,
2010,49,3504)；Palladium (Pd) nano-particle is introduced into inside Beta and MOR molecular sieve crystals by Xiao Fengshou etc. using crystal seed method
(Angew.Chem.Int.Ed., 2017).These methods synthesize to obtain catalyst all with excellent performance, however synthesize
Organic formwork agent or crystal seed have inevitably been used in journey.However, using organic-free template, the direct dynamic without crystal seed
The molecular sieve catalyst that hydro-thermal method one-step synthesis obtains package gold nanoparticle in crystal is not reported so far.
ZSM-5 molecular sieve has unique three-dimensional straight channel, high silica alumina ratio, industrially with extensive use.By gold
Nano-particle is introduced into ZSM-5 molecular sieve crystals, and the 3 D pore canal of ZSM-5 molecular sieve forms limitation to gold nano grain and makees
With the anti-sintering property and reaction stability of gold nano grain can be effectively improved.Thus, using organic-free template without crystalline substance
The one step hydro-thermal green synthesis method of dynamic of kind prepares and gold nano grain is wrapped up in the molecular sieve crystal with high stability energy
Au@ZSM-5 catalyst has great importance.
The content of the invention：
It is an object of the invention to provide catalyst and its preparation sides that gold nano grain is wrapped up in a kind of molecular sieve crystal
Method is directly prepared by the method for a step dynamic autoclaved technology, and organic formwork agent and crystalline substance need not be used in the synthetic method
Kind.
The present invention mixes Jin Yuan with the sial Primogel of synthesis of molecular sieve, in golden presoma and sial Primogel
Primary structure units combine, then the continuous self assembly of primary structure units containing gold during dynamic thermostatic heating stirring
It grows up, and the mode of dynamic agitation promotes gold to be dispersed in synthesized gel rubber, ultimately produces package gold nano grain in crystal
Au@ZSM-5 molecular sieves.Au@ZSM-5 molecular sieves catalyst prepared by the present invention is reacted in the high-temperature oxydation of carbon monoxide
In there is the stability of superelevation, successive reaction 8 days still keeps grain size and catalytic performance constant, has very strong anti-sintering
Performance and reaction stability.
The catalyst of package gold nano grain, Jenner described in the catalyst in a kind of molecular sieve crystal provided by the invention
Rice grain is wrapped the crystals for being embedded in molecular sieve ZSM-5, and gold nano grain is limited be subject to molecular sieve pore passage and improved
Its anti-sintering property, keeps high stability in pyroreaction；Using sour water solution silicon source in the catalyst preparation, both without using having
Machine template, it is not required that using crystal seed, in preparation process by the way of dynamic crystallization.
The preparation method of the catalyst of package gold nano grain in a kind of molecular sieve crystal provided by the present invention, this method tool
Body step is as follows：
(1) mixture of silicon source and water is placed in acid medium and hydrolyzed, when stirring 2~12 is small at 20~95 DEG C of temperature,
Mixture solution after being hydrolyzed；
(2) mixed solution of silicon source and water is added in the mixture solution that step (1) obtains, added after mixing
Inorganic base adjusts mixed liquor pH value to alkalescence, and obtained mixture, which is placed at 20~60 DEG C of temperature, stirs 1~15h of aging；
(3) golden presoma is added in into the mixture after step (2) aging, reaction mixing is obtained after stirring 5~60min
Object, the molar ratio of the reaction mixture total composition are：SiO2/Al2O3=20-100, Au/SiO2=0.05-0.4, H2O/SiO2
=10-60；
(4) reaction mixture obtained by step (3) is transferred in the stainless steel dynamic response kettle equipped with polytetrafluoro liner, with
At a temperature of the stainless steel dynamic response kettle is heated to 100~180 DEG C afterwards, using dynamic thermostatic crystallization, 8~72h of crystallization is treated
Product is taken out into reaction kettle afterwards, product is washed after being cooled to room temperature, is filtered, crystal is dried to obtain in 80~120 DEG C of baking ovens
The solid product Au@ZSM-5 molecular sieves of interior encapsulation gold nano grain.
The silicon source is any one in methyl orthosilicate, ethyl orthosilicate, Ludox and silica；Acid medium
For the aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid, pH value is 1.0~6.0.
Source of aluminium is any one in aluminum nitrate, sodium aluminate, aluminum sulfate and aluminium isopropoxide.The gold presoma is chlorine
Auric acid or chlorauride.The mode of the dynamic crystallization is dynamic magnetic agitation, the electronic propeller agitation of dynamic and dynamic rotary are stirred
Any one in mixing
Without using organic formwork agent and crystal seed in the preparation method of the present invention, thermal energy consumption and ring that roasting is brought are avoided
Border is polluted, and preparation process is more environmentally protective；The dynamic agitation crystal pattern that the present invention uses can be effectively promoted gold nano
Particles self assemble enters inside molecular sieve crystal, and gold nanometer particle grain size is small, is evenly distributed；Prepared Au@ZSM-5 molecules
In sieve catalyst, gold nano grain is encapsulated in inside molecular sieve crystal well, the table in the reaction of carbon monoxide high-temperature oxydation
Reveal high anti-sintering property and reaction stability.
Description of the drawings：
Fig. 1 is the XRD diagram of sieve sample, and wherein a is the XRD diagram of 1 gained sieve sample of examples of implementation, and b is to implement
The XRD diagram of 3 gained sieve sample of example；
Fig. 2 is the HRTEM figures of 1 gained sieve sample of examples of implementation, and wherein Fig. 2 b are the amplifications of Fig. 2 a；
Fig. 3 is performance test of 1 sieve sample of examples of implementation in 400 DEG C of Oxidation of Carbon Monoxide react；
Fig. 4 is HRTEM of the sieve sample after Oxidation of Carbon Monoxide 8 days in examples of implementation 1.
Specific embodiment：
The present invention is described further With reference to embodiment, but not thereby limiting the invention.
Embodiment 1：Ethyl orthosilicate 10g is taken, adds in the 0.12M aqueous hydrochloric acid solutions of 32ml thereto, adjusts the water of solution
PH value is solved to 1.0, when 20 DEG C of stirring hydrolysis 12 are small, 0.75g aluminum sulfate and the sodium hydroxide of 0.8g added, stirs aging
It wherein adds in gold chloride 0.1g after 10h to this again, stirs 0.5h so that the molar ratio of mixture total composition is SiO2:
0.05Al2O3:40H2O:0.005Au is then encapsulated into high pressure Dynamic Hydrothermal reaction kettle, the crystallization 48h at 180 DEG C, by institute
It obtains product to wash to neutrality, Au@ZSM-5 molecular sieves is obtained after centrifugation, dry, roasting.Its X-ray diffraction spectrogram (XRD) is shown in
A in Fig. 1.
Evaluating catalyst method：The catalytic oxidation of carbon monoxide carries out in fixed-bed quartz reactor.Catalyst
Dosage is 10mg, and unstripped gas is carbon monoxide and oxygen, and mixed gas flow 33mL/min, reaction temperature is 400 DEG C.Activity
Test surfaces, the Au@ZSM-5 catalyst prepared using this method sustained response at 400 DEG C are active constant after 8 days.One oxygen
Change the test of carbon reactivity worth and see Fig. 3.Catalyst sustained response after 8 days at 400 DEG C, the Au being wrapped in molecular sieve crystal
Nanoparticle size is constant, and HRTEM figures are shown in Fig. 4.
Embodiment 2：According to the operating procedure and operating condition of embodiment 1, the difference is that improving the addition of gold chloride
Amount to 0.6g, crystallization time 72h, the product finally obtained is Au@ZSM-5 catalyst.The evaluation method of catalyst is the same as implementation
Example 1.Active testing shows using Au@ZSM-5 catalyst prepared by this method in Oxidation of Carbon Monoxide reaction, at 400 DEG C
8 days activity of sustained response are constant.
Embodiment 3：According to the operating procedure and operating condition of embodiment 1, the difference is that silicon source is methyl orthosilicate,
The acid solution of silicon source is hydrolyzed as hydrochloric acid, the product finally obtained is Au@ZSM-5 catalyst.The XRD diagram of product is shown in the b in Fig. 1.
The evaluation method of catalyst is the same as embodiment 1.Active testing shows using Au@ZSM-5 catalyst prepared by this method in an oxidation
In oxidation of coal reaction, 8 days activity of sustained response are constant at 400 DEG C.
Embodiment 4：According to the operating procedure and operating condition of embodiment 1, the difference is that silicon source is Ludox, hydrolysis
The acid solution of silicon source is nitric acid, and the product finally obtained is Au@ZSM-5 catalyst.The evaluation method of catalyst is the same as embodiment 1.
Active testing shows using Au@ZSM-5 catalyst prepared by this method in Oxidation of Carbon Monoxide reaction, continues at 400 DEG C anti-
Answer 8 days activity constant.
Embodiment 5：According to the operating procedure and operating condition of embodiment 1, the difference is that silicon source is silica, it is brilliant
The change time is 50h, and the product finally obtained is Au@ZSM-5 catalyst.The evaluation method of catalyst is the same as embodiment 1.Active testing
Show using Au@ZSM-5 catalyst prepared by this method in Oxidation of Carbon Monoxide reaction, sustained response work in 8 days at 400 DEG C
Property is constant.
Embodiment 6：According to the operating procedure and operating condition of embodiment 1, the difference is that silicon source is sodium aluminate, hydrolysis
The acid solution of silicon source is phosphoric acid, and the product finally obtained is Au@ZSM-5 catalyst.The evaluation method of catalyst is the same as embodiment 1.
Active testing shows using Au@ZSM-5 catalyst prepared by this method in Oxidation of Carbon Monoxide reaction, continues at 400 DEG C anti-
Answer 8 days activity constant.
Embodiment 7：According to the operating procedure and operating condition of embodiment 1, the difference is that silicon source is aluminium isopropoxide, most
The product obtained eventually is Au@ZSM-5 catalyst.The evaluation method of catalyst is the same as embodiment 1.Active testing shows using we
Au ZSM-5 catalyst prepared by method is in Oxidation of Carbon Monoxide reaction, and 8 days activity of sustained response are constant at 400 DEG C.
Embodiment 8：According to the operating procedure and operating condition of embodiment 1, the difference is that silicon source is aluminum nitrate, finally
Obtained product is Au@ZSM-5 catalyst.The evaluation method of catalyst is the same as embodiment 1.Active testing shows using this method
The Au@ZSM-5 catalyst of preparation is in Oxidation of Carbon Monoxide reaction, and 8 days activity of sustained response are constant at 400 DEG C.
Embodiment 9：According to the operating procedure and operating condition of embodiment 1, the difference is that the hydrolysis medium of silicon source is
Hydrochloric acid solution, the product finally obtained are Au@ZSM-5 catalyst.The evaluation method of catalyst is the same as embodiment 1.Active testing table
It is bright, using Au@ZSM-5 catalyst prepared by this method in Oxidation of Carbon Monoxide reaction, 8 days activity of sustained response at 400 DEG C
It is constant.
Embodiment 10：According to the operating procedure and operating condition of embodiment 1, difference is chlorauride in Jin Yuan, finally
Obtained product is Au@ZSM-5 catalyst.The evaluation method of catalyst is the same as embodiment 1.Active testing shows using this method
The Au@ZSM-5 catalyst of preparation is in Oxidation of Carbon Monoxide reaction, and 8 days activity of sustained response are constant at 400 DEG C.
Claims (6)
- A kind of 1. catalyst of package gold nano grain in molecular sieve crystal, it is characterised in that gold nano described in the catalyst Grain is wrapped the crystals for being embedded in molecular sieve ZSM-5, and gold nano grain is limited be subject to molecular sieve pore passage and improves it and resist Sintering character keeps high stability in pyroreaction；Using sour water solution silicon source in the catalyst preparation, both without using organic mould Plate agent, it is not required that using crystal seed, in preparation process by the way of dynamic crystallization.
- 2. the preparation method of catalyst described in claim 1, it is characterised in that this method is as follows：(1) mixture of silicon source and water is placed in acid medium and hydrolyzed, when stirring 2~12 is small at 20~95 DEG C of temperature, obtained Mixture solution after hydrolysis；(2) mixed solution of silicon source and water is added in the mixture solution that step (1) obtains, added after mixing inorganic Alkali adjusts mixed liquor pH value to alkalescence, and obtained mixture, which is placed at 20~60 DEG C of temperature, stirs 1~15h of aging；(3) golden presoma is added in into the mixture after step (2) aging, obtains reaction mixture after stirring 5~60min, institute The molar ratio for stating reaction mixture total composition is：SiO2/Al2O3=20-100, Au/SiO2=0.05-0.4, H2O/SiO2=10- 60；(4) reaction mixture obtained by step (3) is transferred in the stainless steel dynamic response kettle equipped with polytetrafluoro liner, then will The stainless steel dynamic response kettle is heated at a temperature of 100~180 DEG C, will after 8~72h of crystallization using dynamic thermostatic crystallization Product takes out reaction kettle, washs product after being cooled to room temperature, filters, is dried to obtain in crystal and seals in 80~120 DEG C of baking ovens Fill the solid product Au@ZSM-5 molecular sieves of gold nano grain.
- 3. preparation method according to claim 2, it is characterised in that the silicon source for methyl orthosilicate, ethyl orthosilicate, Any one in Ludox and silica；Acid medium is any one in the aqueous solution of sulfuric acid, hydrochloric acid, phosphoric acid or nitric acid Kind, pH value is 1.0~6.0.
- 4. preparation method according to claim 2, it is characterised in that source of aluminium be aluminum nitrate, sodium aluminate, aluminum sulfate and Any one in aluminium isopropoxide.
- 5. preparation method according to claim 2, it is characterised in that the gold presoma is gold chloride or chlorauride.
- 6. preparation method according to claim 2, it is characterised in that the mode of the dynamic crystallization for dynamic magnetic agitation, Dynamically electronic propeller agitation and dynamic rotary stirring in any one.
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Cited By (4)
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| CN111659457A (en) * | 2020-05-12 | 2020-09-15 | 浙江大学 | Preparation method of catalyst for catalytic elimination of carbon monoxide at room temperature |
| CN112844457A (en) * | 2021-02-03 | 2021-05-28 | 浙江工业大学上虞研究院有限公司 | Preparation of catalyst and application of catalyst in toluene methanol alkylation reaction |
| CN113457721A (en) * | 2021-07-21 | 2021-10-01 | 昆明理工大学 | High-temperature oxygen-deficient catalytic combustion catalyst and preparation method and application thereof |
| CN114160130A (en) * | 2021-12-21 | 2022-03-11 | 黑龙江省能源环境研究院 | Limited-area nanogold ordered porous monolithic catalyst and preparation method thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111659457A (en) * | 2020-05-12 | 2020-09-15 | 浙江大学 | Preparation method of catalyst for catalytic elimination of carbon monoxide at room temperature |
| CN111659457B (en) * | 2020-05-12 | 2021-06-08 | 浙江大学 | Preparation method of catalyst for catalytic elimination of carbon monoxide at room temperature |
| CN112844457A (en) * | 2021-02-03 | 2021-05-28 | 浙江工业大学上虞研究院有限公司 | Preparation of catalyst and application of catalyst in toluene methanol alkylation reaction |
| CN113457721A (en) * | 2021-07-21 | 2021-10-01 | 昆明理工大学 | High-temperature oxygen-deficient catalytic combustion catalyst and preparation method and application thereof |
| CN113457721B (en) * | 2021-07-21 | 2022-11-15 | 昆明理工大学 | High-temperature oxygen-deficient catalytic combustion catalyst and preparation method and application thereof |
| CN114160130A (en) * | 2021-12-21 | 2022-03-11 | 黑龙江省能源环境研究院 | Limited-area nanogold ordered porous monolithic catalyst and preparation method thereof |
| CN114160130B (en) * | 2021-12-21 | 2024-03-19 | 黑龙江省能源环境研究院 | Ordered porous monolithic catalyst of limited-domain nano-gold and preparation method thereof |
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