CN102513151A - Method for preparing high-performance nano gold catalyst - Google Patents
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- CN102513151A CN102513151A CN2011100631170A CN201110063117A CN102513151A CN 102513151 A CN102513151 A CN 102513151A CN 2011100631170 A CN2011100631170 A CN 2011100631170A CN 201110063117 A CN201110063117 A CN 201110063117A CN 102513151 A CN102513151 A CN 102513151A
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a method for preparing a high-performance nano gold catalyst, characterized by introducing basic nitrogen atoms having coordination ability into the skeletal structure of a titanium-silicon molecular sieve by high temperature modification, modulating and shielding the surface acidity of the titanium-silicon molecular sieve, enhancing the interaction between gold and the carrier, increasing the capture rate and dispersiveness of gold, inhibiting the migration of the gold particles on the carrier surface, so as to increasing the catalytic activity and stability of the nano gold catalyst. The prepared nano gold catalyst is mainly used for preparing epoxypropane through directly carrying out epoxidation on propylene in the coexistence of hydrogen/oxygen and used for other catalytic oxidation reactions.
Description
Technical field
The present invention relates to a kind of preparation method of high-performance nano Au catalyst, prepared nano catalyst can be used for hydrogen and oxygen concurrent conditions used for preparing propylene oxide by direct propylene oxidation, also can be used for other catalytic oxidation.
Background technology
Expoxy propane (PO) is a kind of important Organic Chemicals, is the third-largest derivative of propylene, is mainly used in to produce PPG, propane diols and other chemical products.The production method that PO is gone up in industry at present mainly contains chlorohydrination and conjugated oxidation.Domesticly mostly adopt chlorohydrination, but chlorohydrination exists problems such as equipment corrosion and environmental pollution be serious, produces 1tPO and produces the chloride organic wastewater of 60t approximately.The shortcoming of conjugated oxidation is need be integrated with the process of co-product styrene (tert-butyl alcohol), receive market limitation to a certain degree, and this process is complicated, invests huge.In recent years, through the unremitting effort of researcher, with H
2O
2For the oxidation catalyst of cyclopropene development aspect of oxidant having obtained outstanding progress.Particularly HTS (like TS-1) catalyst is with H
2O
2For the successful Application in the propylene ring oxidation reaction of oxidant is that PO synthetic opened up new green catalysis approach (Clerici, M.G.J Catal, 1991,129 (1): 159).Its shortcoming is that Dilute Hydrogen Peroxide Solution (30%) cost is higher for this technology, and freight volume is big, and follow-up distillation load is too big.To H
2O
2The problem that cost is still too high, people have carried out many synthetic H of original position in reaction system that how to lay particular emphasis on subsequently
2O
2And be used for the research of propylene ring oxidation reaction.Dow and BASF AG adopt anthraquinone original position to synthesize H
2O
2And being used for PO production, this integrated chemical process has greatly been reduced H
2O
2Cost, make via H
2O
2The industrialization of propylene catalytic epoxidation become possibility.Because this technology is without H
2O
2, greatly reduce production cost.The reactor pattern is that gas one is liquid-solid three-phase suspension bed, pressurized operation, but course of reaction generates a part of propane accessory substance inevitably, and need the higher propylene of purity.
Is the direct epoxidation technology of propylene gas phase of raw material with the molecular oxygen, has advantages such as environmental friendliness and atom economy property because of it and receive people day by day and pay close attention to widely.Gas-solid phase catalysis epoxidation can be avoided because of environmental problems that organic solvent brought such as use methyl alcohol, and is even more ideal Green Chemistry process.The researcher adopts Au/TiO
2With catalyst such as Au/ molecular sieve containing titaniums, realized H
2And O
2Propylene gas-phase epoxidation reaction under the coexistence has obtained the PO selectivity more than 90% (Hayashi, T.J.Catal., 1998,178 (2): 566; Chowdhury.B.Angew Chem Int Ed, 2006,45 (3): 412).Owing to also relate to this research focus of golden catalysis simultaneously, this system has caused extensive concern both domestic and external (Hashmi, A.S.K.Angew.Chem.Int.Ed., 2006,45:7896, Arcadi, A.Chem.Rev., 2008,108 (8): 3266).Nano catalyst has good low-temperature catalytic oxidation activity, is one of great discovery of catalytic field in recent years.Found Au catalyst at present in (1) environmental improvement, like the organic matter catalytic combustion, hydrogen sulfide, sulfur dioxide are eliminated dioxindole oxidation Decomposition, NO
xReduction is eliminated.(2) Hydrogen Energy exploitation is like the CO oxidation in CO oxidation and the hydrogen stream, water gas shift reation.(3) chemical reaction process is an alkene like acetylene hydrochlorination, the direct synthesize hydrogen peroxide of hydrogen-oxygen, propine selective hydration, from cruel ammoxidation of the direct synthesis of acetic acid ethene of acetate, ethene and oxygen etc.(4) selective oxidation has a good application prospect like fields such as alkene epoxidation, pure oxidation system aldehyde or acid, formoxy-system carboxylic acid, glucose oxidase preparation of gluconic acid.
But there is the difficult problem of a poor stability in nano-Au catalyst, and generally needed only tens hours even shorter service life, therefore improves the stability of Au catalyst, and prolonging its service life is that the Au catalyst is realized the key issue that commercial applications will solve.In order to solve nano gold catalysis is propylene conversion low (＜5%), the H that exists in the direct epoxidation systems of propylene gas phase of raw material with the molecular oxygen
2Utilization rate low with problems such as catalysqt deactivation is fast, people had carried out multi-faceted improvement to this agent system in recent years.As adopt CsCl and Ba (NO
3)
2Deng alkali metal or alkaline-earth metal salt decorative (Uphade, B.S.Appl.Catal.A, 2000,190 (1-2): 43; Sinha, A.K.Angew.Chem.Int.Ed., 2004,43 (12): 1546) can catalyst neutralisation the acidic site on surface, further improve the PO selectivity; The three-dimensional vermiform titanium-containing meso-porous molecular sieve that adopts the macropore structure is as carrier (Sinha, A.K.Angew.Chem.Int.Ed., 2004,43 (12): 1546), can overcome the restriction of mass transfer; Handle through catalyst surface being carried out silanization, can strengthen the hydrophobicity of catalyst surface, make PO desorption more easily; In reaction gas, add trimethylamine to poison Lewis acidic site Ti isolated on the carrier
4+, can suppress the follow-up conversion of PO, also can suppress H simultaneously
2Burning on the Au particle surface improves H
2The stability of utilization rate and catalyst (Chowdhury.B.Angew Chem Int Ed, 2006,45 (3): 412).(as: carrier contains a kind of element in alkali metal, alkaline-earth metal, the rare earth metal to US 2001002015-A1 through five kinds of methods; The carrier silanization, 500 ℃～1200 ℃ high-temperature calcination) oxide carrier is handled reduction its acidity (being no more than 0.15mmol/g) and improved the nanometer gold catalyst catalyzing performance.Use NH
3NO
3(2005,232 (1): prepare nano catalyst with deposition sedimentation again 38), the utilization rate of gold has improved four times, has generated the NH on gold-ammino-complex and the carrier on the catalyst for Cumaranatunge, L.J.Catal. to modify micropore titanium silicon molecular sieve TS-1
4 +Remove residual Cl
-Improved the catalytic performance of catalyst, the generating rate of PO has reached 134gPOh
-1Kg
Cat -1Use NH
3NO
3Modify mesoporous titanium-silicon molecular screen Ti-SBA-15 (Sacaliuc-Parvulescu, E.J.Catal., 2008,259 (1): 43), thereby increased carrier surface-OH quantity and Ti near the concentration of amine increase the dispersion that golden adsorption potential also helps nanogold particle.So the performance of carrier and carrier surface is directly determining the catalytic performance of nano catalyst, the existence of carrier has promoted the stability of nano Au particle.In addition,, perhaps mix other element and take blocking effect, also can suppress the migration of gold, improve the stability of Au catalyst through letting gold and other metal form alloy.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high-performance nano Au catalyst; Mainly be through high temperature modified, in the skeleton structure of HTS, introduce basic nitrogen atom, the surface acidity of modulation and shielding HTS with coordination ability; Strengthen the interaction between gold and the carrier; Improve the capture rate and the decentralization of gold, suppress the migration of gold grain, thereby improve the catalytic activity and the stability of nano catalyst at carrier surface.The nano catalyst of the present invention preparation is mainly used in that propylone direct opoxidation prepares propylene oxide reaction under the hydrogen/oxygen concurrent conditions, also can be used for other catalytic oxidation.
The present invention provides a kind of preparation method of high-performance nano Au catalyst, it is characterized in that said nano catalyst prepares through following steps:
(1) preparation of HTS matrix: under high degree of agitation that titanium source, silicon source, template and distilled water is evenly mixed according to certain ratio, stirring at room 1-2h obtains HTS precursor colloidal sol.Precursor colloidal sol is changed in the autoclave with PTFE lining, handle 10-96h 50-200 ℃ of crystallization.After crystallization finishes, after supercooling, filtering perhaps centrifugation, washing and drying and other steps, in air atmosphere, remove template at last, obtain the HTS matrix in 550 ℃ of roastings.
(2) the high temperature modified processing of HTS: the HTS matrix that step (1) prepares is put into tube furnace constant temperature zone, at N
2Protection is warming up to temperature required down; Feed NH then
3Or at high temperature can decompose and produce NH
3Other alkaline gas, after certain hour is handled in modification under this temperature at N
2Room temperature is reduced in protection nature cooling down, obtains nitrogenous HTS carrier.
(3) preparation of nano catalyst: with certain density gold chloride (HAuCl
4) solution is heated to 70 ℃, under agitation the pH with solution is adjusted to 6-9, and the nitrogenous HTS that takes by weighing certain mass joins in the chlorauric acid solution, after continuing to stir 1h solution is cooled to room temperature, obtains nano catalyst through filtration, washing, drying.
The said titanium of step among the preparation method provided by the invention (1) source is water-soluble or titanium compound that can hydrolysis in water, and these compounds can be TiCl
3, TiCl
4, butyl titanate (TBOT), metatitanic acid tetra isopropyl ester (TIOP), tetraethyl titanate (TEOT).
The said silicon of step among the preparation method provided by the invention (1) source can be Ludox, silicon gel, the positive esters of silicon acis of tetramethyl (TMOS), tetraethyl orthosilicate ester (TEOS).
The said template of step among the preparation method provided by the invention (1) can be TMAH (TMAOH), tetraethyl ammonium hydroxide (TEAOH), TPAOH (TPAOH), TBAH (TBAOH); Also can be quaternary ammonium salt and/or quaternary ammonium base cationoid surfactant; Also can be primary amine class neutral surface active agent, can also be the polyvinyl alcohol nonionic surface active agent.
The Ti content of the said HTS of step among the preparation method provided by the invention (1) is 0.1～10wt%, preferred 0.5～3wt%.
The said high-temperature process temperature of step among the preparation method provided by the invention (2) is 300-1200 ℃, preferred 600-900 ℃.
The said high-temperature process time of step among the preparation method provided by the invention (2) is 1-36 hour, preferred 3-20 hour.
The concentration of the said chlorauric acid solution of step among the preparation method provided by the invention (3) is 0.1-50mM, preferred 1-10mM.
The said pH conditioning agent of step among the preparation method provided by the invention (3) can be NaOH, KOH, Na
2CO
3, NaHCO
3, ammoniacal liquor, urea etc.
The ratio of said nitrogenous HTS of step among the preparation method provided by the invention (3) and chlorauric acid solution is 1-100g/L, preferred 5-50g/L.
The specific embodiment
Below specify through concrete embodiment:
Embodiment 1: the preparation of nitrogenous titanium-silicon molecular sieve TS-1
With ethyl orthosilicate (TEOS) is that silicon source, butyl titanate (TBOT) are that titanium source, TPAOH (TPAOH) are template.At first, the TBOT of required proportioning and TEOS are mixed the TPAOH solution that the back slowly drips aequum under the ice-water bath condition, the control rate of addition produces white precipitate to avoid the quick hydrolysis of TBOT.Dropwise continued and at room temperature stir 1-2h and obtain colourless transparent solution, slowly drip a certain amount of water then, again gained solution is removed the ethanol that the TEOS hydrolysis produces in 70-80 ℃ of heating evaporation, obtaining molar ratio of material is 1SiO
2: 0.01TiO
2: 0.3TPAOH: 28H
2The HTS precursor colloidal sol of O.At last, precursor colloidal sol is transferred in the stainless steel autoclave with Telfon substrate in 175 ℃ of following crystallization processing 72h.Crystallization finishes after after cooling, centrifugation, washing and the drying, in air, obtain micropore titanium silicon molecular sieve TS-1 in 550 ℃ of roasting 5h at last.
The titanium-silicon molecular sieve TS-1 3.5g that takes by weighing above-prepared puts into the tube furnace constant temperature zone; Under nitrogen atmosphere, be raised to 700 ℃ through 5h by room temperature, nitrogen flow 100ml/min feeds ammonia then; Ammonia flow is 80ml/min; Carry out high temperature modified processing 3h, drop to room temperature at nitrogen atmosphere at last, obtain nitrogenous titanium-silicon molecular sieve TS-1 N_3.The Ti content of sample is 0.82wt%, and the BET specific area is 412m
2/ g.
Embodiment 2: the preparation of nano catalyst
100ml chlorauric acid solution (1.2mM) is heated to 70 ℃, with the N of 1M
2CO
3Solution is regulated pH to 8.9.Under high degree of agitation, add the nitrogenous titanium-silicon molecular sieve TS-1 N_3 that 1 gram embodiment 1 prepares, after the stirring reaction 15min, add the Ba (NO of 5ml 0.04mol/L
3)
2Solution continues to stir 45min under same temperature.Be cooled to the separating obtained sample of suction filtration after the room temperature, after the washing of 50 ml distilled waters, drying at room temperature is spent the night in vacuum drying chamber, obtains nano catalyst at 300 ℃ of roasting 4h at last, and the average grain diameter of nano Au particle is 2-3nm.
Embodiment 3: used for preparing propylene oxide by direct propylene oxidation under the hydrogen/oxygen concurrent conditions
The catalytic performance of nano catalyst is to estimate on 6 millimeters the quartz ampoule tubular microreactors at internal diameter.Catalyst amount is 0.3g, and the flow of hydrogen, oxygen, propylene and nitrogen is respectively 3.5,3.5,3.5 and 24.5ml/min, and air speed is 7000, and reaction pressure is 0.1MPa.Before beginning reaction, catalyst is used the H of 12.5Vol% respectively under 250 ℃
2And O
2Preliminary treatment 30min is then at N
2Be cooled to 150 ℃ in the atmosphere, logical people H
2, C
3H
6And O
2Begin reaction.Product is with FID and the on-line analysis of TCD gas-chromatography are housed.The performance of catalyst is weighed with the generating rate of the selectivity of propylene conversion, expoxy propane and expoxy propane and is compared.Catalytic reaction result lists in the table one.
Embodiment 4: the preparation of nitrogenous HTS carrier
After mixing 2.0g polysorbas20,24g deionized water and 27.4g TPAOH, slowly add 36g TEOS, stir 1h; Obtain settled solution, drip the aqueous isopropanol 6.0g that contains 0.90g TBOT again, continue to stir 1h; Obtain the slightly settled solution of thickness; Change in the stainless steel autoclave that contains the Telfon substrate in 160 ℃ of following crystallization 18h, cooled and filtered or centrifugation, product uses deionized water fully to wash to pH to be neutrality; Dry under 100 ℃ of conditions, in air, behind 550 ℃ of roasting 5h, obtain micro porous molecular sieve TS-1.
The HTS 6.5g that takes by weighing above-prepared puts into tube furnace; Under nitrogen atmosphere, be warmed up to 700 ℃ through 5h by room temperature, nitrogen flow 400ml/min feeds ammonia then; Ammonia flow is flow 80ml/min; Carry out modification and handle 15h, drop to room temperature at nitrogen atmosphere at last, obtain nitrogenous titanium-silicon molecular sieve TS-1 N_15.The Ti content of sample is 1.32wt%.
Embodiment 5: the preparation of nano catalyst
100ml chlorauric acid solution (1.2mM) is heated to 70 ℃ is heated to 70 ℃; Be that to regulate the pH value be about 7 for the NaOH solution of 1mol/L with the molar concentration; The carrier molecule sieve TS-1 N_15 that takes by weighing 1g joins in this solution, stirs 1h; Stop heating,, wash with the 50ml deionized water with solution room temperature cooled and filtered; At last at ambient temperature, vacuum drying obtains Au catalyst.
Embodiment 6: used for preparing propylene oxide by direct propylene oxidation under the hydrogen/oxygen concurrent conditions
Evaluating catalyst is undertaken by the mode of embodiment 3, and the preliminary treatment of different is catalyst changes activation in reaction gas atmosphere into, and 4h is warmed up to 150 ℃, and catalytic reaction result lists in the table one.
Embodiment 7: according to the preparation method of embodiment 4, the quality of butyl titanate was 0.6 gram when different was preparation.The Ti content of sample is 0.80wt%, and the BET specific area is 471m
2/ g.Mode according to embodiment 5 preparation nano catalysts and embodiment 6 is estimated catalytic performance, and reaction result is listed in the table one.
Embodiment 8: use the carrier among the embodiment 7, according to the preparation method of embodiment 5, different is that chlorauric acid solution concentration is (1.9mM).Mode according to embodiment 6 is estimated catalytic performance, and reaction result is listed in the table one.
Embodiment 9: according to the preparation method of embodiment 7, different is that chlorauric acid solution concentration is (3.6mM).Mode according to embodiment 6 is estimated catalytic performance, and reaction result is listed in the table one.
Embodiment 10: according to the preparation method of embodiment 4, different is is 20h the high-temperature process time.Mode according to embodiment 5 preparation nano catalysts and embodiment 6 is estimated catalytic performance, and reaction result is listed in the table one.
Embodiment 11: according to the preparation method of embodiment 4, different is is 36h the high-temperature process time.Mode according to embodiment 5 preparation nano catalysts and embodiment 6 is estimated catalytic performance, and reaction result is listed in the table one.
The catalytic performance of table one, nano catalyst
Claims (10)
1. the preparation method of a high-performance nano Au catalyst is characterized in that said nano catalyst is through the following steps preparation:
(1) preparation of HTS matrix: under high degree of agitation that titanium source, silicon source, template and distilled water is evenly mixed according to certain ratio, stirring at room 1-2h obtains HTS precursor colloidal sol; Precursor colloidal sol is changed in the autoclave with PTFE lining, handle 10-96h 50-200 ℃ of crystallization; After crystallization finishes, after supercooling, filtering perhaps centrifugation, washing and drying and other steps, in air atmosphere, remove template at last, obtain the HTS matrix in 550 ℃ of roastings;
(2) the high temperature modified processing of HTS: the HTS matrix that step (1) prepares is put into tube furnace constant temperature zone, at N
2Protection is warming up to temperature required down; Feed NH then
3Or at high temperature can decompose and produce NH
3Other alkaline gas, after certain hour is handled in modification under this temperature at N
2Room temperature is reduced in protection nature cooling down, obtains nitrogenous HTS carrier;
(3) preparation of nano catalyst: with certain density gold chloride (HAuCl
4) solution is heated to 70 ℃, under agitation the pH with solution is adjusted to 6-9, and the nitrogenous HTS that takes by weighing certain mass joins in the chlorauric acid solution, after continuing to stir 1h solution is cooled to room temperature, obtains nano catalyst through filtration, washing, drying.
2. according to the preparation method of the described nano catalyst of claim 1, it is characterized in that said titanium source is water-soluble or titanium compound that can hydrolysis in water, these compounds are TiCl
3, TiCl
4, butyl titanate (TBOT), metatitanic acid tetra isopropyl ester (TIOP) or tetraethyl titanate (TEOT).
3. according to the preparation method of the described nano catalyst of claim 1, it is characterized in that said silicon source is Ludox, silicon gel, the positive esters of silicon acis of tetramethyl (TMOS) or tetraethyl orthosilicate ester (TEOS).
4. according to the preparation method of the described nano catalyst of claim 1, it is characterized in that said template is TMAH (TMAOH), tetraethyl ammonium hydroxide (TEAOH), TPAOH (TPAOH), TBAH (TBAOH), quaternary ammonium base cationoid surfactant, primary amine class neutral surface active agent or polyvinyl alcohol nonionic surface active agent.
5. according to the preparation method of the described nano catalyst of claim 1, the Ti content that it is characterized in that said HTS is 0.1～10wt%, preferred 0.5～3wt%.
6. according to the preparation method of claims 1 described nano catalyst, it is characterized in that said high-temperature process temperature is 300-1200 ℃.
7. according to the preparation method of claims 1 described nano catalyst, it is characterized in that the said high-temperature process time is 1-36 hour.
8. according to the preparation method of claims 1 described nano catalyst, the concentration that it is characterized in that said chlorauric acid solution is 0.1-50mM.
9. according to the preparation method of claims 1 described nano catalyst, it is characterized in that said pH conditioning agent can be NaOH, KOH, Na
2CO
3, NaHCO
3, ammoniacal liquor or urea.
10. according to the preparation method of claims 1 described nano catalyst, the ratio of nitrogenous HTS of its characteristic and chlorauric acid solution is 1-100g/L.
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Cited By (10)
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| CN106582890A (en) * | 2015-10-15 | 2017-04-26 | 神华集团有限责任公司 | Carrier of Fischer-Tropsch synthesis catalyst, preparation method thereof, Fischer-Tropsch synthesis catalyst and preparation method thereof |
| CN106807936A (en) * | 2015-12-01 | 2017-06-09 | 中国科学院大连化学物理研究所 | A kind of processing method of the gold nano grain of organo-functional group protection |
| CN107216296A (en) * | 2016-03-22 | 2017-09-29 | 中国石油化工股份有限公司 | The method that expoxy propane is prepared in micro passage reaction |
| CN109502600A (en) * | 2018-11-29 | 2019-03-22 | 天津城建大学 | A kind of preparation method and applications of the mediator modified molecular sieve of anthraquinone |
| CN111822044A (en) * | 2020-07-21 | 2020-10-27 | 成都中科凯特科技有限公司 | Modification method of Au/TS-1 catalyst |
| CN113813982A (en) * | 2021-10-11 | 2021-12-21 | 华东理工大学 | Integral N-modified TS-1 catalyst carrier and preparation method thereof |
| CN115106124A (en) * | 2022-07-19 | 2022-09-27 | 华东理工大学 | Titanium-silicon molecular sieve solid-supported gold catalyst and preparation method and application thereof |
| CN115283012A (en) * | 2022-08-25 | 2022-11-04 | 华东理工大学 | Roasting method for reducing titanium species outside framework of titanium-silicon molecular sieve, titanium-silicon molecular sieve and application of titanium-silicon molecular sieve |
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| CN107216296A (en) * | 2016-03-22 | 2017-09-29 | 中国石油化工股份有限公司 | The method that expoxy propane is prepared in micro passage reaction |
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| 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 |
| CN115106124A (en) * | 2022-07-19 | 2022-09-27 | 华东理工大学 | Titanium-silicon molecular sieve solid-supported gold catalyst and preparation method and application thereof |
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