CN104907021A - Preparation method of porous silicon dioxide pellets loaded with metal catalyst under synergistic effect - Google Patents
Preparation method of porous silicon dioxide pellets loaded with metal catalyst under synergistic effect Download PDFInfo
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- CN104907021A CN104907021A CN201510291695.8A CN201510291695A CN104907021A CN 104907021 A CN104907021 A CN 104907021A CN 201510291695 A CN201510291695 A CN 201510291695A CN 104907021 A CN104907021 A CN 104907021A
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Abstract
The invention relates to a preparation method of porous silicon dioxide pellets loaded with a metal catalyst under a synergistic effect. Aiming at two difficulties of energy shortage and environment pollution, along with the advancement of energy-saving and new-energy industries in China, the requirement on fuel battery materials in the future is increasingly expanded. According to the invention, silicon dioxide in rice husks is mainly taken as a substrate, and the porous silicon dioxide pellets loaded with the metal catalyst are prepared due to the synergistic effect, so that the application performance of the composite catalyst in batteries is improved. The whole preparation method is simple in process, materials are cheap and easily available, and the cost can be remarkably lowered.
Description
Technical field
The present invention relates to a kind of preparation method of porous silica microballoon of the lower metal supported catalyst that acts synergistically, be specifically related to the porous silica microballoon being prepared metal supported catalyst by synergy original position.
Background technology
Rice husk is as the discarded object in rice process, and be a kind of and abundant biomass resource, its output is huge.The Chinese country huge as rice husk output, its annual production about more than 4,000 ten thousand tons, about accounting for the half of world's annual production.Because rice husk surface is extremely hard, rough and uneven in surface, density is very little, volume large, be unfavorable for transport, for its utilization brings certain difficulty.In most cases all burnt by as agricultural wastes, also create disaster hidden-trouble while of extremely unfavorable to environmental protection, this simply dealt mode wastes the huge energy.In recent years, along with the enhancing of people's environmental consciousness and rice husk utilize the progress of technology, rice husk is relatively efficiently used.Containing the amorphous silica of about 20% in rice husk, the silica in rice husk is through biological purification not containing objectionable impurities (as plumbous, arsenic), and be applicable to food, toothpaste, cosmetics, the demand of the industry such as medicine, market potential is huge.If can be that highly purified porous silica produced by raw material with rice husk, then both can solve the pollution problem of rice husk to environment, considerable economic benefit can also have been brought.Earth silicon material, because having good chemical stability, heat endurance, insulating properties, has good combination interface with silicon semiconductor material, and cheap and easy to get.Therefore be widely used in fields such as catalyst carrier, dielectric layer, window material and the sub-materials of silicon based opto-electronics.Porous silica has larger specific area, narrower pore-size distribution and can the aperture of modulation because of it, increases the contact area of catalyst, accelerates reaction rate, have good development prospect as the immobilized carrier of various metal.
Patent CN102172538A invention provide a kind of titanium IV compound/nano silicon dioxide supported catalyst, mainly emphasize following some: the titanium IV compound that finishing has the nano silicon of organic modifiers and load on described nano silicon; The general formula of described titanium IV compound is Ti (CnH2n+1O) 4; Described organic modifiers is the titanate esters of phosphate ester-containing group.Catalyst reaction activity provided by the invention is high, and use amount is few, selective good, excellent catalytic effect, and employ cheap raw material, reduce cost, this invention additionally provides the preparation method of described catalyst, mild condition, simple to operate, be applicable to large-scale industrial production.Patent CN102941119A discloses a kind of preparation method of loading silicon dioxide with heteropoly acid cesium-promoted catalyst.It is made up of silicon dioxide carried 1 ~ 40% heteropoly acid caesium weighed.Gained catalyst phenol conversion is high, the nitrated selective height of ortho phenol; Preparation method is simple, and catalytic activity is high, and post catalyst reaction is easily separated, reusable, is with a wide range of applications.Patent CN101301608 discloses a kind of SiO 2 supported nanometer silver catalyst, its preparation method and the application in catalytic hydrogenation of nitro compound reaction thereof.1.0g silica joins to be dissolved with in 20 ~ 50ml aqueous solution of 0.016g ~ 0.064g silver nitrate by preparation method, stir 8 ~ 12 hours in 40 DEG C, add 10 ~ 50ml ethanol, be warming up to 110 DEG C of solvent thermal reactions 8 ~ 12 hours, filter out light yellow solid, within 4 ~ 12 hours, namely obtain silicon dioxide carried Nano silver grain catalyst by dry at 100 ~ 120 DEG C for this solid.This invention synthesized by catalyst application prepare in amino aryl aroma compounds in nitroaromatic selective hydrogenation, can realize with optimal conditions transforming completely.Patent CN101224422 discloses a kind of SiO 2 supported nanometer silver catalyst, its preparation method and the application in chloro nitro-aromatic and nitryl aromatic alkene, aldehyde, ketone, nitrile, acid amides Selective catalytic hydrogenation react thereof.Synthetic method includes a certain amount of AgNO for ethyl orthosilicate and amine propyl-triethoxysilicane being joined by 1: 0.1 ~ 1: 2.5 mass ratios
3ammonia spirit in, stirred at ambient temperature, to forming gel, is dried after 4 ~ 12 hours in 100 ~ 200 DEG C, is obtained catalyst.This catalyst synthesized by invention solves the two problems existed in current aromatic nitro compound catalytic hydrogenation reaction: produce dechlorination side reaction during (1) chloro nitro-aromatic hydrogenating reduction; (2), when having alkene, aldehyde, ketone, nitrile, amide group to coexist, reaction selectivity is poor.Patent CN103861625A discloses a kind of load Ni
2the preparation method of P catalyst.Its key step comprises: adopt infusion process to prepare silica, MCM-41, SBA-15, aluminium oxide, titanium oxide, HY molecular sieve or the molecular sieve carried nickel oxide precursor of HZSM-5; By reducing loaded for load nickel oxide precursor Ni presoma in fixed bed reactors, then pass into triphenylphosphine or tri octyl phosphine solution passing in hydrogen and uniform temperature downhill reaction device, after constant temperature phosphatization certain hour, original position obtains load Ni
2p catalyst.Load Ni is prepared with the load nickel phosphate temperature-programmed reduction method usually adopted
2p catalyst is compared, and operation is simple for the method, the aluminium oxide in phosphorus species and carrier can also be avoided to react and generate aluminum phosphate, can effectively utilize phosphorus species.The preparation method of the monodisperse silica microspheres that patent CN104003408A continous way is controlled, this technique comprises nucleating step, growth step, separating step.This technique can realize the monodisperse silica microspheres batch preparation of high sphericity, narrow domain size distribution, the present invention is in the nucleation link of silicon dioxide microsphere seed, reaction system is boiling system, conduct heat under strong convection state, mass transfer is good, can homogeneous phase fast nucleation, and can solve the agglomeration traits of prior art, reaction time is short, and obtains the narrower mono-dispersion microballoon seed of domain size distribution.The present invention adopts one step growth or multistep growth, and the coring and increment stage is separated, and can obtain sphericity high, the monodisperse silica microspheres of size tunable, and domain size distribution deviation is less than 2%, performance is more excellent.And according to actual needs, the silicon dioxide microsphere of the various particle size of 20 ~ 10000nm monodisperse silica microspheres can be obtained, many deficiencies of prior art can be overcome.
In above patent, the main silicon of major part patent is former is positive esters of silicon acis, and the present invention mainly utilizes high value added product silica in rice husk as raw material, the porous silica microballoon of metal supported catalyst is prepared under synergy utilizes one-step method, study its application in electrochemistry, the research for this respect has no to be reported.
Summary of the invention
For realizing experimental program provided by the present invention be:
First utilize acid solution and alkali lye to carry out two step liquefaction to rice husk, extract alkali lignin and sodium metasilicate.The filtrate of then will extract in above-mentioned step, absolute ethyl alcohol, distilled water puts into there-necked flask by a certain percentage, controlling Contact Temperature is 25 ~ 90 DEG C, under the condition stirred, with acid solution, titration is carried out to filtrate, when the pH of solution reaches 7 ~ 9, adding wherein by the quality of a small amount of anhydrous alcohol solution is the polyethylene glycol (molecular weight is 200 ~ 20000) of 5% ~ 50% of silica, after reaction 2h, then the quality adding nitric acid dissolve is the metal salt solution of 1% ~ 30% of silica, continue to carry out titration to filtrate, the pH of solution is made to reach 3, reaction 1 ~ 6h, be settled out lignin and the silica composite of a series of metal supported catalyst, Separation of Solid and Liquid, dry lignin and the silicon dioxide composite material that can obtain uniform metal supported catalyst, then at the temperature lower calcination of 500 ~ 800 DEG C, the porous silica microballoon of metal supported catalyst can be obtained.
For better understanding the present invention, below in conjunction with embodiment the present invention done and describe in detail further, but the scope of protection of present invention being not limited to the scope that embodiment represents.
Embodiment 1: first utilize acid solution and alkali lye to carry out two step liquefaction to rice husk, extracts alkali lignin and sodium metasilicate.Then the filtrate of extracting in above-mentioned step, absolute ethyl alcohol, distilled water are put into there-necked flask in the ratio of 2: 1: 1, controlling Contact Temperature is 80 DEG C, under the condition stirred, with the HCl solution of 2mol/L, titration is carried out to filtrate, when the pH of solution reaches 9, adding wherein by the quality of a small amount of anhydrous alcohol solution is the polyethylene glycol (molecular weight is 2000) of 20% of silica, after reaction 2h, the quality then adding nitric acid dissolve is the AgNO of 5% of silica
3solution, continue to carry out titration to filtrate, the pH of solution is made to reach 3, reaction 3h, be settled out lignin and the silica composite of metal supported catalyst, Separation of Solid and Liquid, drying can obtain lignin and the silicon dioxide composite material of uniform metal supported catalyst, then at the temperature lower calcination of 800 DEG C, the porous silica microballoon of carried metal silver catalyst can be obtained.
Embodiment 2: change loaded Ag NO in reaction
3amount be 10%, other steps, with embodiment 1, obtain the porous silica microballoon of carried metal silver catalyst.
Embodiment 3: changing slaine is Ni (NO
3)
2, other steps, with embodiment 1, obtain the porous silica microballoon of carried metal Raney nickel.
Embodiment 3: changing slaine is Co (NO
3)
2, other steps, with embodiment 1, obtain the porous silica microballoon of carried metal Co catalysts.
Embodiment 4: changing slaine is Fe (NO
3)
3, other steps, with embodiment 1, obtain the porous silica microballoon of carried metal iron catalyst.
Embodiment 5: change load C o (NO in reaction
3)
2amount be 10%, other steps, with embodiment 3, obtain the porous silica microballoon of carried metal Co catalysts.
Embodiment 6: change load Fe (NO in reaction
3)
3amount be 10%, other steps, with embodiment 4, obtain the porous silica microballoon of carried metal iron catalyst.
Claims (3)
1. a preparation method for the porous silica microballoon of the lower metal supported catalyst of synergy, concrete steps are as follows:
First utilize acid solution and alkali lye to carry out two step liquefaction to rice husk, extract alkali lignin and sodium metasilicate.The filtrate of then will extract in above-mentioned step, absolute ethyl alcohol, distilled water puts into there-necked flask by a certain percentage, controlling Contact Temperature is 25 ~ 90 DEG C, under the condition stirred, with acid solution, titration is carried out to filtrate, when the pH of solution reaches 7 ~ 9, adding wherein by the quality of a small amount of anhydrous alcohol solution is the polyethylene glycol (molecular weight is 200 ~ 20000) of 5% ~ 50% of silica, after reaction 2h, then the quality adding nitric acid dissolve is the metal salt solution of 1% ~ 30% of silica, continue to carry out titration to filtrate, the pH of solution is made to reach 3, reaction 1 ~ 6h, be settled out lignin and the silica composite of a series of metal supported catalyst, Separation of Solid and Liquid, dry lignin and the silicon dioxide composite material that can obtain uniform metal supported catalyst, then at the temperature lower calcination of 500 ~ 800 DEG C, the porous silica microballoon of metal supported catalyst can be obtained.
2. a preparation method for the porous silica microballoon of a kind of lower metal supported catalyst that acts synergistically as claimed in claim 1, is characterized in that: slaine can be HAuCl
4, Fe (NO
3)
3, AgNO
3, Cu (NO
3)
2, Ni (NO
3)
2, Pd (NO
3)
2, Co (NO
3)
2deng.
3. a preparation method for the porous silica microballoon of a kind of lower metal supported catalyst that acts synergistically as claimed in claim 1, is characterized in that: acid solution can be the inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106540696A (en) * | 2016-11-14 | 2017-03-29 | 天津工业大学 | A kind of method prepared by rice husk base metal supported catalyst mesoporous silicon oxide |
| CN109833896A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst |
-
2015
- 2015-06-01 CN CN201510291695.8A patent/CN104907021A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106540696A (en) * | 2016-11-14 | 2017-03-29 | 天津工业大学 | A kind of method prepared by rice husk base metal supported catalyst mesoporous silicon oxide |
| CN109833896A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst |
| CN109833896B (en) * | 2017-11-29 | 2022-04-12 | 中国科学院大连化学物理研究所 | Preparation method of high-dispersion noble metal slurry bed hydrogenation catalyst |
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