CN101229510B - Synthesis and applications of silicate containing Bi - Google Patents

Synthesis and applications of silicate containing Bi Download PDF

Info

Publication number
CN101229510B
CN101229510B CN2008100705632A CN200810070563A CN101229510B CN 101229510 B CN101229510 B CN 101229510B CN 2008100705632 A CN2008100705632 A CN 2008100705632A CN 200810070563 A CN200810070563 A CN 200810070563A CN 101229510 B CN101229510 B CN 101229510B
Authority
CN
China
Prior art keywords
bismuth
sio
silicate
acid
source
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN2008100705632A
Other languages
Chinese (zh)
Other versions
CN101229510A (en
Inventor
陈晓晖
郑婧
黄清明
程燕
魏可镁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fuzhou University
Original Assignee
Fuzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fuzhou University filed Critical Fuzhou University
Priority to CN2008100705632A priority Critical patent/CN101229510B/en
Publication of CN101229510A publication Critical patent/CN101229510A/en
Application granted granted Critical
Publication of CN101229510B publication Critical patent/CN101229510B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Abstract

The invention relates to a synthesis method and application of silicate containing bismuth, pertaining to the catalyst technical field of materials science. While preparing powder catalysis materials containing bismuth silicate (Bi2SiO5), bismuth source is dissolved into an acidity solution to obtain bismuth solution; according to molar ratio of 25:1-0.5:1 of silicon atoms in silicon source and bismuth atoms in bismuth source, the silicon source and the bismuth source are mixed, and according to requirement, certain amount of carrier is added; the pH value of the obtained material is adjustedto 5-12; then the powder bismuth silicate (Bi2SiO5) or power catalysis material containing bismuth silicate (Bi2SiO5) can be made after the steps of stirring, aging, washing, drying, grinding and firing, wherein, the mass percentage of bismuth silicate (Bi2SiO5) is 100-5 percent; the mass percentage of carrier is 0-95 percent. The invention employs simple method to prepare catalyst material of bismuth silicate (Bi2SiO5) with good crystallinity; the catalyst material can be applied to photocatalysis and oxidation process of hydrocarbons.

Description

A kind of synthetic and application of silicate of bismuth-containing
Technical field
The present invention relates to a kind of silicate synthetic of the bismuth-containing with special crystal structure, particularly relate to bismuth silicate (Bi 2SiO 5) and contain bismuth silicate (Bi 2SiO 5) the preparation method of powdery catalysis material, the prepared material that contains bismuth silicate can be used as the catalyst and the photochemical catalyst of organic selective oxidation, belongs to the material science catalyst technical field.
Background technology
Bismuth silicate (Bi 2SiO 5) belong to rhombic system, Cmc2 1Space group, lattice constant a=15.19A, b=5.468A, c=5.314A, Z=4 (Fei Yiting, model generation. Journal of Inorganic Materials, 1997,12:469～476), be by [Bi 2O 2] 2+Separated isolated [the SiO of layer 3] 2-Chain constitutes, i.e. Bi 4[O 4] [Si 2O 6].Bi 2SiO 5Monocrystal mainly has character (Fei Yiting, model generation, Sun Renying such as alive of dielectric, thermoelectricity and nonlinear optics, Journal of Inorganic Materials, 1998,13:798～802), its non-centrosymmetrical crystal structure makes it might have ferroelectric property, and potential purposes is arranged aspect photoelectric material.
At present, Bi 2SiO 5Synthetic method mainly be solid-phase synthesis and sol-gal process, synthesize single Bi the earliest 2SiO 5Crystalline phase be J.Ketterer (J.Ketterer, V.Kramer, Freiburg, Neues Jahrbuch fur Mineralogie-Monatshefte.1986,1:13～18), with Bi 2O 3(Furak Co.) and SiO 2(Degussa) 1000-1040 ℃ of fusion, quench in the cold water, make 400-520 ℃ of one week of crystallization and be lurid Bi 2SiO 5Crystalline phase.Fei Yiting etc. (Fei Yiting, model generation, Sun Renying, silicate journal, 1999,27:230～236) are to Bi 2O 3-SiO 2When studying, system finds metastable compound Bi 2SiO 5Exist only in the metastable phase balance chart.Work as Bi 2O 3-SiO 2System begins to cool down SiO from melt (1012～1013 ℃) 2Molar fraction at 30～50% o'clock, that separate out is Bi 2SiO 5Phase and Bi 2O 3The mixing crystalline phase; SiO 2Near molar fraction 50% time, separate out single Bi at 845 ℃ 2SiO 5Phase; If further improve SiO 2Molar fraction (SiO 2Surpass 50%) time, then in the crystallization except Bi 2SiO 5SiO has also appearred in addition 2, gained silicon bismuth compound is not pure Bi 2SiO 5Bai Chaohui etc. (Bai Chaohui, Ba Xuewei, Jia Ru, Chinese Journal of Inorganic Chemistry, 2006,22:1327～1329) people utilizes Prepared by Sol Gel Method Bi 4Si 3O 12(BSO) in the process of nano-powder, having obtained principal crystalline phase in the time of 550～650 ℃ is Bi 2SiO 5And Bi 2O 3The mixing crystalline phase, along with the rising of reaction temperature, Bi 2SiO 5And Bi 2O 3Constantly reaction has generated the target product Bi of principal crystalline phase for cube crystalline phase at 750 ℃ 4Si 3O 12Wang Yan etc. (Wang Yan, Wang Xiufeng is in Cheng Long. inorganic chemicals industry, 2007,39:38～40; Wang Yan, Wang Xiufeng is in Cheng Long. silicate circular, 2007,26:378～381) use Bi 2O 3And SiO 2Be raw material, press amount of substance than n (Bi 2O 3): n (SiO 2The sample of the about 60g of)=1: 1 preparation.Wet mixing 1.5h in the sample elder generation ethanol of falling people, it is even to guarantee sample to grind the dried 0.5h of mixing after the infrared oven dry again.750 ℃ of roasting 1h, Bi at this moment 12SiO 20And Bi 2SiO 5The diffraction maximum of XRD stronger, temperature retention time lengthening, Bi 2SiO 5The XRD diffraction maximum weaken Bi 12SiO 20Diffraction maximum further strengthen.Jenni etc. are by ALD (atomic layer deposition) method (JenniHarjuoja, Samuli Vayrynen, Matti Putkonen.Journal of Crystal Growth, 2006,286:376～383), at N 2When the Bi-Si-O of the Si under the atmosphere on the MgO buffer (100) carries out 800 ℃ of annealing in process, obtained Bi 2SiO 5Film.These bismuth silicates (Bi 2SiO 5) synthetic method very complicated, and if do not adopt high-temperature melting method all can not obtain pure bismuth silicate (Bi 2SiO 5).
Both at home and abroad and bismuth silicate (Bi 2SiO 5) relevant patent seldom, patent CN200510046593.6 discloses and has a kind ofly contained the metal oxide of various active components such as molybdenum, bismuth, iron, nickel, samarium and be the catalyst that carrier is formed with silica, aluminium oxide or its mixture, can be used for propylene, isobutene ammonia oxidizing prepares than high selectivity acrylonitrile, methacrylonitrile etc.All mention solid solution Bi in the lattice structure of Ca-Ti ore type or laminated perovskite type among patent CN200610004826 and the CN01817413.2 2SiO 5As the preparation method of the semiconductor film original paper of component, and not to be used for chemical catalysis material field.Have only and disclose a kind of Bil in the patent application 200610024511.2 2SiO 20The synthetic method of nano-powder and in Application in Photocatalysis.
In sum, bismuth silicate (Bi 2SiO 5) crystal is a kind of metasable state material, all do not relate to pure bismuth silicate (Bi in the document of publishing at present 2SiO 5) crystal synthetic and contain the application of the material of this crystal at catalytic field.
Summary of the invention
The purpose of this invention is to provide a kind of bismuth silicate (Bi that contains 2SiO 5) the preparation method and the application thereof of the powdery catalysis material that is used for oxidation and photocatalytic process.By adopting simple technology and equipment, obtain well-crystallized's powdered silicate bismuth (Bi 2SiO 5) or contain bismuth silicate (Bi 2SiO 5) the powdery catalysis material, this catalysis material is having good catalytic activity aspect organic selective oxidation, ammoxidation and the photocatalysis.
Theme of the present invention is by the bismuth salt of solubility and siliceous compound, synthesizes the good powdery Bi of crystal formation 2SiO 5, resulting powdery Bi 2SiO 5With with carrier-bound Bi 2SiO 5All have good catalytic oxidation and photocatalytic activity.
Bismuth-containing silicate provided by the present invention is bismuth silicate (Bi 2SiO 5), the Bi with feature 2SiO 5The powder x-ray diffraction of crystal (XRD) chromatogram characteristic is characterized in that this catalysis material contains the bismuth silicate (Bi with catalytic activity 2SiO 5), and each constituent mass percentage composition is as follows in this material: bismuth silicate (Bi 2SiO 5) the quality percentage composition be 100%～5%, the quality percentage composition of carrier is 0～95%.This catalysis material can be in gas phase or liquid phase light-catalyzed reaction with H 2O 2, organic peroxide, inorganic peroxide or oxygen is the purposes of making catalyst in the oxidation operation of oxidant or the ammoxidation reaction.
The silicate that contains the Bi atom provided by the present invention, its structure are bismuth silicate (Bi 2SiO 5), be a kind of metasable state material, can be on carrier high degree of dispersion, the oxidation activity height has higher activity stability.Preferred bismuth silicate (Bi in this catalysis material 2SiO 5) the quality percentage composition 100%～15%.Described carrier is to be selected from silica gel, titanium dioxide, aluminium oxide, imvite, kaolin, the molecular sieve one or more.Preferred carrier is to be selected from silica gel, titanium dioxide and the molecular sieve one or more.Wherein molecular sieve can be the molecular sieve of pure silicon, also can be to contain heteroatomic molecular sieve, both can be that micropore can be a mesopore molecular sieve also, but all be the effect of carrier or co-catalyst in catalysis material.Gained powdery catalysis material can carry out the industry use after playing common shaping of catalyst means processing such as sheet, extrusion.
The Bi of containing silicate provided by the present invention can be used as the catalyst in oxidation such as the oxidation of oxidation, alkane, cycloalkane and the aromatic hydrocarbons of the oxidation of photochemical catalyst and alkene and epoxidation, aldehyde and alcohol, the hydroxylating of phenols or the ammoxidation reaction, and oxidant can be H 2O 2, organic peroxide, inorganic peroxide, oxygen etc.Wherein alkene is the open chain hydrocarbon that contains carbon-carbon double bond, and the epoxidation of alkene is exactly that the open chain oxidizing hydrocarbon that will contain carbon-carbon double bond becomes corresponding epoxide, makes Styryl oxide as epoxidation of styrene; Alkane and cycloalkane are all to be the hydrocarbon of forming with carbon-carbon single bond, alkane is the open chain type, and cycloalkane is to form ring-type, and alkane and cycloalkane become corresponding alcohol, aldehydes or ketones through oxidation, generate cyclohexanone or cyclohexanol as cyclohexane oxidation, hexane oxidation generates hexanol; Aromatic hydrocarbons is the hydrocarbon with benzene ring structure, and the oxidation of aromatic ring will generate corresponding phenol, and the oxidation of the similar alkane of oxidation of side chain on the aromatic ring generates corresponding alcohol, aldehydes or ketones; Alcohol is the hydrocarbon of hydroxy functional groups, and the oxidation of alcohol generates corresponding aldehydes or ketones, and for example isopropanol oxidation generates acetone; Aldehyde is the hydrocarbon that contains the carbonyl functional group, and the oxidation of aldehyde generates corresponding acid; The hydroxy derivatives of the phenol aromatic hydrocarbons that to be hydroxyl directly link to each other with aromatic ring, the oxidation of phenol generates corresponding polyphenol, generates benzenediol etc. as oxidation of phenol.Described " ammoxidation reaction " is called " oximation reaction " again, and being has ketone and ammonia and hydrogen peroxide to react the reaction that generates corresponding oxime jointly, and for example cyclohexanone and ammonia and hydroperoxidation generate cyclohexanone oxime.Photocatalysis is under the effect with ultraviolet light or visible light, on catalyst transform light energy to be become the required energy of chemical reaction, makes the process of reactions such as oxidation that chemical substance takes place, decomposition.The catalyst of photocatalytic process can be used in aspects such as air cleaning, deodorizing, anti-fouling and self-cleaning, water purification, sterilization, have security and persistent characteristics, the for example oxidation of the oxidation of formaldehyde, benzene in the air, the oxidation of the parachlorophenol in the water, the decomposition of methyl orange etc.
Bismuth silicate (the Bi that contains provided by the present invention 2SiO 5) the preparation method of grained catalyst comprise, the bismuth source is dissolved in obtains bismuth-containing solution in the acid solution, mol ratio according to the bismuth atom in silicon atom in the silicon source and the bismuth source is 25: 1～0.5: 1, under 5～80 ℃ condition, silicon source solution is added in the above-mentioned bismuth-containing solution, add a certain amount of carrier as required; Under 10～70 ℃ condition, regulate pH value to 5～12, stir after 0.5～12 hour ageing 0.5～72 hour with alkaline matter.Extremely neutral through deionized water filtration or centrifuge washing, oven dry, after the grinding, roasting is 1～12 hour in 400～700 ℃ of following air, can get powdered silicate bismuth (Bi 2SiO 5) or contain bismuth silicate (Bi 2SiO 5) the powdery catalysis material.
Wherein said bismuth source is the bismuth salt that dissolves in nitric acid, is selected to comprise in nitrate, acetate, sulfate, the carbonate one or more, as bismuth nitrate (Bi (NO 3) 35H 2O), bismuth sulfate (Bi 2(SO 4) 3), basic bismuth carbonate ((BiO) 2CO 30.5H 2O), bismuth acetate etc.; Wherein said silicon source is to be selected from silica gel, silica sol liquid, silicate or the organosilicon acid esters one or more.Wherein said acid solution is the mixture of acid and solvent, acid is for being selected from nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, the ethanedioic acid one or more, solvent be selected from water and can with the miscible alcohol of water, ether, aldehyde, ketone in one or more, as the methanol aqueous solution of nitric acid, the ethanol water of sulfuric acid etc.Silicon source solution is the mixture of silicon source and solvent, solvent be selected from water and can with the miscible alcohol of water, ether, aldehyde, ketone in one or more, as the mixture of methanol solution, Ludox and the silester ethanolic solution of silester etc.Alkaline matter is the mixture of alkali compounds and solvent, alkali compounds is to be selected from NaOH, ethylenediamine, ethamine or the ammonia one or more, solvent be selected from water and can with the miscible alcohol of water, ether, aldehyde, ketone in one or more, as the ethanolic solution of the methanol solution of NaOH, ethylenediamine, ammoniacal liquor etc.The preferred mol ratio of the bismuth atom in silicon atom in the silicon source and the bismuth source is 15: 1～0.5: 1.
Stirring described in the preparation method of the Bi of containing silicate provided by the present invention is carried out according to the condition of prior art, be not particularly limited, general condition is in having the withstand voltage still of teflon-lined stainless steel, stirs 0.5～12 hour down and under the self-generated pressure in 10～70 ℃.
Ageing described in the preparation method of the Bi of containing silicate provided by the present invention is carried out according to the condition of prior art, be not particularly limited, general condition is in having the withstand voltage still of teflon-lined stainless steel, leaves standstill 0.5～12 hour down and under the self-generated pressure in 10～70 ℃.
Of the present invention contain bismuth silicate catalysis material, compare with common bismuth silicate synthetic method, need not by complicated procedures of forming such as high temperature crystallizations, synthetic method is simple, and it is low to consume energy, simultaneously the catalysis material of gained, good with the matching of other carriers, compare with the catalyst such as Bi molecular sieve, molecular sieve containing titanium that contain of routine, have the catalytic efficiency height, the advantage of reactivity good stability.
Below by embodiment the synthetic and application of a kind of bismuth-containing silicate of the present invention is described further, but protection scope of the present invention is not subjected to the restriction of these embodiment.
In each of the embodiments described below, agents useful for same is commercially available chemically pure reagent or industrial primes.
Embodiment 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5 are the concrete preparation method who contains the bismuth silicate catalysis material of the present invention.
Embodiment 6, embodiment 7 are the application example of bismuth-containing catalyzed by silicate material of the present invention.
Comparative Examples is the synthetic method of contrast catalysis material Ti-MCM-4l.
Description of drawings
Fig. 1 is the pure powdered silicate bismuth of gained (Bi 2SiO 5) x-ray diffractogram of powder (XRD) of sample.
Can be when using other non-unformed carrier at the powder x-ray diffraction peak of the expression vector that in catalysis material, superposes out, but can not change bismuth silicate (Bi 2SiO 5) the distribution and the intensity at powder x-ray diffraction peak.
Embodiment 1
Mol ratio according to the bismuth atom in silicon atom in the silicon source and the bismuth source is 0.5: 1, with the Bi (NO of 1.0mol 3) 35H 2O is dissolved in the sulfuric acid of 1M of 5000mL, under 15 ℃, the silester of 0.5mol and the mixed liquid of 8.56mol ethanol are added in the sulfuric acid solution of above-mentioned bismuth-containing, methanol solution with 50% ethylenediamine under 35 ℃ condition is regulated pH value to 7, stir after 5 hours, in 65 ℃ of ageings 24 hours.After sample taken out repeatedly washing and filtering and dry grinding then, roasting was 10 hours in 480 ℃ of following air, obtains containing bismuth silicate (Bi 2SiO 5) the powdery catalysis material, it is numbered T-1, its powder x-ray diffraction (XRD) crystalline phase figure as shown in Figure 1,13.54 corresponding 200 crystal faces of ° diffraction maximum of locating, 28.00 corresponding 111 crystal faces of ° diffraction maximum of locating, 34.18 corresponding 311 crystal faces of ° diffraction maximum of locating, 39.53 ° of corresponding 002 crystal faces of the diffraction maximum of locating.XRD spectra is measured on Phillip X ' pert-MPD type powder x-ray diffraction, adopts Co Ka radiation, and power is 40KV * 20mA.
Embodiment 2
Mol ratio according to the bismuth atom in silicon atom in the silicon source and the bismuth source is 5: 2, with the Bi of 0.1mol 2(SO 4) 3Be dissolved in the nitric acid of 1M of 1300mL, under 15 ℃, the silester of 0.5mol and the mixed liquid of 4.28mol acetone are added in the salpeter solution of above-mentioned bismuth-containing, the ammonia spirit with 25% under 35 ℃ condition is regulated pH value to 8, stir after 10 hours, in 52 ℃ of ageings 36 hours.After sample taken out repeatedly washing and filtering and dry grinding then, roasting was 7 hours in 540 ℃ of following air, obtains containing bismuth silicate (Bi 2SiO 5) the powdery catalysis material, it is numbered T-2, the test condition of its XRD spectra is with embodiment 1, the peak type of crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 3
Mol ratio according to the bismuth atom in silicon atom in the silicon source and the bismuth source is 12: 1, with the Bi of 0.05mol 2(SO 4) 3Be dissolved in the nitric acid of 1M of 1500mL, under 25 ℃, the silester of 1.2mol and the mixed liquid of 5.48mol ethanol are added in the salpeter solution of above-mentioned bismuth-containing, ethanolic solution with 80% ethylenediamine under 25 ℃ condition is regulated pH value to 11, stir after 10 hours, in 45 ℃ of ageings 48 hours.After sample taken out repeatedly washing and filtering and dry grinding then, roasting was 9 hours in 550 ℃ of following air, obtains containing bismuth silicate (Bi 2SiO 5) the powdery catalysis material, it is numbered T-3, the test condition of its XRD spectra is with embodiment 1, the peak type of crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 4
Mol ratio according to the bismuth atom in silicon atom in the silicon source and the bismuth source is 8: 1, with the Bi of 0.1mol 2(SO 4) 3Be dissolved in the nitric acid of 1M of 1800mL, under 30 ℃, the silester of 1.6mol and the mixed liquid of 5.28mol methyl alcohol are added in the salpeter solution of above-mentioned bismuth-containing, the granular colloidal silica H that adds 0.8mol, ammonia spirit with 25% under 28 ℃ condition is regulated pH value to 10, stir after 10 hours, in 40 ℃ of ageings 60 hours.After sample taken out repeatedly washing and filtering and dry grinding then, roasting was 8 hours in 560 ℃ of following air, obtains containing bismuth silicate (Bi 2SiO 5) the powdery catalysis material, it is numbered T-4, the test condition of its XRD spectra is with embodiment 1, the peak type of crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Embodiment 5
Mol ratio according to the bismuth atom in silicon atom in the silicon source and the bismuth source is 1: 1, with the five water bismuth nitrate (Bi (NO of 1.0mol 3) 35H 2O) be dissolved in the nitric acid of 1M of 1500mL, under 30 ℃, the silester of 1.0mol and the mixed liquid of 8.56mol methyl alcohol are added in the salpeter solution of above-mentioned bismuth-containing, the granular colloidal silica H that adds 0.1mol, ammonia spirit with 15% under 28 ℃ condition is regulated pH value to 9, stir after 10 hours, in 30 ℃ of ageings 40 hours.After sample taken out repeatedly washing and filtering and dry grinding then, roasting was 9 hours in 500 ℃ of following air, obtains containing bismuth silicate (Bi 2SiO 5) the powdery catalysis material, it is numbered T-5, the test condition of its XRD spectra is with embodiment 1, the peak type of crystalline phase figure diffraction maximum and position and Fig. 1 are similar.
Comparative Examples
The effect that the method that the explanation of this Comparative Examples proposes according to people such as S.C.Laha. (Microporous and Mesoporous Materials,, the 53rd phase, 163～177 pages in 2002) is synthesized the Ti-MCM-41 molecular sieve.
With 0.21mol softex kw (CTAB), 1.0mol Ludox (SiO 2Concentration is 0.5mol/L), 0.4mol TPAOH (TMAOH), 0.02mol butyl titanate (TBOT), 0.1mol phosphoric acid (H 3PO 4), 320ml distilled water mixes, the mixed liquor mole consists of TMAOH: Ti: CTAB: SiO 2: H 3PO 4: H 2O=0.4: 0.02: 0.21: 1: 0.1: 125, should mix liquid immigration band teflon-lined autoclave and leave standstill crystallization 48 hours, 120 ℃ of crystallization temperatures.After the crystallization sample is taken out repeatedly washing and filtering and dry then, 550 ℃ of roasts promptly got the Ti-MCM-41 molecular sieve in 10 hours.It is numbered Ti-MCM-41.
Embodiment 6
Present embodiment explanation the inventive method gained contains the powdery catalysis material of bismuth silicate and the method gained Ti-MCM-41 of Comparative Examples is used for the catalytic effect that styrene oxidation reacts.
The foregoing description gained contains bismuth silicate (Bi 2SiO 5) catalysis material T-1, T-2, T-3, T-4, the Ti-MCM-41 that T-5 and Comparative Examples are prepared, according to catalyst: styrene: methyl alcohol: repefral=0.25: 4: 50: 2 mass ratio puts into that a band stirs and the stainless steel cauldron of cooling water jecket mixes, be warming up to 70 ℃, then under stirring condition according to methyl alcohol: it is 30% aqueous hydrogen peroxide solution that the mass ratio of hydrogen peroxide=8: 1 adds mass concentration, reaction is 1.5 hours under this temperature, products therefrom is measured each product and is distributed on the HP6890 gas-chromatography, the results are shown in Table 1
Table 1 contains bismuth silicate (Bi 2SiO 5) catalysis material to the catalytic activity of styrene oxidation reaction
Numbering Conversion ratio (%) Selectivity (%) A Selectivity (%) B Benzaldehyde productive rate (%)
T-1 58.6 74.3 25.7 43.5
T-2 49.4 61.5 38.5 30.4
T-3 47.9 62.6 37.4 30.0
T-4 55.4 62.3 37.7 34.5
T-5 40.8 70.7 29.3 28.8
Ti-MCM-41 27.7 50.3 49.7 13.9
A: benzaldehyde B: accessory substance comprises the styrene glycol and the methyl benzoate of formaldehyde, polystyrene, minute quantity
In table 1:
Cinnamic molal quantity before molal quantity/reaction that styrene reduces before and after cinnamic conversion ratio=reaction * 100%
Molal quantity * 100% that styrene reduces before and after the molal quantity of the benzaldehyde of the selectivity=generation of benzaldehyde/reaction
From The above results as can be seen, compare with comparative catalyst Ti-MCM-41, the styrene conversion rate of the catalyst of the present invention's preparation all is higher than 40%, and selectivity is not less than 60%, has higher oxidation activity and selectivity.
Embodiment 7
The powdery catalysis material that the gained of present embodiment explanation the inventive method embodiment 1 contains bismuth silicate is used for the water degradation performance of Methyl orange.
Get the catalysis material 0.05 gram T-1 that embodiment 1 makes, ultrasonic dispersion is after 20 minutes in 100mL distilled water, and the methyl orange concentration that contains that the adding methyl orange solution is made 200mL is 20ppm, and catalyst concn is 250mgL -1Suspension, air stirs and it fully to be adsorbed in 20 minutes under the lucifuge condition, uses 12W ultra violet lamp (irradiation distance 3.5cm, irradiated area 33.3cm then 2, solution deep 6cm, 25～26 ℃ of reaction temperatures), the pH value is 5～6, reacts after 200 minutes, centrifugation eliminates TiO 2After, measure absorbance (510nm wavelength) with 722 spectrophotometers (U.S. Varian company, Cary 50), determine remaining methyl orange concentration.With commercially available commercial TiO 2Photochemical catalyst P25 (Germany, Degussa company) has carried out contrast test, and the methyl orange conversion ratio on the T-1 is 80.5%, and the methyl orange conversion ratio on the P25 is 64.7%.Catalyst activity of the present invention is higher than commercially available catalyst about 15.8%.
Embodiment 8
Present embodiment explanation the inventive method embodiment 1 gained contain bismuth silicate (Bi 2SiO 5) powdery catalysis material be used to the to degrade effect of benzene in air.
(granularity is 1～2mm), in the photo catalysis reactor that pack into a quartz ampoule and four 6 watts of ultraviolet lamp tubes are formed, feeds and contains 500ugmL to get catalysis material 0.5 gram that embodiment 1 makes -1The air of benzene, 35 ℃～36 ℃ of temperature, reaction pressure 0.11MPa (gauge pressure).In air speed is 1800 hours -1Under the condition, the conversion ratio of benzene is 87.4%, contains bismuth silicate (Bi to embodiment 1 preparation under same reaction conditions 2SiO 5) catalysis material T-1 and commercially available TiO 2Photochemical catalyst P25 catalyst (Germany, Degussa company) has carried out the contrast experiment, and the conversion ratio of the last benzene of T-1 is 71.8%, and the conversion ratio of the last benzene of P25 is 61.3%.Catalyst activity of the present invention is higher than P25 about 10.5%.
From The above results as can be seen, compare with comparative catalyst P25, the catalysis material of the present invention preparation in light-catalyzed reaction by advantages of high catalytic activity.

Claims (7)

1. a powdery that is used for oxidation and photocatalytic process contains bismuth silicate Bi 2SiO 5The preparation method of catalysis material, it is characterized in that concrete preparation process is as follows:
The bismuth source is dissolved in obtains bismuth-containing solution in the acid solution, mol ratio according to the bismuth atom in silicon atom in the silicon source and the bismuth source is 25: 1～0.5: 1, under 5～80 ℃ condition, silicon source solution is added in the above-mentioned bismuth-containing solution, add a certain amount of carrier as required, under 10～70 ℃ condition, regulate pH value to 5～12 with alkaline matter, stir after 0.5～12 hour, ageing 0.5～72 hour, extremely neutral through deionized water filtration or centrifuge washing, oven dry is after the grinding, roasting is 1～12 hour in 400～700 ℃ of following air, can get powdery Bi 2SiO 5Or contain Bi 2SiO 5The powdery catalysis material; Each constituent mass percentage composition is as follows in this material: bismuth silicate Bi 2SiO 5Be 100%～5%; Carrier is 0～95%;
Carrier is to be selected from silica gel, titanium dioxide, aluminium oxide, imvite, kaolin, the molecular sieve one or more.
2. according to the preparation method of claim 1, wherein said bismuth source is the bismuth salt that dissolves in nitric acid, is selected from nitrate, acetate, sulfate, the carbonate one or more; Described silicon source is to be selected from silica gel, silica sol liquid, silicate or the organosilicon acid esters one or more.
3. according to the preparation method of claim 1, wherein said acid solution is the mixture of acid and solvent, acid is for being selected from nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, the ethanedioic acid one or more, solvent be selected from water and can with the miscible alcohol of water, ether, aldehyde, ketone in one or more.
4. according to the preparation method of claim 1, silicon source solution is the mixture of silicon source and solvent, solvent be selected from water and can with the miscible alcohol of water, ether, aldehyde, ketone in one or more.
5. according to the preparation method of claim 1, wherein said alkaline matter is the mixture of alkali compounds and solvent, alkali compounds is to be selected from NaOH, ethylenediamine, ethamine or the ammonia one or more, solvent be selected from water and can with the miscible alcohol of water, ether, aldehyde, ketone in one or more.
6. according to the preparation method of claim 1, the mol ratio of the bismuth atom in silicon atom in the silicon source and the bismuth source is 15: 1～0.5: 1.
7. contain bismuth silicate Bi according to any preparation in the claim 1-6 item 2SiO 5The application of powdery catalysis material, it is characterized in that this material is to make catalyst in the oxidation reaction of oxidant in light-catalyzed reaction, with organic peroxide, inorganic peroxide or oxygen.
CN2008100705632A 2008-01-31 2008-01-31 Synthesis and applications of silicate containing Bi Expired - Fee Related CN101229510B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008100705632A CN101229510B (en) 2008-01-31 2008-01-31 Synthesis and applications of silicate containing Bi

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008100705632A CN101229510B (en) 2008-01-31 2008-01-31 Synthesis and applications of silicate containing Bi

Publications (2)

Publication Number Publication Date
CN101229510A CN101229510A (en) 2008-07-30
CN101229510B true CN101229510B (en) 2010-09-08

Family

ID=39896494

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008100705632A Expired - Fee Related CN101229510B (en) 2008-01-31 2008-01-31 Synthesis and applications of silicate containing Bi

Country Status (1)

Country Link
CN (1) CN101229510B (en)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101709508B (en) * 2009-11-10 2011-10-26 陕西科技大学 Preparation method of bismuth-containing eulytite bismuth silicate crystals
CN101816957B (en) * 2010-03-12 2011-11-09 华南师范大学 Photochemical preparation method of phyllosilicate loaded metal sulphide photocatalyst
CN101979320B (en) * 2010-10-12 2012-10-10 陕西科技大学 Method for preparing Bi2SiO5 powder by molten salt growth method
CN102275945B (en) * 2011-07-06 2012-10-17 陕西科技大学 Method for preparing scintillation bismuth silicon oxide powder
CN102275943B (en) * 2011-07-06 2012-10-17 陕西科技大学 Method of preparing bismuth silicate powder with molten-salt growth method
CN102275942A (en) * 2011-07-06 2011-12-14 陕西科技大学 Preparation method of bismuth silicate nanopowder
CN102351203B (en) * 2011-07-06 2013-01-23 陕西科技大学 Method for preparing flaky bismuth silicate powder
CN102275944A (en) * 2011-07-06 2011-12-14 陕西科技大学 Preparation method of new scintillating bismuth silicate powder
CN102716701B (en) * 2012-06-21 2014-07-23 华中师范大学 Method for preparing nickel-doped bismuth silicon oxide microspheres by ultrasonic spray
CN103145135B (en) * 2013-03-08 2014-11-19 中国科学院上海硅酸盐研究所 Method for preparing bismuth silicate nano-powder with single phase
CN103447024B (en) * 2013-09-10 2016-06-08 重庆大学 The preparation method of a kind of bismuthino strontium magnetic photocatalyst and bismuthino strontium magnetic photocatalyst thereof
CN105967721A (en) * 2016-05-05 2016-09-28 陕西科技大学 Preparation method of Bi2SiO5 porous material
CN105967747A (en) * 2016-05-05 2016-09-28 陕西科技大学 Stable-state Bi4Si3O12 porous material preparation method
CN105967722A (en) * 2016-05-05 2016-09-28 陕西科技大学 Preparation method of Bi4Si3O12 porous material
CN105967745A (en) * 2016-05-05 2016-09-28 陕西科技大学 Preparation method of porous stable state Bi12SiO20 block
CN105967746A (en) * 2016-05-05 2016-09-28 陕西科技大学 Preparation method of porous Bi2SiO5 block
CN108640123B (en) * 2018-05-02 2021-12-03 贵州大学 Preparation method of bismuth-titanium intercalated montmorillonite
CN108816243A (en) * 2018-06-11 2018-11-16 福州大学 A kind of propylene gas-phase epoxidation catalyst and preparation method thereof under normal pressure
CN108816242A (en) * 2018-06-11 2018-11-16 福州大学 A kind of low temperature propylene gas-phase epoxidation catalyst and preparation method thereof
CN109279614B (en) * 2018-11-13 2022-03-22 中山大学 Bi2SiO5Bismuth silicate film material and preparation method and application thereof
CN111330588A (en) * 2018-12-19 2020-06-26 福州大学 High-activity propylene gas-phase epoxidation catalyst and preparation method thereof
CN109529863A (en) * 2019-01-08 2019-03-29 福州大学 A kind of the stable type propylene and oxygen gas-phase epoxidation catalyst of high activity
US11123715B2 (en) 2019-11-22 2021-09-21 King Fahd University Of Petroleum And Minerals Mesoporous composite catalysts containing bismuth silicate and transition metal oxide
CN111017982B (en) * 2019-12-31 2022-02-01 中南大学 Nano-grade rare earth silicate powder material and application thereof
CN111437809B (en) * 2020-04-29 2023-08-01 江苏纳欧新材料有限公司 Preparation method and application of rare earth element doped bismuth silicate photocatalyst
CN114477745B (en) * 2021-12-31 2022-11-22 连云港晶大石英有限公司 Photosensitive quartz tube and preparation method thereof

Also Published As

Publication number Publication date
CN101229510A (en) 2008-07-30

Similar Documents

Publication Publication Date Title
CN101229510B (en) Synthesis and applications of silicate containing Bi
Jiang et al. Catalytic hydroxylation of benzene to phenol with hydrogen peroxide using catalysts based on molecular sieves
Hulea et al. Styrene oxidation with H2O2 over Ti-containing molecular sieves with MFI, BEA and MCM-41 topologies
EP1110910B1 (en) A titanium-silicalite molecular sieve and the method for its preparation
Shylesh et al. Vanadium-containing ordered mesoporous silicates: Does the silica source really affect the catalytic activity, structural stability, and nature of vanadium sites in V-MCM-41?
Eimer et al. Mesoporous titanosilicates synthesized from TS-1 precursors with enhanced catalytic activity in the α-pinene selective oxidation
CN100537427C (en) Titanosilicate, process for its production, and its use in producing oxidized compound
JP5669786B2 (en) Titanium-silicon molecular sieve and method for producing the same, and method for producing cyclohexanone oxime using the molecular sieve
Dapurkar et al. Novel mesoporous (Cr) MCM-48 molecular sieves: Promising heterogeneous catalysts for selective oxidation reactions
Oliveira et al. Limonene oxidation over V2O5/TiO2 catalysts
JPH1095610A (en) Production of micro-and mesoporous metallic silicate, formed product without containing binder and oxidation catalyst comprising the same compound
CN108793181B (en) Titanium-silicon molecular sieve, preparation and application thereof
JP5075498B2 (en) Method for producing titanosilicate
EP2914547B1 (en) A tin-containing zeolitic material having an mww-type framework structure
RO113812B1 (en) Oxidizing catalysts and process for utilizing the same
US6989444B2 (en) Process for producing lactam
US6387349B1 (en) Process for the microwave induced preparation of crystalline microporous titanium silicalite
US5885546A (en) Process for the preparation of titanium silicates
Somma et al. Oxidation of geraniol and other substituted olefins with hydrogen peroxide using mesoporous, sol–gel-made tungsten oxide–silica mixed oxide catalysts
CN102295524A (en) Method for preparing cyclohexanol and cyclohexanone by selective oxidation of cyclohexane
US6991678B2 (en) Process for preparing microporous crystalline titanium silicate
CN1982291B (en) Process for producing oxime
Subrahmanyam et al. Synthesis, characterisation and catalytic properties of vanadium substituted mesoporous aluminophosphates
US9371239B2 (en) Tin-containing zeolitic material having an MWW-type framework structure
Xin et al. Novel efficient synthesis of glycol monoethers over a niobium-containing MCM-41 mesoporous molecular sieve

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20100908

Termination date: 20180131