CN104549377A - Hydrothermal preparation method for iodine-doped TiO2 nano-catalyst and application thereof in catalysis of trans-carotene configuration inversion - Google Patents
Hydrothermal preparation method for iodine-doped TiO2 nano-catalyst and application thereof in catalysis of trans-carotene configuration inversion Download PDFInfo
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Abstract
The invention relates to a hydrothermal preparation method for an iodine-doped TiO2 nano-catalyst and an application thereof in heterogeneous catalysis of trans-carotene configuration inversion. The preparation method is characterized in that the high-activity iodine-doped TiO2 nano-catalyst is rapidly prepared by adopting a hydrothermal pre-crystallization and vacuum roasting combined process, namely, firstly TiO2 nanoparticles are prepared by using a hydrothermal method, and then the iodine-doped TiO2 nano-catalyst is prepared by adopting a vacuum drying-vacuum roasting process. According to the catalyst prepared by the method, compared with the iodine-doped TiO2 nano-catalyst prepared by the conventional sol-gel method, the crystallization degree is obviously improved, the thermal stability is greatly improved, the period of the preparation process is greatly shortened, and the use amount of the organic solvent is greatly reduced. The catalyst has high activity in catalyzing inversion from all-trans-carotene into cis-isomers thereof, and has the advantages of short inversion time, high inversion efficiency, stable catalytic activity, repeated utilization and the like.
Description
Technical field
The present invention relates to a kind of preparation method of nanocatalyst and the purposes of heterogeneous catalysis trans-carotenoid configuration conversion thereof, hydro-thermal pre-crystallization-vacuum baking combination process is particularly adopted to prepare a method for high reactivity I2 doping nano titania catalyzer fast, for transconfiguration carotenoid is converted into cis-configuration carotenoid.Belong to inorganic nano catalytic material and technical field of health-care food production.
Background technology
Carotenoid is the compound that a class has special physiological function and pharmacological function, to HUMAN HEALTH important role.Under the space steric effect that methylates, the conjugated double bond in carotenoid molecule can not rotate arbitrarily, and therefore carotenoid has the steric isomer far below theoretical amount.Common Lyeopene steric isomer comprises alltrans, 5-cis, 7-cis, 9-cis, 13-cis and 15-cis etc., and common β-carotene steric isomer comprises alltrans, 9-cis, 13-cis and 15-cis-isomeride etc.
Natural carotenoid in food (as tomato) mainly exists, then based on cis-configuration in tissue and cell with alltrans structure.Existing result of study shows, carotenoid such as All-cislycopene, the Cis-β-Carotene of cis-configuration all have the biological value higher than its all trans isomer, stronger physiologically active usually.In addition, in All-cislycopene the anti-oxidant activity of 5-cis-isomeride and stability the highest, in Cis-β-Carotene, 9-cis-isomeride suppresses atherosclerosis, to reduce the activity of cancer morbidity the strongest.Therefore, improve the accounting of cis-configuration in carotenoid, particularly to improve in Lyeopene 9-Cis-β-Carotene accounting in 5-All-cislycopene accounting or β-carotene, will the physiologically active significantly improving carotenoid product be expected to.
Take carotenoid as raw material, the common methods being prepared high-cis configuration accounting carotenoid by isomerization process has thermic isomerization technique and photoisomerization technology.
Thermic isomerization technique refers to reflux in organic phase, or direct heating promotes that its configuration transforms from alltrans configuration to cis-configuration under certain condition.Patent PCT/EP2007/006747, PCT/EP02/00708, US7126036, CN101575256 individually disclose a kind of in organic phase reflux prepare All-cislycopene technology, but these technology ubiquity complicated operations, the cycle is long, 5-All-cislycopene content is low shortcoming.
Photoisomerization technology can be divided into direct photochemistry isomery technology and iodine to urge photochemistry isomery technology.Direct photochemistry isomery technology, namely under certain temperature and a wavelength range illumination condition, takes to keep away oxygen measure and makes the double bond place group of activeconstituents that the method for cis-anti-configuration conversion occur.CN10131 4554 discloses one and utilizes direct photochemistry isomerization reaction, take all-trans lycopene as the method that All-cislycopene isomer prepared by raw material.Photoisomerization technology also exists obvious deficiency, such as, need special reaction unit; Reaction scale is difficult to expand; If take iodine as catalyzer, iodine easily distils loss first, and it is more difficult second to remove after reaction, and the security of product does not ensure, unavoidably adds production cost simultaneously.
Except above-mentioned thermic isomerization technique and photoisomerization technology, CN201410736320.3 discloses a kind of method utilizing I2 doping nano titania catalyzer heterogeneous catalysis trans-carotenoid configuration conversion.But this I2 doping nano titania method for preparing catalyst exists, and product degree of crystallization is low, thermostability is poor, raw materials cost is higher, preparation technology's cycle is long and solvent is difficult to reclaim the shortcomings such as the environmental issue brought, thus not only production efficiency is low, contaminate environment to cause the preparation of this catalyzer, and waste iodine resource, which also limits its industrial applications.
To have products therefrom purity high because of it for hydrothermal synthesis method, and the advantages such as good dispersity, granularity are easy to control, are applied in fields such as catalyzer.Patent CN103418334A discloses a kind of high adsorptive type N, I codoped TiO
2the hydrothermal preparing process of porous network structure powder, and with obtained porous powder, Adsorption experiment has been carried out to cationic dyestuff solution.Patent CN103638953A discloses a kind of preparation method of I2 doping titanium dioxide-graphene composite photocatalyst of degradable organic pollutant.Yet there are no and utilize the pre-crystallization of hydro-thermal and vacuum baking combination process to prepare high reactivity I2 doping nano titania catalyzer, and use it for the bibliographical information of catalysis trans-carotenoid configuration conversion.
Summary of the invention
The object of the invention is to the deficiency overcoming prior art CN201410736320.3, a kind of hydro-thermal pre-crystallization-vacuum baking combination process is provided to prepare the quick of I2 doping nano titania catalyzer and the preparation method of environmental protection, the carotenoid that this catalyzer can be used for catalysis Lyeopene, β-carotene obtains high-cis configuration accounting, as bread and cheese batching, functional food ingredient or dietary supplements raw material.
Technical scheme of the present invention is as follows:
The preparation method of I2 doping nano titania catalyzer, its concrete steps are as follows:
(1) the pre-crystallization of hydro-thermal
To join in the aqueous solution containing iodine compound, complexing agent, and mix, obtain mixture A; Inhibitor is joined in titanic acid ester, mix, obtain mixture B; Under room temperature and vigorous stirring, mixture B is slowly added drop-wise in mixture A, after dropwising, continues to stir 2-6h, obtain titania sol liquid; Titania sol liquid is placed in the container of hydrothermal reaction kettle, temperature 80-160 DEG C, react under time 12-36h condition, reaction solution is isolated to the Nano titanium dioxide of pre-crystallization;
(2) vacuum baking process
By the titanium dioxide obtained in step (1) through 60-100 DEG C, after vacuum tightness is the dry 12h of 0.1MPa, grind to form titania powder for the first time; Be 0.1MPa by it in vacuum tightness, temperature is under 160-220 DEG C of condition, roasting 2.0-4.0h, and grinding obtains I2 doping nano titania catalyzer again.
Described is potassiumiodide or sodium iodide containing iodine compound;
Described titanic acid ester is tetrabutyl titanate or titanium isopropylate;
Described inhibitor is acetic acid or methyl ethyl diketone;
Described complexing agent is polyvinylpyrrolidone or polyoxyethylene glycol.
Mass ratio containing iodine compound and titanic acid ester is 2: 100-6: 100;
The volume ratio of inhibitor and titanic acid ester is 1: 20-1: 1;
Complexing agent is 1: 50-1: 20 with the mass ratio containing iodine compound.
The purposes of I2 doping nano titania catalyzer heterogeneous catalysis trans-carotenoid configuration conversion, it is reflux under lucifuge condition by trans Lyeopene or β-carotene, catalyzer and ethyl acetate, reaction terminates reaction solution after cooling, centrifugation catalyzer, boil off ethyl acetate through vacuum again, obtain Lyeopene or the β-carotene of high-cis accounting.
Beneficial effect of the present invention
And have been reported compared with technique, the innovation that the present invention prepares I2 doping nano titania catalyzer is:
(1) by after titanic acid ester and inhibitor mixed, directly prepare colloidal sol with the reactant aqueous solution containing complexing agent, this step, without the need to ethanol effect, thus greatly reduces solvent use cost than prior art;
(2) colloidal sol in above-mentioned (1) is carried out hydro-thermal reaction, instead of adopt the sol-gel method of prior art.The advantage of this improvement is: first, reacted mixed solution only needs centrifugally operated can isolate the Nano titanium dioxide of pre-crystallization, this is also convenient to the recycling of organic solvent, thus reduce the production cost of catalyzer, and in the ageing process of prior art processes, solvent is difficult to be recycled, thus present invention addresses the environmental issue of prior art existence; Secondly, this step required time is only about 1/8 of prior art aging step, thus substantially increases the efficiency of catalyst preparing;
(3) gained catalyzer of the present invention is compared with existing I2 doping nano titania catalyzer, not only increases the isomerized activity of its catalysis all-trans-carotenoid, and it has high, thermally-stabilised good, the advantage that catalytic activity is more stable of degree of crystallinity.
The application's gained catalyzer turns to cis-isomeride to catalysis transconfiguration carotenoid isomery and demonstrates high reactivity, more than 75% is reached for All-cislycopene accounting total in product during Lyeopene isomerization, reach more than 50% for Cis-β-Carotene accounting total in product during the isomerization of catalysis β-carotene, and 5-All-cislycopene and the 9-Cis-β-Carotene of high level can be obtained.This catalyst preparation time is about only 1/4 of existing sol-gel law technology.This catalyzer has that preparation technology is simple, efficient, economical, recycling, eco-friendly feature.The cis carotenoid that this catalyst obtains contributes to improving the functional of protective foods, thus widens carotenoid Application Areas.
Accompanying drawing explanation
Fig. 1. the catalyzer obtained in the embodiment of the present invention 5 is according to catalyst activity evaluation method in summary of the invention, and isoversion all-trans lycopene (purity 90%) reacts the HPLC spectrogram after 2h.As can be seen from Figure 1, total All-cislycopene percentage contents is 83.75, and wherein the percentage contents of 5-All-cislycopene is 19.91.
Fig. 2. the catalyzer obtained in the embodiment of the present invention 5 is according to catalyst activity evaluation method in summary of the invention, and isoversion content full cis-beta-carotene (purity 90%) reacts the HPLC spectrogram after 2h.As can be seen from Figure 2, total Cis-β-Carotene percentage contents is 55.62, and wherein the percentage contents of 9-Cis-β-Carotene is 22.78.
Fig. 3. the catalyzer obtained in the embodiment of the present invention 5, detect the picture figure obtained through transmission electron microscope (TEM), as can be seen from Figure 3, catalyzer is nano level particle.
Fig. 4. the catalyzer obtained with reference examples 1 in the embodiment of the present invention 5, detect the spectrogram obtained through X-ray diffraction (XRD), as can be seen from Figure 4, gained catalyzer of the present invention is single Anatase, and its better crystallinity degree is in existing sol-gel law technology.
Fig. 5. the catalyzer obtained in the embodiment of the present invention 5, detects the N obtained through specific surface area measuring instrument
2adsorption-desorption curve and corresponding graph of pore diameter distribution, the specific surface area according to BET equation and BJH method calculation sample is 189.851m
2/ g, mean pore size are
as can be seen from Figure 5, catalyst sample detects and occurs obvious hysteresis loop, and adsorption isothermal line is typical IV type, and it has meso-hole structure.
Fig. 6 and Fig. 7. the catalyzer before the vacuum baking obtained in the embodiment of the present invention 5 and reference examples 1, the spectrogram obtained is detected through thermogravimetric analyzer (TG), from Fig. 6 and Fig. 7, within the scope of 50 ~ 200 DEG C, embodiment 5 gained catalyzer weightlessness only 1.465%, far below 10.76% of reference examples 1, this illustrates that gained catalyzer of the present invention has good thermostability.
Fig. 8. the catalyzer of the catalyzer obtained in the embodiment of the present invention 5 and reference examples 1, according to catalyst activity evaluation method in summary of the invention, its increase with recycling number of times affects result histogram to Lyeopene is isomerized, as can be seen from Figure 7, the catalyst obtained in embodiment 5 reacts 1 time to 5 times, total All-cislycopene percentage contents is down to 71.4 from 83.75, and its percentage contents of the catalyzed reaction of reference examples 1 is down to 60.03 from 79.41.With the increase of catalyzer recycling number of times, total the reason that All-cislycopene percentage contents declines: one is the increase with catalyzer recycling number of times, unavoidably has catalyst quality to lose; Two is that the active iodine of titanium dichloride load exists mass loss.This illustrates that the stability of the application gained catalyzer is higher than existing sol-gel law technology.
Embodiment
For a better understanding of the present invention, below in conjunction with embodiment, the present invention is described in further detail, but the scope of protection of present invention is not limited to the scope that embodiment is limit.
The reagent that following examples of the present invention adopt is all purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and be analytical pure without special instruction, wherein tetrabutyl titanate (relative density is 0.996), titanium isopropylate are chemical pure.
In order to hydro-thermal pre-crystallization-vacuum heat treatment process operation steps in the expression embodiment of the present invention clearly, to contrast with prior art (CN201410736320.3), gained method for preparing catalyst of the present invention is divided into following 6 steps and describes in detail, wherein step (1) ~ (4) are the pre-crystallization technical matters of hydro-thermal, and (5) and (6) are vacuum baking treatment technology technique.
Embodiment 1
(1) at normal temperatures, 200mg Kl, 4mg polyvinylpyrrolidone is joined in 20mL deionization pure water, mixes, obtain mixture A;
(2) 0.5mL acetic acid is joined in 10mL tetrabutyl titanate (closing 10g), mix, obtain mixture B;
(3) under room temperature and intense agitation, mixture B is slowly added drop-wise in mixture A, after dropwising, continues to stir 2h;
(4) reaction solution of step (3) is placed in the container of hydrothermal reaction kettle, react under temperature 80 DEG C, time 12h condition, reaction solution obtains titanium dioxide precipitation through centrifugal;
(5) by the titanium dioxide precipitation obtained in step (4) through 60 DEG C, after vacuum tightness is the dry 12h of 0.1MPa, grind to form titania powder for the first time;
(6) titania powder will obtained in step (5) is 0.1MPa in vacuum tightness, and temperature is under 160 DEG C of conditions, roasting 2h, and grinding obtains I2 doping nano titania catalyzer again.
The evaluation of catalytic activity: in the round-bottomed flask of 25mL, adds Lyeopene or β-carotene, 10mg catalyzer and 20mL ethyl acetate that 20mg purity is 90% respectively; After round-bottomed flask being connected condensing works and nitrogen oxygen exhauster, be placed in 77 DEG C of water-bath lucifuge reaction 2h, ice-water bath cools, after the centrifugal 10min of 10,000 r/min, get 100 μ L reaction solutions, be settled to 5mL by ethyl acetate, after 0.22 μm of membrane filtration, with liquid chromatograph, detect Lyeopene respectively at 472nm place with area normalization method and detect Isomers percentage contents in β-carotene at 450nm place.Chromatographic column: YMC C30 post (5 μm, 250mm × 4.6mm); Moving phase: A phase: methyl alcohol: acetonitrile=25: 75, B phase: methyl tertiary butyl ether 100%; Gradient condition: 0 ~ 20min, A phase reduces to 50% by 100%, 20 ~ 40min, A phase keeps 50%; Sample solvent: ethyl acetate; Flow velocity: 1mL/min; Column temperature: 30 DEG C; Sample size: 20 μ L.Total All-cislycopene percentage contents is 60.26, and total Cis-β-Carotene percentage contents is 35.38.
The raw material that each step of embodiment 2 to embodiment 6 adopts and processing condition such as table 1 show:
Table 1
Reference examples 1 prepares I2 doping nanocatalyst for sol-gel method, and according to this case catalyst activity evaluation method, it compares with the embodiment 5 of hydrothermal method, the raw material that each step adopts and processing condition as shown in table 2:
Table 2
Compare from the reference examples 1 of table 2 with the catalytic result of embodiment 5 gained catalyzer, invention increases the activity of catalyzer, and hydrothermal method in step (1) and (2) without the need to ethanol effect, thus greatly reduce the preparation cost of catalyzer.Hydrothermal method only needs 12h in step 3, and required time reaches 96h in sol-gel method, hydrothermal process not only substantially increases the preparation efficiency of catalyzer, and only need centrifugal can Separation and Recovery solvent, thus solve environmental protection that solvent evaporates in sol-gel method causes and the problem that catalyst preparing cost improves.To sum up, hydrothermal method is prepared I2 doping nanocatalyst technique and is more applicable for suitability for industrialized production needs.
Above-mentioned embodiment does not limit technical scheme of the present invention in any form, and the technical scheme that the mode that every employing is equal to replacement or equivalent transformation obtains all drops on protection scope of the present invention.
Claims (6)
1. the hydrothermal preparing process of I2 doping nano titania non-catalytic, is characterized in that adopting hydro-thermal pre-crystallization-vacuum baking combination process, and preparation speed is fast, and its step is as follows:
(1) the pre-crystallization of hydro-thermal
To join in the aqueous solution containing iodine compound, complexing agent, and mix, obtain mixture A; Inhibitor is joined in titanic acid ester, mix, obtain mixture B; Under room temperature and vigorous stirring, mixture B is slowly added drop-wise in mixture A, after dropwising, continues to stir 2-6h, obtain titania sol liquid; Titania sol liquid is placed in the container of hydrothermal reaction kettle, temperature 80-160 DEG C, react under time 12-36h condition, reaction solution is isolated to the Nano titanium dioxide of pre-crystallization.
(2) vacuum baking process
By the titanium dioxide that obtains in step (1) through 60-100 DEG C, after the dry 12h of vacuum tightness 0.1MPa, grind to form titania powder for the first time; By it at vacuum tightness 0.1MPa, temperature is under 160-220 DEG C of condition, roasting 2.0-4.0h, and grinding obtains I2 doping nano titania catalyzer again.
2. the preparation method of I2 doping nano titania catalyzer according to claim 1, is characterized in that described is potassiumiodide or sodium iodide containing iodine compound; Described titanic acid ester is tetrabutyl titanate or titanium isopropylate; Described inhibitor is acetic acid or methyl ethyl diketone; Described complexing agent is polyvinylpyrrolidone or polyoxyethylene glycol.
3. the preparation method of I2 doping nano titania catalyzer according to claim 1, is characterized in that the described mass ratio containing iodine compound and titanic acid ester is 2: 100-6: 100; The volume ratio of inhibitor and titanic acid ester is 1: 20-1: 1; Complexing agent is 1: 50-1: 20 with the mass ratio containing iodine compound.
4. based on I2 doping nano titania catalyst prod prepared by technique described in claim 1.It is characterized in that the TiO of single Anatase
2.
5. I2 doping nano titania catalyst prod according to claim 4, it has the purposes of heterogeneous catalysis trans-carotenoid configuration conversion, it is characterized in that its reflux under lucifuge condition with trans Lyeopene or β-carotene, catalyzer and ethyl acetate respectively, reaction terminates rear reaction solution after cooling, centrifugation catalyzer, boil off ethyl acetate through vacuum again, can obtain cis-configuration accounting reach more than 75% Lyeopene or cis-configuration accounting reach more than 50% β-carotene.
6. the purposes of I2 doping nano titania catalyzer heterogeneous catalysis trans-carotenoid configuration conversion according to claim 5, when it is characterized in that being respectively used to catalysis Lyeopene, β-carotene isomerization, can obtain fast 5-All-cislycopene accounting reach 19.91% Lyeopene and 9-Cis-β-Carotene accounting reach 22.78% β-carotene.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108047167A (en) * | 2017-12-26 | 2018-05-18 | 中国科学院海洋研究所 | A kind of method for preparing fucoxanthin cis-isomer |
| CN111153658A (en) * | 2020-02-28 | 2020-05-15 | 成都新柯力化工科技有限公司 | Diatom ooze for catalytically degrading formaldehyde by using visible light and preparation method thereof |
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