CN104549377B - I2 doping TiO2The hydrothermal preparing process of nanocatalyst and its purposes of catalysis trans-carotenoid configuration conversion - Google Patents
I2 doping TiO2The hydrothermal preparing process of nanocatalyst and its purposes of catalysis trans-carotenoid configuration conversion Download PDFInfo
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Abstract
The present invention relates to the purposes that the hydrothermal preparing process of the non-photochemical catalyst of I2 doping nano titania and its heterogeneous catalysis trans-carotenoid configuration convert.The preparation method quickly prepares high activity I2 doping nano titania catalyst using the pre- crystallization of hydro-thermal and vacuum baking group technology, titanium dioxide nano granule first is prepared with hydro-thermal method, then vacuum dried vacuum baking technique obtains I2 doping nano titania catalyst.Compared with I2 doping nano titania catalyst prepared by the sol-gal process of routine, the catalyst crystal degree prepared by the present invention significantly improves, heat endurance greatly improves, the preparation technology cycle significantly shortens and organic solvent usage amount is greatly reduced.The catalyst is converted into its cis-isomer to catalysis alltrans carotenoid has high activity, has the advantages that transformation time is short, transformation efficiency is high, catalytic activity is stable and repeatable utilization.
Description
Technical field
The present invention relates to a kind of preparation method of nanocatalyst and its heterogeneous catalysis trans-carotenoid configuration to convert
Purposes, particularly one kind using the pre- crystallization of hydro-thermal-vacuum baking group technology quickly prepares high activity I2 doping titanium dioxide
The method of nanocatalyst, for anti-configuration carotenoid to be converted into cis-configuration carotenoid.Belong to inorganic nano
Catalysis material and technical field of health-care food production.
Background technology
Carotenoid is a kind of compound with special physiological function and pharmacological function, is had to health important
Effect.Under the space steric effect that methylates, the conjugated double bond in carotenoid molecule can not arbitrarily rotate, therefore carotenoids
Element has the steric isomer far below theoretical amount.Common lycopene steric isomer includes that alltrans, 5- be cis, 7-
It is cis, 9- is cis, 13- is cis and 15- is cis etc., common beta carotene steric isomer include alltrans, 9- it is cis,
13- is cis and 15- cis-isomers etc..
Natural carotenoid in food (such as tomato) mainly exists with alltrans structure, and in tissue and cell
In then based on cis-configuration.Existing result of study shows, the carotenoid such as All-cislycopene, cis β of cis-configuration-
Carrotene generally all has the biological value higher than its all trans isomer, stronger physiologically active.In addition, cis tomato
The antioxidation activity of 5- cis-isomers and stability highest in red pigment, 9- cis-isomers suppress dynamic in Cis-β-Carotene
Pulse atherosclerosis, reduce the active most strong of cancer illness rate.Therefore, the accounting of cis-configuration in carotenoid is improved, particularly
9- Cis-β-Carotene accountings in 5- All-cislycopenes accounting or beta carotene are improved in lycopene, will be expected to significantly carry
The physiologically active of high carotenoid product.
Using carotenoid as raw material, the common side of high-cis configuration accounting carotenoid is prepared by isomerization processing
Method has thermic isomerization technique and photoisomerization technology.
Thermic isomerization technique refers to be heated to reflux in organic phase, or directly heats under certain condition to promote it
Configuration converts from alltrans configuration to cis-configuration.Patent PCT/EP2007/006747, PCT/EP02/00708,
US7126036, CN101575256 individually disclose one kind and are heated to reflux preparing All-cislycopene technology in organic phase, but
These technology generally existing complex operations, the shortcomings that cycle is long, 5- All-cislycopene contents are low.
Photoisomerization technology can be divided into direct photochemistry isomery technology and iodine promotees photochemistry isomery technology.Direct photochemistry
Isomery technology, i.e., under the conditions of certain temperature and certain wave-length coverage illumination, take and keep away oxygen measure and make the double bond of active component
Locate the method that cis- anti-configuration conversion occurs for group.CN10131 4554 discloses one kind and utilizes direct photochemistry isomerization reaction,
The method that All-cislycopene isomers is prepared using all-trans lycopene as raw material.There is obvious for photoisomerization technology
Deficiency, such as need special reaction unit；Reaction scale is difficult to scale up；If using iodine as catalyst, first iodine
Easily distillation loss, it is more difficult to be removed after second reacting, and the security of product does not ensure, while inevitable add is produced into
This.
In addition to above-mentioned thermic isomerization technique and photoisomerization technology, CN201410736320.3 discloses one kind
The method converted using I2 doping nano titania catalyst heterogeneous catalysis trans-carotenoid configuration.But the I2 doping
Nano titania method for preparing catalyst exist product degree of crystallization is low, heat endurance is poor, cost of material is higher, prepare
The shortcomings of process cycle length and solvent are difficult to reclaim caused environmental issue, so as to cause the preparation of the catalyst not only to be given birth to
Production efficiency is low, pollution environment, and wastes iodine resource, and which also limits its industrial applications.
Products therefrom purity is high because it has for hydrothermal synthesis method, good dispersion, the advantages that granularity is easy to control, in catalyst etc.
Field is applied.Patent CN103418334A discloses a kind of high absorbent-type N, I codopes TiO2Porous network structure powder
Hydrothermal preparing process, and the porous powder made from has carried out Adsorption experiment to dye of positive ion solution.Patent
CN103638953A discloses a kind of system of I2 doping titanium dioxide-graphene composite photocatalyst of degradable organic pollutant
Preparation Method.It yet there are no and prepare high activity I2 doping nano titania using the pre- crystallization of hydro-thermal and vacuum baking group technology
Catalyst, and use it for being catalyzed the document report of trans-carotenoid configuration conversion.
The content of the invention
It is an object of the invention to overcome the shortcomings of prior art CN201410736320.3, there is provided a kind of pre- crystalline substance of hydro-thermal
Change-vacuum baking group technology prepares the quick and environmentally friendly preparation method of I2 doping nano titania catalyst, the catalysis
Agent can be used for catalysis lycopene, beta carotene to obtain the carotenoid of high-cis configuration accounting, as ordinary food dispensing,
Functional food ingredient or dietary supplements raw material.
Technical scheme is as follows：
The preparation method of I2 doping nano titania catalyst, it is comprised the following steps that：
(1) the pre- crystallization of hydro-thermal
Iodine compound will be contained, complexing agent is added in the aqueous solution, be well mixed, obtain mixture A；Inhibitor is added
Into titanate esters, it is well mixed, obtains mixture B；In room temperature and under being stirred vigorously, mixture B is slowly dropped to mixture A
In, after being added dropwise, continue to stir 2-6h, obtain titania sol liquid；Titania sol liquid is placed in hydrothermal reaction kettle
Container in, reacted under the conditions of 80-160 DEG C of temperature, time 12-36h, reaction solution is isolated to the nanoscale dioxy of pre- crystallization
Change titanium；
(2) vacuum baking is handled
By the titanium dioxide obtained in step (1) after 60-100 DEG C, vacuum are 0.1MPa dryings 12h, first grinding
Into titania powder；In vacuum it is 0.1MPa by it, under the conditions of temperature is 160-220 DEG C, is calcined 2.0-4.0h, grinds again
Mill obtains I2 doping nano titania catalyst.
Described is KI or sodium iodide containing iodine compound；
Described titanate esters are butyl titanate or tetraisopropyl titanate；
Described inhibitor is acetic acid or acetylacetone,2,4-pentanedione；
Described complexing agent is polyvinylpyrrolidone or polyethylene glycol.
Mass ratio containing iodine compound and titanate esters is 2: 100-6: 100；
The volume ratio of inhibitor and titanate esters 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 catalyst heterogeneous catalysis trans-carotenoid configuration conversion, being will be anti-
Lycopene or beta carotene, the catalyst and ethyl acetate of formula are heated to reflux under the conditions of lucifuge, and reaction terminates reaction solution warp
After cooling, centrifugation catalyst, then through ethyl acetate is evaporated in vacuo, obtain lycopene or the β-carrot of high-cis accounting
Element.
Beneficial effects of the present invention
Compared with having been reported technique, the innovation that the present invention prepares I2 doping nano titania catalyst is：
(1) by after titanate esters and inhibitor mixed, directly prepare colloidal sol with the reactant aqueous solution containing complexing agent, the step without
Need ethanol to act on, thus solvent use cost is greatly reduced than prior art；
(2) colloidal sol in above-mentioned (1) is subjected to hydro-thermal reaction, rather than the sol-gel process using prior art.This is changed
The advantage entered is：First, reacted mixed liquor only needs centrifugally operated to may separate out the Nano titanium dioxide of pre- crystallization,
This also allows for the recycling of organic solvent, so as to reduce the production cost of catalyst, and the ageing of prior art processes
During, solvent is difficult to be recycled, so as to which present invention addresses environmental issue existing for prior art；Its
It is secondary, the step for the time required to be only prior art aging step 1/8 or so, so as to substantially increase the effect of catalyst preparation
Rate；
(3) present invention gained catalyst not only increases it and urged compared with existing I2 doping nano titania catalyst
Change the activity of all-trans-carotenoid isomerization, and that it has that crystallinity is high, thermostabilization is good, catalytic activity is more stable is excellent
Point.
Catalyst obtained by the application is isomerized to cis-isomer to catalysis anti-configuration carotenoid and shows high work
Property, total All-cislycopene accounting reaches more than 75% in product during for lycopene isomerization, for being catalyzed beta carotene
Total Cis-β-Carotene accounting reaches more than 50% in product during isomerization, and the cis tomato reds of 5- that can obtain high level
Element and 9- Cis-β-Carotenes.The catalyst preparation time is about only the 1/4 of existing sol-gel law technology.The catalyst has
There is the characteristics of simple preparation technology, efficient, economy, reuse, be environment-friendly.The cis class Hu trailing plants that the catalyst obtains
Bu Su is favorably improved the feature of health food, so as to widen carotenoid application field.
Brief description of the drawings
The catalyst obtained in Fig. 1 embodiment of the present invention 5 is according to catalyst activity evaluation method in the content of the invention, catalysis
HPLC spectrograms after isomerization all-trans lycopene (purity 90%) reaction 2h.From fig. 1, it can be seen that total All-cislycopene phase
It is 83.75 to percentage composition, wherein the percentage contents of 5- All-cislycopenes are 19.91.
The catalyst obtained in Fig. 2 embodiment of the present invention 5 is according to catalyst activity evaluation method in the content of the invention, catalysis
HPLC spectrograms after isomerization content full cis-beta-carotene (purity 90%) reaction 2h.As can be seen from Figure 2, total Cis-β-Carotene
Percentage contents are 55.62, and wherein the percentage contents of 9- Cis-β-Carotenes are 22.78.
The catalyst obtained in Fig. 3 embodiment of the present invention 5, the picture figure obtained through transmission electron microscope (TEM) detection, can from Fig. 3
Know, catalyst is nano level particle.
The catalyst obtained in Fig. 4 embodiment of the present invention 5 with reference examples 1, the spectrum obtained through X-ray diffraction (XRD) detection
Figure, as can be seen from Figure 4, present invention gained catalyst is single Anatase, and its better crystallinity degree is in existing sol-gel law technology
's.
The catalyst obtained in Fig. 5 embodiment of the present invention 5, the N for detecting to obtain through specific surface area measuring instrument2Adsorption-desorption
Curve and corresponding graph of pore diameter distribution, the specific surface area that sample is calculated according to BET equations and BJH methods is 189.851m2/ g, put down
Equal aperture isAs can be seen from Figure 5, there is obvious hysteresis loop in catalyst sample detection, and adsorption isotherm is in typical
IV types, it has meso-hole structure.
Catalyst before the vacuum baking obtained in Fig. 6 and Fig. 7 embodiment of the present invention 5 and reference examples 1, through thermogravimetric analysis
The spectrogram that instrument (TG) detection obtains, it was found from Fig. 6 and Fig. 7, in the range of 50~200 DEG C, the gained catalyst weightlessness of embodiment 5 is only
1.465%, far below the 10.76% of reference examples 1, this explanation present invention gained catalyst has good heat endurance.
The catalyst obtained in Fig. 8 embodiment of the present invention 5 and the catalyst of reference examples 1, according to catalyst in the content of the invention
Activity rating method, it, can from Fig. 7 with influence result block diagram of the increase of recycling number to lycopene isomerization
Know, the catalyst obtained in embodiment 5 reacts 1 time to 5 times, and total All-cislycopene percentage contents drop from 83.75
To 71.4, and the catalytic reaction of reference examples 1 its percentage contents are down to 60.03 from 79.41.With catalyst recycling time
Several increases, the reason for total All-cislycopene percentage contents decline：First, the increase of number is reused with catalyst,
Unavoidably there is catalyst quality loss；Second, there is mass loss in the active iodine of titanium dichloride load.This explanation the application institute
The stability of catalyst is obtained higher than existing sol-gel law technology.
Embodiment
For a better understanding of the present invention, with reference to embodiment, the present invention is described in further detail, but the present invention
Claimed scope is not limited to the scope that embodiment is limited.
Reagent is purchased from Chemical Reagent Co., Ltd., Sinopharm Group, no special instruction used by following examples of the present invention
It is that analysis is pure, wherein butyl titanate (relative density 0.996), tetraisopropyl titanate are pure for chemistry.
In order to more clearly express the pre- crystallization of hydro-thermal-vacuum heat treatment process operating procedure in the embodiment of the present invention, with
Just compareed with prior art (CN201410736320.3), it is detailed that present invention gained method for preparing catalyst is divided into following 6 steps
State, 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 polyvinylpyrrolidones are added in 20mL deionization pure water, mixed
Uniformly, mixture A is obtained；
(2) 0.5mL acetic acid is added in 10mL butyl titanates (closing 10g), is well mixed, obtains mixture B；
(3) under room temperature and intense agitation, mixture B is slowly dropped in mixture A, after being added dropwise, after
Continuous stirring 2h；
(4) reaction solution of step (3) is placed in the container of hydrothermal reaction kettle, it is anti-under the conditions of 80 DEG C of temperature, time 12h
Should, the centrifuged titanium dioxide precipitation of reaction solution；
(5) by the titanium dioxide precipitation obtained in step (4) after 60 DEG C, vacuum are 0.1MPa dryings 12h, for the first time
It is ground into titania powder；
(6) titania powder that will be obtained in step (5), it is 0.1MPa in vacuum, under the conditions of temperature is 160 DEG C,
2h is calcined, regrinding obtains I2 doping nano titania catalyst.
The evaluation of catalytic activity：In 25mL round-bottomed flask, be separately added into 20mg purity be 90% lycopene or
Person's beta carotene, 10mg catalyst and 20mL ethyl acetate；Round-bottomed flask is connected into condensing unit and nitrogen oxygen exhauster
Afterwards, it is placed in lucifuge in 77 DEG C of water-baths and reacts 2h, ice-water bath cooling, after 10,000 r/min centrifuge 10min, takes 100 μ L reaction solutions, use
Ethyl acetate is settled to 5mL, after 0.22 μm of membrane filtration, with liquid chromatograph, with area normalization method respectively at 472nm
Detect lycopene and Isomers percentage contents in beta carotene are detected at 450nm.Chromatographic column：YMC C30 posts (5
μm, 250mm × 4.6mm)；Mobile phase：A phases：Methanol: acetonitrile=25: 75, B phases：Methyl tertiary butyl ether(MTBE) 100%；Gradient condition：0
~20min, A phase are reduced to 50% by 100%, and 20~40min, A phases keep 50%；Sample solvent：Ethyl acetate；Flow velocity：
1mL/min；Column temperature：30℃；Sample size：20μL.Total All-cislycopene percentage contents are 60.26, total cis β-carrot
Plain percentage contents are 35.38.
Raw material and process conditions such as table 1 show used by embodiment 2 to 6 each step of embodiment：
Table 1
Reference examples 1 are that sol-gel process prepares I2 doping nanocatalyst, according to this case catalyst activity evaluation method,
It is compared with the embodiment 5 of hydro-thermal method, and raw material and process conditions are as shown in table 2 used by each step：
Table 2
It was found from the reference examples 1 of table 2 are compared with the catalytic result of the gained catalyst of embodiment 5, the present invention improves catalysis
The activity of agent, and hydro-thermal method acts in step (1) and (2) without ethanol, so as to greatly reduce the preparation cost of catalyst.
Hydro-thermal method only needs 12h in step 3, and is not only substantially increased for up to 96h, hydrothermal process needed for sol-gel process
The preparation efficiency of catalyst, and only need centrifugation to separate and recover solvent, waved so as to solve solvent in colloidal sol-gel method
The problem of environmental protection and catalyst preparation cost caused by hair improve.To sum up, hydro-thermal method prepares I2 doping nanocatalyst technique
It is more applicable for industrialized production needs.
The above-mentioned embodiment technical scheme that the invention is not limited in any way, it is every to use equivalent substitution or wait
The technical scheme that the mode of effect conversion is obtained all falls within protection scope of the present invention.
Claims (3)
1. a kind of purposes of the non-photochemical catalyst heterogeneous catalysis trans-carotenoid configuration conversion of I2 doping nano titania,
It is heated to reflux with trans lycopene or beta carotene and ethyl acetate under the conditions of lucifuge respectively, reaction is anti-after terminating
Liquid is answered after cooling down, centrifuge catalyst, then through ethyl acetate is evaporated in vacuo, you can obtain cis-configuration accounting and reach 75%
Lycopene or cis-configuration accounting above reaches more than 50% beta carotene；
The non-photochemical catalyst of I2 doping nano titania is made by following technique：
(1) the pre- crystallization of hydro-thermal
Iodine compound will be contained, complexing agent is added in the aqueous solution, be well mixed, obtain mixture A；Inhibitor is added to metatitanic acid
In ester, it is well mixed, obtains mixture B；In room temperature and under being stirred vigorously, mixture B is slowly dropped in mixture A, dripped
After adding, continue to stir 2-6h, obtain titania sol liquid；Titania sol liquid is placed in the container of hydrothermal reaction kettle
In, reacted under the conditions of 80-160 DEG C of temperature, time 12-36h, reaction solution is isolated to the nanoscale titanium dioxide of pre- crystallization
Titanium；
(2) vacuum baking is handled
By the titanium dioxide obtained in step (1) after 60-100 DEG C, vacuum 0.1MPa dry 12h, dioxy is ground into for the first time
Change titanium powder；By it in vacuum 0.1MPa, under the conditions of temperature is 160-220 DEG C, 2.0-4.0h is calcined, regrinding obtains iodine
The non-photochemical catalyst of doping titanium dioxide nano.
2. purposes according to claim 1, it is characterised in that be respectively used to be catalyzed lycopene, beta carotene isomerization
When, it can quickly obtain that 5- All-cislycopene accountings reach 19.91% lycopene and 9- Cis-β-Carotene accountings reach
To 22.78% beta carotene.
3. purposes according to claim 1, it is characterised in that the non-photochemical catalyst of I2 doping nano titania is single
The TiO of one Anatase2。
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| 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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| CN102188986A (en) * | 2011-03-31 | 2011-09-21 | 北京化工大学 | Preparation of visible light response titanium base film and method for degrading binary dye |
| EP2730622A1 (en) * | 2012-11-07 | 2014-05-14 | Honeywell Romania S.R.L. | Dye-sensitized solar cells and methods of making same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102188986A (en) * | 2011-03-31 | 2011-09-21 | 北京化工大学 | Preparation of visible light response titanium base film and method for degrading binary dye |
| EP2730622A1 (en) * | 2012-11-07 | 2014-05-14 | Honeywell Romania S.R.L. | Dye-sensitized solar cells and methods of making same |
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| Preparation and characterization of PVA–I complex doped mesoporous TiO2 by hydrothermal method;Shi Qian等;《Applied Surface Science》;20130306;第273卷;第769-775页 * |
| 高含量全反式番茄红素的全合成方法研究;俞伊莎等;《浙江化工》;20141231;第45卷(第8期);第17-20,28页 * |
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