CN105236479A - Preparation method of high activity oxidized nanocrystalline cellulose based titanium dioxide - Google Patents
Preparation method of high activity oxidized nanocrystalline cellulose based titanium dioxide Download PDFInfo
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Abstract
The invention discloses a preparation method of nano titanium dioxide with a high catalytic activity. The preparation method comprises the following steps: preparing raw materials: a butyl titanate precursor and diformyl nanocrystalline cellulose, which is obtained through an oxidization treatment; optionally adding a thickening agent and a surfactant, preparing a butyl titanate solution and a diformyl nanocrystalline cellulose solution, mixing two solutions under high speed sheering to obtain a uniform mixture, and subjecting the mixture to a gelation and high temperature calcination treatment to obtain the target product. According to the preparation method, oxidized nanocrystalline cellulose rich in diformyl groups is taken as the basic material, and under the effects of auxiliary materials such as thickening agent, surfactant, and the like, during the process of hydrothermal-freeze drying and gradient-heating calcination, the n-butyl titanate precursor is induced to carry out crystallization so as to form wheat-ear-shaped nano titanium dioxide crystal particles. The crystal particles can be well dispersed in water, thus the efficiency on processing the pigments in wastewater is effectively improved, and the provided titanium dioxide can degrade more than 98.5% of methyl orange within 12 minutes, in the best case.
Description
Technical field
The present invention relates to a kind of preparation method of nano titanium oxide, particularly relate to a kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, belong to the preparing technical field of inorganic nonmetallic nanometer material.
Background technology
In recent years, day by day serious along with World Environment Problems, luminous energy catalysis has become the important means of degraded environmental pollutant.Titanium dioxide is inexpensive with it, nontoxic, the advantage of good stability, is used widely in photocatalysis field.In early stage research, mostly by titania powder and waste water composition suspension system, but its suspension system often also exist solid particulate easily reunite and catalyst efficiency difference etc. shortcoming, and one of its reason to be exactly the particle of titanium dioxide larger, dispersed poor, and the probability of collision of catalyzer and target molecule is low.Therefore, how to prepare and there is good dispersion and highly active titanium dioxide optical catalyst, become a hot issue in titanium dioxide Synthesis and applications field.Current numerous research has been devoted to that particle diameter is less, in the middle of the exploitation of the titania of state porous or polymolecularity, to increase its specific surface area, improve photocatalytic activity.
In the last few years, the preparation method of industry engineering technical personnel for the purpose of the stability improving titanium dioxide and photocatalytic activity aspect had done a large amount of research-and-development activitys, and its various modification approach also more to be seen in patent documentation and periodical literature.Based on Mierocrystalline cellulose as natural polymer the abundantest that a kind of earth is originated, there is renewable and characteristic that is fully biodegradable, and the hydroxyl that Mierocrystalline cellulose exists can impel titanium dichloride load in cellulosic surface, be conducive to the recycling of titanium dioxide, and Mierocrystalline cellulose itself has favourable absorption, can some organic pollutants in adsorbent solution, and there is the ability strengthening catalytic rate, alleviate the problem of environmental pollution well, therefore cause the very big concern of people.Prepare the method for nano titanium oxide using Mierocrystalline cellulose or nano-cellulose as base material/inductor, disclosed by following patent documentation:
1, Chinese invention patent specification sheets publication number CN103934036A (publication date on July 23rd, 2014) " a kind of preparation method of novel titanium dioxide-cellulose composite material " discloses a kind of preparation method of novel titanium dioxide-cellulose composite material, the mixing solutions of titanium tetrachloride and water is prepared by low temperature, then adding Mierocrystalline cellulose is that template carries out hyperthermic treatment, obtain titanium dioxide nanocrystalline and be carried on matrix material on Mierocrystalline cellulose, this matrix material has very strong catalytic capability under visible light, can fast by rhodamine B, the catalytic organism degradeds such as methylene blue.
2, Chinese invention patent specification sheets publication number CN103203206A (publication date on July 17th, 2013) " Cellulose/titanium dioxide/silica aerogel and preparation method thereof " discloses a kind of Cellulose/titanium dioxide/silica aerogel and preparation method thereof, it is mainly nucleome with nano-cellulose, nano titanium oxide in first load, and then coated silica layer, through ageing, aging, hydrophobization, the steps such as adhesion-molded and drying treatment, obtain Cellulose/titanium dioxide/silica aerogel, this aerogel has snappiness, high strength, the characteristic such as antibacterial, flak jackets can be widely used in, lagging material, the field such as compression-resistant material and speciality coating.
3, Chinese invention patent specification sheets publication number CN102522211A (publication date on June 27th, 2012) " a kind of method of preparing nanometer titanium dioxide slurry through cellulose acidification process " discloses a kind of method of preparing nanometer titanium dioxide slurry through cellulose acidification process, raw material comprises: titanium dioxide powder, acid solution dispersion agent, surface stabilizer, surfactant, first with acid solution process titanium dioxide powder.Then the titanium dioxide powder processed has been dissolved in surface stabilizer, tensio-active agent, in point solution that acid solution powder is mixed with, finally stirring heats up to concentrate and obtains certain density slurry, this product has raw material and is easy to get, cheap for manufacturing cost, stable performance and output efficiency advantages of higher.
4, Chinese invention patent specification sheets publication number CN102849964A (publication date on January 2nd, 2013) " preparation method of titanium dioxide nanometer microcrystal interface fusion structural material " discloses a kind of nano titania crystallite interface preparation method, the ethanolic soln of preparing titanium dioxide P25 powder, ethyl cellulose respectively, add propyl carbinol, water-bath steams ethanol and makes accurate colloid; With butyl (tetra) titanate, ethanol and ethyl acetate preparation precursor solution, with 1molL
-1salpeter solution, deionized water and second alcoholic liquor, be added dropwise to precursor solution and centrifugal, gets supernatant liquor and put into accurate colloid, obtain titanium dioxide slurry, be printed onto on conductive glass by titanium dioxide slurry by screen printing technique after grinding.In a kettle., add deionized water and concentrated hydrochloric acid, then tilt to put into reaction soln by above-mentioned conductive glass and react, obtain this material, this material effectively can improve the efficiency of dye sensitization solar battery.
5, the preparation method of the disclosed a kind of nano-fibre supported nano titanium oxide mesoporous material of Chinese invention patent specification sheets publication number CN103172897A (publication date on June 26th, 2013) " a kind of preparation method of nano-fibre supported nano titanium oxide mesoporous material ", this invention adopts bigger serface, the biomass cellulose nanofibrils of high length-diameter ratio is load, by solgel reaction by hydrogen bond by nano titanium oxide scion grafting in nanofiber surface, effective reaction area is provided for it, and stop the fast nucleation of gel titania particle, this technique can regulate mesoporous pore size by the moisture content in regulation and control mixed system, thus it is strong to obtain mechanical property, load effect is good, the composite mesoporous aerogel material that specific surface area is large.
6, Chinese invention patent specification sheets publication number CN1907864A (publication date on February 7th, 2007) " method of preparing nano titanium dioxide crystallization induced by nano microcrystalline cellulose " is disclosed a kind of using nano micro crystal cellulose as crystallization inductor, and induction preparation is square, the method for acicular nanometer titanium dioxide.The method first configures the nano micro crystal cellulose aqueous dispersions that weight percent concentration is 0.01% ~ 5%, add auxiliary agent again, after supersound process, compare for 1:1 ~ 1:150 by dry nano micro crystal cellulose and four titania weight, in nano micro crystal cellulose aqueous dispersions, drip titanium tetrachloride, stirring reaction at 20 DEG C ~ 120 DEG C, the reaction times is 2h-15h, by adjusting above-mentioned processing condition, nano titanium oxide that is square, needle-like can be obtained respectively.
In foregoing invention patent 1-4, the not mentioned use of Mierocrystalline cellulose in titanium dioxide compound preparation being of a size of Nano grade, and although patent of invention 5-6 employs nanofiber or nano micro crystal cellulose, but patent of invention 5 does not relate to the preparation of the titanium dioxide nanoparticle of specific form, and patent of invention 6 does not adopt the step of high-temperature calcination, and its to prepare product be square or needle-like.In addition, patent of invention 5-6 does not all mention the improvement degree of obtained nanometer titanium dioxide titanium products in catalytic activity.
In addition, preparation result in the prior art around nano titanium dioxide crystal shows, the dispersiveness of common particulate titanium dioxide in application system is poor, and cannot contact completely with target compound, to realize abundant reaction, this also greatly limit the range of application of its finished product.
How to prepare the titanium dioxide optical catalyst with good dispersion and high catalytic activity, becoming the problem that titanium dioxide optical catalyst industry engineering technical personnel extremely pay close attention to, is also the problem of titanium dioxide optical catalyst industry engineering technical personnel urgently R and D.
Summary of the invention
Object of the present invention, aim to provide a kind of preparation method with highly active oxidation nanometer titanium dioxide, described preparation method is for adopting homogeneous sol and high-temperature calcination, the main raw material selected is presoma and base material, auxiliary material is thickening material, tensio-active agent, or tensio-active agent is not added in mixed solution, described presoma is mainly tetrabutyl titanate, described base material is the oxidation nanometer crystalline cellulose being rich in dialdehyde base, described thickening material is inorganic salts thickening material, described tensio-active agent is anion surfactant, or amphoterics or nonionogenic tenside, in preparation manipulation process, by being controlled dialdehyde base nanometer crystal Mierocrystalline cellulose to butyl (tetra) titanate degree of gelation in hydro-thermal-freezing dry process, and combine the calcination processing means slowly heated up, advantageously a kind of pattern of inductive formation is the high-activity nano sized titanium dioxide crystal grain of wheat head shape, this crystal grain has good distribution in water, and effectively can improve its processing efficiency to pigment in waste water, thus overcome the deficiency of prior art existence.
For realizing object of the present invention, the technical scheme adopted is:
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, it is characterized in that: described highly active oxidation nanometer crystalline cellulose based titanium dioxide main raw material is presoma and nano-grade cellulosic base material, auxiliary material is thickening material, tensio-active agent, or tensio-active agent is not added in mixed solution, described presoma is mainly tetrabutyl titanate, described base material is the oxidation nanometer crystalline cellulose being rich in dialdehyde base, described thickening material is inorganic salts thickening material, described tensio-active agent is anion surfactant, or amphoterics or nonionogenic tenside, adopt the preparation method of homogeneous sol and high-temperature calcination, be prepared into the oxidation nanometer crystalline cellulose based titanium dioxide in wheat head pattern, the preparation method of described homogeneous sol and high-temperature calcination, comprise five step by step rapid:
One), under low velocity shear, the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent, or does not add tensio-active agent in colloidal solution;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction;
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloidal solution B;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape;
Above-mentioned five step by step rapid operating process are as follows:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent, or does not add tensio-active agent in colloidal solution
Getting tetrabutyl titanate presoma joins in appropriate organic solvent solution, the mass ratio of presoma and organic solvent is 1:5 ~ 8, by one/multiple thickening material, one/kinds of surface promoting agent, add in colloidal solution after mixing, or do not add tensio-active agent in colloidal solution, adding hydrochloric acid modulation pH is 3 ~ 4, low velocity shear machine process 25min ~ 35min and prepare to obtain the organic solvent solution A of presoma, the speed control of shears low velocity shear is 2000r/min ~ 3000r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is that 3:1 ~ 6:1 takes sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, it is 40 DEG C ~ 60 DEG C in temperature in the material concentration of 5% ~ 8%, pH reacts 4h ~ 6h under the condition of 3 ~ 4.5, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 6000 μm of ol/g ~ 7500 μm ol/g (being measured by the alkali method that consumes) can be obtained, products obtained therefrom is rhabdolith structure, further by the colloid emulsion B that the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose is 3% ~ 8%,
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 5000r/min ~ 8000r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 20000r/min ~ 23000r/min down cut 5min ~ 10min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 3 ~ 4;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, hydro-thermal shearing treatment 0.5h ~ 1h is carried out under the rotating speed of 18000r/min ~ 20000r/min, it is 45 DEG C ~ 55 DEG C that bath temperature controls, by gained colloidal sol after room temperature condition ageing 48h ~ 50h, carry out lyophilize, time of drying, control was 8 ~ 10h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 415 DEG C ~ 435 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained after calcination processing 1h at this temperature ~ 1.5h, this crystal morphology is special wheat head shape, and reactive behavior is high.
Described dialdehyde base oxidation nanometer crystalline cellulose, for the nanocrystalline cellulose being rich in aldehyde radical obtained through sodium periodate oxidation process, its size index is length 30nm ~ 180nm, diameter 2nm ~ 60nm, described Cellulose nanocrystal is self-control or commercially available, approach of wherein making by oneself can by hydrolysis, enzymolysis or mechanical treatment sulfate wood pulp, cotton pulp, linters, the biomass starting material of agricultural waste material, or synthesize bacteria cellulose by mushroom, or extraction obtains cellulose substances from tunicate, wherein the typical preparation process of an example is described below: commercially available vitriol needle cotton starch plate, it is 3% ~ 6% that material concentration controls, at 38 DEG C, 1h ~ 3h is reacted in the sulfuric acid acid solution of 64.3%, dilution, centrifugal, washing, obtained after dry.
Described thickening material, be sodium-chlor, ammonium chloride, the Repone K of inorganic salts thickening material, its add-on is 2% ~ 8%.
Described tensio-active agent is that anion surfactant is aided with amphoterics or nonionogenic tenside, wherein anion surfactant is sodium lauryl sulphate, polyoxyethylenated alcohol sodium sulfate, Xylo-Mucine, fatty alcohol polyoxyethylene ether sulfate, Seconary Alkane Sulphonate Sodium, wherein amphoterics or nonionogenic tenside are Oleum Cocois single ethanol amide, ethylene glycol bisthioglycolate hard fatty acid ester.
Described physical shear process adopts high-speed shearing machine to carry out, wherein in the process for preparation of precursor solution, adopt slow-revving 2000r/min ~ 3000r/min, adopt high-revolving 20000r/min ~ 23000r/min when preparing mixed solution, and in hydrothermal treatment process, adopt high-revolving 18000r/min ~ 20000r/min.
Described calcination processing step, is staged temperature-rise period, is first warming up to 200 DEG C with the step rate of 5 DEG C/min, then adjust temperature rise rate be 15 DEG C/min until 415 DEG C ~ 435 DEG C, calcination processing 1h at this temperature ~ 1.5h.
The pattern of described nano titanium dioxide crystal particle is wheat head shape form.
Compared with prior art, the advantage that has of the present invention and beneficial effect as follows:
Advantage
Selected substrate material takes from the natural fiber after oxide treatment, security and biodegradability high, the favorable repeatability of product preparation flow.And the nano titanium oxide in wheat head shape pattern can give its higher catalytic reaction activity.
Beneficial effect
1, the present invention adopts oxidation nanometer crystalline cellulose containing dialdehyde group as base material first, and the technological guide presoma tetrabutyl titanate crystallization combined by high speed shear homogeneous and hydrothermal treatment consists becomes the crystal grain of wheat head shape pattern nano titanium oxide; Meanwhile, by process optimization, changed by the treatment step of high-temperature calcination and become staged heating mode, finally obtain a kind of nano titanium oxide of wheat head shape pattern, it has good water dispersible and high reactive behavior.
2, the raising of titanium dioxide reactive behavior can suitably reduce its consumption, thus reduces the disadvantageous effect to environment, and effectively reduces its application cost.
3, provide one highly active, in the preparation technology of the titania nanoparticles of wheat head shape pattern, this both opened a Tiao Xin road for the application of cellulose materials, also effectively extended the range of application of titanium dioxide.
4, the Application Areas of nano titania of the present invention is extensive, can as photocatalyst material, solar cell material and lithium ion battery negative material etc.
Accompanying drawing explanation
Fig. 1 is the atomic force microscope images (wheat head shape, magnification ratio is shown in scale) of the high-activity nano titanium dioxide of wheat head shape pattern.
Embodiment
Below in conjunction with specific embodiment, technical scheme of the present invention is further described.
Embodiment 1
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, adopt the preparation method of homogeneous sol and high-temperature calcination, its raw materials is made up of presoma and base material two parts, and be aided with thickening material, tensio-active agent, or tensio-active agent is not added in mixed solution, presoma is wherein tetrabutyl titanate, described base material is the oxidation nanometer crystalline cellulose being rich in dialdehyde base, auxiliary material then comprises inorganic salts thickening material, and anion surfactant be aided with appropriate amphoterics or nonionogenic tenside, the pattern of the titanium dioxide crystal particle of described preparation is wheat head shape, highly active nano-scale solid particulate, in water, there is good distribution, and effectively can improve its processing efficiency to pigment in waste water, its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent, or does not add tensio-active agent in colloidal solution
Getting tetrabutyl titanate presoma joins in appropriate organic solvent solution, the mass ratio of presoma and organic solvent is 1:5 ~ 1:8, by one/multiple thickening material, one/kinds of surface promoting agent, add to after mixing in colloidal solution, or tensio-active agent is not added in colloidal solution, adding hydrochloric acid modulation pH is 3 ~ 4, the present embodiment pH is 3.5, low velocity shear machine process 25min ~ 35min, process 30min in the present embodiment, and prepare to obtain the organic solvent solution A of presoma, the speed control of shears low velocity shear is 2000r/min ~ 3000r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is 3:1 ~ 6:1, the present embodiment mass ratio is designed to 4:1, take sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, in the material concentration of 5% ~ 8%, the present embodiment material concentration is designed to 6%, it is 40 DEG C ~ 60 DEG C in temperature, the present embodiment temperature design 40 DEG C, pH is under the condition of 3 ~ 4.5, the present embodiment pH designs 4.5, reaction 4h ~ 6h, the present embodiment reaction times design 4h, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 6000 μm of ol/g ~ 7500 μm ol/g (being measured by the alkali method that consumes) can be obtained, aldehyde group content that the present embodiment obtains is up to 6800 μm of ol/g, product is rhabdolith structure, further by the colloid emulsion B that the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose is 3% ~ 8%, the concentration of the oxidation nanometer crystalline cellulose that the present embodiment obtains is 6%,
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 5000r/min ~ 8000r/min, the present embodiment comparatively slow speed of revolution is designed to 6000r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 20000r/min ~ 23000r/min down cut 5min ~ 10min, shear time in the present embodiment is 10min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 3 ~ 4, the pH of the present embodiment hierarchy of control is 3;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, hydro-thermal shearing treatment 0.5h ~ 1h is carried out under the rotating speed of 18000r/min ~ 20000r/min, it is 45 DEG C ~ 55 DEG C that bath temperature controls, in the present embodiment, time of hydro-thermal shearing treatment and bath temperature are controlled as 1h and 45 DEG C, by gained colloidal sol after room temperature condition ageing 48h ~ 50h, carry out lyophilize, control time of drying, for 8h ~ 10h, to be respectively the present embodiment digestion time and time of drying 50h and 9h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 415 DEG C ~ 435 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained after calcination processing 1h at this temperature ~ 1.5h, its pattern is wheat head shape, as shown in Figure 1, and reactive behavior is high.
Described presoma is tetrabutyl titanate.
Described organic solvent is ethanol, and the mixture of one or both solvents in Virahol, selects ethanol in the present embodiment, and wherein the mass ratio of butyl (tetra) titanate and ethanol is 1:5.
Described dialdehyde base oxidation nanometer crystalline cellulose, be the nanocrystalline cellulose being rich in aldehyde radical obtained through sodium periodate oxidation process, its size index is length 30nm ~ 180nm, diameter 2nm ~ 60nm.Described Cellulose nanocrystal is self-control or commercially available, approach of wherein making by oneself can by the biomass starting material of hydrolysis, enzymolysis or mechanical treatment sulfate wood pulp, cotton pulp, linters, agricultural waste material, or synthesize bacteria cellulose by mushroom, or extraction obtains cellulose substances from tunicate, wherein the typical preparation process of an example is described below: commercially available vitriol needle cotton starch plate, it is 3% ~ 6% that material concentration controls, in the sulfuric acid acid solution of 64.3%, at 38 DEG C, react 1h ~ 3h, dilution, centrifugal, washing, dry after obtained.
Described thickening material, be sodium-chlor, ammonium chloride, the Repone K of inorganic salts thickening material, select sodium-chlor in the present embodiment, its add-on is 0.5g.
Described tensio-active agent is that anion surfactant is aided with amphoterics or nonionogenic tenside, wherein anion surfactant preferably sodium dodecyl sulfate, polyoxyethylenated alcohol sodium sulfate, Xylo-Mucine, fatty alcohol polyoxyethylene ether sulfate, Seconary Alkane Sulphonate Sodium, wherein amphoterics or nonionogenic tenside are Oleum Cocois single ethanol amide, ethylene glycol bisthioglycolate hard fatty acid ester, select sodium lauryl sulphate and ethylene glycol bisthioglycolate hard fatty acid ester in the present embodiment, its consumption is respectively 0.25g and 0.1g.
Described physical shear process adopts high-speed shearing machine to carry out, wherein in the process for preparation of precursor solution, adopt slow-revving 2000r/min ~ 3000r/min, select 3000r/min in the present embodiment, high-revolving 20000r/min ~ 23000r/min is adopted when preparing mixed solution, the present embodiment adopts 20000r/min, and in hydrothermal treatment process, adopt high-revolving 18000r/min ~ 20000r/min, and the present embodiment is implemented to select 19000r/min.
Described calcination processing step, for staged temperature-rise period, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 415 DEG C ~ 435 DEG C, calcination processing 1h at this temperature ~ 1.5h, the concrete heating step that this enforcement adopts is first be warming up to 200 DEG C with the step rate of 5 DEG C/min, and then adjusting speed is that 15 DEG C/min is warming up to 415 DEG C, calcination processing 1h at this temperature.
Described nano titanium dioxide crystal particle, its pattern is wheat head shape, as shown in Figure 1.
Evaluate titanium dioxide granule reactive behavior: adopt tropeolin-D to carry out assess sample photocatalysis performance under ultraviolet light as photodegradation object, the nano titanium oxide prepared by 0.1g joins in 50mL mass concentration 20mg/L tropeolin-D standardized solution, the ultraviolet high voltage mercury lamp of 250W is adopted to carry out irradiating (luminous range 10cm) after stirring, after 3min sample thief is centrifugal, by its absorbancy of spectrophotometric determination, and the degradation rate calculating tropeolin-D is known, titanium dioxide crystal particle reaction activity prepared by the present invention is high, the degradation rate of tropeolin-D can be made in 12min more than 96.5%.
Embodiment 2
A kind of preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process is identical with embodiment 1, be just Virahol and the thickening material selected unlike: the organic solvent selected be Repone K, and in mixed solution, do not add amphoteric surface's agent alive, its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent
Getting 5g tetrabutyl titanate presoma joins in Virahol, the mass ratio of tetrabutyl titanate and Virahol is 1:6.5, by 0.2g Repone K thickening material, 0.35g polyoxyethylenated alcohol sodium sulfate anion surfactant, 0.15g Oleum Cocois single ethanol amide nonionogenic tenside is added in mixed solution respectively, adding hydrochloric acid modulation pH is 3, low velocity shear machine process 25min and prepare to obtain the organic solvent solution A of presoma, and the speed control of shears low velocity shear is 2000r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is that 3:1 takes sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, it is 47 DEG C in temperature in the material concentration of 6.5%, pH reacts 5h under the condition of 3, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 6800 μm of ol/g (being measured by the alkali method that consumes) can be obtained, products obtained therefrom is rhabdolith structure, is the colloid emulsion B of 6% further by the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose;
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 5000r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 20000r/min down cut 10min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 3.5;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Be transferred in water bath with thermostatic control by above-mentioned mixed emulsion, under the rotating speed of 20000r/min, carry out hydro-thermal shearing treatment 0.5h, it is 45 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 50h, carries out lyophilize, controls time of drying as 10h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 435 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained at this temperature after calcination processing 1h, its pattern is wheat head shape, as shown in Figure 1, and reactive behavior is high.
Evaluate titanium dioxide crystal particle reaction active: adopt tropeolin-D to carry out assess sample photocatalysis performance under ultraviolet light as photodegradation object, the nano titanium oxide prepared by 0.1g joins in 50mL mass concentration 20mg/L tropeolin-D standardized solution, the ultraviolet high voltage mercury lamp of 250W is adopted to carry out irradiating (luminous range 10cm) after stirring, after 3min sample thief is centrifugal, by its absorbancy of spectrophotometric determination, and the degradation rate calculating tropeolin-D is known, titanium dioxide crystal particle reaction activity prepared by the present invention is high, the degradation rate of tropeolin-D can be made in 12min more than 97.2%.
Embodiment 3
A preparation method for highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process is identical with embodiment 1, be just Virahol and the thickening material selected unlike: the organic solvent selected is ammonium chloride.Its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent
Getting 6g tetrabutyl titanate presoma joins in Virahol, the mass ratio of tetrabutyl titanate and Virahol is 1:5.5, by 0.5g ammonium chloride thickening material, 0.3g sodium lauryl sulphate anion surfactant, 0.15g ethylene glycol bisthioglycolate hard fatty acid ester nonionogenic tenside is added in mixed solution respectively, adding hydrochloric acid modulation pH is 3.5, low velocity shear machine process 28min and prepare to obtain the organic solvent solution A of presoma, and the speed control of shears low velocity shear is 2300r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is that 4:1 takes sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, it is 45 DEG C in temperature in the material concentration of 7%, pH reacts 6h under the condition of 4.5, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 6200 μm of ol/g (being measured by the alkali method that consumes) can be obtained, products obtained therefrom is rhabdolith structure, is the colloid emulsion B of 8% further by the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose;
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 5000r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 22000r/min down cut 8min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 3;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Be transferred in water bath with thermostatic control by above-mentioned mixed emulsion, under the rotating speed of 19000r/min, carry out hydro-thermal shearing treatment 1h, it is 50 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 48h, carries out lyophilize, controls time of drying as 8h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape pattern
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 420 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained at this temperature after calcination processing 1h, its pattern is wheat head shape, as shown in Figure 1, and reactive behavior is high.
Evaluate titanium dioxide granule reactive behavior: adopt tropeolin-D to carry out assess sample photocatalysis performance under ultraviolet light as photodegradation object, the nano titanium oxide prepared by 0.1g joins in 50mL mass concentration 20mg/L tropeolin-D standardized solution, the ultraviolet high voltage mercury lamp of 250W is adopted to carry out irradiating (luminous range 10cm) after stirring, after 3min sample thief is centrifugal, by its absorbancy of spectrophotometric determination, and the degradation rate calculating tropeolin-D is known, titanium dioxide crystal particle reaction activity prepared by the present invention is high, the degradation rate of tropeolin-D can be made in 12min more than 96.7%.
Embodiment 4
A preparation method for highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process is identical with embodiment 1, be just Virahol and the thickening material selected unlike: the organic solvent selected is Repone K, and its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent
Getting 5g tetrabutyl titanate presoma joins in Virahol, the mass ratio of tetrabutyl titanate and Virahol is 1:7, by 0.8g Repone K thickening material, 0.35g Xylo-Mucine anion surfactant, 0.15g Oleum Cocois single ethanol amide nonionogenic tenside is added in mixed solution respectively, adding hydrochloric acid modulation pH is 3, low velocity shear machine process 30min and prepare to obtain the organic solvent solution A of presoma, and the speed control of shears low velocity shear is 2200r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is that 5:1 takes sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, it is 50 DEG C in temperature in the material concentration of 6%, pH reacts 5.5h under the condition of 3, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 7300 μm of ol/g (being measured by the alkali method that consumes) can be obtained, products obtained therefrom is rhabdolith structure, is the colloid emulsion B of 8% further by the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose;
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 5500r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 23000r/min down cut 7min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 3.5;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Be transferred in water bath with thermostatic control by above-mentioned mixed emulsion, under the rotating speed of 20000r/min, carry out hydro-thermal shearing treatment 1h, it is 50 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 50h, carries out lyophilize, controls time of drying as 9h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 435 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained at this temperature after calcination processing 1.2h, its pattern is wheat head shape, as shown in Figure 1, and reactive behavior is high.
Evaluate titanium dioxide granule reactive behavior: adopt tropeolin-D to carry out assess sample photocatalysis performance under ultraviolet light as photodegradation object, the nano titanium oxide prepared by 0.1g joins in 50mL mass concentration 20mg/L tropeolin-D standardized solution, the ultraviolet high voltage mercury lamp of 250W is adopted to carry out irradiating (luminous range 10cm) after stirring, after 3min sample thief is centrifugal, by its absorbancy of spectrophotometric determination, and the degradation rate calculating tropeolin-D is known, titanium dioxide crystal particle reaction activity prepared by the present invention is high, the degradation rate of tropeolin-D can be made in 12min more than 98%.
Embodiment 5
A preparation method for highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process is identical with embodiment 1, be just Virahol and the thickening material selected unlike: the organic solvent selected is ammonium chloride, and its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent
Getting 5g tetrabutyl titanate presoma joins in Virahol, the mass ratio of tetrabutyl titanate and Virahol is 1:5, by 0.6g ammonium chloride thickening material, 0.5g fatty alcohol polyoxyethylene ether sulfate anion surfactant, 0.15g ethylene glycol bisthioglycolate hard fatty acid ester nonionogenic tenside is added in mixed solution respectively, adding hydrochloric acid modulation pH is 3.5, low velocity shear machine process 28min and prepare to obtain the organic solvent solution A of presoma, and the speed control of shears low velocity shear is 2300r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is that 6:1 takes sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, it is 43 DEG C in temperature in the material concentration of 8%, pH reacts 5.5h under the condition of 4, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 6500 μm of ol/g (being measured by the alkali method that consumes) can be obtained, products obtained therefrom is rhabdolith structure, is the colloid emulsion B of 8% further by the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose;
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 5000r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 20000r/min down cut 8min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 3;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Be transferred in water bath with thermostatic control by above-mentioned mixed emulsion, under the rotating speed of 19000r/min, carry out hydro-thermal shearing treatment 0.55h, it is 48 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 48h, carries out lyophilize, controls time of drying as 8h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape pattern
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 425 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained at this temperature after calcination processing 1.5h, its pattern is wheat head shape, as shown in Figure 1, and reactive behavior is high.
Evaluate titanium dioxide granule reactive behavior: adopt tropeolin-D to carry out assess sample photocatalysis performance under ultraviolet light as photodegradation object, the nano titanium oxide prepared by 0.1g joins in 50mL mass concentration 20mg/L tropeolin-D standardized solution, the ultraviolet high voltage mercury lamp of 250W is adopted to carry out irradiating (luminous range 10cm) after stirring, after 3min sample thief is centrifugal, by its absorbancy of spectrophotometric determination, and the degradation rate calculating tropeolin-D is known, titanium dioxide crystal particle reaction activity prepared by the present invention is high, the degradation rate of tropeolin-D can be made in 12min more than 97%.
Embodiment 6
A preparation method for highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process is identical with embodiment 1, be just Virahol and the thickening material selected unlike: the organic solvent selected is Repone K, and its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent
Getting 3g tetrabutyl titanate presoma joins in Virahol, the mass ratio of tetrabutyl titanate and Virahol is 1:6, by 0.35g Repone K thickening material, 0.5g Seconary Alkane Sulphonate Sodium anion surfactant, 0.15g ethylene glycol bisthioglycolate hard fatty acid ester nonionogenic tenside is added in mixed solution respectively, adding hydrochloric acid modulation pH is 3.5, low velocity shear machine process 28min and prepare to obtain the organic solvent solution A of presoma, and the speed control of shears low velocity shear is 2800r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is that 5:1 takes sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, it is 55 DEG C in temperature in the material concentration of 6.5%, pH reacts 5.5h under the condition of 3, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 7200 μm of ol/g (being measured by the alkali method that consumes) can be obtained, products obtained therefrom is rhabdolith structure, is the colloid emulsion B of 6.5% further by the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose;
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 8000r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 22000r/min down cut 8min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 4;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Be transferred in water bath with thermostatic control by above-mentioned mixed emulsion, under the rotating speed of 19500r/min, carry out hydro-thermal shearing treatment 1h, it is 55 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 48h, carries out lyophilize, controls time of drying as 9h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape pattern
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 430 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained at this temperature after calcination processing 1.5h, its pattern is wheat head shape, as shown in Figure 1, and reactive behavior is high.
Evaluate titanium dioxide granule reactive behavior: adopt tropeolin-D to carry out assess sample photocatalysis performance under ultraviolet light as photodegradation object, the nano titanium oxide prepared by 0.1g joins in 50mL mass concentration 20mg/L tropeolin-D standardized solution, the ultraviolet high voltage mercury lamp of 250W is adopted to carry out irradiating (luminous range 10cm) after stirring, after 3min sample thief is centrifugal, by its absorbancy of spectrophotometric determination, and the degradation rate calculating tropeolin-D is known, titanium dioxide crystal particle reaction activity prepared by the present invention is high, the degradation rate of tropeolin-D can be made in 12min more than 97.8%.
Embodiment 7
A preparation method for highly active nano titanium oxide, its step of preparation process is identical with embodiment 1, just unlike: the thickening material selected is Repone K, and does not add tensio-active agent, and its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, add thickening material in the solution
Getting 5.5g tetrabutyl titanate presoma joins in Virahol, the mass ratio of tetrabutyl titanate and Virahol is 1:7.5,0.95g Repone K thickening material is added in mixed solution, adding hydrochloric acid modulation pH is 3, low velocity shear machine process 30min and prepare to obtain the organic solvent solution A of presoma, the speed control of shears low velocity shear is 2500r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is that 3.5:1 takes sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, it is 52 DEG C in temperature in the material concentration of 7.5%, pH reacts 6h under the condition of 4, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 7000 μm of ol/g (being measured by the alkali method that consumes) can be obtained, products obtained therefrom is rhabdolith structure, is the colloid emulsion B of 6% further by the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose;
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 6500r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 21000r/min down cut 9min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 3.5;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Be transferred in water bath with thermostatic control by above-mentioned mixed emulsion, under the rotating speed of 20000r/min, carry out hydro-thermal shearing treatment 1h, it is 55 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 50h, carries out lyophilize, controls time of drying as 9h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape pattern
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 425 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained at this temperature after calcination processing 1.2h, its pattern is wheat head shape, as shown in Figure 1, and reactive behavior is high.
Evaluate titanium dioxide granule reactive behavior: adopt tropeolin-D to carry out assess sample photocatalysis performance under ultraviolet light as photodegradation object, the nano titanium oxide prepared by 0.1g joins in 50mL mass concentration 20mg/L tropeolin-D standardized solution, the ultraviolet high voltage mercury lamp of 250W is adopted to carry out irradiating (luminous range 10cm) after stirring, after 3min sample thief is centrifugal, by its absorbancy of spectrophotometric determination, and the degradation rate calculating tropeolin-D is known, titanium dioxide crystal particle reaction activity prepared by the present invention is high, the degradation rate of tropeolin-D can be made in 12min more than 97.5%.
Embodiment 8
A preparation method for highly active oxidation nanometer crystalline cellulose based titanium dioxide, its step of preparation process is identical with embodiment 1, just unlike: the thickening material selected is ammonium chloride, and does not add tensio-active agent, and its preparation process operating process is:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, add thickening material in the solution
Getting 7g tetrabutyl titanate presoma joins in Virahol, the mass ratio of tetrabutyl titanate and Virahol is 1:8, by 0.95g ammonium chloride thickening material, 0.9g polyoxyethylenated alcohol sodium sulfate anion surfactant, 0.55g Oleum Cocois single ethanol amide and 0.3g ethylene glycol bisthioglycolate hard fatty acid ester nonionogenic tenside are added in mixed solution, adding hydrochloric acid modulation pH is 3.5, low velocity shear machine process 30min and prepare to obtain the organic solvent solution A of presoma, the speed control of shears low velocity shear is 2600r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is that 4.5:1 takes sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, it is 50 DEG C in temperature in the material concentration of 5%, pH reacts 6h under the condition of 3.5, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 7500 μm of ol/g (being measured by the alkali method that consumes) can be obtained, products obtained therefrom is rhabdolith structure, is the colloid emulsion B of 6.5% further by the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose;
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 6000r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 22500r/min down cut 10min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 3;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Be transferred in water bath with thermostatic control by above-mentioned mixed emulsion, under the rotating speed of 20000r/min, carry out hydro-thermal shearing treatment 1h, it is 55 DEG C that bath temperature controls, and by gained colloidal sol after room temperature condition ageing 49h, carries out lyophilize, controls time of drying as 10h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape pattern
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 435 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained at this temperature after calcination processing 1.5h, its pattern is wheat head shape, as shown in Figure 1, and reactive behavior is high.
Evaluate titanium dioxide granule reactive behavior: adopt tropeolin-D to carry out assess sample photocatalysis performance under ultraviolet light as photodegradation object, the nano titanium oxide prepared by 0.1g joins in 50mL mass concentration 20mg/L tropeolin-D standardized solution, the ultraviolet high voltage mercury lamp of 250W is adopted to carry out irradiating (luminous range 10cm) after stirring, after 3min sample thief is centrifugal, by its absorbancy of spectrophotometric determination, and the degradation rate calculating tropeolin-D is known, titanium dioxide crystal particle reaction activity prepared by the present invention is high, the degradation rate of tropeolin-D can be made in 12min more than 98.5%.
In the present invention, adopt and degrade obtained nanocrystalline cellulose after sodium periodate oxidation by natural fiber, obtain a kind of oxidation nanometer crystalline cellulose being rich in dialdehyde group, using it as supporting substrates, and in conjunction with the effect of the auxiliary material such as thickening material, tensio-active agent, heat up in the reaction process of calcining in hydro-thermal-lyophilize and follow-up staged, it is wheat head shape nano titanium dioxide crystal particle that the crystallization of induction presoma tetrabutyl titanate becomes pattern.
In the present invention, described tetrabutyl titanate, thickening material and tensio-active agent, be chemical reagent.
Pattern of the present invention is wheat head shape nano titanium dioxide crystal particle, reports in China's patent documentation and periodical literature owing to having not yet to see, and therefore pattern of the present invention is the first report of the real genus of wheat head shape nano titanium dioxide crystal particle.This invention product has good aqueous dispersion, has good value for applications.
The excellent performance of product of the present invention, utilisation technology can contain multiple field such as assembling and synthesis of photochemical catalysis, finishing material, lagging material, solar cell and lithium ion battery negative material.
It is high that the inventive method prepares titanium dioxide crystal particle wheat head pattern particle reaction activity, tropeolin-D is adopted to carry out assess sample photocatalysis performance under ultraviolet light as photodegradation object, the oxidation nanometer crystalline cellulose of the 7500 μm ol/gs (by alkali consume method measured) the highest by aldehyde group content of 0.1g is joined in 50mL mass concentration 20mg/L tropeolin-D standardized solution as the titanium dioxide prepared by carrier, the ultraviolet high voltage mercury lamp of 250W is adopted to carry out irradiating (luminous range 10cm) after stirring, after 3min sample thief is centrifugal, by its absorbancy of spectrophotometric determination, and it is known after calculating the degradation rate of tropeolin-D, the titanium dioxide crystal beaded catalyst of this invention product can make the degradation rate of tropeolin-D more than 98.5% in 12min.
The above is only the preferred embodiment of the present invention; it should be pointed out that the professional for the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (9)
1. the preparation method of a highly active oxidation nanometer crystalline cellulose based titanium dioxide, it is characterized in that: described highly active oxidation nanometer crystalline cellulose based titanium dioxide main raw material is presoma and nano-grade cellulosic base material, auxiliary material is thickening material, tensio-active agent, or tensio-active agent is not added in mixed solution, described presoma is mainly tetrabutyl titanate, described base material is the oxidation nanometer crystalline cellulose being rich in dialdehyde base, described thickening material is inorganic salts thickening material, described tensio-active agent is anion surfactant, or amphoterics or nonionogenic tenside, adopt the preparation method of homogeneous sol and high-temperature calcination, be prepared into the oxidation nanometer crystalline cellulose based titanium dioxide in wheat head shape pattern, the preparation method of described homogeneous sol and high-temperature calcination, comprise five step by step rapid:
One), under low velocity shear, the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent, or does not add tensio-active agent in colloidal solution;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction;
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloidal solution B;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape;
Above-mentioned five step by step rapid operating process are as follows:
One), the organic solvent solution A of preparation presoma tetrabutyl titanate, selectivity adds thickening material in the solution, tensio-active agent, or does not add tensio-active agent in colloidal solution
Getting tetrabutyl titanate presoma joins in appropriate organic solvent solution, the mass ratio of presoma and organic solvent is 1:5 ~ 1:8, by one/multiple thickening material, one/kinds of surface promoting agent, add in colloidal solution after mixing, or do not add tensio-active agent in colloidal solution, adding hydrochloric acid modulation pH is 3 ~ 4, low velocity shear machine process 25min ~ 35min and prepare to obtain the organic solvent solution A of presoma, the speed control of shears low velocity shear is 2000r/min ~ 3000r/min;
Two) the colloid emulsion B of dialdehyde base oxidation nanometer crystalline cellulose, is obtained by oxidizing reaction
Sodium periodate in mass ratio: nanocrystalline cellulose is that 3:1 ~ 6:1 takes sample, be transferred in there-necked flask, flask leads to nitrogen lucifuge, it is 40 DEG C ~ 60 DEG C in temperature in the material concentration of 5% ~ 8%, pH reacts 4h ~ 6h under the condition of 3 ~ 4.5, the bis oxide aldehyde radical nanocrystalline cellulose of aldehyde group content up to 6000 μm of ol/g ~ 7500 μm ol/g (being measured by the alkali method that consumes) can be obtained, products obtained therefrom is rhabdolith structure, further by the colloid emulsion B that the concentration controlling the add-on of deionized water and obtain oxidation nanometer crystalline cellulose is 3% ~ 8%,
Three), keep pH in suitable scope, under slow-revving physical shear, solution A is dropwise added in colloid emulsion B
Under the comparatively slow speed of revolution of 5000r/min ~ 8000r/min, the organic solvent solution A of presoma tetrabutyl titanate is dropwise dripped in the colloid emulsion B of hydrotropisms's carrier, after dropping terminates, improve rotating speed to 20000r/min ~ 23000r/min down cut 5min ~ 10min, two kinds of emulsions are fully mixed, in the process, by adding the pH of hydrochloric acid and the hierarchy of control in 3 ~ 4;
Four), hydrothermal treatment consists in conjunction with lyophilize, fully complete gel reaction
Above-mentioned mixed emulsion is transferred in water bath with thermostatic control, hydro-thermal shearing treatment 0.5h ~ 1h is carried out under the rotating speed of 18000r/min ~ 20000r/min, it is 45 DEG C ~ 55 DEG C that bath temperature controls, by gained colloidal sol after room temperature condition ageing 48h ~ 50h, carry out lyophilize, control time of drying as 8h ~ 10h;
Five), high-temperature calcination, slowly heated up by rate mode, be incubated, obtain the target product of wheat head shape
The gel of freeze-drying is transferred in High Temperature Furnaces Heating Apparatus, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjusting temperature rise rate is that 15 DEG C/min is until 415 DEG C ~ 435 DEG C, the Powdered titanium dioxide crystal particle of white can be obtained after calcination processing 1h at this temperature ~ 1.5h, this crystal grain pattern is wheat head shape, and reactive behavior is high.
2. the preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide according to claim 1, it is characterized in that: described presoma, is tetrabutyl titanate.
3. the preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide according to claim 1, it is characterized in that: described organic solvent, is ethanol, the mixture of one or both solvents in Virahol.
4. the preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide according to claim 1, it is characterized in that: described dialdehyde base oxidation nanometer crystalline cellulose, for the nanocrystalline cellulose being rich in aldehyde radical obtained through sodium periodate oxidation process, its size index is length 30nm ~ 180nm, diameter 2nm ~ 60nm, described Cellulose nanocrystal is self-control or commercially available, approach of wherein making by oneself can by hydrolysis, enzymolysis or mechanical treatment sulfate wood pulp, cotton pulp, linters, the biomass starting material of agricultural waste material, or synthesize bacteria cellulose by mushroom, or extraction obtains cellulose substances from tunicate, wherein the typical preparation process of an example is described below: commercially available vitriol needle cotton starch plate, it is 3% ~ 6% that material concentration controls, at 38 DEG C, 1h ~ 3h is reacted in the sulfuric acid acid solution of 64.3%, dilution, centrifugal, washing, obtained after dry.
5. the preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide according to claim 1, it is characterized in that: described thickening material, be sodium-chlor, ammonium chloride, the Repone K of inorganic salts thickening material, its add-on is 2% ~ 8%.
6. the preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide according to claim 1, it is characterized in that: described tensio-active agent is that anion surfactant is aided with amphoterics or nonionogenic tenside, wherein anion surfactant preferably sodium dodecyl sulfate, polyoxyethylenated alcohol sodium sulfate, Xylo-Mucine, fatty alcohol polyoxyethylene ether sulfate, Seconary Alkane Sulphonate Sodium, wherein amphoterics or the preferred Oleum Cocois single ethanol amide of nonionogenic tenside, ethylene glycol bisthioglycolate hard fatty acid ester.
7. the preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide according to claim 1, it is characterized in that: described physical shear process adopts high-speed shearing machine to carry out, wherein in the process for preparation of precursor solution, adopt slow-revving 2000r/min ~ 3000r/min, adopt high-revolving 20000r/min ~ 23000r/min when preparing mixed solution, and in hydrothermal treatment process, adopt high-revolving 18000r/min ~ 20000r/min.
8. the preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide according to claim 1, it is characterized in that: described calcination processing step, for staged temperature-rise period, first 200 DEG C are warming up to the step rate of 5 DEG C/min, then adjust temperature rise rate be 15 DEG C/min until 415 DEG C ~ 435 DEG C, calcination processing 1h at this temperature ~ 1.5h.
9. the preparation method of highly active oxidation nanometer crystalline cellulose based titanium dioxide according to claim 1, is characterized in that: the pattern of described nano titanium dioxide crystal particle is wheat head shape form.
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Cited By (8)
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| CN105936514A (en) * | 2016-06-12 | 2016-09-14 | 长兴中昊化工有限公司 | Making process of rutile type titanium dioxide nano-powder |
| CN108034007A (en) * | 2017-12-06 | 2018-05-15 | 江南大学 | A kind of preparation method of dialdehyde cellulose nano whisker |
| CN108043399A (en) * | 2017-12-13 | 2018-05-18 | 南京林业大学 | A kind of method that nanocrystalline cellulose template prepares photochemical catalyst |
| CN110551326A (en) * | 2019-08-23 | 2019-12-10 | 北京化工大学 | Cellulose nanocrystal/titanium dioxide chiral nematic structure composite film and preparation method thereof |
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| JP2021527028A (en) * | 2018-11-19 | 2021-10-11 | チョーチアン チンイー ニュー マテリアル テクノロジー カンパニー リミテッドＺｈｅｊｉａｎｇ Ｊｉｎｇｙｉ Ｎｅｗ Ｍａｔｅｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．Ｌｔｄ | Inorganic-organic hybrid core shell type nanorod and light bulb with the nanorod |
| CN113668252A (en) * | 2021-08-23 | 2021-11-19 | 无锡市鸿庆无纺布有限公司 | Nano non-woven fabric based on nano cellulose antibacterial material and preparation method thereof |
| CN114477279A (en) * | 2022-01-19 | 2022-05-13 | 陕西瑞科新材料股份有限公司 | Green preparation method of nano titanium dioxide |
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| CN105936514A (en) * | 2016-06-12 | 2016-09-14 | 长兴中昊化工有限公司 | Making process of rutile type titanium dioxide nano-powder |
| CN108034007A (en) * | 2017-12-06 | 2018-05-15 | 江南大学 | A kind of preparation method of dialdehyde cellulose nano whisker |
| CN108043399A (en) * | 2017-12-13 | 2018-05-18 | 南京林业大学 | A kind of method that nanocrystalline cellulose template prepares photochemical catalyst |
| JP2021527028A (en) * | 2018-11-19 | 2021-10-11 | チョーチアン チンイー ニュー マテリアル テクノロジー カンパニー リミテッドＺｈｅｊｉａｎｇ Ｊｉｎｇｙｉ Ｎｅｗ Ｍａｔｅｒｉａｌ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．Ｌｔｄ | Inorganic-organic hybrid core shell type nanorod and light bulb with the nanorod |
| US11248168B2 (en) | 2018-11-19 | 2022-02-15 | Zhejiang Jingyi New Material Technology Co. Ltd | Inorganic-organic hybrid core-shell nanorod and light valve having the nanorod |
| JP7026847B2 (en) | 2018-11-19 | 2022-02-28 | チョーチアン チンイー ニュー マテリアル テクノロジー カンパニー リミテッド | Inorganic-organic hybrid core shell type nanorods and light bulbs with the nanorods |
| CN110551326A (en) * | 2019-08-23 | 2019-12-10 | 北京化工大学 | Cellulose nanocrystal/titanium dioxide chiral nematic structure composite film and preparation method thereof |
| CN111704161A (en) * | 2020-06-15 | 2020-09-25 | 闽江学院 | Hierarchical titanium dioxide microspheres and preparation method and application thereof |
| CN111704161B (en) * | 2020-06-15 | 2022-09-13 | 闽江学院 | Hierarchical titanium dioxide microspheres and preparation method and application thereof |
| CN113668252A (en) * | 2021-08-23 | 2021-11-19 | 无锡市鸿庆无纺布有限公司 | Nano non-woven fabric based on nano cellulose antibacterial material and preparation method thereof |
| CN114477279A (en) * | 2022-01-19 | 2022-05-13 | 陕西瑞科新材料股份有限公司 | Green preparation method of nano titanium dioxide |
| CN114477279B (en) * | 2022-01-19 | 2024-06-04 | 陕西瑞科新材料股份有限公司 | Green preparation method of nano titanium dioxide |
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