TWI257317B - Titanium dioxide photocatalyst synthetic method in crystallized form - Google Patents

Abstract

This invention brings up a titanium dioxide photocatalyst synthetic method in crystallized form including the steps of: diluting titanium tetrachloride and titanium sulfate, and then adjusting PH value between 7 and 9 by ammonia water, adding suitable oxidizer and inorganic acid through water filtering and in accompaniment with operational conditions to form titanium dioxide photocatalyst sol gel solution. The invention can display as achromatization and (golden) yellow sol gel liquid in coordination with operational conditions and density with photocatalyst scale of 0.5 to 10% (dependent on conditions).

Description

1257317 Amendment 曰 _ Case No. 92112034 V. Description of the Invention (1) [Technical Fields of the Invention] II: Ming: The technical department of the genus provides a kind of crystalline titanium dioxide: the method of 'applied to household appliances/lighting" air cleaning/kitchen Use two r a house exterior wall / furniture cleaning / car interior and wastewater treatment 2::: Qin (1) 02) Photocatalyst synthesis method. More directly, m = the species using the chemical treatment program 'Nano-meter scal>> aqueous solution' whose particle distribution is 2~5〇 dry-emulsified titanium content is 〇·5~10%. /,

I [Prior Art] Quantity:: Beginning in the 1950s, we can see in the academic literature about the manufacture of semiconductors from titanium oxide. Existing chemicals (special ear-prepared children, most of them in the past 98 years are based on their chemical reactions and semiconductor reactions = the structure of the crystal structure and the particles of the 丨 丨 研 研 九 九 九 九 九 九 九 九 九 九 九 九Μ *L ;, ',, (3) significantly affect the progress of the reaction and the efficiency of the second guinea to the ore or anatase / rutile structure, the: the synthesis method of the two Qin, and almost no mention of titanium dioxide First, the application of the catalyst in the environment is clean. The research on the synthetic method of milk. ΐϊί: In the development of applied technology, the effect of processing is very little, and it is really influential. 'Synthesis method for the photocatalyst according to the literature, titanium dioxide light touches the human body into a method The micro-particle-shaped two-gasification method, the mouth-forming method, and the chemical synthesis manufacturing is made by grinding and pulverizing method (the most common ^ although there are nine wolves and more dioxins - seeing is produced by Degussa company 1257317

The P-25 is produced by the grinding and pulverizing method), but the titanium dioxide particles produced by this method have uneven particle sizes (both in the range of 1 〇 to 5 〇〇 nm) and the crystal forms are not compatible, and only the field paint cosmetic/correction The use of liquids, etc., can not effectively play the role of photocatalyst. Although some grinding processes are slightly modified, such as ultrasonic wave scanning method with ultrasonic vibration or chemical grinding method with acid solution, particle size and uniformity can be improved, but its effect is limited, but it is not obvious for the crystal structure. The effect is limited, and the scope of application of the finished product remains unchanged. As for the chemical synthesis method, liquid synthesis is the main one. Although there is a literature mentioning the formation of a titanium oxide photocatalyst film by chemical vapor deposition (CVD), the product is stable, high in purity and photocatalytic, but it is expensive to manufacture and only applies to specific products, so it cannot be applied. Mass production. The liquid synthesis method is divided into an organic solvent method and an aqueous solution method, and the aqueous solution method is preferred. Among them, the organic solvent method is to form titanium dioxide (powder or film) by using titanium alkoxide (Ti-oxyalkyl: Ti(0R)4) in different solvents under different heating conditions, and this part includes 曰本Japanese Laid-Open Patent Publication No. Hei 4-83537, the titanium alkoxide is heated in ethylene glycol; JP-A-7-101A, the titanium oxide is heated in an alcohol amine to obtain titanium dioxide; Titanium is expensive, and operation must be carried out under high temperature and high pressure. Therefore, it is generally used only for the production of catalysts for industrial chemicals. This method cannot be used as far as the cost of civilian products is concerned. In the aqueous solution synthesis method, most of the Japanese patents or the Japanese published 4 are used as the main method, including the Japanese Patent Publication No. 7-171408, which is heated after adding an adhesive to the tetrachlorotitanium carbide solution; or the special open plan 6_2935 1 9 Directly heating the aqueous solution of titanium tetrachloride in a condition of pH 3 3

Page 6 1257317 _ Case No. _92122034 V. Description of the invention (3) —-^ Correction of the sol of titanium dioxide. The biggest disadvantage of this method is that the formed sol liquid contains a large amount of chloride ions, resulting in the stability of the sol is not I, and it is easy to decompose and precipitate. Japanese Laid-Open Patent Publication No. Hei 9-71418, in which a hypoxic reaction is carried out by adding a hydrogen peroxide solution to a titanium hydroxide aqueous solution under the condition of pH = 6-8, or a special opening of the hydroxide hydroxide is added to the titanium hydroxide. ΡΗ = 2_6 under the conditions of long-term low-temperature reaction, the resulting titanium dioxide sol, although the particles have reached the ^ ^ grade (10nm range), but because the crystallization is mainly amorphous, although it can be used for table = treatment, But the role of photocatalyst is not good. Japanese Laid-Open Patent Publication No. Hei 7-28614, the entire disclosure of which is incorporated herein by reference. The characteristics of hydrogen peroxide are limited to less than 2%, which causes troubles in use. ’,

Patent No. 1 35895 of the Republic of China, in which an organic acid is added to an aqueous solution of titanium tetrachloride and heated to form anatase at a temperature of 70 t or more, and the product is in conformity with the photocatalyst requirements regardless of the crystal form and particle distribution. The chlorine content in the solution is very high (1 gram / liter or more), and the stability of the finished product is the main bottleneck. Patent No. 34998 No. 1, the patent discloses that titanium tetrachloride is reacted with ammonia water at pH = 2-6 to precipitate a precipitate (titanium hydroxide or orthotitanic acid); Adding hydrogen peroxide under ~8 C) and stirring for a long time under low temperature, the resulting amorphous titanium dioxide has nothing to do with the case. Patent No. 3 9 3 342 is to heat titanium dioxide to form titanium dioxide, and then add it with a simple acid (such as nitric acid, etc.) to wash away the residual sulfate and dissolve the titanium dioxide to reduce the particle size. It has nothing to do with it. Patent No. 443992 is a method for forming a titanium dioxide film, rather than a method for forming a sol.

Revised on the day of the month of 1257317----92122034 V. Description of invention (4) In addition, 'European French patent 255 1 743 is the formation of alkaline earth metal titanate, ", 'wind supply for post-processing, the subject matter The present invention is different from the present invention. The present invention provides a method for synthesizing a crystalline dioxygen photocatalyst comprising: (1) a dilution procedure 10: a compound of titanium in a suitable acid Diluting 1 〇0 in the solution; ', (i丨) Neutralization Procedure 1 2: Adjust the concentration of ammonia water, add the dilution solution containing titanium compound at the set addition rate, and adjust to pH = 5~9 1 2 〇 (111) Washing procedure 1 3: Filtering the precipitated n-decanoic acid by filtration 13 (1 v) Conversion procedure 1 4: Mixing and washing the ortho-titanic acid in pure water (deionized water) After homogenization, the selected oxidant or inorganic acid 14 0 is added; (V) heating procedure i 5 : the transformed solution is aged at a set temperature and time for 15 〇; (Vi) the sol is completed after completion of the sol pH adjustment / transition / divided into finished products 1 6 〇. * ΐϊϊ ΐϊϊ 目 目 目 目 目 目 目 目 目 目 目Points (including high biomass, poor stability, crystallographic dissonance, etc.) = work: exhibited a series of process settings, synthesis of nano-scale titanium oxide sol process, including dilution, neutralization, washing, Five steps of conversion and heating. In the dilution process, the raw materials used in the present invention include titanium tetrachloride and

Page 8 1257317 --- nickname 92112034 _ _ _ 5, invention description (5) titanium sulfate, etc., the above titanium compound dissolved in an acidic aqueous solution of PH $ 0 'stirred to a completely clear homogeneous solution, then Perform a neutralization procedure. Wherein the content of the ruthenium compound is controlled within the range of 5 to 20% depending on the demand of the finished product. The operating temperature is preferably less than 30 °C. The stirring speed was 30 to 60 Orpm. The neutralization step is carried out by adding an ammonia hydroxide solution (ammonia water) in an amount of 10 to 35% at a set addition rate to the stirred aqueous solution of the titaniumate until the pH = 5-9. The reaction process should be moderately temperature controlled to ensure that the temperature is below 2 〇. 〇, the mixing speed is maintained at 1 2 〇 - 1 2 0 0 rpm. At the time of neutralization, the titanium compound is changed from an aqueous solution state to orthotitanic acid or titanium hydroxide to form a white powder suspension. After neutralization, the filter or cake is filtered by the acid or titanium hydroxide, and the filter cake is placed in tap water or soft water, stirred until completely dispersed, and then concentrated for a certain period of time, wherein the tap water is filtered and the cake is The ratio must be at least greater than $ / 1 . The washing step of stirring and dispersing and filtering as described above is at least three times or more. The stirring speed of each washing step is maintained at 1 20-1 200 rpm for at least 1 minute, and preferably 30 minutes, and the filtering device used may be a dehydrator, a press, a vacuum filter or a centrifuge. ^ Put the washed filter cake in deionized water, stir and disperse evenly, add oxidizing agent or inorganic acid as needed. The oxidizing agent usable in the present invention includes chloric acid, periodic acid, potassium permanganate, sodium permanganate, nitric acid, etc., and the added concentration is from gram/liter to 200 g/liter, and the inorganic salt used includes hydrazine. Hydrogen, hydrogen bromide, hydrochloric acid, perchloric acid, sulfuric acid, nitric acid, phosphoric acid, periodic acid, etc., is added in an amount of 1 ml / liter ~ 12 〇 ml / liter. In the case of the addition of an oxidizing agent or a mineral acid, the term "completely depending on the finished product requirements", the addition of the oxidizing agent is preferred as one. The finished product should be used directly; if the finished product is to be used, it can be added only to the spray or to the film or

1257317 ______ Case No. 92122034 Year of the month Amendment V. Description of invention (6) For subsequent processing or high concentration, it is necessary to add inorganic acid or a combination of the two. The type of inorganic salt selected depends on the application target of the finished product (ie, the material to be processed) and environmental considerations. The ortho-titanate sol after adding an oxidizing agent or a mineral acid is subjected to a conversion reaction at a set temperature and time. In the present invention, the conversion temperature is 10 to 95 ° C (depending on the additive), and the time is at least 1 For more than 0 minutes, the stirring speed is maintained at 3 〇~3 〇〇r ρπι. The converted liquid is adjusted to a temperature of 50 to 95, and the mixture is continuously heated and stirred for 4 to 24 hours, and the stirring speed is maintained at 3 Torr to 3 〇〇Γ ρ η to carry out the ripening reaction. The matured sol solution is filtered through a filter, and is packaged and packaged.实施 [Embodiment] The present invention provides a method for synthesizing a crystalline titanium dioxide photocatalyst, and the following examples are given to illustrate the contents of the present invention, but the scope of the present invention is not limited to such examples: Example 1: In 20 liters Add 1 liter of deionized water to the reaction tank, set the stirring speed at 300 rpm, keep the temperature in the ice bath at 5 to 1 Torr, and take titanium tetrachloride (TiC14) (content 98%) to 500 gram to quantify The pump is continuously added with water at a rate of 4 ml/min (4 ml/min); when it is completely added, it is continuously mixed for 2 hours (to the liquid is clear and transparent), then with a concentration of 2% by weight of ammonia per minute. At the speed of the addition, the stirring speed is increased to 6 rpm and the pH change is continuously observed. When the pH reaches 4·〇, the ammonia water is added at a rate of 2 to 4 ml per minute to ΡΗ = 7·5~8. between. The solution was filtered through a vacuum filter to filter the white filter cake (containing orthotitanic acid) into a 200 liter cleaning tank.

Page 10 MM 921220^月日1257317 V. Invention description (7) The correction has been placed in the front of the bucket, and the time is 2 hours (^, 3 people ^ 1 〇 () liter, the stirring speed is set to 6〇计?111 - Washing filter repeats three;: Combine: " So V then proceeded. This. Put 20 liters of ϋP in the tank to move the filter cake into the conversion and heating tank After the addition, the water was continuously stirred, and the stirring speed was maintained at 3 rpm. (ΗΠ 毫 V 加入 = = = = = 度 度 度 度 度 度 度 度 度 度 , , , , , , , , , , , , , , , , , , 〇 状 持 持 持 持 持 持 持 持 持 持 持 持 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 as as as as as as as as as as as as as as as as as as as as as 5~50nm, in the spray = treatment or post-treatment to form a film, all can be hairpin: 曰 = action; with ultraviolet light irradiation, can play the sterilization of π embodiment 2: the processing steps are the same, but in The conversion process was changed to (4) Λ _ Π〇 4) and the amount added was 75 g. The operating conditions were the same as i = one. A transparent aqueous solution, the pH, the content of titanium dioxide is about 1%, and the particles are distributed in the range of 5~3〇ηπι to form flaky crystals; the titanium dioxide obtained in the present method contains an appropriate amount of manganese (Μη), which has a reinforcing effect on decontamination and sterilization. However, due to the very small amount of potassium, it is not applicable to the industrial use example 3: the treatment procedure is the same as in the first embodiment, but the amount of titanium tetrachloride is changed to 2.5 kg, and the modified peroxy acid (HCIO4) is changed to 150 ml. The remaining conditions are as before, the treated ceria photocatalyst is the same as in the first embodiment, but the content of diterpene in the sol is about 5%; the product is high in photocatalyst content, except that it can be used as a blood.丨»»丨|/丨|^»丨丨·—.;: ________________________—--- Page 11 1257317 —- a case number 92112034 date correction ___ five, invention description (8) mold, go The function of dirt and sterilization can also be used for exterior wall treatment or sanitary equipment. Example 4: In a 20-liter reaction tank, 9 liters of deionized water was added, and the stirring speed was 6 〇〇 rp η ', and then 1 liter of sulfuric acid was added, and then titanium sulfate (τ丨〇s〇4) was obtained. , added to the above stirred dilute sulfuric acid in portions, continuously mixed until completely dissolved (at least 2 hours or more) ° and then added with 20% ammonia water at a rate of 丨〇 ml per minute, after which the operation steps are as in the first embodiment. The resulting finished product was the finished product of Example 1. Example 5: The treatment procedure is the same as in the first embodiment, but in the acidification process, the phosphoric acid (Hp〇4) is used instead of the perchloric acid, and the phosphoric acid is used in an amount of 1 to 15 ml; the curing temperature is increased to 90 to 95 C. , 8 to 12 hours, can also obtain a colorless to yellow titanium dioxide photocatalyst transparent sol, its composition and content is the same as the first example, but due to dissolution, containing a small amount of phosphate, can effectively achieve cleaning and adsorption Example 6: ~ Rn ^ treatment steps and operating conditions are as in the first embodiment, but the curing temperature is changed to 70 without hydrazine / one reaction for a period of time to 24 hours, and a composition and function such as a beta-column-one titanium oxide photocatalyst transparent sol can also be obtained. Example 7: 乂"Processing steps and operating conditions are as in Example 1 'but the conversion is changed to 10 ml '3 addition of 50 ml of disc acid, and the rest of the operation = 'heating temperature is increased to 90~95t, reaction The time is 6 hours ^ and the function is as in the fifth embodiment of the ceria photocatalyst transparent sol.

Page 12 1257317

Case No. 921220: U V. Description of the invention (9) The treatment steps and operating conditions are as follows: in the second embodiment, the amount is 8 gram, and the addition of phosphorus bismuth, manganese, S, potassium, and the addition amount of 95 t, the reaction time is 8 hours. The temperature of the titanium dioxide photocatalyst sol can be increased to 90~, and the composition and function can be obtained. For the second embodiment, the present invention is further shown as follows: 乂r raw and shellfish, it is excellent, Play the role of self-cleaning and decontamination; « 2, with the irradiation of ultraviolet light, can play the role of sterilization. 3. Effectively achieve the effects of cleaning and adsorption. In summary, the present invention has met the application requirements of the invention patent, and Mai filed an application in accordance with the law, praying for the examination of the member of the bureau, and granting the patent right of the invention. Φ

Page 13 1257317 Case No. 92122034 Year of the Moon Correction Brief Description of the Drawing The first figure is a block diagram of the titanium dioxide photocatalyst synthesis method of the present invention. The second drawing is a block diagram of the production program of the present invention. [Description of the figure] Dilution procedure·· 1 0 Dissolve and dilute the titanium compound in an appropriate acid solution·· 1 0 0 Neutralization procedure · · 1 2 i Adjust the concentration of ammonia water and add titanium at the set addition rate. In the dilution of the compound, adjust to ρΗ = 5~9 · · 1 2 0 Washing procedure·· 1 3 Wash and precipitate the precipitated orthotitanic acid························· After adding ortho-titanic acid in pure water (deionized water), add the selected oxidizing agent or inorganic acid · · 1 40 aging procedure · · 1 5 The transformed solution is matured according to the set temperature and time. 0 sol-completed sol·· 1 6 After pH adjustment/transition/packing, it is finished product·· 1 6 0 Φ

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Claims (1)

1257317 —-_Case No. 92112034__年月日日_Amendment_16. Patent application scope 1. A method for synthesizing a nanometer (nano-meter scale) photocatalyst at a temperature lower than 1 利用 using a series of process settings. A functional crystalline titanium dioxide sol method comprising: (i) a dilution procedure: a titanium compound titanium tetrachloride (TiCl4) or titanium sulfate (Ti0 (S04)) in a suitable acid solution (diluted hydrochloric acid for tetrachloroethylene) The titanium system 'dilute sulfuric acid is used in the titanium sulfate system) to dissolve and dilute at a slow rising speed from 3 rpm to 250~60Orpm, and the temperature during dilution is kept at 4~20 C 'reaction time is 1~4 hours. The concentration of the acid solution is 〇~4M (mol/L), and the concentration of the titanium compound after dilution is 5~2〇wt/L%; — (U) Neutralization procedure · Ammonia water (hydrogen) with a concentration of 10~25% Ammonium oxide solution), add 30% diluted solution of cerium-containing compound by the (earth) dilution procedure at a rate of 30 ml/min, and slowly increase to 1 2 〇r{)m, then increase to 500~ 800rpm turbulence speed evenly adjust the pH value to pH = 7~9, neutralization reaction For 4 hours, the temperature during neutralization is kept at 4~30 〇C; (iii) Washing procedure: Filter the orthotitanic acid or titanium hydroxide precipitated by the (1 1) neutralization procedure into a filter cake. Add 3 to 2 times the tap water volume of the filter cake, and increase the speed from 2 rpm to 5 〇〇 8 〇〇 rpm at a slower speed. Mix evenly for 2 minutes, then filter. It is a cake; the step of washing it is repeated 2~5 times; (iv) Conversion procedure: adding the cake washed by (iii) washing procedure to the quantitative pure water water) to slowly increase the speed From 30rpm to 25〇~6〇〇rpm, the stirring speed is 1257317. VI, apply for patent-case! Range 92122034 After the addition of the selected oxidant (addition amount is " oxidizing agent used to include chlorinated acid, sodium periodate, potassium permanganate, nitric acid or inorganic acid (added amount is liters ), 1 row of conversion, the inorganic acids used in the conversion include perchloric acid, perrhenic acid, nitric acid, phosphoric acid, hydrochloric acid, sulfuric acid, hydrogen bromide, hydrogen iodide, and the temperature during the conversion is maintained at 1 〇~9 5 °C. , the conversion time is 1 0~1 2 0 minutes; (v) ripening procedure: The solution converted by the (iv) conversion procedure is set according to the set temperature (5 〇~9 5 C), time (4~2 4 hours) At a slow rate of increase from 30 rpm to 250~60 rpm, the stirring speed is evenly stirred for aging; the sol that has been matured is adjusted, filtered, and packaged to be the finished product. 2 If the patent application is the first item The method wherein the apparatus used for the filtration may be a dewatering machine, a filter press, a vacuum filter or a centrifuge. Page 16 1257317 _ Case No. 92112034 _ 'Year of the Moon / Chinese hair (four) (Inventive name Oxidation photocatalyst ^^ The present invention provides a ^r曰] one / this method is to use titanium tetrachloride; a weathering Qin photocatalyst synthesis The method is adjusted to between Ρίί=7. 0~9.0, after the process, with ammonia water (bribe 3) sword and inorganic acid, with the operating conditions, the second = f: f into the appropriate aqueous solution of oxidized glue. The product of the invention = The titanium oxide photocatalyst is dissolved in the (4) yellow sol liquid, which is: (the color of the material is not determined by the color).琛3 is 0. 5~1〇% (according to condition five, (:) represents the picture: the first picture (a) the case represents the picture element > ^,, _>» dilution program · 1 〇 representative symbol Brief description: Titanium compound in the appropriate acid solution and the program · · 1 2 〒 A solution · · i 〇〇 to adjust the concentration of ammonia, according to the set release, adjust to pH = 5~9 · · Γ ^Speed added titanium compound containing rare six, English invention summary (invention name · · - 2 0 case number 92112034 1257317 Abstract of Chinese invention (Invention name: Synthetic method of crystalline titanium dioxide photocatalyst) Washing procedure: Washing of ortho-titanic acid precipitated in Shendian············································· After stirring and mixing in deionized water, add the selected oxidizing agent or inorganic acid··································································· ·· 1 After the pH adjustment / transition / attack is the finished product 6 0 Sixth, English invention U (invention name: y