Abstract:
A process for photocatalytic removal of organic substances from waste waters, wherein by way of photocatalyst use is made of granulates based on pyrogenically prepared titanium dioxide having the following physicochemical characteristic data: 
     
       
         
               
               
               
             
                   
                   
               
                   
                          Mean grain diameter: 
                 10 to 150 μm 
               
                   
                 BET surface: 
                 25 to 100 m 2 /g 
               
                   
                 pH value: 
                 3 to 6 
               
                   
                 Compacted bulk density: 
                 100 to 1,200 g/l.

Description:
INTRODUCTION AND BACKGROUND 
     The present invention relates to a process for photocatalytic removal of organic substances from waste waters. 
     Pyrogenic titanium oxide (commercially available as Degussa TiO 2  P 25) is distinguished by its variety of possible applications in the field of photocatalysis as shown in the following sources: 
     (R. W. Matthews, S. R. McEvoy, J. Photochem. Photobiol.A: Chem., 64 (1992) 231-246; 
     R. I. Bickley et.al., Journal of Solid State Chemistry, 92 (1991), 178-190; 
     R. Franke, C. Franke, Chemosphere, Vol. 39, No. 15 (1999), 2651-2659; and 
     H. Zen, JETI (1998), 46 (10), 66-67). 
     It is used as reference material with high photocatalytic activity; see (V. Loddo et.al., Applied Catalysis B: Environmental 20 (1999), 29 -45.) 
     SUMMARY OF THE INVENTION 
     The present invention provides a process for photocatalytic removal of organic substances from waste waters, said process being characterized in that by way of the photocatalyst use is made of granulates based on pyrogenically prepared titanium dioxide having the following physicochemical characteristic data: 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 mean particle diameter: 
                 10 to 150 μm 
               
               
                   
                 BET surface area: 
                 25 to 100 m 2 /g 
               
               
                   
                 pH value: 
                 3 to 6 
               
               
                   
                 compacted bulk density: 
                 100 to 1,200 g/l. 
               
               
                   
                   
               
             
          
         
       
     
     The granulate that is capable of being used in accordance with the invention can be prepared by pyrogenically prepared titanium dioxide being dispersed in water and spray-dried and by the granulates obtained being optionally tempered at a temperature from 150 to 1,100° C. for a period from 1 to 8 h. 
     The pyrogenic titanium dioxide can be prepared from TiCl 4  by a known method by means of high-temperature or flame hydrolysis (Ullmanns Enzyklopädie der technischen Chemie, 4 th  Edition, Volume 21, page 464 (1982)). 
     The dispersion in water for preparing the granulates can exhibit a concentration of titanium dioxide from 3 to 25 wt. %. 
     Organic auxiliary substances may be added to the dispersion in order to enhance the stability of the dispersion and to improve the particle morphology after spray drying. 
     For example, the following auxiliary substances may be employed: 
     polyalcohols, polyethers, surfactants based on fluorohydrocarbons, alcohols. 
     Spray drying can be carried out at a temperature from 200 to 600° C. Spinning-disc atomizers or nozzle atomizers may be employed in this process. 
     Tempering of the granulates can be carried out both in a stationary bed, such as in chamber kilns for example, and in an agitated bed, such as in rotary-tube dryers for example. 
     By varying the feed materials and the conditions in the course of spraying and tempering, the physicochemical parameters of the granulates, such as the specific surface area, the particle-size distribution, the compacted bulk density and the pH value, can be varied within the specified limits. 
     No additional auxiliary substances are required for the granulation. In comparison with non-spray-dried titanium dioxide, which has no defined agglomerate size, the titanium-dioxide granulate according to the invention has a defined particle size. 
     The titanium-dioxide granulate according to the invention enables dust-free handling. By reason of the high compacted bulk density, less packaging effort is required for transportation. 
    
    
     BRIEF DESCRIPTION OF DRAWING 
     The present invention will be further understood with reference to the drawing which shows the rate of progression of the degradation of chlorinated hydrocarbon according to the process of the invention as compared with a standard. 
    
    
     DETAILED DESCRIPTION OF INVENTION 
     The process according to the invention can be carried out at a temperature from 20 to 40° C. The concentration of organic substances may amount to from 10 to 150 mg/ml. The organic substances that can be removed with the process according to the invention may be: 
     4-chlorophenol, (4-CP) 
     dichloroacetic acid (DCA) 
     trichloroethylene (TCE) 
     dichloroethane (DCE) 
     The process according to the invention has the advantage that the noxious substances are degraded more rapidly than with non-granulated titanium dioxide P 25 and that the titanium-dioxide granulate according to the invention can be separated from the reaction mixture better than non-granulated titanium dioxide P 25 (better sedimentation). 
     EXAMPLES 
     By way of pyrogenically prepared titanium dioxide a titanium dioxide P 25 having the following physicochemical characteristic data is employed. It is known from the series of publications entitled “Pigmente”, No. 56: “Hochdisperse Metalloxide nach dem Aerosilverfahren”, 4th Edition, February 1989, Degussa AG (Table 1) 
     
       
         
               
               
             
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                 Titanium dioxide 
               
               
                   
                 P 25 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 CAS Registry Number 
                 13463-67-7 
               
               
                   
                 Behaviour in relation to water 
                 hydrophilic 
               
               
                   
                 Appearance 
                 loose white 
               
               
                   
                   
                 powder 
               
               
                   
                 Surface according to BET 1)  m 2 /g 
                 50 ± 15 
               
               
                   
                 Mean size of primary particles nm 
                 21 
               
               
                   
                 Compacted bulk density 2)  g/l 
                 about 100 
               
               
                   
                 Specific weight 10)  g/ml 
                 about 3.7 
               
               
                   
                 Loss on drying 3)  upon leaving delivery 
                 &lt;1.5 
               
               
                   
                 mechanism % 
               
               
                   
                 (2 hours at 105° C.) 
               
               
                   
                 Loss on ignition 4) 7)  (2 hours at 1,000° C.) 
                 &lt;2 
               
               
                   
                 pH value 5)  (in 4-% aqueous dispersion) 
                 3-4 
               
               
                   
                 SiO 2   8)   
                 &lt;0.2 
               
               
                   
                 Al 2 O 3   8)   
                 &lt;0.3 
               
               
                   
                 Fe 2 O 3   8)   
                 &lt;0.01 
               
               
                   
                 TiO 2   8)   
                 &gt;99.5 
               
               
                   
                 ZrO 2   8)   
                 — 
               
               
                   
                 HfO 2   8)   
                 — 
               
               
                   
                 HCl 8)9)   
                 &lt;0.3 
               
               
                   
                 Sieve residue 6)  (according to Mocker, 45 
                 &lt;0.05 
               
               
                   
                 μm) % 
               
               
                   
                   
               
               
                   
                   1) according to DIN 66131  
               
               
                   
                   2) according to DIN ISO 787/XI, JIS K 5101/18 (not sieved)  
               
               
                   
                   3) according to DIN ISO 787/II, ASTM D 280, JIS K 5101/21  
               
               
                   
                   4) according to DIN 55921, ASTM D 1208, JIS K 5101/23  
               
               
                   
                   5) according to DIN ISO 787/IX;ASTM D 1207; JIS K 5101/24  
               
               
                   
                   6) according to DIN ISO 787/XVIII; JIS K 5101/20  
               
               
                   
                   7) relative to the substance dried for 2 hours at 105° C.  
               
               
                   
                   8) relative to the substance annealed for 2 hours at 1,000° C.  
               
               
                   
                   9) HCl content is a constituent of the loss on ignition  
               
               
                   
                   10) determined with the air-comparison pycnometer  
               
             
          
         
       
     
     With a view to preparing the titanium dioxides, a volatile titanium compound is injected through a nozzle into an oxyhydrogen flame consisting of hydrogen and air. In most cases, titanium tetrachloride is used. This substance hydrolyzes under the influence of the water arising in the course of the hydrogen/oxygen reaction to form titanium dioxide and hydrochloric acid. After leaving the flame, the titanium dioxide enters a so-called coagulation zone in which the primary particles and primary aggregates of titanium dioxide agglomerate. The product, which at this stage is present as a type of aerosol, is separated from the gaseous companion substances in cyclones and is subsequently subjected to aftertreatment with moist hot air. 
     The particle sizes of the titanium dioxides can be varied with the aid of the reaction conditions, such as, for example, flame temperature, proportion of hydrogen or oxygen, amount of titanium tetrachloride, dwell-time in the flame or length of the coagulation path. These are matters understood in the art. 
     The BET surface area is determined with nitrogen in accordance with DIN 66 131. 
     The compacted bulk volume is determined following the model of ASTM D 4164-88. 
     Instruments: Stamping volumeter STA V 2003 produced by Engelsmann according to: 
     DIN 53194, Section 5.2. b-f 
     measuring cylinder 250 ml, graduation marks every 2 ml 
     balance with max. margin of error±0.1 g 
     Implementation 
     Set the counter mechanism of the stamping volumeter to 1,000 strokes. 
     Tare the measuring cylinder. 
     Charge granulate into the measuring cylinder up to 250-ml mark. 
     Note the weight of the sample (±0.1 g). 
     Insert the measuring cylinder into the stamping volumeter and switch the instrument on. 
     End of stamping → instrument switches off automatically after 1,000 strokes. 
     Read off the stamped bulk volume to a precision of 1 ml. 
     Calculation 
     
       
         
               
               
             
               
               
               
             
           
               
                   
                   
               
               
                   
                 Calculation 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 E: 
                 weight of granulate sample in g 
               
               
                   
                 V: 
                 volume read off in ml 
               
               
                   
                 W: 
                 water content in wt. % (determined in accordance with 
               
               
                   
                   
                 test specification P001) 
               
               
                   
                   
               
             
          
         
       
     
     
       
         
           
             
               compacted 
                
               
                   
               
                
               bulk 
                
               
                   
               
                
               density 
             
             = 
             
               
                 E 
                 × 
                 
                   ( 
                   
                     100 
                     - 
                     W 
                   
                   ) 
                 
               
               
                 V 
                 × 
                 100 
               
             
           
         
                 
         
             
         
      
     
     The pH value is determined in 4-% aqueous dispersion; in the case of hydrophobic catalyst supports, in water ethanol 1 : 1. 
     Preparation of the Granulates That Can be Used in Accordance With the Invention 
     The pyrogenically prepared titanium dioxide is dispersed in completely desalinated water. In this process, use is made of a dispersion unit that operates in accordance with the rotor/stator principle. The dispersions arising are spray-dried. Separation of the finished product is effected via a filter or cyclone. 
     Tempering of the spray granulates may be effected in muffle furnaces. The data relating to the spray drying are recorded in Table 2. 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Data relating to the spray drying of aqueous TiO 2 P25 dispersions 
               
             
          
           
               
                   
                 Quantity 
                 Quantity 
                   
                 Speed of 
                 Operating 
                 Exhaust-air 
                   
               
               
                   
                 of H 2 O 
                 of TiO 2 P25 
                 Atomization 
                 spray disc 
                 temperature 
                 temperature 
                   
               
               
                 Example 
                 [kg] 
                 [kg] 
                 with 
                 [rpm] 
                 [° C.] 
                 [° C.] 
                 Separation 
               
               
                   
               
             
          
           
               
                 1 
                 10 
                 1.5 
                 disc 
                 35,000 
                 345 
                 100 
                 cyclone 
               
               
                 2 
                 10 
                 1.5 
                 disc 
                 45,000 
                 370 
                 105 
                 cyclone 
               
               
                 3 
                 10 
                 1.5 
                 disc 
                 20,000 
                 350 
                  95 
                 cyclone 
               
               
                 4 
                 10 
                 2.5 
                 disc 
                 15,000 
                 348 
                 100 
                 cyclone 
               
               
                 5 
                 100 
                 15 
                 2-component 
                 — 
                 445 
                 130 
                 filter 
               
               
                   
                   
                   
                 nozzle 
               
               
                 6 
                 100 
                 15 
                 disc 
                 10,000 
                 450 
                 105 
                 filter 
               
               
                 7 
                 10 
                 2.5 
                 disc 
                 20,000 
                 348 
                 105 
                 cyclone 
               
               
                 8 
                 10 
                 1.5 
                 disc 
                 15,000 
                 348 
                 105 
                 cyclone 
               
               
                 9 
                 10 
                 2.5 
                 disc 
                 35,000 
                 300 
                 105 
                 cyclone 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Physicochemical data for the spray-dried products 
               
             
          
           
               
                   
                 Surface 
                 Compacted 
                   
                 d 50   
                   
                   
               
               
                 Ex- 
                 acc. to 
                 bulk 
                   
                 value 
               
               
                 am- 
                 BET 
                 density 
                 pH 
                 (Cilas) 
                 Loss on 
                 Loss on 
               
               
                 ple 
                 [m 2 /g] 
                 [g/l] 
                 value 
                 [μm] 
                 drying [%] 
                 ignition [%] 
               
               
                   
               
               
                 1 
                 51 
                 641 
                 3.9 
                 14.6 
                 0.9 
                 0.9 
               
               
                 2 
                 50 
                 612 
                 3.7 
                 10.6 
                 0.8 
                 1.0 
               
               
                 3 
                 52 
                 680 
                 3.5 
                 25.0 
                 0.8 
                 1.0 
               
               
                 4 
                 51 
                 710 
                 3.7 
                 43.6 
                 0.8 
                 1.2 
               
               
                 5 
                 52 
                 660 
                 4.0 
                 17.1 
                 0.9 
                 0.9 
               
               
                 6 
                 53 
                 702 
                 3.9 
                 27.5 
                 0.9 
                 0.9 
               
               
                 7 
                 50 
                 708 
                 3.5 
                 26.7 
                 1.1 
                 0.6 
               
               
                 8 
                 53 
                 696 
                 3.9 
                 30.1 
                 1.0 
                 0.9 
               
               
                 9 
                 49 
                 640 
                 3.7 
                 16.0 
                 0.7 
                 0.8 
               
               
                   
               
             
          
         
       
     
     The process according to the invention is tested for its photocatalytic activity in the course of the photocatalytic degradation of chlorinated hydrocarbons under UV irradiation in optionally acidified, aqueous suspension. 
     By way of reference value (zero value), use is made of the photocatalytic rate of degradation of chlorinated hydrocarbons under UV irradiation in optionally acidified aqueous suspension when pure titanium dioxide Degussa P 25 is employed as photocatalyst. The duration of the experiments with Degussa P 25 amounts to a maximum of 360 minutes. 
     1. Experimental procedure for determining the rate of photocatalytic degradation of chlorinated hydrocarbons in suspension 
     The total running-time of the experiments for the purpose of investigating the rate of photocatalytic degradation of chlorinated hydrocarbons such as 4-CP (4-chlorophenol) under UV irradiation in purely aqueous or acidified aqueous suspension amounts to a maximum of 360 minutes (min). 
     The degradative reaction is implemented in a stirred-tank reactor. In addition, the suspension to be investigated is pumped from the storage container to the stirred-tank reactor and back, so that a uniform UV irradiation is guaranteed. The initial pH value of the suspension lies in the range 2-6; preferably pH=2-3. The temperature in the stirred-tank reactor lies within the range from 25-40° C., preferably between 30 and 35° C. The concentration of the photocatalytically active titanium dioxide employed in the given case (TiO 2  P 25 or granulated TiO 2 ) amounts to 1 g/l. The concentration of the hydrocarbon is between 10 and 150 mg/l, preferably around 120 mg/l. 
     The temperature is maintained in the aforementioned constant range by means of continuous pumping from the storage vessel to the UV irradiation unit and back, and in addition by cooling of the UV lamp system by means of cooling water. Continuous monitoring of the progress of the degradation of the chlorinated hydrocarbons under UV irradiation takes place for the entire duration of the degradative reaction. From this determination of the TOC value (TOC=Total Organic Carbon=organically bound carbon) which takes place at regular intervals it is possible for the factor TOC/TOC 0  to be determined (TOC 0 =initial concentration of the organically bound carbon in suspension). TOC/TOC 0  specifies the percentage TOC content at a particular time of withdrawal. 
     In a TOC/TOC 0 -time curve the progression of the degradation of chlorinated hydrocarbons such as 4-CP (4-chorophenol) is plotted. The rate of degradation of TiO 2  P 25 is also tested under the same conditions by way of standard. The overall shape of the curve is recorded. 
     TiO 2  P 25: 
     120 mg/l of 4-CP (4-chlorophenol) and 1 g/l of TiO 2  P 25 in acidified aqueous suspension are charged into the storage vessel and into the stirred-tank reactor and treated in accordance with the manner of proceeding described above. A TOC/TOC 0 -time curve is recorded. After 360 min., 40.5% of the initial TOC content is present. 
     Granulated TiO 2  (according to invention): 
     120 mg/l of 4-CP (4-chlorophenol) and 1 g/l of granulated TiO 2 , according to Example 1, in acidified aqueous suspension are charged into the storage vessel and into the stirred-tank reactor and treated in accordance with the manner of proceeding described above. A TOC/TOC 0 -time curve is recorded. After 360 min., 35.0% of the initial TOC content of 4-CP (4-chlorophenol) is present. 
     The values ascertained are represented graphically in FIG.  1 . 
     2. Experimental results of the photocatalytic degradation of 4-CP (4-chorophenol) by means of titanium dioxide P 25 and granulated titanium dioxide after 360 minutes (min). 
     
       
         
               
               
               
             
           
               
                   
               
               
                   
                 Residual TOC/TOC 0  at 
                   
               
               
                   
                 t = 360 min. 
                 Improvement 
               
               
                 Catalyst 
                 [%] 
                 [%] 
               
               
                   
               
             
             
               
                 TiO 2  P 25 
                 40.5 
                 / 
               
               
                 Granulated TiO 2   
                 35.0 
                 13.6% 
               
               
                   
               
             
          
         
       
     
     Reactor volume: V reactor =1.7 l 
     Total volume: V reactor =3.0 l 
     Gassed constantly with O 2    
     Radiator: UVH1022 Z4 iron-doped high-pressure mercury-vapour lamp 
     Power output: 500 W (Heraeus) 
     Catalyst concentration: 1 g/l 
     Initial concentration of chlorinated hydrocarbons: c 0 =120 mg/l 
     Initial pH value: pH 0 =2.4 
     Experiments for determining the photocatalytic oxidation 0of chlorinated hydrocarbons (for example, 4-CP) under UV irradiation and using granulated titanium dioxide as photocatalyst take place in purely aqueous or acidified aqueous suspension. The suspension is constantly stirred and continuously irradiated with the iron-doped high-pressure mercury-vapour lamp UVH1022 Z4. A cooling system for the lamp is present, in order to guarantee constant conditions. The suspension is also maintained at constant temperature by continuous pumping from the storage container to the reactor and back and by additional cooling. 
     Further variations and modifications of the foregoing will be apparent to those skilled in the art and are intended to be encompassed by the claims appended hereto. 
     European application 00 112 446.0 is relied on and incorporated herein by reference.