Method and apparatus for producing titanium dioxide

Abstract

A process for reacting titanium tetrachloride vapors with oxygen to produce titanium dioxide wherein the oxygen is introduced into the reactor in at least two points. The process has the ability to control properties, such as particle size, of the raw pigment produced. The temperature of the oxygen introduced to the reactor at the further inlet point is above, below, or at the same temperature of the oxygen introduced at the first inlet point. The further inlet point can be located before or after the all the titanium tetrachloride has been introduced into the reactor. The titanium tetrachloride is introduced at a relatively low temperature, below about 427° C., and the reaction temperature in the reactor is at least about 700° C. The process includes the use of an auxiliary fuel such as carbon monoxide, methane, propane, butane, pentane, hexane, benzene, xylene, toluene, or combinations thereof for increasing the temperature in the reactor. Still further, the process for producing titanium dioxide provides for the addition of aluminum chloride to the reactor. Advantageously, the process allows the pressure in the reactor to be above atmospheric pressure and range between about 0.15 MPa and 4.0 MPa above atmospheric pressure during the production of titanium dioxide. A reactor is also provided with an aluminum chloride generator for heating the titanium tetrachloride and delivering aluminum chloride to the reactor.

1. A process for the production of titanium dioxide comprising reacting titanium tetrachloride with oxygen at atmospheric pressure or above and at a reaction temperature of at least about 700° C. in an oxidation reactor having a first reaction zone and a second reaction zone spaced a distance from the first reaction zone, the oxygen being introduced into the reactor at a first inlet point in the first reaction zone before any titanium tetrachloride is introduced and into at least one further inlet point in the second reaction zone, the titanium tetrachloride introduced into the reactor being heated to a temperature of less than about 427° C. prior to introduction, and controlling the titanium tetrachloride to oxygen ratio in the first reaction zone to thereby control the particle size of the produced titanium dioxide. 
     
     
       2. The process according to  claim 1  wherein the titanium tetrachloride introduced into the reactor is an admixture with aluminum chloride. 
     
     
       3. The process according to  claim 2  wherein the aluminum chloride is formed by reaction of aluminum and chlorine and the heat generated by this reaction is used to heat the titanium tetrachloride introduced into the reactor. 
     
     
       4. The process according to  claim 3  wherein titanium tetrachloride is first heated to a temperature between about 350° C. and about 400° C. before being passed to an aluminum chloride generator. 
     
     
       5. The process according to  claim 3  wherein the mixture of titanium tetrachloride and aluminum chloride is conducted to the reactor by a pipework constructed from a ceramics material. 
     
     
       6. The process according to  claim 1  wherein the walls of the reactor between the first inlet point and the further inlet point are constructed from a ceramics material. 
     
     
       7. The process according to  claim 2  wherein aluminum chloride is introduced in an amount sufficient to produce between about 0.3 and about 3.0 percent by weight Al 2 O 3  in the product titanium dioxide. 
     
     
       8. The process according to  claim 7  wherein the amount of aluminum chloride is sufficient to produce from about 0.3 to about 1.5 percent by weight Al 2 O 3  in the product titanium dioxide. 
     
     
       9. The process according to  claim 1  wherein the titanium tetrachloride is introduced into the reactor at a temperature of about 399° C. 
     
     
       10. The process according to  claim 2  wherein the aluminum chloride is mixed with titanium tetrachloride prior to introduction into the reactor. 
     
     
       11. The process according to  claim 1  wherein oxygen introduced at the first inlet point is preheated to a temperature between about 815° C. and about 982° C. 
     
     
       12. The process according to  claim 11  wherein said oxygen introduced at the first inlet point is preheated to a temperature of about 954° C. 
     
     
       13. The process according to  claim 1  wherein oxygen introduced at the further inlet point is heated to a temperature between about 25° C. and about 1037° C. and is introduced in an amount sufficient to react with unreacted titanium tetrachloride. 
     
     
       14. The process according to  claim 13  wherein at least about 50 percent by weight of the oxygen is introduced at the first inlet point. 
     
     
       15. The process according to  claim 14  wherein from about 50 to about 95 percent by weight of the oxygen is introduced at the first inlet point. 
     
     
       16. The process according to  claim 15  wherein from about 60 to about 95 percent by weight of the oxygen is introduced at the first inlet point. 
     
     
       17. The process according to  claim 1  wherein the amount of oxygen introduced is equivalent to at least about 5 percent by weight more than is required to completely oxidize the titanium tetrachloride. 
     
     
       18. The process according to  claim 17  wherein the amount of oxygen introduced is equivalent to at least about 10 percent by weight more than is required to completely oxidize the titanium tetrachloride. 
     
     
       19. The process according to  claim 1  wherein the pressure in the reactor is between about 0.15 MPa and about 4.0 MPa above atmospheric pressure. 
     
     
       20. The process according to  claim 1  wherein an auxiliary fuel is added to the oxygen being introduced to the reactor at the first inlet point. 
     
     
       21. The process according to  claim 20  wherein the auxiliary fuel is carbon monoxide, methane, propane, butane, pentane, hexane, benzene, xylene, toluene, or combinations thereof. 
     
     
       22. The process according to  claim 1  wherein the oxygen being introduced to the reactor at the first inlet point is heated with plasma. 
     
     
       23. The process according to  claim 1  wherein a potassium salt is added to oxygen introduced at the first inlet point before mixing with the titanium tetrachloride, the potassium salt being added in an amount equivalent to form about 400 parts per million to about 600 parts per million potassium chloride by weight with respect to the titanium dioxide product. 
     
     
       24. The process according to  claim 23  wherein the amount of potassium is equivalent to more than about 20 parts per million by weight with respect of titanium dioxide product. 
     
     
       25. The process according to  claim 1  wherein the walls of the reactor are cooled. 
     
     
       26. The process according to  claim 25  wherein the walls of the reactor are cooled by providing a purge of nitrogen or chlorine gas. 
     
     
       27. The process according to  claim 1  wherein at least one of the inlet points comprises a circumferential slot in the wall of the reactor. 
     
     
       28. A process for the production of titanium dioxide in an oxidation reactor having a first reaction zone and a second reaction zone spaced a distance from the first reaction zone, the process comprising:
 introducing an amount of oxygen in the first reaction zone;  
 introducing an amount of titanium tetrachloride in the first reaction zone wherein the amount of oxygen introduced in the first reaction zone and the amount of titanium tetrachloride introduced in the first reaction zone defines a titanium tetrachloride to oxygen ratio;  
 reacting the titanium tetrachloride with the oxygen at a reaction temperature of at least about 700° C. to produce titanium dioxide;  
 controlling the titanium tetrachloride to oxygen ratio in the first reaction zone to thereby control the particle size of the produced titanium dioxide; and  
 introducing secondary oxygen in the second reaction zone in an amount sufficient to react with unreacted titanium tetrachloride therein.  
 
     
     
       29. The process according to  claim 28  further comprising admixing the titanium tetrachloride introduced into the reactor with aluminum chloride before introducing the titanium tetrachloride into the reactor. 
     
     
       30. The process according to  claim 29  further comprising:
 generating the aluminum chloride by reacting aluminum with chlorine in an aluminum chloride generator; and  
 heating the titanium tetrachloride introduced into the first reaction zone with heat generated from the aluminum chloride generator.  
 
     
     
       31. The process according to  claim 30  further comprising preheating the titanium tetrachloride to a temperature between about 350° C. and about 400° C. before passing the titanium tetrachloride to the aluminum chloride generator. 
     
     
       32. The process according to  claim 29  wherein the aluminum chloride is introduced in an amount sufficient to produce between about 0.3 and about 3.0 percent by weight Al 2 O 3  in the titanium dioxide product. 
     
     
       33. The process according to  claim 28  further comprising introducing a second addition of titanium tetrachloride into the reactor near the second reaction zone. 
     
     
       34. The process according to  claim 33  further comprising admixing the second addition of titanium tetrachloride introduced into the reactor with aluminum chloride before introducing the titanium tetrachloride into the reactor. 
     
     
       35. The process according to  claim 34  further comprising:
 generating the aluminum chloride by reacting aluminum with chlorine in an aluminum chloride generator; and  
 heating the second addition of titanium tetrachloride introduced into the reactor with heat generated from the aluminum chloride generator.  
 
     
     
       36. The process according to  claim 35  further comprising admixing the titanium tetrachloride introduced into the first reaction zone with the aluminum chloride before introducing the titanium tetrachloride into the first reaction zone. 
     
     
       37. The process according to  claim 36  further comprising heating the titanium tetrachloride introduced into the first reaction zone with the heat generated from the aluminum chloride generator. 
     
     
       38. The process according to  claim 28  wherein the titanium tetrachloride is introduced into the reactor at a temperature of about 399° C. 
     
     
       39. The process according to  claim 37  wherein the second addition of titanium tetrachloride is introduced into the reactor at a temperature of about 399° C. 
     
     
       40. The process according to  claim 37  wherein the titanium tetrachloride introduced into the first reaction zone and the second addition of titanium tetrachloride is introduced into the reactor at a temperature of about 399° C. 
     
     
       41. The process according to  claim 28  further comprising preheating the oxygen introduced in the first reaction zone to a temperature between about 815° C. and about 982° C. 
     
     
       42. The process according to  claim 28  further comprising preheating the secondary oxygen introduced in the second reaction zone to a temperature between about 25° C. and about 1037° C. 
     
     
       43. The process according to  claim 41  wherein from about 50 to about 95 percent by weight of the oxygen introduced in the reactor is introduced in the first reaction zone. 
     
     
       44. The process according to  claim 28  wherein the amount of oxygen introduced in the first reaction zone and the second reaction zone is equivalent to at least about 5 percent by weight more than is required to completely oxidize the amount of titanium tetrachloride introduced in the reactor. 
     
     
       45. The process according to  claim 28  further comprising operating the reactor at a pressure between about 0.15 MPa and about 4.0 MPa above atmospheric pressure. 
     
     
       46. The process according to  claim 28  further comprising adding an auxiliary fuel to the oxygen being introduced in the first reaction zone. 
     
     
       47. The process according to  claim 46  wherein the auxiliary fuel is carbon monoxide, methane, propane, butane, pentane, hexane, benzene, xylene, toluene, or combinations thereof. 
     
     
       48. The process according to  claim 28  further comprising heating the oxygen being introduced in the first reaction zone with plasma. 
     
     
       49. The process according to  claim 28  further comprising heating the secondary oxygen being introduced in the reactor with plasma. 
     
     
       50. A method for producing titanium dioxide particles in at least two reaction zones, comprising:
 ( a )  introducing titanium tetrachloride in a first reaction zone;      ( b )  introducing oxygen into the first reaction zone to oxidize titanium tetrachloride therein and form titanium dioxide; and      ( c )  oxidizing unreacted titanium tetrachloride from the first reaction zone in a second reaction zone by reaction with oxygen to produce additional titanium dioxide;      
       
         wherein the reaction of oxygen and titanium tetrachloride takes place at above atmospheric pressure and at least about  700  degrees Celsius, and the size of the titanium dioxide particles produced through the method is controlled by controlling the ratio of titanium tetrachloride to oxygen in the first reaction zone. 
       
     
     
       51. The method of  claim 50 , further comprising introducing additional titanium tetrachloride into the second reaction zone and oxidizing the additional titanium tetrachloride in the second reaction zone by reaction with oxygen to form titanium dioxide. 
     
     
       52. The method of  claim 50 , wherein the titanium tetrachloride introduced in the first reaction zone is an admixture with aluminum chloride. 
     
     
       53. The method of  claim 52 , wherein the aluminum chloride is formed by reaction of aluminum and chlorine and the heat generated by this reaction is used to heat the titanium tetrachloride introduced into the first reaction zone. 
     
     
       54. The method of  claim 53 , wherein the titanium tetrachloride is first heated to a temperature between about  350  degrees Celsius and about  400  degrees Celsius before being passed to an aluminum chloride generator. 
     
     
       55. The method of  claim 51 , wherein the titanium tetrachloride introduced in the second reaction zone is an admixture with aluminum chloride.