Method for the decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone

Abstract

A method for the enhanced decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone which comprises decomposing cumene hydroperoxide in a non-isothermal manner in the presence of excess acetone whereby the molar ratio of acetone to phenol in a decomposition reactor is from about 1.1:1 to 1.5:1. A method for the selectivity of the decomposition of dicumyl peroxide to alpha methylstyrene also phenol and acetone in the presence of an acidic catalyst which comprises carrying out the decomposition at a temperature of from about 80° to 110° C. A method for carrying out the decomposition of dicumyl peroxide with an acidic catalyst system which comprises performing such decomposition in the presence of the reaction product of (1) an amine with (2) an acidic material which can catalyze the decomposition of CHP. A method for preparing phenol and acetone from the decomposition of CHP with an acidic catalyst which comprises (a) decomposing CHP at a specific acidic catalyst concentration and temperature thereby forming a composition comprising phenol, acetone and dicumyl peroxide, (b) transferring dicumyl peroxide to a plug flow reactor wherein decomposition of dicumyl peroxide to phenol acetone and AMS occurs at a lower acidic catalyst concentration and a higher temperature than the catalyst concentration and temperature in step (a). A method for the decomposition of CHP and producing CHP decomposition products therefrom which comprises recycling the CHP decomposition products to a CHP feedstream in the quantity of from about 10-25 times the weight of the CHP feedstream.

1. An improved method for the decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone wherein the improvement comprises decomposing cumene hydroperoxide in a non-isothermal manner in the presence of excess acetone whereby the molar ratio of acetone to phenol in a decomposition reactor is from about 1.1:1 to 1.5:1 whereby the rate of decomposition of cumene hydroperoxide is reduced and the reaction is more controllable and more selective. 
     
     
       2. The method in accordance with  claim 1  wherein the acetone is thoroughly mixed with the cumene hydroperoxide feed-stream. 
     
     
       3. The method in accordance with  claim 1  wherein the excess acetone is added in accordance with the algorithm
   G acetone=G chp (0.17)([CHP])+40/(G chp [HP])    
       where G acetone is quantity of fed acetone, metric ton/hour; G chp  is quantity of technical cumene hydroperoxide fed to the unit, metric ton/hour; and [CHP] is concentration in technical cumene hydroperoxide, weight %/100. 
     
     
       4. The method in accordance with  claim 1  wherein the cumene hydroperoxide is decomposed in a multiplicity of separate sequential reactors each with a controlled temperature range. 
     
     
       5. The method in accordance with  claim 4   An improved method for the decomposition of cumene hydroperoxide by acidic catalyst to phenol and acetone wherein the improvement comprises decomposing cumene hydroperoxide in a non- isothermal manner in the presence of excess acetone wherein the cumene hydroperoxide is decomposed in a multiplicity of separate sequential reactors each with a controlled temperature range whereby the molar ratio of acetone to phenol in a decomposition reactor is from about  1 . 1 : 1  to  1 . 5 : 1  whereby the rate of decomposition of cumene hydroperoxide is reduced and the reaction is more controllable and more selective, and  wherein a first reactor is operated in a temperature range of about 50° to 62° C. a second reactor in a temperature range of about 62° to 57° C. and the third and last reactor in a temperature range of about 57° to 50° C. 
     
     
       6. The method in accordance with  claim 4    claim 5  wherein portions of the outlet stream of the last sequential reactor is passed into a reactor of plug flow design and smaller size compared to the decomposition reactor wherein the delta T°C. of the inlet temperature and outlet temperature of said plug flow reactor is from about 4° to 16° C. 
     
     
       7. The method in accordance with  claim 1    claim 5  wherein the acidic catalyst is sulphuric acid. 
     
     
       8. The method in accordance with  claim 1  wherein the catalyst is in a concentration of from about 150 to 500 ppm of the weight of cumene hydroperoxide decomposition product. 
     
     
       9. The method in accordance with  claim 1  wherein the temperature of the cumene hydroperoxide decomposition is about 45° to 75° C. 
     
     
       10. The method in accordance with  claim 1  wherein the quantity of cumene hydroperoxide remaining after decomposition is from about 0.3 to 1.5 wt. % of the total weight of the decomposition products. 
     
     
       11. An improved method for the decomposition of dicumyl peroxide to alpha methylstyrene in the presence of an acidic catalyst wherein the improvement comprises carrying out the decomposition at a temperature of from about 80° to 110° C. whereby selectivity is enhanced. 
     
     
       12. The method in accordance with  claim 11   An improved method for the decomposition of dicumyl peroxide to alpha methylstyrene, phenol and acetone, in the presence of an acidic catalyst wherein the improvement comprises:
 ( a )  carrying out a decomposition of cumene hydroperoxide in the presence of an acidic catalyst and excess acetone to produce phenol, acetone, and dicumyl peroxide;    
 ( b )  in a separate vessel, carrying out the decomposition of the dicumyl peroxide from step  ( a )  at a temperature of from about  80 ° to  110 ° C. in the presence of an acidic catalyst whereby selectivity for alpha methyl styrene is enhanced;    
 ( c )  feeding at least a portion of the decomposition products of  ( b )  to a separate vessel wherein the operating temperature is higher and the operating pressure is lower than in step  ( b )  thereby allowing acetone to evaporate; and    
 ( d )  recycling at least a portion of the acetone collected from step  ( c )  to the cumene hydroperoxide decomposition reaction of step  ( a ) wherein the acid catalyst of step ( b ) comprises a reaction product of an amine and an acidic catalyst used to catalyze the decomposition of cumene hydroperoxide.  
 
     
     
       13. The method in accordance with  claim 12  wherein the acidic catalyst used to decompose cumene hydroperoxide is sulphuric acid. 
     
     
       14. The method in accordance with  claim 12  wherein the amine is ammonia. 
     
     
       15. The method in accordance with  claim 14  wherein the acid reaction product is ammonium hydrogen sulfate. 
     
     
       16. An improved method for carrying out the decomposition of dicumyl peroxide with an acidic catalyst system wherein the improvement comprises:
 ( a )  carrying out a decomposition of cumene hydroperoxide in a non - isothermal manner in the presence of an acidic catalyst and excess acetone to produce phenol, acetone, and dicumyl peroxide;    
 ( b )  in a separate vessel,  performing such  the decomposition of the dicumyl peroxide from step ( a ) in the presence of the reaction product of 
 (1) an acidic material which can catalyze the decomposition of cumene hydroperoxide with  
 (2) an amine suitable for partially neutralizing the acidic materials  
 
  whereby a weakly acid material is formed and the decomposition is better controlled;  
 ( c )  feeding at least a portion of the decomposition products of  ( b )  to a separate vessel wherein the operating temperature is higher and the operating pressure is lower than in step  ( b )  thereby allowing acetone to evaporate; and    
 ( d )  recycling at least a portion of the acetone collected from step  ( c )  to the cumene hydroperoxide decomposition reaction .  
 
     
     
       17. A method in accordance with  claim 16  wherein the acidic material is sulphuric acid. 
     
     
       18. A method in accordance with  claim 16  wherein the amine is ammonia. 
     
     
       19. A method in accordance with  claim 17  wherein the amine is ammonia. 
     
     
       20. A method in accordance with  claim 16  wherein the reaction is carried out at a temperature of from about 80° to 110° C. 
     
     
       21. A composition comprising cumene hydroperoxide, cumene, acidic catalyst for decomposition of cumene, dicumyl peroxide, dimethylbenzyl alcohol, phenol, and acetone wherein the acetone is in a molar ratio to phenol of from about 1.1:1 to 1.5:1. 
     
     
       22. A composition comprising cumene, acidic catalyst for decomposing cumene hydroperoxide, dicumyl peroxide, water, phenol, acetone and a reaction product of (1) an amine with (2) an acid which catalyzes the decomposition cumene hydroperoxide. 
     
     
       23. A composition in accordance with  claim 22  wherein the acidic catalyst is sulphuric acid. 
     
     
       24. A composition in accordance with  claim 22  wherein the amine is ammonia. 
     
     
       25. A composition in accordance with  claim 23  wherein the amine is ammonia. 
     
     
       26. A composition in accordance with  claim 25  wherein a reaction product is ammonium hydrogen sulfate. 
     
     
       27. An improved method for preparing phenol and acetone from the decomposition of cumene hydroperoxide with an acidic catalyst wherein the improvement comprises (a) decomposing cumene hydroperoxide at a specific acidic catalyst concentration and temperature whereby a composition comprising phenol, acetone and dicumyl peroxide is formed, (b) transferring dicumyl peroxide to a plug flow reactor wherein decomposition of dicumyl peroxide to phenol, acetone and alphamethylstyrene occurs in a weaker acidic catalyst medium and a higher temperature than the catalyst concentration and temperature in step (a) whereby the dicumyl peroxide decomposition is better controlled. 
     
     
       28. The method in accordance with  claim 27  wherein in step (a) the temperature is from about 70°-90° C. and the catalyst concentration is from about 50-750 ppm of the decomposition mass and in step (b) the temperature is from about 80° to 110° C. and the catalyst in step (a) has been lowered about 10 to 99 mole %. 
     
     
       29. The method in accordance with  claim 27  wherein at least a portion of the lowering of the acid concentration of (a) is accomplished through the addition of an amine. 
     
     
       30. An improved method for maintaining control of an acid catalyzed cumene hydroperoxide decomposition in a multiplicity of sequential reactors wherein the improvement comprises passing a portion of the outlet stream of the last sequential reactor into a reactor of plug flow design and a smaller size compared to the cumene hydroperoxide decomposition reactors wherein the delta T°C. of the inlet temperature and the outlet temperature of said plug flow reactor is from about 4° to 16° C. whereby the smaller size reactor decomposes essentially all of the cumene hydroperoxide remaining in said portion of the outlet stream and provides an analytical indication of the completeness of the cumene hydroperoxide decomposition reaction and the reactors are thereby controlled. 
     
     
       31. The method in accordance with  claim 30  wherein the delta T°C. is from about 5° to 15° C. 
     
     
       32. An improved method for enhancing the decomposition of cumene hydroperoxide and producing cumene hydroperoxide decomposition products therefrom wherein the improvement comprises recycling the cumene hydroperoxide decomposition products to a cumene hydroperoxide feedstream in the quantity of from about 10-25 times the weight of the cumene hydroperoxide feedstream whereby selectivity is higher and safety of the process is improved. 
     
     
       33. The method in accordance with  claim 32  wherein additional acetone is added to the cumene hydroperoxide decomposition products as to maintain a ratio of about 1.1 to 1 to 1.5 to 1 acetone to phenol in the cumene hydroperoxide decomposition reaction. 
     
     
       34. The method in accordance with  claim 33  wherein additional water is added to the cumene hydroperoxide decomposition products to a level not greater than 3 wt. % in the cumene hydroperoxide decomposition mass. 
     
     
       35. The method in accordance with  claim 34  wherein the level is not greater than 2 wt. %. 
     
     
       36. The method in accordance with  claim 35  wherein the level is not greater than 1.5 wt. %. 
     
     
       37. An improved method for enhancing the decomposition of cumene hydroperoxide to phenol and acetone wherein the improvement comprises introducing additional water into the cumene hydroperoxide decomposition reactor. 
     
     
       38. A cumene hydroperoxide decomposition mass produced from the reaction of cumene hydroperoxide with an acid catalyst in a non-isothermal manner having an acetone to phenol mole ratio of about 1.1 to 1 to 1.5 to 1. 
     
     
       39. A method for the efficient generation of recycle acetone in a process which prepares phenol and acetone from cumene comprising
 (a) decomposing dicumylperoxide to phenol, acetone, and alpha methyl styrene    (b) feeding at least a portion of decomposition products of (a) to a separate vessel wherein operating temperature is higher operating pressure is lower than in step (a), thereby allowing acetone to evaporate,    (c) sending at least a portion of acetone collected from step (b) to the cumene hydroperoxide decomposition reaction.