Method for Making a Catalyst Comprising a Phosphorus Modified Zeolite to be Used in an Alcohols Dehydration Process

Abstract

A method of forming a phosphorus modified zeolite includes introducing phosphorus into a zeolite having at least one ten member ring in a structure thereof in an amount of from 0.5 to 30 weight percent, followed by a separation of solid from liquid if any. The method includes mixing the phosphorus modified zeolite with a component selected among binders, salts of alkali-earth metals, salts of rare-earth metals, and clays. The method includes making a catalyst body from the mixture by extruding the mixture into a desired shape. The method optionally includes a drying step, optionally followed by a washing step. The method includes a calcination step, optionally followed by a washing step and drying. An alcohol having at least 2 carbon atoms may be converted into a corresponding olefin in a dehydration process in the presence of the phosphorus modified zeolite.

1 . A method comprising:
 converting an alcohol having at least 2 carbon atoms into a corresponding olefin in a dehydration process, wherein conversion of the alcohol is performed in the presence of a catalyst, wherein said catalyst comprises a phosphorus modified zeolite that is made by a method comprising the following steps in this order:   a) introducing phosphorus into a zeolite comprising at least one ten member ring in a structure thereof in an amount of from 0.5 to 30 weight percent, followed by a separation of solid from liquid if any,   b) mixing the phosphorus modified zeolite of step a) with at least a component selected among one or more binders, salts of alkali-earth metals, salts of rare-earth metals, and clays,   b)* making a catalyst body from the mixture of step b) by extruding the mixture into a desired shape,   c) an optional drying step or an optional drying step followed by a washing step,   d) a calcination step,   d*) an optional washing step followed by drying.   
     
     
         2 . (canceled) 
     
     
         3 . The method according to  claim 1 , wherein the amount of phosphorous introduced into the zeolite at step a) is from 0.5 to 9 wt %. 
     
     
         4 . The method according to  claim 1 , wherein the zeolite contains less than 1000 wppm of sodium, less than 1000 wppm of potassium and less than 1000 wppm of iron. 
     
     
         5 . The method according to  claim 1 , wherein the zeolite contains less than 100 ppm of red-ox and noble elements. 
     
     
         6 . The method according to  claim 1 , wherein alkali-earth metals and salts of rare-earth metals are Ca, Mg, Sr, Ce, La or a combination thereof. 
     
     
         7 . The method according to  claim 1 , wherein the zeolite structure is selected from the MFI, MTT, FER, MEL, TON, MWW, EUO, MFS, ZSM-48. 
     
     
         8 . The method according to  claim 1 , wherein the proportion of the phosphorus modified zeolite is from 15 to 90 wt % of the catalyst. 
     
     
         9 . The method according to  claim 1 , wherein a concentration of the salts of alkali-earth metals and salts of rare-earth metals is from 0.1 to 15 wt % of the catalyst on metal basis (Me). 
     
     
         10 . The method according to  claim 8  wherein a molar ratio of (Al+Me)/P in the catalyst is in the range 0.5 to 3, where the Me is alkali or rare-earth, P is phosphorus, and Al is aluminum. 
     
     
         11 . The method according to  claim 1 , wherein the from 0.5 to 30 weight percent of the phosphorus introduced in step a) is introduced into the zeolite prior to introduction of any binder to the zeolite. 
     
     
         12 . The method according to  claim 1 , wherein the from 0.5 to 30 weight percent of the phosphorus introduced in step a) is introduced into the zeolite prior to introduction of any salts of alkali-earth metals to the zeolite. 
     
     
         13 . The method according to  claim 1 , wherein the from 0.5 to 30 weight percent of the phosphorus introduced in step a) is introduced into the zeolite prior to introduction of any salts of rare-earth metals to the zeolite. 
     
     
         14 . The method according to  claim 1 , wherein the from 0.5 to 30 weight percent of the phosphorus introduced in step a) is introduced into the zeolite prior to introduction of any clays to the zeolite. 
     
     
         15 . The method according to  claim 1 , wherein the from 0.5 to 30 weight percent of the phosphorus introduced in step a) is introduced into the zeolite prior to introduction of any shaping additives to the zeolite. 
     
     
         16 . The method according to  claim 1 , wherein a P/Al ratio in step a) is higher than 1, wherein P is phosphorus and Al is aluminum. 
     
     
         17 . The method according to  claim 1 , wherein, prior to introduction of the phosphorus into the zeolite, the zeolite is steamed, or steamed and then leached. 
     
     
         18 . The method according to  claim 1 , wherein, prior to introduction of the phosphorus, the zeolite has a silicon to aluminum ratio that is below 20. 
     
     
         19 . A method comprising the following steps in this order:
 a) introducing phosphorus into a zeolite comprising at least one ten member ring in a structure thereof in an amount of from 0.5 to 30 weight percent, followed by a separation of solid from liquid if any, to form a phosphorus modified zeolite,   b) mixing the phosphorus modified zeolite of step a) with at least a component selected among one or more binders, salts of alkali-earth metals, salts of rare-earth metals, and clays,   b)* making a catalyst body from the mixture of step b) by extruding the mixture into a desired shape,   c) an optional drying step or an optional drying step followed by a washing step,   d) a calcination step,   d*) an optional washing step followed by drying.