"Synthetic Zeolite, in Particular for Catalytic Hydroisomerization of Higher Paraffins"

Abstract

The invention relates to a zeolite of the ZSM-12 type, especially for the hydroisomerization of higher paraffins, which has a primary crystal size of <0.1 μm; as well as a specific volume, determined by mercury porosimetry at a maximum pressure of 4000 bar, of 30-200 mm 3 /g in a pore radius range of 4-10 nm; and which has further been prepared from a synthesis gel composition comprising an aluminum source, precipitated silica as a silicon source, TEA + as a template, an alkali metal and/or alkaline earth metal ion source M having the valency n; in which the molar H 2 O:SiO 2 ratio is selected between 5 and 15. The invention further relates to a catalyst comprising the above zeolite and its use.

1 - 15 . (canceled) 
     
     
         16 . A process for producing a zeolite of the ZSM-12 type comprising
 preparing a synthesis gel in an aqueous solution or suspension, which comprises
 an aluminum source; 
 a silicon source, comprising precipitated silica; 
 TEA +  as a template; and 
 an alkali metal or alkaline earth metal ion source M having a valency of n, 
 wherein the molar H 2 O:SiO 2  ratio of the gel is within the range from 5 to 15, 
   crystallizing the synthesis gel under hydrothermal conditions, while being stirred, so as to obtain a solid;   removing the solid from the solution, and   utilizing the solid to produce the ZSM-12 type zeolite.   
     
     
         17 . The process as claimed in  claim 16 , characterized in that the molar M n/2 O:SiO 2  ratio in the synthesis gel is within the range from 0.01 to 0.045. 
     
     
         18 . The process as claimed in  claim 16 , characterized in that the molar SiO 2 /Al 2 O 3  ratio is within a range from 50 to 150. 
     
     
         19 . The process as claimed in  claim 16 , characterized in that the crystallization of the synthesis gel is carried out at temperatures of from about 120 to 200° C. 
     
     
         20 . The process as claimed in  claim 16 , characterized in that the solid is washed with demineralized water until the washing water has an electrical conductivity of less than 100 μS/cm. 
     
     
         21 . The process as claimed in  claim 16 , characterized in that the crystallization time is from about 50 to 500 h. 
     
     
         22 . The process as claimed in  claim 16 , characterized in that the solid is washed, dried, comminuted, and calcined. 
     
     
         23 . The process as claimed in  claim 22 , characterized in that the calcination is carried out at a temperature of from 400 to 700° C., for a period of from 3 to 12 h. 
     
     
         24 . The process as claimed in  claim 16 , characterized in that exchangeable cations present in the zeolite of the ZSM-12 type are exchanged by treating with an aqueous solution of an ammonium compound or of an acid, and the solid obtained after the ion exchange is washed, dried and subsequently calcined. 
     
     
         25 . The process as claimed in  claim 16 , characterized in that the zeolite of the ZSM-12 type is shaped into a molding. 
     
     
         26 . The process as claimed in  claim 25 , characterized in that a binder is added to the zeolite of molded product in an amount from 10 to 90% by weight, based on the total weight of the molded product. 
     
     
         27 . The process as claimed in  claim 25 , characterized in that the molded product contains at least one transition group metal. 
     
     
         28 . The process as claimed in  claim 27 , characterized in that the transition group metal comprises a noble metal. 
     
     
         29 - 34 . (canceled) 
     
     
         35 . A zeolite of the ZSM-12 type which has a primary crystal size of ≦0.1 μm; and a specific volume, determined by mercury porosimetry at a maximum pressure of 4000 bar, of 30-200 mm 3 /g with a pore radius range of 4-10 nm. 
     
     
         36 . The zeolite as claimed in  claim 35 , characterized in that the zeolite has a specific volume, determined by nitrogen porosimetry, in a pore radius range of 3-20 nm, of 0.05-0.40 cm 3 /g. 
     
     
         37 . The zeolite as claimed in  claim 35 , characterized with a molar SiO 2 /Al 2 O 3  ratio of from about 50 to 150. 
     
     
         38 . The zeolite as claimed in  claim 35 , characterized with a molar M 2/n O:SiO 2  ratio of from 0.01 to 0.045. 
     
     
         39 . The zeolite as claimed in  claim 35 , characterized wherein the primary crystals have been combined in agglomerates in a proportion of at least 30%. 
     
     
         40 . The zeolite as claimed in  claim 35 , characterized in that the primary crystals have a mean diameter of from about 10 to 70 nm. 
     
     
         41 . The zeolite as claimed in  claim 39 , characterized in that the agglomerates have cavities accessible from their surface or interstices between the primary crystals. 
     
     
         42 . A catalyst for the conversion of organic compounds comprising the zeolite of  claim 35 . 
     
     
         43 . The catalyst as claimed in  claim 42 , characterized in that it is in lump form. 
     
     
         44 . The catalyst as claimed in  claim 42 , further comprising a binder in an amount of from 10 to 90% by weight, based on the total weight of the catalyst. 
     
     
         45 . The catalyst as claimed in  claim 42 , characterized in that the catalyst contains at least one catalytically active component. 
     
     
         46 . The catalyst as claimed in  claim 45 , characterized in that the at least one catalytically active component comprises a transition group metal. 
     
     
         47 . The catalyst as claimed in  claim 46 , characterized in that the transition group metal comprises a noble metal. 
     
     
         48 . The catalyst as claimed in  claim 47 , characterized in that the noble metal comprises platinum. 
     
     
         49 . The catalyst as claimed in  claims 45 , characterized in that the catalytically active component comprises from 0.01 to 40% by weight of the catalyst based on the total weight of the catalyst. 
     
     
         50 . A process for converting organic compounds comprising passing an organic feed stream over or through a catalyst bed comprising the ZSM-12 type catalyst of  claim 42 . 
     
     
         51 . A process for hydroisomerization of higher paraffins having a carbon number greater than 5 carbon atoms, comprising passing a feed stream containing higher paraffins over through a catalyst bed comprising the ZSM-12 type catalyst of  claim 42 . 
     
     
         52 . The process of  claim 51  wherein the higher paraffin comprised n-octane. 
     
     
         53 . The process of  claim 50  wherein the organic compounds comprise aromatics. 
     
     
         54 . The process of  claim 51  wherein the hydroisomerization process is carried out in the presence of hydrogen at a temperature below 290° C. 
     
     
         55 . The process of  claim 51  wherein the hydroisomerization process is carried out at a pressure of 1 to 50 bar at a liquid hourly space velocity (LHSV) of from 0.1 to 10 l per hour. 
     
     
         56 . A process for reforming utilizing the zeolite catalyst of  claim 42 . 
     
     
         57 . A process for increasing the flowability of gas oils utilizing the catalyst of  claim 42 . 
     
     
         58 . A process for catalytic or hydrogenating cracking and oligomerization or polymerization of olefinic or acetylenic hydrocarbons utilizing the catalyst of  claim 42 . 
     
     
         59 . A process for alkylation utilizing the catalyst of  claim 42 . 
     
     
         60 . A process for dehydrogenation and hydrogenation of organic compounds utilizing the catalyst of  claim 42 . 
     
     
         61 . A process for the hydration or dehydration of organic compounds utilizing the catalyst of  claim 42 . 
     
     
         62 . A process for the desulfurization of organic compounds utilizing the catalyst of  claim 42 . 
     
     
         63 . A process for the conversion of alcohols and ethers to hydrocarbons and the conversion of paraffins or olefins to aromatics utilizing the catalyst of  claim 42 .