Process for Obtaining Catalyst Composites MeAPO and Their Use in Conversion of Organics to Olefins

Abstract

A mixture can include 0.01 to 30 weight % of a medium or large pore crystalline silicoaluminate, silicoaluminophosphate materials, or silicoaluminate mesoporous molecular sieves (A), and 99.99 to 70 weight % of a MeAPO molecular sieve. The mixture can be included in a catalyst. An XTO process can include contacting an oxygen-containing, halogenide-containing, or sulphur-containing organic feedstock with the catalyst under conditions effective to convert the organic feedstock to olefin products. A combined XTO and OCP process can include contacting the organic feedstock with the catalyst at conditions effective to convert at least a portion of the organic feedstock to form an XTO reactor effluent including light olefins and a heavy hydrocarbon fraction, separating the light olefins from the heavy hydrocarbon fraction, and contacting the heavy hydrocarbon fraction in an OCP reactor at conditions effective to convert at least a portion of the heavy hydrocarbon fraction to light olefins.

1 - 41 . (canceled) 
     
     
         42 . A catalyst composite comprising:
 at least 0.5% by weight of at least one metal salt, which is stable under temperatures of 200 to 700° C. and pressures of 5 to 5000 kPa, wherein the metal salt comprises a metal selected from a group consisting of Ga, Cs, Sr, Mg, Ca, Ba, Sc, Sn, Li, Co, Zn, and combinations thereof, and wherein the metal salt comprises an anion selected from a group consisting of silicates, borates, and borosilicates;   at least 10% by weight of molecular sieves which comprise 70 to 100% by weight of molecular sieves of at least one small pore aluminosilicate or small pore metalloaluminophosphate (MeAPO) molecular sieve and 0 to 30% by weight of molecular sieves of at least one medium or large pore molecular sieve comprising pore apertures defined by ring sizes of at least 10 tetrahedric atoms;   wherein the at least one small pore aluminosilicate or small pore MeAPO molecular sieve comprises pore apertures defined by ring sizes of up to 8 tetrahedric atoms;   wherein the at least one medium or large pore molecular sieve is selected from the group consisting of crystalline silicoaluminates, silicoaluminophosphates, mesoporous silicoaluminates and combinations thereof.   
     
     
         43 . The catalyst composite of  claim 42 , wherein the metal is selected from a group consisting of Zn, Co, Ca, Mg, and combinations thereof. 
     
     
         44 . The catalyst composite of  claim 42 , wherein the metal is selected from a group consisting of Zn, Co, and combinations thereof. 
     
     
         45 . The catalyst composite of  claim 42 , wherein the metal is selected from a group consisting of Ca, Mg, and combinations thereof. 
     
     
         46 . The catalyst composite of  claim 42 , wherein the MeAPO molecular sieve has predominantly a plate crystal morphology in which the width (W) and the thickness (T) are represented by the formula: W/T≧10. 
     
     
         47 . The catalyst composite of  claim 46 , wherein W/T ranges from 10 to 100. 
     
     
         48 . The catalyst composite of  claim 46 , wherein T ranges from 0.01 to 0.07 μm. 
     
     
         49 . The catalyst composite of  claim 46 , wherein T ranges from 0.04 to 0.07 μm. 
     
     
         50 . The catalyst composite of  claim 42 , wherein the catalyst composite comprises from 0.5% to 10% by weight of the at least one metal salt. 
     
     
         51 . The catalyst composite of  claim 42 , wherein the molecular sieves comprise 70 to 99.9% by weight of the MeAPO molecular sieve and 0.01 to 30% by weight of the medium or large pore molecular sieve. 
     
     
         52 . The catalyst composite of  claim 42 , wherein the molecular sieves comprise 75 to 99.5% by weight of the MeAPO molecular sieve and 0.5 to 25% by weight of the medium or large pore molecular sieve. 
     
     
         53 . The catalyst composite of  claim 42 , wherein the medium pore crystalline silicoaluminate molecular sieves are selected from a group consisting of MFI, FER, MEL and combinations thereof. 
     
     
         54 . The catalyst composite of  claim 42 , wherein the medium pore crystalline silicoaluminate molecular sieve is selected from a group consisting of ZSM-5, silicalite, P-ferrierite, and combinations thereof. 
     
     
         55 . The catalyst composite of  claim 42 , wherein the medium pore silicoaluminophosphate material is AEL. 
     
     
         56 . The catalyst composite of  claim 42 , wherein the large pore crystalline silicoaluminates are selected from a group consisting of FAU, MOR, LTL, MAZ, MWW, BEA, and combinations thereof. 
     
     
         57 . The catalyst composite of  claim 42 , wherein the large pore silicoaluminophosphate materials is AFI. 
     
     
         58 . The catalyst composite of  claim 42 , wherein the mesoporous silicoaluminate is MCM-41. 
     
     
         59 . The catalyst composite of  claim 42 , wherein the MeAPO molecular sieves have essentially a structure CHA or AEI or a mixture thereof. 
     
     
         60 . The catalyst composite of  claim 42 , wherein the MeAPO molecular sieves have essentially the structure SAPO-18, SAPO-34, SAPO-44, SAPO-17, SAPO-35 or a mixture thereof. 
     
     
         61 . The catalyst composite of  claim 42 , wherein MeAPO is an intergrown phase of two MeAPO having AEI and CHA framework types. 
     
     
         62 . The catalyst composite of  claim 42 , wherein the MeAPO molecular sieve has an empirical chemical composition on an anhydrous basis, after synthesis and calcination, expressed by the formula H x Me y Al z P k O 2 , in which:
     y+z+k= 1; and   x is less than or equal to y, wherein:
 y has a value ranging from 0.0008 to 0.4; 
 z has a value ranging from 0.25 to 0.67; and 
 k has a value ranging from 0.2 to 0.67. 
   
     
     
         63 . The catalyst composite of  claim 42 , wherein the MeAPO has been prepared by a method comprising:
 forming a reaction mixture containing a texture influencing agent (TIA), an organic templating agent (TEMP), and a reactive source wherein the reactive source is a reactive inorganic source of MeO 2  essentially insoluble in the TIA, Al 2 O 3 , P 2 O 5  or combinations thereof;   crystallizing the above reaction mixture thus formed until crystals of the metalloaluminophosphate (MeAPO) are formed;   recovering a solid reaction product;   washing it with water to remove the TIA; and   calcinating it to remove the organic template.   
     
     
         64 . The catalyst composite of  claim 42 , wherein in the MeAPO, Me is a metal selected from a group consisting of Si, Ge, Mg, Zn, Fe, Co, Ni, Mn, Cr, Ca, Ba, Mo, Cu, Ga, Sn, Ti, and mixtures thereof. 
     
     
         65 . The catalyst composite of  claim 64 , wherein Me is Si. 
     
     
         66 . The catalyst composite, of  claim 42 , wherein a metal selected from a group consisting of Si, Mg, Zn, Ge, Fe, Co, Ni, Mn, Cr, Ca, Ba, Mo, Cu, Ga, Sn, Ti, and mixtures thereof is added to the molecular sieve(s) before blending with the metal salt. 
     
     
         67 . The catalyst composite of  claim 42 , wherein the composite further comprises metal phosphates and/or sulphates comprising at least one metal selected from a group consisting of Zn, Co, Ca, Mg, Ga, Al, Cs, Sr, Ba, Sc, Sn, and Li. 
     
     
         68 . The catalyst composite of  claim 42 , wherein the metal salt is introduced to the molecular sieve(s) by one of the following two methods:
 during the formulation step of the catalyst by mechanically blending the molecular sieve with a metal silicate forming a precursor; or   physical blending of a previously formulated molecular sieve and a previously formulated metal silicate in situ in an XTO and/or OCP reaction medium.   
     
     
         69 . The catalyst composite of  claim 68 , wherein after introduction of the metal salt to the molecular sieve(s), the catalyst composite is post-treated by calcination, reduction, steaming, or P-modification of zeolites. 
     
     
         70 . A process for making an olefin product from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock wherein the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock is contacted in an XTO reactor with the catalyst composite of  claim 42  under conditions effective to convert the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock to produce an XTO reactor effluent comprising a heavy hydrocarbon fraction and olefin products comprising ethylene and propylene. 
     
     
         71 . The process of  claim 70 , wherein the XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction is sent to a fractionation section to separate said light olefins from the heavy hydrocarbon fraction and the heavy hydrocarbon fraction is recycled to the XTO reactor at conditions in the XTO reactor effective to convert at least a portion of the heavy hydrocarbon fraction to olefin products. 
     
     
         72 . The process of  claim 71 , wherein the olefin products are fractionated to form a stream comprised essentially of ethylene and at least a part of said stream is recycled to the XTO reactor to increase the propylene production. 
     
     
         73 . The process of  claim 70 , wherein the XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction is sent to a fractionation section to separate the light olefins from said heavy hydrocarbon fraction and the heavy hydrocarbon fraction is sent in an OCP reactor at conditions in the OCP reactor effective to convert at least a portion of the heavy hydrocarbon fraction to light olefins. 
     
     
         74 . The process of  claim 73 , wherein the OCP reactor effluent is sent to a fractionator and the light olefins are recovered and hydrocarbons having 4 carbon atoms or more are recycled to an inlet of the OCP reactor, and mixed with the heavy hydrocarbon recovered from the effluent of the XTO reactor. 
     
     
         75 . The process of  claim 74 , wherein before recycling the hydrocarbons having 4 carbon atoms or more to the inlet of the OCP reactor, the hydrocarbons having 4 carbon atoms or more are sent to a second fractionator to purge heavies. 
     
     
         76 . The process of  claim 75 , wherein ethylene is recycled to the OCP reactor, and wherein the ethylene is from the fractionation section of the XTO reactor, from the fractionation section of the OCP reactor, from both the fractionation section of the XTO reactor and the fractionation section of the OCP reactor, or from a common recovery section. 
     
     
         77 . The process of  claim 75 , wherein ethylene is recycled to the XTO reactor, and wherein the ethylene is from the fractionation section of the XTO reactor, from the fractionation section of the OCP reactor, from both the fractionation section of the XTO reactor and the fractionation section of the OCP reactor, or from a common recovery section. 
     
     
         78 . The process of  claim 70 , wherein the ethylene is polymerized with one or more comonomers. 
     
     
         79 . The process of  claim 70 , wherein the propylene is polymerized with one or more comonomers.