초록 ▼

The present invention relates to a mixture comprising 0.01 to 30% by weight of at least one medium or large pore crystalline silicoaluminate, silicoaluminophosphate materials or silicoaluminate mesoporous molecular sieves (co-catalyst) (A) and respectively 99.99 to 70% by weight of at least a MeAPO

The present invention relates to a mixture comprising 0.01 to 30% by weight of at least one medium or large pore crystalline silicoaluminate, silicoaluminophosphate materials or silicoaluminate mesoporous molecular sieves (co-catalyst) (A) and respectively 99.99 to 70% by weight of at least a MeAPO molecular sieve. The present invention also relates to catalysts consisting of the above mixture or comprising the above mixture. The present invention also relates to a process (hereunder referred as “XTO process”) for making an olefin product from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock, wherein said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock is contacted with the above catalyst (in the XTO reactor) under conditions effective to convert the oxygen-containing, halogenide-containing or sulphur-containing organic feedstock to olefin products (the XTO reactor effluent). The present invention also relates to a process (hereunder referred as “combined XTO and OCP process”) to make light olefins from an oxygen-containing, halogenide-containing or sulphur-containing organic feedstock comprising: contacting said oxygen-containing, halogenide-containing or sulphur-containing organic feedstock in the XTO reactor with the above catalyst at conditions effective to convert at least a portion of the feedstock to form an XTO reactor effluent comprising light olefins and a heavy hydrocarbon fraction; separating said light olefins from said heavy hydrocarbon fraction; and contacting said heavy hydrocarbon fraction in the OCP reactor at conditions effective to convert at least a portion of said heavy hydrocarbon fraction to light olefins.

대표청구항 ▼

1. 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 is selected from the group consisting of Mg2B2O5.H2O, CaMgB6O11.6H2O (hydroboracite), Ca2B6O11.5H2O (col

1. 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 is selected from the group consisting of Mg2B2O5.H2O, CaMgB6O11.6H2O (hydroboracite), Ca2B6O11.5H2O (colemanite), Ca4B10O19.7H2O, Mg(BO2).8H2O, Ca(BO2).2H2O, BaB6O10.4H2O, CaSi6O17(OH)2 (xonotlite), CaMg(Si2O6)x, Mg2(Si2O6)x, CaAl2Si2O8 and combinations thereof;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;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. 2. The catalyst composite of claim 1, wherein the catalyst composite comprises from 0.5% to 10% by weight of the at least one metal salt. 3. 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 is CaSi6O17(OH)2 (xonotlite);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;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. 4. The catalyst composite of claim 1, 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. 5. The catalyst composite of claim 1, 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. 6. The catalyst composite of claim 1, wherein the medium pore crystalline silicoaluminate molecular sieves are selected from the group consisting of MFI, FER, MEL and combinations thereof. 7. The catalyst composite of claim 1, wherein the medium pore crystalline silicoaluminate molecular sieve is selected from the group consisting of ZSM-5, silicalite, P-ferrierite and combinations thereof. 8. The catalyst composite of claim 1, wherein the medium pore silicoaluminophosphate material is AEL. 9. The catalyst composite of claim 1, wherein the large pore crystalline silicoaluminates are selected from the group consisting of FAU, MOR, LTL, MAZ, MWW, BEA and combinations thereof. 10. 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 is selected from the group consisting of Mg2B2O5.H2O, CaMgB6O11.6H2O (hydroboracite), Ca2B6O11.5H2O (colemanite), Ca4B10O19.7H2O, Mg(BO2).8H2O, Ca(BO2).2H2O, BaB6O10.4H2O, CaSi6O17(OH)2 (xonotlite), CaMg(Si2O6)x, Mg2(Si2O6)x, CaAl2O8 and combinations thereof;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, and mesoporous silicoaluminates and combinations thereof; andwherein the large pore silicoaluminophosphate materials is AFI. 11. 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 is selected from the group consisting of Mg2B2O5.H2O, CaMgB6O11.6H2O (hydroboracite), Ca2B6O11.5H2O (colemanite), Ca4B10O19.7H2O, Mg(BO2).8H2O, Ca(BO2).2H2O, BaB6O10.4H2O, CaSi6O17(OH), (xonotlite), CaMg(Si2O6)x, Mg2(Si2O6)x, and CaAl2Si2O8 and combinations thereof;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, and mesoporous silicoaluminates and combinations thereof; andwherein the mesoporous silicoaluminate is MCM-41. 12. The catalyst composite of claim 1, wherein the MeAPO molecular sieves have essentially a structure CHA or AEI or a mixture thereof. 13. The catalyst composite of claim 1, wherein the MeAPO molecular sieves have essentially the structure SAPO-18, SAPO-34, SAPO-44, SAPO-17, SAPO-35 or a mixture thereof. 14. The catalyst composite of claim 1, wherein MeAPO is an intergrown phase of two MeAPO having AEI and CHA framework types. 15. The catalyst composite of claim 1, wherein the MeAPO molecular sieve has an empirical chemical composition on an anhydrous basis, after synthesis and calcination, expressed by the formula HxMeyAlzPkO2, in which: y+z+k=1; andx 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,k has a value ranging from 0.2 to 0.67. 16. The catalyst composite of claim 1, wherein W/T ranges from 10 to 100. 17. The catalyst composite of claim 1, wherein T ranges from 0.01 to 0.07 μm. 18. The catalyst composite of claim 16, wherein T ranges from 0.04 to 0.07 μm. 19. The catalyst composite of claim 1, wherein the MeAPO is 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 MeO2 essentially insoluble in the TIA, Al2O3, P2O5 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; andcalcinating it to remove the organic template. 20. The catalyst composite of claim 1, wherein in the MeAPO, Me is a metal selected from the group consisting of Si, Ge, Mg, Zn, Fe, Co, Ni, Mn, Cr, Ca, Ba, Mo, Cu, Ga, Sn, Ti and mixtures thereof. 21. The catalyst composite of claim 20, wherein Me is Si. 22. The catalyst composite of claim 1, wherein a metal selected from the 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. 23. The catalyst composite of claim 1, wherein the composite further comprises metal phosphates and/or sulphates comprising at least one metal selected from the group consisting of Zn, Co, Ca, Mg, Ga, Al, Cs, Sr, Ba, Sc, Sn, and Li. 24. The catalyst composite of claim 1, 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 the previously formulated molecular sieve and the previously formulated metal silicate in situ in an XTO and/or OCP reaction medium. 25. The catalyst composite of claim 24, wherein after introduction of the metal salt to the molecular sieves, the composite can be post-treated by calcinations, reduction steaming or P-modification of any zeolites. 26. 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 1 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. 27. The process of claim 26, 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. 28. The process of claim 26, 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. 29. The process of claim 26, 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. 30. The process of claim 29, 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. 31. The process of claim 30, wherein before recycling the hydrocarbons having 4 carbon atoms or more to an inlet of the OCP reactor, the hydrocarbons having 4 carbon atoms or more are sent to a second fractionator to purge heavies. 32. The process of claim 29, wherein in order to adjust the propylene to ethylene ratio of the whole process, ethylene in whole or in part is recycled to the OCP reactor and the ethylene can either come from the fractionation section of the XTO reactor or from the fractionation section of the OCP reactor or from both the fractionation section of the XTO reactor and the fractionation section of the OCP reactor or from a common recovery section. 33. The process of claim 29, wherein in order to adjust the propylene to ethylene ratio of the whole process, ethylene in whole or in part is recycled to the XTO reactor and the ethylene can either come from the fractionation section of the XTO reactor or from the fractionation section of the OCP reactor or from both the fractionation section of the XTO reactor and the fraction section of the OCP reactor or from a common recovery section. 34. The process of claim 26, wherein ethylene is further polymerized with one or more comonomers. 35. The process of claim 26, wherein propylene is further polymerized with one or more comonomers.