This invention provides a process for manufacturing a catalyst with a desired attrition index, comprising the steps of selecting at least one molecular sieve having a morphology and size index (MSI) of from 1 to about 1000 to secure said desired attrition index of said catalyst.
Description
DESCRIPTION OF THE DRAWINGS
FIG. 1 shows SEM image of sample A.
FIG. 2 shows SEM image of sample B.
FIG. 3 shows ARI results of examples 1-10 versus morphologies of samples A, B, C, D, and E.
Claims
1. A process for manufacturing a catalyst with a desired attrition rate index, comprising the steps of:
a. selecting a molecular sieve having a morphology selected from a group consisting of cube morphology, stacked platelet and cube morphology, platelet morphology, and thin platelet morphology to secure said desired attrition index of said catalyst; orb. combining at least two molecular sieves having different morphologies selected from a group consisting of cube morphology, stacked platelet and cube morphology, platelet morphology, and thin platelet morphology and adjusting the weight ratio of said molecular sieves to secure said desired attrition index of said catalyst.
2. The process of claim 1, wherein said catalyst further comprises clay and binder, said catalyst has a core clay to alumina ratio and a surface clay to alumina ratio; said core clay to alumina ratio being within ±20% of said surface clay to alumina ratio.
3. The process of claim 2, wherein said attrition rate index (ARI) is less than 0.69 wt. %/hr.
4. The process of claim 2, wherein said catalyst has an apparent bulk density of at least 0.75 g/ml.
5. The process of claim 1, wherein said molecular sieve(s) is selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, AlPO-5, AlPO-11, AlPO-18, AlPO-31, AlPO-34, AlPO-36, AlPO-37, AlPO-46, metal containing molecular sieves thereof, an silicoaluminophosphate having an X-ray diffraction pattern having at least one reflection peak in each of the following ranges in the 5 to 25 (2θ) range:
6. The process of claim 2, wherein said clay is a natural or synthetic clay.
7. The process of claim 2, wherein said binder is an inorganic oxide sol of alumina or silica.
8. The process of claim 5, wherein said X-ray diffraction pattern has no reflection peak in the 9.8 to 12.0 (2θ) range.
9. The process of claim 5, wherein said X-ray diffraction pattern has no broad feature centered at about 16.9 (2θ).
10. The process of claim 5, wherein said reflection peak in the 17.7-18.1 (2θ) range has a relative intensity between 0.09 and 0.40 with respect to the reflection peak at 17.9 (2θ) in the diffraction pattern of SAPO-34, all diffraction patterns being normalized to the intensity value of the reflection peak in the 20.5-20.7 (2θ) range.
11. A process of making a metalloaluminophosphate molecular sieve catalyst having a desired attrition index, comprising the steps of:
a. selecting a metalloaluminophosphate molecular sieve having a morphology selected from a group consisting of cube morphology, stacked platelet and cube morphology, platelet morphology, and thin platelet morphology to secure said desired attrition index of said catalyst; orb. combining at least two metalloaluminophosphate molecular sieves having different morphologies selected from a group consisting of cube morphology, stacked platelet and cube morphology, platelet morphology, and thin platelet morphology and adjusting the weight ratio of said molecular sieves to secure said desired attrition index of said catalyst;andc. mixing said metalloaluminophosphate molecular sieve(s), clay and binder to a mixture at a breakage energy effective to break apart agglomerates and aggregates; andd. drying said mixture to produce a dried metalloaluminophosphate molecular sieve catalyst having an attrition index of not greater than 0.69 wt. %/hr.
12. The process of claim 11, wherein said mixture is dried by spray drying.
13. The process of claim 11, wherein said breakage energy is at least 10−5 cal cm−2.
14. The process of claim 11, wherein said metalloaluminophosphate molecular sieve(s) is selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, AlPO-5, AlPO-11, AlPO-18, AlPO-31, AlPO-34, AlPO-36, AlPO-37, AlPO-46, metal containing molecular sieves thereof, an silicoaluminophosphate having an X-ray diffraction pattern having at least one reflection peak in each of the following ranges in the 5 to 25 (2θ) range:
15. The process of claim 11, wherein said clay is a natural or synthetic clay.
16. The process of claim 11, wherein said binder is an inorganic oxide sol of alumina or silica.
17. The process of claim 11, wherein said metalloaluminophosphate molecular 9′ sieve(s), said clay and said binder are mixed together to form a mixture having a viscosity of at least 500 cP.
18. The process of claim 11, wherein said mixture is aged prior to drying.
19. The process of claim 11, wherein said mixture has a solids content of at least 40 wt %, based on total weight of the mixture.
20. The process of claim 11, wherein said metalloaluminophosphate molecular sieve, clay and binder are mixed together at a binder to molecular sieve weight ratio of at least 0.20:1.
21. The process of claim 11, wherein said metalloaluminophosphate molecular sieve, clay and binder are mixed together at a binder content of at least 5 wt %, based on total weight of the mixture, excluding liquid.
22. A process for manufacturing a catalyst with a desired attrition index, comprising the steps of selecting at least one molecular sieve having a morphology and size index (MSI) of from 1 to about 1000 to secure said desired attrition index of said catalyst.
23. The process of claim 22, wherein said molecular sieve having a morphology and size index (MSI) of from 1 to about 5.
24. The process of claim 22, wherein said molecular sieve is metalloaluminophosphate molecular sieves.
25. The process of claim 22, wherein said catalyst further comprises clay and binder, said catalyst has a core clay to alumina ratio and a surface clay to alumina ratio; said core clay to alumina ratio being within ±20% of said surface clay to alumina ratio.
26. The process of claim 22, wherein said catalyst has an apparent bulk density of at least 0.75 g/ml.
27. The process of claim 22, wherein said molecular sieve(s) comprises an silicoaluminophosphate having an X-ray diffraction pattern having at least one reflection peak in each of the following ranges in the 5 to 25 (2θ) range:
28. A process of making a metalloaluminophosphate molecular sieve catalyst having a desired attrition index, comprising the steps of:
a. selecting at least one molecular sieve having a morphology and size index (MSI) of from 1 to about 1000 to secure said desired attrition index of said catalyst;b. mixing said metalloaluminophosphate molecular sieve(s), clay and binder at a breakage energy effective to break apart agglomerates and aggregates;c. drying said mixture to produce a dried metalloaluminophosphate molecular sieve catalyst having an attrition rate index (ARI) of not greater than 0.69 wt. %/hr; and wherein said mixture is dried by spray drying, said breakage energy is at least 10−5 cal cm−2, said clay is a natural or synthetic clay, said binder is an inorganic oxide sol of alumina or silica.
29. The process of claim 28, wherein said metalloaluminophosphate molecular sieve(s) is selected from the group consisting of SAPO-5, SAPO-8, SAPO-11, SAPO-16, SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37, SAPO-40, SAPO-41, SAPO-42, SAPO-44, SAPO-47, SAPO-56, AlPO-5, AlPO-11, AlPO-18, AlPO-31, AlPO-34, AlPO-36, AlPO-37, AlPO-46, metal containing molecular sieves thereof, an silicoaluminophosphate having an X-ray diffraction pattern having at least one reflection peak in each of the following ranges in the 5 to 25 (2θ) range:
30. The process of claim 28, wherein said metalloaluminophosphate molecular sieve(s), said clay and said binder are mixed together to form a mixture having a viscosity of at least 500 cP.
31. A process for manufacturing olefin product from oxygenate, comprising the steps of:
a. introducing a catalyst of any preceding claim into a reaction system;b. contacting the catalyst composition with oxygenate in the reaction system to form olefin product; andc. withdrawing said olefin product.
32. The process of claim 31, wherein said oxygenate comprises methanol, said olefin product comprises ethylene and propylene.
Patent Application
20070203385
