1. A fluidizable cracking catalyst, comprising:
from about 5% to less than 50% by volume a substantially inert core comprising mullite; and
from 50% to about 95% by volume of an active shell comprising a NaY zeolite catalyst and a matrix, wherein the NaY zeolite catalyst is crystallized in the active shell after a slurry containing microspheres of mullite, NaY zeolite precursor, and matrix precursor is spray-dried,
wherein the cracking catalyst maintains at least about 45% of original NaY zeolite surface area through standardized steaming.
2. The fluidizable cracking catalyst of claim 1, wherein the substantially inert core has an average cross section from about 30 to about 60 microns the active shell has an average thickness from about 5 to about 30 microns.
3. The fluidizable cracking catalyst of claim 1 having an average particle size from about 50 to about 100 microns.
4. The fluidizable cracking catalyst of claim 1, wherein the substantially inert core further comprises alpha-alumina.
5. The fluidizable cracking catalyst of claim 1, wherein the active shell comprises from about 40% to about 90% by weight of zeolite catalyst and from about 10% to about 60% by weight of matrix.
6. The fluidizable cracking catalyst of claim 1, wherein the matrix comprises at least one of silica, alumina such as gamma-alumina, mullite, silica-alumina, silica-magnesia, and clays such as kaolinite, halloysite, or montmorillonite.
7. The fluidizable cracking catalyst of claim 1 having a pore volume distribution wherein a first set of pores containing a porosity from about 0.03 to about 0.13 mlg have a pore diameter of at least about 40 \u212b and at most about 100 \u212b, a second set of pores containing a porosity from about 0.03 to about 0.19 mlg have a pore diameter of at least about 100 \u212b and at most about 600 \u212b, and a third set of pores containing a porosity from about 0.01 to about 0.24 mlg have a pore diameter of at least about 600 \u212b and at most about 20,000 \u212b.
8. The fluidizable cracking catalyst of claim 1 having a first set of pores containing a porosity from about 0.05 to about 0.13 mlg have a pore diameter of at least about 40 \u212b and at most about 100 \u212b, a second set of pores containing a porosity from about 0.03 to about 0.11 mlg have a pore diameter of at least about 100 \u212b and at most about 600 \u212b, and a third set of pores containing a porosity from about 0.02 to about 0.01 mlg have a pore diameter of at least about 600 \u212b and at most about 20,000 \u212b.
9. The fluidizable cracking catalyst of claim 1 having a first set of pores containing a porosity from about 0.04 to about 0.12 mlg have a pore diameter of at least about 40 \u212b and at most about 100 \u212b, a second set of pores containing a porosity from about 0.1 to about 0.18 mlg have a pore diameter of at least about 100 \u212b and at most about 600 \u212b, and a third set of pores containing a porosity from about 0.15 to about 0.21 mlg have a pore diameter of at least about 600 \u212b and at most about 20,000 \u212b.
10. The fluidizable cracking catalyst of claim 1 having a surface area from about 100 to about 250 m2g.
11. The fluidizable cracking catalyst of claim 1, wherein the substantially inert core has a surface area of less than about 100 m2g.
12. The fluidizable cracking catalyst of claim 1, wherein the active shell surrounds at least about 75% of the substantially inert core surface.
13. A method of making a fluidizable cracking catalyst with an active shell at least partially surrounding a substantially inert core containing mullite, comprising:
forming a slurry by combining at least water, about 1 to about 70 parts by weight hydrous kaolin, from about 1 to about 70 parts by weight spinel-form calcined kaolin, from about 1 to about 70 parts by weight mullite kaolin, and from about 1 to about 70 parts by weight substantially inert core microspheres containing mullite, and a zeolite precursor; and
spray drying the slurry to form particles containing the substantially inert core microspheres with an active shell at least partially surrounding the substantially inert core; and
crystallizing zeolite in the active shell to create the fluidizable cracking catalyst.
14. The method of claim 13 further comprising calcining the spray dried particles.
15. The method of claim 13, wherein the slurry comprises from about 40% by weight to about 70% by weight solids.
16. The method of claim 13, wherein the slurry further comprises at least one of a zeolite initiator or a source of sodium silicate.
17. The method of claim 13, wherein the zeolite shell precursor has a particle size where at least 90% by weight has a particle size of about 2 microns or less.
18. The method of claim 13, wherein the slurry comprises metakaolin.
19. The method of claim 13, wherein the inert core microspheres are internally seeded with a zeolite initiator.
20. The method of claim 13, wherein the slurry further comprises an aqueous zeolite initiator.
21. A cracking process, comprising:
contacting a hydrocarbon feedstream and a cracking catalyst comprising from about 5% to less than 50% by volume a substantially inert core containing mullite and from 50% to about 95% by volume of an active shell comprising a zeolite catalyst and a matrix in a reactor at a temperature from about 300 to about 800\xb0 C. to provide a cracked product,
wherein the cracking catalyst is prepared by spray drying a slurry, comprising water, microspheres of the substantially inert core, a zeolite precursor, and a matrix precursor, and crystallizing the zeolite catalyst in the active shell.
22. The cracking process of claim 21, wherein the hydrocarbon feedstream comprises one or more of gas oil, steam cracked gas oil and residues, heavy and reduced petroleum crude oil, petroleum atmospheric distillation bottom, petroleum vacuum distillation bottom, heating oil, pitch, asphalt, bitumen, other heavy hydrocarbon residues, tar sand oils, shale oil, liquid products derived from coal liquefaction processes, steam heating oil, jet fuel, diesel, kerosene, gasoline, coker naphtha, steam cracked naphtha, catalytically cracked naphtha, hydrocrackate, reformate, raffinate reformate, Fischer-Tropsch liquids, Fischer-Tropsch gases, natural gasoline, distillate, virgin naphtha, C5+ olefins, C5+ paraffins, ethane, propane, butanes, butenes, or butadiene.
23. The cracking process of claim 21, wherein the cracked product comprises one or more of hydrogen, light olefins, light paraffins, olefins having more than five carbon atoms, paraffins having more than five carbon atoms, cracked naphtha, cracked gas oil, tar, or coke.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A process for the preparation of statin derivatives which comprises the reaction of the intermediate of formula I
wherein X is halogen, acyloxy, activated hydrocarbyloxy, activated hydrocarbylthio or \u2014N(CH3)\u2014OCH3, Ra is a hydroxy-protecting group and Rb is a carboxy-protecting group, with chain lengthening, including the following reaction steps, as described below, wherein the intermediate of formula (I) reacts with an ethylene of formula II
wherein Ya is halogen or hydrogen; there being obtained a keto compound of formula III
wherein Ya is halogen or hydrogen, Xa is halogen or acyloxy, Ra is hydrogen, obtainable after removal of a hydroxy-protecting group Ra, or a hydroxy-protecting group and Rb is a carboxy-protecting group; the compound of formula III is reacted further in accordance method (2) wherein
in accordance with method (2), a compound of formula III wherein Ya is hydrogen or halogen, and Xa is halogen preferred or acyloxy, while Ra and Rb are as defined for compounds of formula III, is reacted in the presence of a base, with elimination of hydrohalic acid HX, to form an olefin of formula VII
wherein Ya\u2032 is hydrogen or halogen, Ra is hydrogen or a hydroxy-protecting group and Rb is a carboxy-protecting group; the corresponding compound wherein Ya\u2032 is iodine being prepared, if desired, by additional reaction with an iodide salt;
andor a compound of formula VII wherein Ya\u2032 is hydrogen or halogen, Ra is hydrogen or a hydroxy-protecting group and Rb is a carboxy-protecting group is then, if necessary, freed of a hydroxy-protecting group Ra, if present, and is subsequently reduced diastereoselectively to form a syn-diol compound of formula VIII
wherein Ra\u2032 is hydrogen and Rc\u2032 is hydrogen, or, after subsequent introduction of protecting groups, Ra\u2032 and Rc\u2032 are each independently of the other hydrogen or a protecting group, with the proviso that at least one of the two radicals is a protecting group, or Ra\u2032 and Rc\u2032 together are a bridging hydroxy-protecting group; Rb is a carboxy-protecting group, and Ya\u2032 is hydrogen or halogen;
and, in a case where the introduction of a bridging hydroxy-protecting group is desirable, if necessary, when Ra\u2032 and Rc\u2032 are each hydrogen, the bridging hydroxy-protecting group formed by Ra\u2032 and Rc\u2032 together being introduced using a suitable reagent;
and the resulting compound of formula VIII is then cleaved oxidatively to form an aldehyde of formula IX
wherein Ra\u2032 and Rc\u2032 are each independently of the other hydrogen or a hydroxy-protecting group or together are a bridging hydroxy-protecting group; and Rb\u2032 is a carboxy-protecting group; it being possible for the compound of formula X to be used directly as synthon for the preparation of statin derivatives, or it is reacted further with iodoform, diiodomethane or methyl iodide to form an iodine compound of formula X
wherein Ra\u2032, Rb\u2032 and Rb\u2032 are as defined for compounds of formula IX;
wherein in the processes mentioned above, at any stage, even where not explicitly mentioned, if necessary one or more or all of the protecting groups present in the compounds of formulae I*, I to XIII are removed or one or more or all of the functional groups that are not to participate in a reaction, or that would interfere with the reaction, are converted into protected groups by the introduction of suitable protecting groups, and it being possible for the compounds of formulae I*, I to XIII, where salt-forming groups are present and the reaction in question is not impaired, also to be in salt form.
2. A process according to claim 1, for the preparation of statin precursors of formula VII described below, which comprises as reaction steps the reaction of the intermediate of formula I wherein X is halogen, acyloxy, activated hydrocarbyloxy, activated hydrocarbylthio or \u2014N(CH3)OCH3, Ra is a hydroxy-protecting group and Rb is a carboxy-protecting group with an ethylene of formula II
wherein Ya is halogen or hydrogen; there being obtained a keto compound of formula III
wherein Ya is hydrogen or halogen and Xa is halogen or acyloxy, Ra is hydrogen, obtainable after removal of a hydroxy-protecting group Ra, or a hydroxy-protecting group and Rb is a carboxy-protecting group; and conversion thereof by reaction in the presence of a base, with elimination of hydrohalic acid HX, into an olefin of formula VII
wherein Ya\u2032 is hydrogen or halogen, Ra is hydrogen or a hydroxy-protecting group and Rb is a carboxy-protecting group; the corresponding compound wherein Ya\u2032 is iodine being obtainable by additional reaction with an iodide salt;
and at any stage, even where not explicitly mentioned, if necessary one or more or all of the protecting groups present in the compounds of formulae I, III andor VII are removed or one or more or all of the functional groups that are not to participate in a reaction, or that would interfere with the reaction, are converted into protected groups by the introduction of suitable protecting groups, and it being possible for the compounds of formulae I, III andor VII, where salt-forming groups are present and the reaction in question is not impaired, also to be in salt form.
3. A process according to claim 2 for the preparation of a compound of formula VIII described below, which additionally comprises the reaction of the compound of formula VII mentioned in claim 2, which, if necessary, is freed of the hydroxy-protecting group Ra, with diastereoselective reduction to form a syn-diol compound of formula VIII
wherein Ra\u2032 is hydrogen and Rc\u2032 is hydrogen, or, after subsequent introduction of protecting groups, Ra\u2032 and Rc\u2032 are each independently of the other hydrogen or a protecting group, with the proviso that at least one of the two radicals is a protecting group, or Ra\u2032 and Rc\u2032 together are a bridging hydroxy-protecting group; Rb is a carboxy-protecting group, and Ya\u2032 is hydrogen or halogen;
and, in a case where the introduction of a bridging hydroxy-protecting group is desirable, if necessary, when Ra\u2032 and Rc\u2032 are each hydrogen, the bridging hydroxy-protecting group formed by Ra\u2032 and Rc\u2032 together being introduced using a suitable reagent;
it being possible for the compound of formula VIII, where salt-forming groups are present and the reaction in question is not impaired, also to be in salt form.
4. A process according to claim 3 for the preparation of a compound of formula IX described below, which additionally comprises the reaction of the compound of formula VIII mentioned in claim 3, and oxidative cleavage thereof to form an aldehyde of formula IX
wherein Ra\u2032 and Rc\u2032 are each independently of the other hydrogen or a hydroxy-protecting group or together are a bridging hydroxy-protecting group; and Rb\u2032 is a carboxy-protecting group; it being possible for the compound of formula VIII, where salt-forming groups are present and the reaction in question is not impaired, also to be in salt form.
5. A process according to claim 4 for the preparation of a compound of formula X described below, which additionally comprises the reaction of the compound of formula IX mentioned in claim 4 with iodoform, diiodomethane or methyl iodide to form an iodine compound of formula X
wherein Ra\u2032, Rb\u2032 and Rc\u2032 are as defined for compounds of formula IX; it being possible for the compound of formula IX, where salt-forming groups are present and the reaction in question is not impaired, also to be in salt form.
6. A compound of formula I
wherein X is halogen, acyloxy, activated hydrocarbyloxy, activated hydrocarbylthio or \u2014N(CH3)OCH3, Ra is hydrogen or a hydroxy-protecting group and Rb is a carboxy-protecting group.
7. A compound of formula I according to claim 6 wherein X is halogen, Ra is hydrogen, lower alkanoyl, lower alkoxy-lower alkanoyl, lower alkoxymethoxy or lower alkoxyethoxymethoxy and Rb is lower alkyl.
8. A compound of formula I according to claim 7, selected from the following compounds: monoethyl-3(R)-acetoxyglutaric acid chloride or bromide, monoethyl-3(R)-methoxyacetoxyglutaric acid chloride or bromide, monoethyl-3(R)-methoxymethoxyglutaric acid chloride or bromide and monoethyl-3(R)-(2-methoxyethoxyethyl)-oxymethoxyglutaric acid chloride or bromide.
9. A compound of formula VII
wherein Ya\u2032 is hydrogen or halogen, Ra is hydrogen or a hydroxy-protecting group and Rb is a carboxy-protecting group.
10. A compound of formula VII according to claim 9, selected from the group consisting of 3(R)-acetoxy-5-oxohept-6-enoic acid ethyl ester, 3(R)-hydroxy-5-oxo-hept-6-enoic acid ethyl ester, 3(R)-acetoxy-5-oxohept-6-enoic acid ethyl ester, 3(R)-methoxymethoxy-5-oxohept-6-enoic acid ethyl ester, 3(R)-(2-methoxyethyl)-oxymethoxy-5-oxohept-6-enoic acid ethyl ester and 3(R)-hydroxy-5-oxo-hept-6-enoic acid ethyl ester.
11. A compound of formula VIII
wherein Ra\u2032 and Rc\u2032 are each independently of the other hydrogen or a protecting group, or Ra\u2032 and Rc\u2032 together are a bridging hydroxy-protecting group; Rb is a carboxy-protecting group, and Ya\u2032 is hydrogen or halogen.
12. A compound of formula VIII according to claim 11 named (3R,5S)-dihydroxy-hept-6-enoic acid ethyl ester.