In one aspect, the invention includes a reactor apparatus for pyrolyzing a hydrocarbon feedstock, the apparatus including: a reactor component comprising a refractory material in oxide form, the refractory material having a melting point of at least 2060° C. and which remains in oxide form when expo
In one aspect, the invention includes a reactor apparatus for pyrolyzing a hydrocarbon feedstock, the apparatus including: a reactor component comprising a refractory material in oxide form, the refractory material having a melting point of at least 2060° C. and which remains in oxide form when exposed to a gas having carbon partial pressure of 10−22 bar, an oxygen partial pressure of 10−10 bar, at a temperature of 1200° C. In some embodiments, the reactor comprises a regenerative pyrolysis reactor apparatus and in other embodiments it includes a reverse flow regenerative reactor apparatus. In other aspects, this invention includes a method for pyrolyzing a hydrocarbon feedstock using a pyrolysis reactor system comprising the step of providing in a heated region of a pyrolysis reactor system for pyrolyzing a hydrocarbon feedstock, apparatus comprising a refractory material in oxide form, the refractory material having a melting point of at least 2060° C. and that remains in oxide form when exposed to a gas having a carbon partial pressure of 10−22 bar, an oxygen partial pressure of 10−10 bar, at a temperature of 1200° C.
대표청구항▼
1. A reactor apparatus for pyrolyzing a hydrocarbon feedstock, said apparatus including: a reactor component comprising a refractory material in oxide form, the refractory material having a melting point of no less than 2060° C. and which remains in oxide form when exposed to a gas having carbon par
1. A reactor apparatus for pyrolyzing a hydrocarbon feedstock, said apparatus including: a reactor component comprising a refractory material in oxide form, the refractory material having a melting point of no less than 2060° C. and which remains in oxide form when exposed to a gas having carbon partial pressure of 10−22 bar, an oxygen partial pressure of 10−10 bar, at a temperature of 1200° C. 2. The apparatus of claim 1, wherein said reactor apparatus comprises a regenerative pyrolysis reactor apparatus. 3. The apparatus of claim 2, wherein said regenerative pyrolysis reactor apparatus comprises a reverse flow regenerative reactor apparatus. 4. The apparatus of claim 1, wherein said refractory material remains in said oxide form when exposed to a gas having carbon partial pressure of 10−22 bar, an oxygen partial pressure of 10−10 bar, at a temperature of 1200° C. 5. The apparatus of claim 1, wherein said refractory material has a melting point of no less than 2160° C. 6. The apparatus of claim 1, wherein said refractory material remains in said oxide form when exposed to a gas having a carbon partial pressure of 10−15 bar, an oxygen partial pressure of 10−10 bar, and a temperature of 1800° C. 7. The apparatus of claim 1, wherein said refractory material remains in said oxide form when exposed to a gas having a carbon partial pressure of 10−14 bar, an oxygen partial pressure of 10−10 bar, and a temperature of 2000° C. 8. The apparatus of claim 1, wherein said refractory material remains in said oxide form when exposed to a reference pyrolysis gas mixture having a carbon partial pressure of 10−12 bar, an oxygen partial pressure of 10−10 bar, and at a temperature over the full range of from 1500° C. to 2000° C. 9. The apparatus of claim 1, wherein the crystalline structure of said refractory material is cubic during heat-up from 1250° C. to 2250° C. 10. The apparatus of claim 1, wherein the crystalline structure of said refractory material is cubic during cool-down from 2250° C. to 1250° C. 11. The apparatus of claim 1, wherein the vapor pressure of said refractory material is less than 10−7 bar at 2000° C. 12. The apparatus of claim 1, wherein said reactor component includes at least one member selected from the group consisting of flow channels, a reaction fluid mixer, and a reaction heat sink member. 13. The apparatus of claim 1, wherein said reactor component comprises a honeycomb monolith having flow channels within said monolith for conducting at least one member selected from the group consisting of a pyrolysis reactant and a pyrolysis product through said monolith. 14. The apparatus of claim 1, wherein said reactor component has a thermal shock resistance rating that demonstrates a total crack length per unit area after quenching said reactor component from 1100° C. into a water bath to a temperature of 50° C. is not greater than 30 cm/cm2. 15. The apparatus of claim 1, wherein said reactor component comprises a modulus of rupture mechanical flexural strength of not less than 13.8 MPa at a temperature in a range of from 1000° C. to 2000° C. 16. The apparatus of claim 1, wherein said refractory material has porosity at 20° C. in the range of from 2 to 28 vol. % based upon the volume of said refractory material. 17. The apparatus of claim 1, comprising at least 50 wt. % yttrium oxide (yttria) based upon the total weight of said refractory material. 18. The apparatus of claim 1, comprising at least 80 wt. % yttria based upon the total weight of said refractory material. 19. The apparatus of claim 1, wherein said refractory material comprises at least a first grain mode comprising yttria and a second grain mode comprising yttria. 20. The apparatus of claim 1, wherein said refractory materials substantially exclude oxides of toxic ceramics. 21. The apparatus of claim 20, wherein said oxides of toxic ceramics include beryllium and thorium. 22. The apparatus of claim 1, wherein said refractory material comprises; (i) at least 20 wt. % of a first grain mode based upon the total weight of said refractory material, said first grain mode having a D50 grain size in the range of from 5 to 2000 μm; and(ii) at least 1 wt. % of second grain mode based upon the total weight of said refractory material, said second grain mode having a D50 grain size in the range of from 0.01 μm up to not greater than one-fourth the D50 grain size of said first grain mode. 23. The apparatus of claim 1, wherein said refractory material comprises at least one member selected from the group consisting of yttria, an yttrium containing compound, and combinations thereof. 24. The apparatus of claim 1, wherein said refractory material comprises at least one member selected from the group consisting of yttria, another yttrium containing compound, a zirconium containing compound, and combinations thereof. 25. The apparatus of claim 24, wherein said refractory material further comprises from 0.001 wt. % to 5 wt. % based upon the weight of said refractory material, of compounds that comprise elements selected from the group consisting of Al, Si, Mg, Ca, Fe, Mn, Ni, Co, Cr, Ti, Hf, V, Nb, Ta, Mo, W, Sc, La, and Ce, and mixtures thereof. 26. The apparatus of claim 1 used in a pyrolysis reactor for pyrolyzing a hydrocarbon feedstock, at a temperature of no less than 1200° C. 27. The apparatus of claim 1 used in a pyrolysis reactor for pyrolyzing a hydrocarbon feedstock, at a temperature of no less than 1500° C. 28. The apparatus of claim 1 used in a pyrolysis reactor for pyrolyzing a hydrocarbon feedstock, at a temperature of no less than 2000° C. 29. The apparatus of claim 1, wherein said reactor component includes at least one member selected from the group consisting of a honeycomb monolith, a reactor bed, a reactor conduit, and a reactant mixer. 30. The apparatus of claim 1, wherein said regenerative pyrolysis reactor comprises at least one member selected from the group consisting of a deferred combustion reactor, gasification reactor, syngas reactor, steam cracking reactor, and fired furnace. 31. The apparatus of claim 1, further comprising a first reactor and a second reactor in flow communication with said first reactor, at least one member selected from the group consisting of said first reactor and said second reactor comprising said refractory material. 32. A regenerative, refractory corrosion resistant, pyrolysis reactor system for pyrolyzing a hydrocarbon feedstock comprising: a first reactor and a second reactor in flow communication with said first reactor, at least one of said first reactor and said second reactor comprising a refractory material in oxide form, said refractory material having a melting point of not less than 2060° C. and which remains in oxide form when exposed to a gas having a carbon partial pressure of 10−22 bar, a reference oxygen partial pressure of 10−10 bar, and a temperature of 1200° C. 33. The reactor system of claim 32, wherein said refractory material has porosity at 20° C. in the range of from 2 to 28 vol. % based upon the volume of said refractory material. 34. The reactor system of claim 32, wherein said reactor system further comprises: (i) said first reactor further comprises a first channel for conveying a first reactant through said first reactor and a second channel for conveying a second reactant through said first reactor, the first reactant exothermically reacting with the second reactant to generate heat;(ii) said second reactor is heated by said heat to a temperature of at least 1500° C. for pyrolyzing a hydrocarbon feedstock in said second reactor, wherein said second reactor comprises said refractory material. 35. The reactor system of claim 32, wherein said reactor system comprises a reverse flow regenerative reactor system. 36. The reactor system of claim 32, further comprising a reactant mixer section intermediate said first reactor and said second reactor to combine at least a portion of said first reactant with at least a portion of said second reactant, said reactant mixer section comprising said refractory material. 37. The reactor system of claim 32, wherein said refractory material includes yttria and/or another yttrium containing compound, said refractory material including a grain structure having a D50 grain size in the range of from 0.01 μm to 2000 μm. 38. A method for mitigating carbide-oxide ceramic corrosion of a refractory material in the presence of a pyrolyzed hydrocarbon feedstock, said method comprising the steps of providing in a heated region of a pyrolysis reactor system for pyrolyzing a hydrocarbon feedstock, apparatus comprising a refractory material in oxide form, said refractory material having a melting point of not less than 2060° C. and that remains in oxide form when exposed to a gas having a carbon partial pressure of 10−22 bar, an oxygen partial pressure of 10−10 bar, at a temperature of 1200° C. 39. The method of claim 38, wherein said refractory material has a melting point of no less than 2160° C. 40. The method of claim 38, wherein said refractory material remains in the oxide form when exposed to a gas having a carbon partial pressure of 10−12 bar, an oxygen partial pressure of 10−10 bar, and at a temperature over the full range of from 1500° C. to 2000° C. 41. The method of claim 38, wherein the crystalline structure of said refractory material is cubic during heat-up from 1250° C. to 2200° C. 42. The method of claim 38 wherein the vapor pressure of said refractory material is less than 10−7 bar at 2000° C. 43. A method for pyrolyzing a hydrocarbon feedstock using a pyrolysis reactor system comprising the steps of: (a) providing in a heated region of a pyrolysis reactor system for pyrolyzing a hydrocarbon feedstock, apparatus comprising a refractory material in oxide form, said refractory material having a melting point of no less than 2060° C. and that remains in oxide form when exposed to a gas having a carbon partial pressure of 10−22 bar, an oxygen partial pressure of 10−10 bar, at a temperature of 1200° C. 44. The method of claim 43, further comprising the steps of: (b) heating said heated region to a temperature of no less than 1200° C.;(c) introducing a hydrocarbon feedstock into said heated region; and(d) pyrolyzing said hydrocarbon feedstock using heat from said heated region. 45. The method of claim 43, further comprising the step of heating said heated region to a temperature in a range of from 1500° C. to 2000° C. 46. The method of claim 43, wherein said refractory material remains in the oxide form when exposed to a gas having a carbon partial pressure of 10−12 bar, an oxygen partial pressure of 10−10 bar, and at a temperature over the full range of from 1500° C. to 2000° C. 47. The method of claim 43, wherein said refractory material has porosity of from 2 vol. % to 28 vol. %. 48. The method of claim 43, further comprising the step of heating said heated region by deferred combustion. 49. The method of claim 43, further comprising the steps of: (i) flowing at least one reactant in a first direction through said reactor system;(ii) reacting said at least one reactant within said reactor system to heat said heated region; and(iii) flowing a hydrocarbon feedstock through said heated region to pyrolyze at least a portion of said hydrocarbon feedstock and produce a cracked hydrocarbon product. 50. The method of claim 43, wherein said step (a) of providing said refractory material comprises providing a refractory material comprising at least 50 wt. % yttria based upon the total weight of said refractory material. 51. The method of claim 43, wherein said step (a) of providing said refractory material comprises providing a refractory material comprising at least 80 wt. % yttria based upon the total weight of said refractory material. 52. The method of claim 43, wherein said step (a) of providing said refractory material comprises providing a refractory material comprising at least 90 wt. % yttria based upon the total weight of said refractory material. 53. The method of claim 43, wherein said refractory material comprises a D50 grain size in the range of from 0.01 to 2000 μm. 54. The method of claim 43, wherein the vapor pressure of said refractory material is no greater than 10−7 bar at 2000° C.
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