Pyrolysis reactor materials and methods
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 an oxygen partial pressure of 10 −15 bar, a carbon partial pressure above the carbon partial pressure of the zirconium carbide and zirconium oxide phase transition at the same temperature, and at temperatures below the temperature of the zirconium triple point at the oxygen partial pressure of 10 −15 bar; and ii) when exposed to a gas having an oxygen partial pressure of 10 −15 bar and at temperatures above the zirconium triple point at the oxygen partial pressure of 10 −15 bar. 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 the above refractory material.
1. A method for mitigating carbide-oxide ceramic corrosion of a refractory material in the presence of a pyrolyzed hydrocarbon feedstock, the method comprising providing, in a heated region of a pyrolysis reactor system for pyrolyzing a hydrocarbon feedstock, at least one refractory material in oxide form having a melting point of not less than 2060° C., wherein the refractory material remains in oxide form during at least one of the following two scenarios:
i) when the refractory material is exposed to both (A) a first temperature in the presence of a gas having an oxygen partial pressure of 10 −15 bar and a carbon partial pressure above that exhibited by zirconium carbide at the zirconium carbide's phase transition to zirconium oxide at the first temperature, and (B) a second temperature in the presence of a gas having an oxygen partial pressure of 10 −15 , the second temperature being below that of zirconium's triple point; and
ii) when the refractory material is exposed to a temperature in the presence of a gas having an oxygen partial pressure of 10 −15 bar, the temperature being above that of zirconium's triple point; and
wherein the refractory material includes
a) at least 20 wt. % of a first grain mode based upon the total weight of the refractory material, the first grain mode comprising yttria and having a D50 grain size in the range of from 5 to 2000 μm; and
b) at least 1 wt. % of a second grain mode based upon the total weight of the refractory material, the second grain mode comprising yttria and 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 the first grain mode.
2. The method of claim 1 , wherein the refractory material remains in oxide form when exposed to a gas having a carbon partial pressure of 10 −11 bar, an oxygen partial pressure of 10 −15 bar, at a temperature of 2050° C.
3. The method of claim 1 , wherein the refractory material remains in the oxide form when exposed to a gas having a carbon partial pressure of 10 −10 bar, an oxygen partial pressure of 10 −15 bar, and at a temperature over the full range of from 1800° C. to 2100° C.
4. The method of claim 1 , wherein the refractory material exhibits a cubic crystalline structure when exposed to a temperature in the range of from 1250° C. to 2200° C.
5. The method of claim 1 wherein the refractory material has a vapor pressure of less than 10 −7 bar at 2000° C.
6. A method for mitigating carbide-oxide ceramic corrosion of a refractory material located in a heated region of a pyrolysis reactor system, the method comprising (I) introducing a hydrocarbon feedstock into the heated region, (ii) pyrolyzing the hydrocarbon feedstock under pyrolysis conditions, wherein the pyrolysis conditions include a temperature ≥1200° C. and a pressure from about 5 to 50 psia, and (III) exposing the refractory material to the hydrocarbon pyrolysis conditions, wherein
(A) the refractory material has a melting point of not less than 2060° C. and remains in oxide form when exposed to a first temperature of 2050° C. in the presence of a gas having (i) a carbon partial pressure of 10 −11 bar at the first temperature and (ii) an oxygen partial pressure of 10 −15 bar at the first temperature, and
(B) the refractory material includes:
a) at least 20 wt. % of a first grain mode based upon the total weight of the refractory material, the first grain mode comprising yttria and having a D50 grain size in the range of from 5 to 2000 μm; and
b) at least 1 wt. % of a second grain mode based upon the total weight of the refractory material, the second grain mode comprising yttria and 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 the first grain mode.
7. The method of claim 6 , wherein the refractory material exhibits a cubic crystalline structure when exposed to a temperature in the range of from 1250° C. to 2200° C.
8. The method of claim 6 , wherein the refractory material has a vapor pressure of less than 10 −7 bar at 2000° C.
9. A method for mitigating carbide-oxide ceramic corrosion of a refractory material located in a heated region of a pyrolysis reactor system, the method comprising (I) introducing a hydrocarbon feedstock into the heated region, (ii) pyrolyzing the hydrocarbon feedstock under pyrolysis conditions using heat from the heated region, wherein the pyrolysis conditions include a temperature ≥1200° C., a residence time of from 0.001 to 1.0 seconds, and a pressure from about 5 to 50 psia, and (III) exposing the refractory material to the hydrocarbon pyrolysis conditions, wherein
(A) the refractory material has a melting point of not less than 2060° C. and remains in oxide form when exposed to any temperature in the range of from 1800° C. to 2100° C. in the presence of a gas having (i) a carbon partial pressure of 10 −10 bar at the exposing temperature and (ii) an oxygen partial pressure of 10 −15 bar at the exposing temperature, and
(B) the refractory material includes:
a) at least 20 wt. % of a first grain mode based upon the total weight of the refractory material, the first grain mode comprising yttria and having a D50 grain size in the range of from 5 to 2000 μm; and
b) at least 1 wt. % of a second grain mode based upon the total weight of the refractory material, the second grain mode comprising yttria and 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 the first grain mode.
10. The method of claim 9 , wherein the refractory material exhibits a cubic crystalline structure when exposed to a temperature in the range of from 1250° C. to 2200° C.
11. The method of claim 9 , wherein the refractory material has a vapor pressure of less than 10 −7 bar at 2000° C.