초록 ▼

The present invention is directed to the upgrading of heavy petroleum oils of high viscosity and low API gravity that are typically not suitable for pipelining without the use of diluents. It utilizes a short residence-time pyrolytic reactor operating under conditions that result in a rapid pyrolyti

The present invention is directed to the upgrading of heavy petroleum oils of high viscosity and low API gravity that are typically not suitable for pipelining without the use of diluents. It utilizes a short residence-time pyrolytic reactor operating under conditions that result in a rapid pyrolytic distillation with coke formation. Both physical and chemical changes taking place lead to an overall molecular weight reduction in the liquid product and rejection of certain components with the byproduct coke. The liquid product is upgraded primarily because of its substantially reduced viscosity, increased API gravity, and the content of middle and light distillate fractions. While maximizing the overall liquid yield, the improvements in viscosity and API gravity can render the liquid product suitable for pipelining without the use of diluents. This invention particularly relates to reducing sulfur emissions during the combustion of byproduct coke (or coke and gas), to reducing the total acid number (TAN) of the liquid product, and to reducing the hydrogen sulfide content of one, or more than one component of the product stream. The method comprises introducing a particulate heat carrier into an up-flow reactor, introducing the feedstock at a location above the entry of the particulate heat carrier, allowing the heavy hydrocarbon feedstock to interact with the heat carrier for a short time, separating the vapors of the product stream from the particulate heat carrier and liquid and byproduct solid matter, regenerating the particulate heat carrier in the presence of the calcium compound, and collecting a gaseous and liquid product from the product stream.

대표청구항 ▼

The invention claimed is: 1. A method of reducing the hydrogen sulfide content of a product stream from upgrading a heavy hydrocarbon feedstock and reducing sulfur-based gas emissions in flue gas during said upgrading, comprising: (i) treating the heavy hydrocarbon feedstock with a first portion of

The invention claimed is: 1. A method of reducing the hydrogen sulfide content of a product stream from upgrading a heavy hydrocarbon feedstock and reducing sulfur-based gas emissions in flue gas during said upgrading, comprising: (i) treating the heavy hydrocarbon feedstock with a first portion of calcium compound, (ii) introducing said treated feedstock to an upflow reactor, (iii) rapid thermal processing of the treated feedstock, wherein the rapid thermal processing comprises allowing the treated feedstock to interact with a particulate heat carrier in the upflow reactor run at a temperature in the reactor from 450 to 600° C. for less than 5 seconds, to produce a product stream, and wherein the ratio of the particulate heat carrier to the heavy hydrocarbon feedstock is from 10:1 to 200:1, and (iv) regenerating the particulate heat carrier in a reheater to form a regenerated particulate heat carrier, and (v) recycling the regenerated particulate heat carrier to the upflow reactor, wherein: (a) a second portion of calcium compound is added to the reheater, (b) the particulate heat carrier is different from the first and second portions of calcium compound, and (c) the amount of the first and second portions of calcium compound added is from about 0.2 to about 5 fold the stoichiometric amount of sulfur in the feedstock. 2. The method of claim 1, further comprising a step of removing a mixture comprising the product stream and the particulate heat carrier from the reactor. 3. The method of claim 2, further comprising a step of separating the product stream and the particulate heat carrier from said mixture. 4. The method of claim 3, further comprising a step of collecting a distillate product and a bottoms product from the product stream. 5. The method of claim 4, wherein the bottoms product is subjected to a further step of rapid thermal processing. 6. The method of claim 5, wherein the further step of rapid thermal processing comprises allowing the bottoms product to interact with a particulate heat carrier in the reactor for less than about 5 seconds, wherein the ratio of the particulate heat carrier to the heavy hydrocarbon feedstock is from about 10:1 to about 200:1 to produce a product stream. 7. The method of claim 1, wherein the reheater is run at a temperature in the range from about 600° C. to about 900° C. 8. The method of claim 1, wherein the reheater is run at a temperature in the range from about 600° C. to about 815° C. 9. The method of claim 1, wherein the reheater is run at a temperature in the range from about 700° C. to about 800° C. 10. The method of claim 1, wherein the reactor is run at a temperature in the range from about 480° C. to about 550° C. 11. The method of claim 1, wherein the amount of the first and second portions of calcium compound that is added is from about 1.7 to about 2 fold the stoichiometric amount of sulfur in the heavy hydrocarbon feedstock. 12. The method of claim 1, wherein the first and second portions of calcium compound are selected from the group consisting of calcium acetate, calcium formate, calcium proprionate, a calcium salt-containing bio-oil composition, a calcium salt isolated from a calcium salt-containing bio-oil composition, Ca(OH)2, CaO, CaCO3, and a mixture thereof. 13. The method of claim 1, wherein the first portion of calcium compound is combined with the heavy hydrocarbon feedstock and 0-5 weight % water, relative to the weight of the heavy hydrocarbon feedstock. 14. The method of claim 13, wherein the water is in the form of steam. 15. The method of claim 1, wherein total acid number (TAN) in the liquid product is reduced. 16. The method of claim 1, wherein prior to the step of rapid thermal processing, the feedstock is introduced into a fractionation column that separates a volatile component of the feedstock from a liquid component of the feedstock, and the liquid component is subjected to rapid thermal processing. 17. The method of claim 16, wherein the feedstock is combined with the first portion of calcium compound before being introduced into the fractionation column. 18. The method of claim 1, wherein the first and second portions of calcium compound are selected from the group consisting of Ca(OH)2, CaO, and a mixture thereof. 19. The method of claim 1, wherein the first and second portions of calcium compound are Ca(OH)2. 20. The method of claim 1, wherein the heavy hydrocarbon feedstock is: 1) a high TAN value, low sulfur content heavy hydrocarbon feedstock; 2) a low TAN value, high sulfur content heavy hydrocarbon feedstock; or 3) a high TAN value, high sulfur content heavy hydrocarbon feedstock. 21. The method of claim 1, wherein the TAN value of the treated heavy hydrocarbon feedstock is at least three fold lower when compared to an identical heavy hydrocarbon feedstock untreated by a calcium containing compound. 22. The method of claim 1, wherein the TAN value of the treated heavy hydrocarbon feedstock is no greater than 1.65 (mg KOH/g). 23. The method of claim 1, wherein the TAN value of the treated heavy hydrocarbon feedstock is less than 0.55 (mg KOH/g). 24. The method of claim 1, wherein the first and second portions of calcium compound are selected from Ca(OH)2, CaO, and CaCO3. 25. The method of clam 1, wherein the first and second portions of calcium compound are selected from CaO and CaCO3. 26. The method of claim 1, wherein the first and second portions of calcium compound are a fine powder. 27. The method of claim 1, wherein the particulate heat carrier is sand. 28. The method of claim 1, wherein the size of the particulate heat carrier is greater than the size of the first and second portions of calcium compound. 29. The method of claim 1, wherein the amount of the first and second portions of calcium compound required to lower the level of sulfur-based gas emissions is reduced. 30. The method of claim 1, wherein up to 5 wt. % water, relative to the weight of the heavy hydrocarbon feedstock, is present. 31. The method of claim 1, wherein up to 5 wt. % water, relative to the weight of the heavy hydrocarbon feedstock, is added together with the calcium compound. 32. The method of claim 1, wherein the reduction of the sulfur-based gas emissions is at least 85% lower than that produced by an identical method in the absence of a calcium containing compound. 33. The method of claim 1, wherein the reduction of the sulfur-based gas emissions is at least 90% lower than that produced by an identical method in the absence of a calcium containing compound. 34. The method of claim 1, wherein the reduction of the sulfur-based gas emissions is at least 95% lower than that produced by an identical method in the absence of a calcium containing compound. 35. The method of claim 1, wherein the TAN value of the liquid product produced by said method is at least five fold lower when compared to a liquid product produced by an identical method processing a feedstock in the absence of a calcium containing compound. 36. A method of reducing the hydrogen sulfide content of a product stream from upgrading a heavy hydrocarbon feedstock, comprising: (i) rapid thermal processing of the heavy hydrocarbon feedstock in the presence of a calcium compound and optionally in the presence of water, the rapid thermal processing comprises allowing the heavy hydrocarbon feedstock to interact with a particulate heat carrier in an upflow reactor run at a temperature in the range from 450° C. to 600° C. for less than 5 seconds, to produce the product stream, and the ratio of the particulate heat carrier to the heavy hydrocarbon feedstock is from 10:1 to 200:1; (ii) regenerating the particulate heat carrier in a reheater to form a regenerated particulate heat carrier, in the presence of the calcium compound; and (iii) recycling the regenerated particulate heat carrier to the upflow reactor; wherein: a) the particulate heat carrier is different from the calcium compound; and b) the amount of the calcium compound added to the heavy hydrocarbon feedstock is from about 0.2 to about 5 fold the stoichiometric amount of sulfur in said feedstock. 37. The method of claim 36, wherein the sulfur-based gas emissions is at least 85% lower than that produced by an identical method in the absence of a calcium containing compound. 38. The method of claim 36, wherein the heavy hydrocarbon feedstock is: 1) a high TAN value, low sulfur content heavy hydrocarbon feedstock; 2) a low TAN value, high sulfur content heavy hydrocarbon feedstock; or 3) a high TAN value, high sulfur content heavy hydrocarbon feedstock. 39. The method of claim 36, wherein the calcium compound is selected from Ca(OH)2, CaO, and CaCO3. 40. The method of claim 36, wherein the amount of the calcium compound required to lower the level of sulfur-based gas emissions is reduced. 41. The method of claim 36, wherein the TAN value of the liquid product produced by said method is at least five fold lower when compared to a liquid product produced by an identical method processing a feedstock in the absence of a calcium containing compound. 42. A method of reducing the hydrogen sulfide content of a product stream from upgrading a heavy hydrocarbon feedstock, comprising: (i) rapid thermal processing of the heavy hydrocarbon feedstock in the presence of a calcium compound, the rapid thermal processing comprises allowing the heavy hydrocarbon feedstock to interact with a particulate heat carrier in an upflow reactor run at a temperature in the range from 450° C. to 600° C. for less than 5 seconds, to produce a product stream, and the ratio of the particulate heat carrier to the heavy hydrocarbon feedstock is from 10:1 to 200:1; (ii) regenerating the particulate heat carrier in a reheater to form a regenerated particulate heat carrier, in the presence of the calcium compound; and (iii) recycling the regenerated particulate heat carrier to the upflow reactor; wherein: a) the particulate heat carrier is sand; and b) the amount of the calcium compound added to the heavy hydrocarbon feedstock is from about 0.2 to about 5 fold the stoichiometric amount of sulfur in said feedstock. 43. The method of claim 42, wherein prior to said rapid thermal processing the heavy hydrocarbon feedstock: (i) treating the heavy hydrocarbon feedstock with the calcium compound, and (ii) introducing said treated feedstock to the upflow reactor. 44. The method of claim 42, wherein the TAN value of the treated heavy hydrocarbon feedstock is at least three fold lower when compared to an identical heavy hydrocarbon feedstock untreated by a calcium containing compound. 45. The method of claim 42, wherein the size of the particulate heat carrier is greater than the size of the calcium compound. 46. The method of claim 42, wherein the reduction of the sulfur-based gas emissions is at least 90% lower than that produced by an identical method in the absence of a calcium containing compound. 47. A method of reducing the amount of calcium compound required to reduce the hydrogen sulfide content of a product stream from upgrading a heavy hydrocarbon feedstock, comprising: (i) rapid thermal processing of the heavy hydrocarbon feedstock in the presence of a fine powder calcium compound, the rapid thermal processing comprises allowing the heavy hydrocarbon feedstock to interact with a particulate heat carrier in an upflow reactor run at a temperature in the range from 450° C. to 600° C. for less than 5 seconds, to produce a product stream, and the ratio of the particulate heat carrier to the heavy hydrocarbon feedstock is from 10:1 to 200:1; (ii) regenerating the particulate heat carrier in a reheater to form a regenerated particulate heat carrier, in the presence of the fine powder calcium compound; and (iii) recycling the regenerated particulate heat carrier to the upflow reactor; wherein: a) the particulate heat carrier is different from the fine powder calcium compound; b) the amount of the fine powder calcium compound added to the heavy hydrocarbon feedstock is from about 0.2 to about 5 fold the stoichiometric amount of sulfur in said feedstock; and c) the reduction of the sulfur emissions is at least 85% lower than that produced by an identical method in the absence of a calcium containing compound. 48. The method of claim 47, wherein the calcium compound is Ca(OH)2. 49. The method of claim 47, wherein the particulate heat carrier is sand. 50. The method of claim 47, wherein the size of the particulate heat carrier is greater than the size of the calcium compound. 51. A method of reducing the hydrogen sulfide content of a product stream from upgrading a heavy hydrocarbon feedstock, comprising: (i) treating the heavy hydrocarbon feedstock with Ca(OH)2; (ii) introducing said treated feedstock to an upflow reactor; (iii) rapid thermal processing of the treated feedstock, in the presence of the Ca(OH)2, the rapid thermal processing comprises allowing the treated feedstock to interact with a particulate heat carrier in the upflow reactor run at a temperature in the reactor from 450° C. to 600° C. for less than 5 seconds, to produce a product stream, and the ratio of the particulate heat carrier to the heavy hydrocarbon feedstock is from 10:1 to 200:1; (iv) regenerating the particulate heat carrier in a reheater to form a regenerated particulate heat carrier, in the presence of the Ca(OH)2; and (v) recycling the regenerated particulate heat carrier to the upflow reactor; wherein: (a) the Ca(OH)2 is added to the reheater; (b) the particulate heat carrier is sand; and (c) the amount of the Ca(OH)2 added to the heavy hydrocarbon feedstock is from about 0.2 to about 5 fold the stoichiometric amount of sulfur in said feedstock. 52. The method of claim 51, wherein the TAN value of the treated heavy hydrocarbon feedstock is at least three fold lower when compared to an identical heavy hydrocarbon feedstock untreated by a calcium containing compound. 53. The method of claim 51, wherein up to 5 wt. % water, relative to the weight of the heavy hydrocarbon feedstock, is present. 54. The method of claim 51, wherein the reduction of the sulfur-based gas emissions is at least 95% lower than that produced by an identical method in the absence of a calcium containing compound. 55. The method of claim 51, wherein the TAN value of the liquid product produced by said method is at least five fold lower when compared to a liquid product produced by an identical method processing a feedstock in the absence of a calcium containing compound.