Process for co-producing commercially valuable products from byproducts of heavy oil and bitumen upgrading process

• US 9,156,691 B2
• Filed: 10/21/2014
• Issued: 10/13/2015
• Est. Priority Date: 04/20/2011
• Status: Active Grant

• Current Assignee: Expander Energy Inc.
• Original Assignee: Expander Energy Inc.
• Inventors: Kresnyak, Steve
• Primary Examiner(s): PARSA, JAFAR F
• Application Number:
  US14/520,040
• Publication Number:
  US 20150038599A1
• Time in Patent Office: 357 Days
• Field of Search: 518/700, 518/702, 518/705, 423/359, 564/67, 564/69
• US Class Current: 1/1
• CPC Class Codes: C01B 21/087 containing one or more hydrogen atoms
• CPC Class Codes: C01B 2203/0205 containing a reforming step
• CPC Class Codes: C01B 2203/0233 the reforming step being a steam reforming step
• CPC Class Codes: C01B 2203/0244 the reforming step being an autothermal reforming step, e.g. secondary reforming processes
• CPC Class Codes: C01B 2203/0255 containing a non-catalytic partial oxidation step
• CPC Class Codes: C01B 2203/0283 containing a CO-shift step, i.e. a water gas shift step
• CPC Class Codes: C01B 2203/0405 Purification by membrane separation
• CPC Class Codes: C01B 2203/043 Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 2203/1047 Group VIII metal catalysts
• CPC Class Codes: C01B 2203/1082 Composition of support materials
• CPC Class Codes: C01B 2203/1211 Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
• CPC Class Codes: C01B 2203/141 At least two reforming, decomposition or partial oxidation steps in parallel
• CPC Class Codes: C01B 3/34 by reaction of hydrocarbons with gasifying agents
• CPC Class Codes: C01B 3/382 Multi-step processes
• CPC Class Codes: C01B 3/384 the catalyst being continuously externally heated
• CPC Class Codes: C01B 3/501 by diffusion
• CPC Class Codes: C01B 3/52 by contacting with liquids; Regeneration of used liquids C01B3/508 takes precedence
• CPC Class Codes: C01B 3/56 by contacting with solids; Regeneration of used solids C01B3/508 takes precedence
• CPC Class Codes: C01B 32/50 : Carbon dioxide
• CPC Class Codes: C07C 1/0485 : Set-up of reactors or accessories; Multi-step processes
• CPC Class Codes: C07C 273/04 : from carbon dioxide and ammonia
• CPC Class Codes: C07C 29/1518 : one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis
• CPC Class Codes: C10G 2/30 : from carbon monoxide with hydrogen
• CPC Class Codes: C10G 21/003 : Solvent de-asphalting
• CPC Class Codes: C10G 2300/1022 : Fischer-Tropsch products
• CPC Class Codes: C10G 2300/1077 : Vacuum residues
• CPC Class Codes: C10G 2300/206 : Asphaltenes
• CPC Class Codes: C10G 2300/42 : Hydrogen of special source or of special composition
• CPC Class Codes: C10G 45/00 : Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
• CPC Class Codes: C10G 45/58 : to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins C10G32/00 takes precedence; improving or increasing the octane number or aromatic content of naphtha C10G35/00
• CPC Class Codes: C10G 47/00 : Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions C10G15/00 takes precedence; destructive hydrogenation of non-melting solid carbonaceous or similar materials C10G1/06
• CPC Class Codes: C10G 67/049 : The hydrotreatment being a hydrocracking
• CPC Class Codes: C10G 7/00 : Distillation of hydrocarbon oils
• CPC Class Codes: C10G 9/00 : Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
• CPC Class Codes: C10J 2300/0913 : Carbonaceous raw material
• CPC Class Codes: C10J 2300/0959 : Oxygen
• CPC Class Codes: C10J 2300/1659 : to liquid hydrocarbons
• CPC Class Codes: C10J 3/00 : Production of combustible gases containing carbon monoxide from solid carbonaceous fuels destructive distillation processes C10B
• CPC Class Codes: C10K 3/06 : by mixing with gases
• CPC Class Codes: Y02P 30/00 : Technologies relating to oil refining and petrochemical industry
• CPC Class Codes: Y02P 30/40 : Ethylene production

Abstract

The present invention is directed to modifications of bitumen and heavy oil upgrading and refining processes to synthesize synthetic crude oil and other valuable synthesized hydrocarbon products in an efficient manner along with the production of commercially valuable co-products from by-products formed by the upgrading process.

Claims

1. A process for upgrading or refining heavy oil or bitumen to formulate synthesized hydrocarbons, and for co-producing chemical products from by-products of the upgrading or refining process, comprising:

(a) forming a non-distilled bottom fraction from a source of heavy oil or bitumen feedstock

(b) feeding said bottom fraction to a syngas generating circuit for formulating a hydrogen lean syngas stream via a non-catalytic partial oxidation reaction, wherein said hydrogen lean syngas stream has a hydrogen to carbon monoxide ratio of less than 1;

1;

(c) providing a first hydrogen rich syngas stream from a syngas generator, wherein the first hydrogen rich syngas stream has H₂ to CO ratio of more than 2;

1;

(d) subjecting a portion of said first hydrogen rich syngas stream to a hydrogen separator unit to provide a purified hydrogen by-product stream and a second hydrogen rich syngas stream, wherein the second hydrogen rich syngas stream has H₂ to CO ratio of about 2;

1 or more;

(e) combining said hydrogen lean syngas stream with a portion of the first and/or second hydrogen rich syngas streams to form an optimum hydrogen rich syngas stream having H₂ to CO ratio of about 1.8;

1 to 2.2;

1;

(f) reacting said optimum hydrogen rich syngas stream in a Fischer-Tropsch reactor to formulate synthesized hydrocarbons and Fischer Tropsch vapours;

(g) subjecting at least a portion of said hydrogen lean syngas stream, said first hydrogen rich syngas stream, said second hydrogen rich syngas stream, said Fischer Tropsch vapours or a combination thereof, to a carbon dioxide removal operation to obtain one or more carbon dioxide by-product streams; and

(h) converting near 100% of the carbon of said carbon dioxide by-product stream into said chemical co-products.

2. The process according to claim 1, wherein said valuable co-products comprise methanol, ammonia, urea or any combination thereof.

3. The process as set forth in claim 1, wherein said hydrogen rich syngas generator is selected from the group consisting of a steam methane reformer (SMR), autothermal reformer (ATR), any series or parallel combination thereof or a hybrid combination thereof (XTR).

4. The process according to claim 1, comprising subjecting air to an air separation unit to generate a nitrogen stream and an oxygen stream, wherein said oxygen stream is for the non-catalytic partial oxidation reaction and/or for the syngas generator when said generator comprises an ATR and/or for enriching the sour syngas treatment operation.

5. The process according to claim 1, wherein said commercially valuable co-product is methanol, which is obtained by reacting a portion of said first hydrogen rich syngas stream, said second hydrogen rich syngas stream, said optimum hydrogen rich syngas stream, or a combination thereof, with at least a portion of said one or more CO₂ by-product streams, or at least a portion of said purified hydrogen by-product stream or a combination thereof.

6. The process according to claim 4, wherein said commercially valuable co-product is urea, which is obtained by reacting said nitrogen stream with at least a portion of said purified hydrogen by-product stream to form ammonia and reacting said ammonia with one or more CO₂ streams.

7. The process according to claim 1, wherein said purified hydrogen rich syngas stream is obtained by purification of at least a portion of said first hydrogen rich syngas stream via pressure swing adsorption, membrane or liquid absorption, or by treating at least a portion of said first hydrogen rich syngas stream to a water gas shift (WGS) reaction prior to pressure swing adsorption, membrane or liquid absorption with optional removal of an additional CO₂ by-product stream from the said second hydrogen rich syngas stream.

8. The process according to claim 7, wherein the additional CO₂ by-product stream is used for conversion into said commercially valuable co-products.

9. The process according to claim 1, wherein said bottom fraction is converted to a sour hydrogen lean syngas stream.

10. The process according to claim 9, further including the step of treating said sour hydrogen lean syngas stream to the said sour syngas treatment operation to form a sweet hydrogen lean syngas stream and an additional CO₂ by-product stream for conversion into said commercially valuable co-products.

11. The process according to claim 1, wherein said synthesized hydrocarbons include at least one of paraffinic naphtha, light Fischer-Tropsch liquid, heavy Fischer-Tropsch liquid, or Fischer-Tropsch wax.

12. The process according to claim 11, further including the step of processing said synthesized hydrocarbons in a hydroprocessing unit.

13. The process according to claim 12, wherein said hydroprocessing unit includes at least one operation selected from the group consisting of hydrocracking, thermocracking, hydrotreating, isomerization, fractionation and combinations thereof.

14. The process according to claim 1, wherein CO₂ is further captured in a CO₂ removal operation from flue gas streams resulting from furnaces, boilers, power generation and any other combustion units used in the upgrader to form an additional CO₂ by-product stream for conversion into said commercially valuable co-products.

15. The process according to claim 1, wherein CO₂ is further provided from any other external source other than the upgrader to form an additional CO₂ by-product stream for conversion into said commercially valuable co-products.

16. The process according to claim 1, wherein the bitumen and heavy oil upgrader is capable of near zero green house gas CO₂ emissions.

17. The process according to claim 1, wherein said bitumen is an in situ source.

18. The process according to claim 1, wherein said bitumen is a mineable source.

19. The process of claim 1, wherein the optimum hydrogen rich syngas stream is purified stream obtained after removal of the one or more carbon dioxide streams.