Process for co-producing commercially valuable products from byproducts of fischer-tropsch process for hydrocarbon fuel formulation in a GTL environment

• US 9,315,452 B2
• Filed: 11/13/2014
• Issued: 04/19/2016
• Est. Priority Date: 09/08/2011
• Status: Active Grant

• Current Assignee: Expander Energy Inc.
• Original Assignee: Expander Energy Inc.
• Inventors: Kresnyak, Steve
• Primary Examiner(s): PARSA, JAFAR F
• Application Number:
  US14/540,084
• Publication Number:
  US 20150141535A1
• Time in Patent Office: 523 Days
• Field of Search: 518/700, 518/702, 518/705, 564/67, 564/69, 423/359
• US Class Current: 1/1
• 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 2203/0405 Purification by membrane separation
• CPC Class Codes: C01B 2203/0435 Catalytic purification
• 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 2203/0844 the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
• CPC Class Codes: C01B 2203/0872 Methods of cooling
• CPC Class Codes: C01B 2203/1241 Natural gas or methane
• CPC Class Codes: C01B 2203/1258 Pre-treatment of the feed
• CPC Class Codes: C01B 2203/142 At least two reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/143 Three or more reforming, decomposition or partial oxidation steps in series
• CPC Class Codes: C01B 2203/145 At least two purification steps in parallel
• CPC Class Codes: C01B 2203/147 Three or more purification steps in series
• CPC Class Codes: C01B 3/38 using catalysts
• CPC Class Codes: C01B 3/382 Multi-step processes
• CPC Class Codes: C01C 1/04 Preparation of ammonia by synthesis in the gas phasepreparation or purification of gas mixtures for ammonia synthesis C01B3/025
• 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: C07C 31/04 Methanol
• CPC Class Codes: C10G 2/30 : from carbon monoxide with hydrogen
• CPC Class Codes: C10G 2300/1022 : Fischer-Tropsch products
• CPC Class Codes: C10G 45/02 : to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
• 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 47/22 : Non-catalytic cracking in the presence of hydrogen
• CPC Class Codes: C10K 1/005 : Carbon dioxide
• CPC Class Codes: C10K 1/08 : by washing with liquids; Reviving the used wash liquors gas washers B01D
• CPC Class Codes: C10K 1/32 : with selectively adsorptive solids, e.g. active carbon
• CPC Class Codes: C10L 1/04 : essentially based on blends of hydrocarbons
• CPC Class Codes: C10L 2200/0492 : Fischer-Tropsch products
• CPC Class Codes: C10L 2290/42 : Fischer-Tropsch steps

Abstract

The present invention is directed to the modification of the hydrocarbon production sequence of operations including the Fischer-Tropsch process for the production of hydrocarbon fuels in an efficient manner, along with the production of commercially valuable co-products from by-products of the hydrocarbon production process.

Claims

1. A process for synthesizing hydrocarbons in a Gas-to-Liquid (GTL) environment, and for co-producing chemical products from by-products of the hydrocarbon synthesis process, comprising the steps of:

(a) formulating a first hydrogen rich syngas stream with a syngas generator, wherein said first hydrogen rich synqas stream has a H₂ to CO ratio of more than 2;

1;

(b) 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 said second hydrogen rich syngas stream has a H₂ to CO ratio less than the H₂ to CO ratio of said first hydrogen rich syngas stream;

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

(d) reacting at least a portion of said first hydrogen rich stream, at least a portion of said second hydrogen rich stream and/or at least a portion of said purified hydrogen rich syngas stream in a Fischer-Tropsch reactor to synthesize said hydrocarbons; and

(e) converting said one or more carbon dioxide by-product streams into said chemical co-products.

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

3. The process according to claim 1, wherein said syngas generator comprises a steam methane reformer (SMR), an autothermal reformer (ATR), any series or parallel combination thereof, or a merged unit (XTR) having an autothermal reformer merged in a single unit with a steam methane reformer.

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 syngas generator when said generator comprises an ATR.

5. The process according to claim 1, wherein said chemical co-product is methanol, which is obtained by reacting a portion of said first hydrogen rich syngas stream, a portion of said second hydrogen rich syngas stream, a portion of said purified 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 chemical 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 said one or more CO₂ by-product streams.

7. The process according to claim 1, wherein said purified hydrogen by-product 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 stream.

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

9. The process according to claim 1, wherein said hydrocarbons include at least naphtha, and wherein at least a portion of said naphtha is re-circulated to said syngas generator.

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

11. The process according to claim 10, wherein said Fischer-Tropsch vapours are further treated to a CO₂ removal operation to form an additional CO₂ by-product stream for conversion into said commercially valuable co-products.

12. The process according to claim 1, further including the step of processing said 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 syngas generator or any other furnaces, boilers, power generation and any other combustion units used in the hydrocarbon synthesis process to form an additional CO₂ by-product stream for conversion into said chemical co-products.

15. The process according to claim 1, further comprising providing CO₂ from any other external source other than the hydrocarbon synthesis process to form an additional CO₂ by-product stream for conversion into said chemical co-products.

16. The process according to claim 1, wherein the hydrocarbon synthesis process is capable of near zero green house gas CO₂ emissions.