Polygeneration production of hydrogen for use in various industrial processes

• US 9,957,161 B2
• Filed: 12/04/2016
• Issued: 05/01/2018
• Est. Priority Date: 12/04/2015
• Status: Active Grant

• Current Assignee: Grannus, LLC
• Original Assignee: Grannus, LLC
• Inventors: Merritt, Jr., James Kelly
• Primary Examiner(s): PARSA, JAFAR F
• Application Number:
  US15/368,623
• Publication Number:
  US 20170158504A1
• Time in Patent Office: 513 Days
• CPC Class Codes: B01D 2252/204 Amines
• CPC Class Codes: B01D 2256/16 Hydrogen
• CPC Class Codes: B01D 2257/504 Carbon dioxide
• CPC Class Codes: B01D 53/047 Pressure swing adsorption
• CPC Class Codes: B01D 53/1425 Regeneration of liquid absorbents
• CPC Class Codes: B01D 53/1475 Removing carbon dioxide
• CPC Class Codes: B01D 53/265 by refrigeration (condensation)
• CPC Class Codes: C01B 2203/025 containing a partial oxidation step
• CPC Class Codes: C01B 2203/0255 containing a non-catalytic partial oxidation step
• CPC Class Codes: C01B 2203/0261 containing a catalytic partial oxidation step [CPO]
• CPC Class Codes: C01B 2203/0288 containing two CO-shift steps
• CPC Class Codes: C01B 2203/0415 Purification by absorption in liquids
• CPC Class Codes: C01B 2203/042 Purification by adsorption on solids
• CPC Class Codes: C01B 2203/0425 In-situ adsorption process during hydrogen production
• 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 2203/0465 Composition of the impurity
• CPC Class Codes: C01B 2203/0475 the impurity being carbon dioxide
• CPC Class Codes: C01B 2203/0495 the impurity being water
• CPC Class Codes: C01B 2203/062 Hydrocarbon production, e.g. Fischer-Tropsch process
• CPC Class Codes: C01B 2203/068 Ammonia synthesis
• CPC Class Codes: C01B 2203/0894 : Generation of steam
• CPC Class Codes: C01B 2203/1235 : Hydrocarbons
• CPC Class Codes: C01B 2203/1258 : Pre-treatment of the feed
• CPC Class Codes: C01B 2203/127 : Catalytic desulfurisation
• CPC Class Codes: C01B 2203/146 : At least two purification steps in series
• CPC Class Codes: C01B 3/36 : using oxygen or mixtures containing oxygen as gasifying agents
• CPC Class Codes: C01B 3/48 : followed by reaction of water vapour with carbon monoxide
• 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: C01C 1/0405 : from N2 and H2 in presence of a catalyst
• CPC Class Codes: C01C 1/0488 : Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
• CPC Class Codes: C10G 2/30 : from carbon monoxide with hydrogen
• CPC Class Codes: Y02C 20/20 : of methane
• CPC Class Codes: Y02P 20/151 : Reduction of greenhouse gas [GHG] emissions, e.g. CO2
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts
• CPC Class Codes: Y02P 30/00 : Technologies relating to oil refining and petrochemical industry

Abstract

Provided are processes for production of hydrogen to be used in various industrial processes, including in processes for production of ammonia and urea. Included are polygeneration processes that result in ultra-low emissions.

Claims

1. A method for the production of hydrogen from synthesis gases of an oxygen supplied partial oxidation process, the method comprising the steps of:

supplying a hydrocarbon or carbonaceous feedstock and oxygen to an oxygen supplied partial oxidation process to produce a synthesis gas, the synthesis gas comprising carbon dioxide, carbon monoxide, and hydrogen;

supplying the synthesis gas to a first reactor, the first reactor comprising a catalyst and being configured to convert at least a portion of the carbon monoxide to carbon dioxide and produce a modified synthesis gas;

supplying the modified synthesis gas to a second reactor, the second reactor comprising a catalyst and being configured to convert remaining carbon monoxide to carbon dioxide to produce a carbon dioxide-rich synthesis gas;

supplying the carbon dioxide-rich synthesis gas from the second reactor to a first condenser to remove water and produce a gas stream comprising hydrogen and carbon dioxide;

supplying the hydrogen and carbon dioxide stream to a pressure swing adsorption process to produce a pure hydrogen stream and pressure swing adsorption tail gas; and

extracting exothermic heat for the production of power, heating and cooling of the process, or export of steam.

2. The method of claim 1, further comprising the step of:

supplying the pure hydrogen stream and nitrogen gas from an air separation unit to a fourth reactor, the fourth reactor comprising a catalyst and being configured to produce an ammonia product stream.

3. The method of claim 1, further comprising the step of:

supplying the pure hydrogen stream as a feedstock to a Fischer Tropsch process.

4. The method of claim 1, further comprising the step of:

supplying the synthesis gas or modified synthesis gas to a soot removal process to remove soot.

5. The method of claim 1, further comprising the step of:

supplying at least one of the hydrocarbon or carbonaceous feedstock, the synthesis gas, or the modified synthesis gas to a desulfurization process.

6. The method of claim 1, further comprising the step of:

supplying the gas stream comprising hydrogen and carbon dioxide to an amine separator unit to produce a residual pure carbon dioxide stream and amine treated high hydrogen content stream.

7. The method of claim 1, further comprising the step of:

supplying the gas stream comprising hydrogen and carbon dioxide from the first condenser to a vacuum pressure swing adsorption process to produce a pure carbon dioxide stream and a high hydrogen content stream.

8. The method of claim 1, further comprising the step of:

supplying the pure hydrogen stream to a third reactor, the third reactor comprising a catalyst and being configured for the production of methane from the carbon monoxide and carbon dioxide present in the hydrogen stream, the third reactor producing a methane product stream and a high purity hydrogen stream.

9. The method of claim 1, wherein the oxygen has a purity of at least 93%.

10. The method of claim 1, wherein the composition of the gas stream comprising hydrogen and carbon dioxide comprises between 65-80% hydrogen, between 20-35% carbon dioxide and between 0-8% carbon monoxide.

11. The method of claim 1, wherein the first and second reactor are replaced with one or three reactors.

12. The method of claim 1, wherein at least one gas or tail gas is purged to atmosphere, a fuel cell, or a thermal oxidizer.

13. The method of claim 2, further comprising the step of:

utilizing a hydrogen generator, wherein the hydrogen generator produces hydrogen and oxygen from a water feedstock, wherein the hydrogen is supplied to the fourth reactor and the oxygen is supplied to the oxygen supplied partial oxidation process.

14. The method of claim 1, further comprising the step of:

supplying the pure hydrogen stream to a process selected from the group consisting of a process for the production of urea, ammonium nitrate, nitric acids, diesel exhaust fluids, mixed alcohols;

production of aldehyde alcohols, ethanol, methanol, methyl tert-butyl ether, acetic acid, olefins, synthetic diesel, gasoline, gasoline additives, and dimethyl ether.

15. The method of claim 6, wherein the amine separator unit is a multi-pressure system with one or more carbon dioxide outputs and one or more amine regeneration processes.

16. The method of claim 1, further comprising the step of:

supplying the gas stream comprising hydrogen and carbon dioxide to a demineralized water wash system to decrease concentration of ammonia and hydrogen cyanide in the gas stream comprising hydrogen and carbon dioxide to below 5 parts per million by volume.

17. The method of claim 1, further comprising the step of:

recycling the water removed by the first condensor.

18. The method of claim 1, further comprising utilizing an air separation unit to allow for cold gases within the method to be used as a heat sink in the method.

19. The method of claim 2, further comprising the step of:

utilizing an ammonia refrigeration unit cold gas exit temperature for a heat sink.

20. The method of claim 1, wherein the pressure swing adsorption tail gas is recycled to the first reactor.