# US 2013/0156686 A1 · Hydrogen production with reduced carbon dioxide generation and complete capture

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2013/0156686 A1
- Document ID: US20130156686A1
- Status: Published application
- Kind: A1
- Application number: 13/330,861
- Filed: 2011-12-20
- Published: 2013-06-20
- Earliest claimed: 2011-12-20
- Assignees: American Air Liquide, Inc.; Air Liquide Large Industries U.S. LP
- Inventors: Dennis VAUK; Bhadra S. GROVER
- Web page: https://patentgrep.com/patent/US20130156686A1

## CPC

- C01B 3/382: Processes with two or more reaction steps, of which at least one is catalytic, e.g. steam reforming and partial oxidation
- C01B 3/384: with external heating of the catalyst
- C01B 3/48: followed by reaction of water vapour with carbon monoxide
- C01B 3/52: by contacting with liquids; Regeneration of used liquids
- C01B 3/56: by contacting with solids; Regeneration of used solids
- C01B 2203/0233: the reforming step being a steam reforming step
- C01B 2203/0283: containing a CO-shift step, i.e. a water gas shift step
- C01B 2203/0288: containing two CO-shift steps
- C01B 2203/0415: Purification by absorption in liquids
- C01B 2203/043: Regenerative adsorption process in two or more beds, one for adsorption, the other for regeneration
- C01B 2203/0475: the impurity being carbon dioxide
- C01B 2203/063: Refinery processes
- C01B 2203/0811: by combustion of fuel
- C01B 2203/0822: the fuel containing hydrogen
- C01B 2203/0833: Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
- C01B 2203/1235: Hydrocarbons
- C01B 2203/143: Three or more reforming, decomposition or partial oxidation steps in series
- C01B 2203/148: involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
- C01B 2203/86: Carbon dioxide sequestration
- Y02P 20/10: Process efficiency
- Y02P 30/00: Technologies relating to oil refining and petrochemical industry
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

The present invention is a method of minimizing the emissions of carbon dioxide from a reformer furnace flue gas to the high pressure syngas exit water gas shift reaction unit. Including heating a first gas mixture by indirect heat exchange with one or more of an SMR furnace flue gas or an SMR furnace syngas, further heating the pre-reformed mixture in a primary reformer, thereby generating a second gas mixture comprising hydrogen, carbon monoxide, carbon dioxide, and a flue gas. Introducing the gas mixture into a standard H2 PSA unit, wherein the gas is separated into a hydrogen enriched stream and a PSA tail gas stream, and introducing PSA feed or tail gas stream into a carbon dioxide removal system, wherein the flue gas is separated into a residual flue gas stream and a carbon dioxide enriched stream.

## Claims

### Claim 1

A method of reducing the carbon dioxide production and shifting balance from a reformer furnace flue gas to the high pressure syngas exit water gas shift reaction unit, comprising;
a) providing a first gas mixture;
b) heating said first stream mixture to a first temperature, then introducing said heated first gas mixture into at least one pre-reforming chamber, thereby producing a pre-reformed mixture; said heating being provided by indirect heat exchange with one or more of an SMR furnace flue gas or an SMR furnace syngas.
c) further heating said pre-reformed mixture in a primary reformer, thereby generating a second gas mixture comprising hydrogen, carbon monoxide, carbon dioxide, and a flue gas, wherein said primary reformer comprises tubes filled with catalyst;
d) introducing said second gas mixture into at least one isothermal shift reactor, or a combination of high followed by a low temperature shift reactor, or a medium temperature shift reactor, thereby generating a third gas mixture;
e) introducing said third gas mixture into an amine wash, thereby producing an carbon dioxide enriched stream and a sweet syngas stream,
f) introducing said sweet syngas stream into a standard H2 PSA unit, wherein said sweet syngas stream is separated into a hydrogen enriched stream and a PSA tail gas stream;
g) introducing said PSA tail gas stream as fuel into the reformer furnace along with natural gas, a portion of the feed hydrocarbon stream, a portion of the hydrogen enriched stream, or any other external make-up fuel for the reformer furnace,
wherein step b) is repeated twice, for a total of three pre-reforming steps, where the pre-reforming chamber comprises a total of three beds of pre-reformer catalyst, the temperature at the second pre-reformer is higher than the first pre-reformer, and the temperature at the third pre-reformer is higher than at the second,
wherein the pre-reforming chamber comprises at least three beds of catalyst, wherein an outlet gas from each pre-reformer is heated up in a coil in exchange with SMR furnace flue gas or process syngas before going to a next pre-reformer reactor or before entering the main reformer tubes.

### Claim 2 (depends on 1)

The method of claim 1 wherein the three beds of pre-reformer catalyst are stacked in one vessel with internal heads.

### Claim 3 (depends on 1)

The method of claim 1 wherein the carbon dioxide enriched stream represents greater than 80% of the overall CO2 generated in the SMR.

### Claim 4 (depends on 3)

The method of claim 3, wherein the carbon dioxide enriched stream represents greater than 90% of the overall CO2 generated in the SMR.

### Claim 5 (depends on 1)

The method of claim 1 wherein there is no steam exported from the SMR unit.

### Claim 6 (depends on 1)

The method of claim 1 wherein a portion of the PSA tail gas stream is compressed and recycled to the PSA.

### Claim 7 (depends on 1)

The method of claim 1 wherein a portion of the PSA tail gas stream is compressed and recycled upstream of the reformer.

### Claim 8 (depends on 1)

The method of claim 1 wherein a portion of the PSA tail gas stream is compressed and recycled upstream of the reformer and the PSA.

### Claim 9 (depends on 1)

The method of claim 1 wherein the catalyst in the first prereformer consists of conventional pre-reforming catalyst and subsequent prereformer consists of typical main catalyst bed reforming catalyst.

### Claim 10 (depends on 1)

The method of claim 1 wherein the flue gas from the SMR furnace is utilized for industrial purposes resulting in 100% recovery of the CO2 and no emission of nitrogen oxides from the SMR.

### Claim 11 (depends on 10)

The method of claim 10 where the SMR furnace flue gas is compressed and used for Enhanced Oil Recovery.

### Claim 12 (depends on 11)

The method of claim 11 where the SMR Furnace Flue gas is dried to remove water by passing through a bed of adsorbent.

### Claim 13 (depends on 12)

The method of claim 12 where the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 95%.

### Claim 14 (depends on 10)

The method of claim 10 where the SMR flue gas is contacted with Hydrogen from the PSA and passed over a bed of catalyst to promote combustion of oxygen.

### Claim 15 (depends on 14)

The method of claim 14 where the oxygen content of the flue gas downstream of the combustion zone is less than 0.1 mol %.

### Claim 16 (depends on 15)

The method of claim 15 where the SMR Furnace Flue gas is dried to remove water by passing through a bed of adsorbent.

### Claim 17 (depends on 16)

The method of claim 16 where the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 99%.

### Claim 18 (depends on 1)

The method of claim 1 wherein the product of the pre-reformer consists of a bank of tubes filled with catalyst heated counter-current in contact with the SMR Furnace flue gas for heating with syngas.

### Claim 19 (depends on 18)

The method of claim 18 wherein the carbon dioxide enriched stream represents greater than 85% of the overall CO2 generated in the SMR.

### Claim 20 (depends on 18)

The method of claim 18 where the flue gas from the SMR furnace is utilized for industrial purposes resulting in 100% recovery of the CO2 and no emission of nitrogen oxides from the SMR.

### Claim 21 (depends on 20)

The method of claim 20 where the SMR furnace flue gas is compressed and used for Enhanced Oil Recovery.

### Claim 22 (depends on 21)

The method of claim 21 where the SMR Furnace Flue gas is dried to remove water by passing through a bed of adsorbent.

### Claim 23 (depends on 22)

The method of claim 22 where the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 95%.

### Claim 24 (depends on 20)

The method of claim 20 where the SMR flue gas is contacted with Hydrogen from the PSA and passed over a bed of catalyst to promote combustion.

### Claim 25 (depends on 24)

The method of claim 24 where the oxygen content of the flue gas downstream of the combustion zone is less than 0.1 mol %.

### Claim 26 (depends on 25)

The method of claim 25 where the SMR Furnace Flue gas is dried to remove water by passing through a bed of adsorbent.

### Claim 27 (depends on 26)

The method of claim 26 where the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 99%.

### Claim 28 (depends on 19)

The method of claim 19, wherein the carbon dioxide enriched stream represents greater than 95% of the overall CO2 generated in the SMR.

### Claim 29 (depends on 18)

The method of claim 18 wherein no steam is exported from the SMR unit.

### Claim 30 (depends on 18)

The method of claim 18 wherein a portion of the PSA tail gas stream is compressed and recycled to the PSA.

### Claim 31 (depends on 18)

The method of claim 18 wherein a portion of the PSA tail gas stream is compressed and recycled upstream of the reformer.

### Claim 32 (depends on 18)

The method of claim 18 where a portion of the PSA tail gas stream is compressed and recycled upstream of the reformer and the PSA.

### Claim 33 (depends on 18)

The method of claim 18 wherein the catalyst at the top of the tube consists of conventional pre-reforming catalyst and at the bottom of tube consists of typical main catalyst bed reforming catalyst.

### Claim 34 (depends on 33)

The method of claim 33 wherein the transition between pre-reforming catalyst and main reforming catalyst is done through a series of progressively larger catalyst pellets.

### Claim 35 (depends on 18)

The method of claim 18 wherein the process gas from the exit of the pre-reforming tube is passed through two helical shaped tubes back up the pre-reformer tube.

### Claim 36 (depends on 35)

The method of claim 35 wherein a portion of the heat for the reforming reaction in said tubes is provided by exchange with the exit gas through the helical shaped tubes.

### Claim 37 (depends on 36)

The method of claim 36 where the temperature of the exit gas from the top of the helical tubes is between 500 and 1300 Degrees F.

### Claim 38 (depends on 36)

The method of claim 36 where the temperature of the exit gas from the top of the helical tubes is between 1200 and 1300 Degrees F.

### Claim 39 (depends on 1)

The method of claim 1 where the process gas from the exit of the reforming tube is passed through two helical shaped tubes back up the pre-reformer tube.

### Claim 40 (depends on 39)

The method of claim 39 where a portion of the heat for the reforming reaction in said tubes is provided by exchange with the exit gas through the helical shaped tubes.

### Claim 41 (depends on 39)

The method of claim 39 where the flue gas from the SMR furnace is utilized for industrial purposes resulting in 100% recovery of the CO2 and no emission of nitrogen oxides from the SMR.

### Claim 42 (depends on 41)

The method of claim 41 where the SMR furnace flue gas is compressed and used for Enhanced Oil Recovery.

### Claim 43 (depends on 42)

The method of claim 42 where the SMR Furnace Flue gas is dried to remove water by passing through a bed of adsorbent.

### Claim 44 (depends on 43)

The method of claim 43 where the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 95%.

### Claim 45 (depends on 41)

The method of claim 41 where the SMR flue gas is contacted with Hydrogen from the PSA and passed over a bed of catalyst to promote combustion.

### Claim 46 (depends on 45)

The method of claim 45 where the oxygen content of the flue gas downstream of the combustion zone is less than 0.1 mol %.

### Claim 47 (depends on 46)

The method of claim 46 where the SMR Furnace Flue gas is dried to remove water by passing through a bed of adsorbent.

### Claim 48 (depends on 47)

The method of claim 47 where the Nitrogen+Argon composition of the flue gas downstream of the drier is greater than or equal to 97%.

### Claim 49 (depends on 40)

The method of claim 40 wherein the carbon dioxide enriched stream represents greater than 80% of the overall CO2 generated in the SMR.

### Claim 50 (depends on 49)

The method of claim 49, wherein the carbon dioxide enriched stream represents greater than 90% of the overall CO2 generated in the SMR.

### Claim 51 (depends on 40)

The method of claim 40 where there is no steam exported from the SMR unit.

### Claim 52 (depends on 40)

The method of claim 40 where a portion of the PSA tail gas stream is compressed and recycled to the PSA.

### Claim 53 (depends on 40)

The method of claim 40 where a portion of the PSA tail gas stream is compressed and recycled upstream of the first pre-reformer reactor.

### Claim 54 (depends on 40)

The method of claim 40 where a portion of the PSA tail gas stream is compressed and recycled to the pre-reformer reactor and to the PSA.