# US 11,111,142 B2 · Processes and catalysts for reforming of impure methane-containing feeds

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- Number: US 11,111,142 B2
- Document ID: US11111142B2
- Status: Granted
- Kind: B2
- Application number: 16/134,623
- Filed: 2018-09-18
- Published: 2020-03-19
- Granted: 2021-09-07
- Earliest claimed: 2018-09-18
- Assignees: Gas Technology Institute
- Applicants: Gas Technology Institute
- Inventors: Terry Marker; Jim Wangerow; Pedro Ortiz-Toral; Martin Linck
- Web page: https://patentgrep.com/patent/US11111142B2

## CPC

- C01B 3/40: characterised by the catalyst
- C01B 2203/0233: the reforming step being a steam reforming step
- C01B 2203/0238: the reforming step being a carbon dioxide reforming step
- C01B 2203/0283: containing a CO-shift step, i.e. a water gas shift step
- C01B 2203/0405: Purification by membrane separation
- 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 2203/0485: the impurity being a sulfur compound
- C01B 2203/1035: Catalyst coated on equipment surfaces, e.g. reactor walls
- C01B 2203/1064: Platinum group metal catalysts
- C01B 2203/107: Platinum catalysts
- C01B 2203/1082: Composition of support materials
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

Processes and catalysts for producing hydrogen by reforming methane are disclosed, which afford considerable flexibility in terms of the quality of the reformer feed. This can be attributed to the robustness of the noble metal-containing catalysts described herein for use in reforming, such that a number of components commonly present in methane-containing process streams can advantageously be maintained without conventional upgrading (pretreating) steps, thereby improving process economics. This also allows for the reforming of impure reformer feeds, even in relatively small quantities, which may be characterized as complex gas mixtures due to significant quantities of non-methane components. A representative reforming catalyst comprises 1 wt-% Pt and 1 wt-% Rh as noble metals, on a cerium oxide support.

## Claims

### Claim 1

A process for producing hydrogen, the process comprising:
contacting, under reforming conditions, a reformer feed comprising methane with a reforming catalyst, to provide a reformer product comprising hydrogen and CO produced from reforming of at least a portion of the methane by reaction with H2O present in the reformer feed,
wherein the reforming catalyst comprises, as noble metals, from about 0.5 wt-% to about 2 wt-% Pt and from about 0.5 wt-% to about 2 wt-% Rh on a solid support comprising cerium oxide and less than about 10 wt-% of magnesium oxide, said reforming catalyst comprising less than 0.05% by weight of metals other than Pt and Rh and metals of said solid support, and
wherein the reformer feed comprises CO in a concentration of at least about 0.5 mol-% and ethylene in a concentration of at least about 1 mol-% and has a steam/carbon molar ratio of at least about 2.0,
wherein the reforming conditions include a temperature from about 649° C. (1200° F.) to about 816° C. (1500° F.), a gauge pressure from about 0 kPa to about 517 kPa (75 psig), and a weight hourly space velocity (WHSV) from about 0.1 hr−1 to about 4.0 hr−1, and
wherein a conversion of said methane is at least about 80%.

### Claim 2 (depends on 1)

The process of claim 1, wherein the reformer feed comprises both CO and CO2, in a combined concentration from about 5 mol-% to about 15 mol-%.

### Claim 3 (depends on 1)

The process of claim 1, wherein, prior to the contacting, the reformer feed is combined with a separate steam-containing feed comprising all or a portion of the H2O.

### Claim 4 (depends on 1)

The process of claim 1, wherein the reformer feed comprises less than about 25 mol-% methane.

### Claim 5 (depends on 1)

The process of claim 1, wherein the reformer feed further comprises one or more C2+ paraffinic hydrocarbons.

### Claim 6 (depends on 5)

The process of claim 5, wherein the one or more C2+ paraffinic hydrocarbons, are selected from the group consisting of ethane, propane, butane, pentane, and combinations thereof.

### Claim 7 (depends on 6)

The process of claim 6, wherein the reformer feed comprises ethane and propane, in a combined concentration from about 2 mol-% to about 35 mol-%.

### Claim 8 (depends on 6)

The process of claim 6, wherein the reformer feed further comprises one or more C2+ olefinic hydrocarbons selected from the group consisting of propylene, butene, pentene, and combinations thereof.

### Claim 9 (depends on 8)

The process of claim 8, wherein the reformer feed comprises ethane and ethylene, in a combined concentration from about 3 mol-% to about 30 mol-%.

### Claim 10 (depends on 5)

The process of claim 5, wherein the methane, the ethylene, and the one or more C2+ paraffinic hydrocarbons are reformed with a hydrocarbon conversion of at least about 90%.

### Claim 11 (depends on 1)

The process of claim 1, wherein the reformer product comprises at least about 5 mol-% CO.

### Claim 12 (depends on 1)

The process of claim 1, further comprising, in a downstream water-gas shift (WGS) reactor containing a catalyst comprising both Pt and Rh, each independently present in an amount from about 0.5 wt-% to about 2 wt-%, on a support comprising cerium oxide,
converting at least a portion of the CO in the reformer product to additional H2 by a WGS reaction, to provide a WGS product having an increased H2 concentration, relative to the reformer product.

### Claim 13 (depends on 12)

The process of claim 12, wherein the WGS product comprises at least about 70 mol-% H2, on a water-free basis.

### Claim 14 (depends on 1)

The process of claim 1, wherein the reformer feed comprises natural gas comprising CO2 in a concentration from about 3 mol-% to about 35 mol-%.

### Claim 15 (depends on 1)

The process of claim 1, wherein the concentration of ethylene in the reformer feed is from about 1 mol-% to about 10 mol-%.

### Claim 16

A process for producing hydrogen, the process comprising:
contacting, under reforming conditions, a reformer feed comprising methane with a reforming catalyst, to provide a reformer product comprising hydrogen produced from reforming of at least a portion of the methane by reaction with H2O,
wherein the reforming catalyst comprises, as noble metals, from about 0.5 wt-% to about 2 wt-% Pt and from about 0.5 wt-% to about 2 wt-% Rh on a solid support comprising cerium oxide and less than about 10 wt-% of magnesium oxide, and
wherein the reformer feed comprises ethylene in a concentration of at least about 1 mol-% and has a steam/carbon molar ratio of at least about 2.0.

### Claim 17 (depends on 16)

The process of claim 16, further comprising, prior to said contacting, a hydrogen removal step comprising:
separating hydrogen from a process stream or a sweetened process stream, to provide said reformer feed.

### Claim 18 (depends on 17)

The process of claim 17, wherein said hydrogen removal step comprises separating hydrogen from a sweetened process stream, said sweetened process stream having been subjected to a sulfur removal step, prior to said hydrogen removal step.

### Claim 19 (depends on 17)

The process of claim 17, wherein, prior to said contacting, none of pretreatment steps of (i) hydrotreating, (ii) a water-gas shift (WGS) reaction, (iii) CO2 removal, and (iv) pre-reforming, is used to provide said reformer feed.