# US 4,395,495 A · Production of methanol

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- Number: US 4,395,495 A
- Document ID: US4395495A
- Status: Granted
- Kind: A
- Application number: 06/171,962
- Filed: 1980-07-24
- Granted: 1983-07-26
- Earliest claimed: 1979-08-02
- Assignees: Dut Pty Limited
- Inventors: Donald R. Cummings
- Web page: https://patentgrep.com/patent/US4395495A

## CPC

- 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)
- B01J 8/1836: {Heating and cooling the reactor (B01J8/42 takes precedence)}
- C01B 3/384: with external heating of the catalyst
- C07C 29/1518: {one step being the formation of initial mixture of carbon oxides and hydrogen for synthesis}
- C10G 1/002: {in combination with oil conversion- or refining processes}
- 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 2203/0415: Purification by absorption in liquids
- C01B 2203/0445: Selective methanation
- C01B 2203/047: the impurity being carbon monoxide
- C01B 2203/0475: the impurity being carbon dioxide
- C01B 2203/061: Methanol production
- C01B 2203/065: using hydrotreating, e.g. hydrogenation, hydrodesulfurisation
- C01B 2203/0805: Methods of heating the process for making hydrogen or synthesis gas
- C01B 2203/0811: by combustion of fuel
- C01B 2203/0816: Heating by flames
- C01B 2203/0844: the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
- C01B 2203/0866: by combination of different heating methods
- C01B 2203/0877: by direct injection of fluid
- C01B 2203/0883: by indirect heat exchange
- C01B 2203/0894: Generation of steam
- C01B 2203/1011: Packed bed of catalytic structures, e.g. particles, packing elements
- C01B 2203/1241: Natural gas or methane
- C01B 2203/1247: Higher hydrocarbons
- C01B 2203/1258: Pre-treatment of the feed
- C01B 2203/127: Catalytic desulfurisation
- C01B 2203/146: At least two purification steps in series
- C01B 2203/148: involving a recycle stream to the feed of the process for making hydrogen or synthesis gas
- C01B 2203/1604: Starting up the process
- C01B 2203/1609: Shutting down the process
- C01B 2203/1614: Controlling the temperature
- C01B 2203/80: Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B 2203/84: Energy production
- C10G 2300/107: Atmospheric residues having a boiling point of at least about 538 °C
- C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

In the production of methanol from a methane-containing gaseous feedstock such as natural gas by steam reforming the gas and treating the reformate to produce methanol by inter-reaction of the hydrogen and oxides of carbon in the reformate, the use of part of the feedstock to fire the reformer is avoided by immersing the reformer reactor tubes in a fluidized bed heated by the combustion of a low grade, solid, fossil-based fuel such as coal, lignite, oil shale or asphaltic residues from oil refining. By pressurizing the fluidized bed, all the power requirements of the process can be obtained by expansion of the flue gas, which can also provide the CO.sub.2 balance for the methanol synthesis, and a compressor can be omitted.

## Claims

### Claim 1

In a method of producing methanol from a methane-containing gas by (a) steam reforming said gas at elevated temperature and superatmospheric pressure in a reaction vessel and in the presence of a catalyst to form a reformate containing hydrogen, oxides of carbon and unreacted methane and (b) subjecting a reaction stream comprising said reformate to conditions of elevated temperature and superatmospheric pressure for the formation of methanol by partial reaction of the oxides of carbon with the hydrogen in said reaction stream, the improvement comprising (c) separating the product of step (b) above into a methanol-containing stream and a recycle stream comprising unreacted hydrogen, unreacted oxides of carbon and methane; (d) recycling a first part of said recycle stream, which first part contains hydrogen and oxides of carbon, to step (b); (e) recycling a second part of said recycle stream, which second part contains methane, to step(a); (f) immersing, at least partially and for deriving the heat for the steam reforming step, said reaction vessel in a fluidized bed of finely divided solid which is heated at least in part by the combustion of a solid fossil based fuel; and (g) incorporating into said reaction stream for step (b) carbon dioxide provided from flue gas formed by the combustion of said solid, fossil based fuel.

### Claim 2 (depends on 1)

A method as claimed in claim 1 in which the fluidized bed is also at superatmospheric pressure.

### Claim 3 (depends on 2)

A method as claimed in claim 2 in which power is produced by expanding through an expansion engine flue gas which is recovered at superatmospheric pressure from the fluidized bed and said power is being employed to compress the oxidant gas used in the combustion of the fuel.

### Claim 4 (depends on 2)

A method as claimed in claim 2 in which step (b) is effected at a higher pressure than step (a) and power is being produced by expanding through an expansion engine, flue gas which is recovered at superatmospheric pressure from the fluidized bed, said power being employed to compress the feed to step (b).

### Claim 5 (depends on 2)

A method as claimed in claim 2 in which all the power required for compressing the oxidant gas and the feed to step (b) is supplied by expanding flue gas through the expansion engine.

### Claim 6 (depends on 2)

A method as claimed in claim 2 in which the reformate is provided at substantially the same pressure as said first part of said recycle stream.

### Claim 7 (depends on 1)

A method as claimed in claim 1 in which the solid fuel is coal and the methane-containing gas comprises gas drained from a coalfield from which the coal is supplied.

### Claim 8 (depends on 7)

A method as claimed in claim 7 in which the coal is separated into a high ash fraction which is used as the solid fuel and a low ash fraction.

### Claim 9 (depends on 1)

A method as claimed in claim 1 wherein the solid fuel is a solid residue obtained from refining a crude oil and the methane-containing gas comprises gas associated with the crude oil and/or produced in the refining of the crude oil.

### Claim 10 (depends on 1)

A method as claimed in claim 1 in which waste water from a process employed in the extraction of the fuel is injected into the fluidized bed.

### Claim 11 (depends on 1)

A method as claimed in claim 1 in which at least a part of carbon dioxide is incorporated into said reaction stream by injecting it into said methane-containing gas.

### Claim 12 (depends on 1)

The method as defined in claim 1 wherein a part of the excess carbon dioxide in step (g) is provided from a supplemental source.