# US 7,745,667 B2 · Microchannel apparatus comprising structured walls, chemical processes, methods of making formaldehyde

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- Number: US 7,745,667 B2
- Document ID: US7745667B2
- Status: Granted
- Kind: B2
- Application number: 12/099,142
- Filed: 2008-04-07
- Published: 2009-10-08
- Granted: 2010-06-29
- Earliest claimed: 2008-04-07
- Assignees: Velocys, Inc.
- Inventors: Soumitra Deshmukh; Anna Lee Tonkovich; Terry Manzanec; Bin Yang; Kai Jarosch; Richard Long; Francis P. Daly
- Web page: https://patentgrep.com/patent/US7745667B2

## CPC

- B01J 19/0093: {Microreactors, e.g. miniaturised or microfabricated reactors (laboratory containers with capillary fluid transport in microfabricated channels or chambers B01L3/5027)}
- B01J 23/28: Molybdenum
- B01J 23/8877: {Vanadium, tantalum, niobium or polonium}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0205: {in several steps}
- B01J 37/0225: {of metal substrates}
- B01J 37/0244: {Coatings comprising several layers}
- B01J 37/0248: {Coatings comprising impregnated particles}
- C07C 45/38: being a primary hydroxyl group
- B01J 21/063: {Titanium; Oxides or hydroxides thereof}
- B01J 29/0308: {Mesoporous materials not having base exchange properties, e.g. Si-MCM-41}
- B01J 2219/00822: Metal
- B01J 2219/00835: Comprising catalytically active material
- B01J 2219/00844: Comprising porous material
- B01J 2219/0086: Dimensions of the flow channels
- B01J 2219/00873: Heat exchange
- B01J 2219/00889: Mixing
- B01J 2219/00984: Residence time
- B01J 2229/18: to introduce other elements into or onto the molecular sieve itself
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Methods for controlling series or series-parallel reactions are described. Novel microchannel apparatus having mesoporous structures adjacent to bulk flow paths are described. Methods of synthesizing formaldehyde from methanol are also described.

## Claims

### Claim 1

A method of conducting a series or series parallel reaction, comprising:
passing a first reactant into a microchannel;
passing a second reactant into the microchannel in plural stages;
wherein the first and second reactant react in each stage;
wherein the yield of primary product from the method, based on the first reactant, is at least 90%, and wherein, at the end of each stage, the second reactant is not completely consumed but is present in a range of 0.01 to 10 mol %.

### Claim 2 (depends on 1)

The method of claim 1 wherein the first reactant comprises a liquid and the liquid is fed through into the microchannel through an inlet, the second reactant comprises a gas that is fed through apertures into the microchannel, and wherein the first reactant and the second reactant react at a solid catalyst loaded on to a microchannel wall.

### Claim 3 (depends on 1)

The method of claim 1 wherein 2 or more reactants are fed into the microchannel and one or more of the said 2 or more reactants are also fed into the microchannel through apertures in a plurality of stages.

### Claim 4 (depends on 1)

The method of claim 1 wherein the first reactant is methanol and the second reactant is oxygen, and the primary product is formaldehyde.

### Claim 5 (depends on 1)

The method of claim 1 wherein the methanol and oxygen react over a catalyst comprising a mixture of vanadium and molybdenum oxides disposed on titania disposed on a mesoporous matrix.

### Claim 6 (depends on 1)

The method of claim 1 wherein catalyst is disposed on a mesoporous matrix and the mesoporous matrix is disposed in wells along the length of the microchannel, and further wherein the microchannel comprises a bulk flow channel, and wherein the mesporous matrix is adjacent to the bulk flow channel.

### Claim 7 (depends on 6)

The method of claim 6 wherein the wells comprise a wall and wherein the wall is tapered in the direction of flow through the bulk flow channel.

### Claim 8 (depends on 1)

The method of claim 1 wherein a portion of the second reactant is combined with the first reactant prior to entering the microchannel.

### Claim 9 (depends on 1)

The method of claim 1 comprising controlling the flow of reactants such that at least 90% of the mass flow through the microchannel has a residence time that varies by less than 10% of the mass average residence time.

### Claim 10

A method of conducting a series or series-parallel reaction in a reaction chamber, comprising:
passing a stream comprising a first reactant into a bulk flow path having at least one dimension of 2 mm or less;
wherein, adjacent to the bulk flow path, there is a catalyst supported on a mesoporous matrix;
wherein the first reactant reacts with a second reactant on the catalyst that is supported on a mesoporous matrix;
wherein the volume occupied by the catalyst supported on a mesoporous matrix (wherein the volume occupied by the catalyst includes the volume of the porous support and spaces within the catalyst) plus the volume of bulk flow path that is adjacent to the catalyst supported on a mesporous matrix defines the volume of reaction chamber;
controlling the flow of reactants such that at least 90% of the stream has a residence time in the reaction chamber that varies by less than 10% of the mass average residence time.

### Claim 11 (depends on 10)

The method of claim 10 wherein a product stream is produced and wherein the yield of a single product is at least 90% based on the mass of the first reactant.

### Claim 12 (depends on 10)

The method of claim 10 wherein the first reactant comprises methanol in a methanol-containing stream, the second reactant is O2, and the single product is formaldehyde.

### Claim 13 (depends on 12)

The method of claim 12 wherein O2 is added in stages to the methanol-containing stream and O2 concentration entering in any stage is in the range of 1-10% by volume and exiting any stage is 0.01-1% by volume for all stages in the reactor.

### Claim 14 (depends on 10)

The method of claim 10 wherein flow is controlled such that at least 95 of the flow in the reaction chamber has a residence time that varies by 2% or less.

### Claim 15

A method of synthesizing formaldehyde in microchannel apparatus, comprising:
passing methanol into a channel;
wherein the channel comprises a bulk flow path, a formaldehyde synthesis catalyst supported on a mesoporous matrix adjacent to the bulk flow path, and channel walls comprising plural apertures;
passing oxygen through the plural apertures;
wherein the methanol and the oxygen react on the formaldehyde synthesis catalyst;
wherein the oxygen content is controlled such that the molar % of oxygen does not exceed 10% in any 5 volume % of the channel and wherein the amount (molar) of methanol exceeds the amount of oxygen in any 5 volume % of the channel (where the 5% volume is based a continuous length and covers an entire cross-sectional area over the continuous length); and
producing a product stream comprising formaldehyde in a yield of at least 90% based on the methanol reactant.

### Claim 16

A method of synthesizing formaldehyde in microchannel apparatus, comprising:
passing methanol into a channel;
wherein the channel comprises a bulk flow path, a formaldehyde synthesis catalyst supported on a mesoporous matrix adjacent to the bulk flow path, and channel walls comprising plural apertures;
passing oxygen through the plural apertures;
wherein the methanol and the oxygen react on the formaldehyde synthesis catalyst;
wherein the oxygen content is controlled such that the concentration of oxygen entering any stage of the microchannel apparatus is greater than 1 molar %;
wherein the oxygen content is controlled such that the concentration of oxygen exiting any stage of the microchannel apparatus is greater than 0.01 molar %; and
producing a product stream comprising formaldehyde in a yield of at least 90% based on the methanol reactant.

### Claim 17

A method of synthesizing formaldehyde in microchannel apparatus, comprising:
passing methanol into a channel;
wherein the channel comprises a bulk flow path, a formaldehyde synthesis catalyst supported on a mesoporous matrix adjacent to the bulk flow path, and channel walls comprising plural apertures;
passing oxygen through the plural apertures;
wherein the methanol and the oxygen react on the formaldehyde synthesis catalyst;
wherein the plural apertures are spaced an uneven intervals; and
producing a product stream comprising formaldehyde in a yield of at least 90% based on the methanol reactant.

### Claim 18 (depends on 17)

The method of claim 17 wherein the oxygen is added to the methanol in plural stages and wherein the O2 content remains at a level of at least 0.01% (volume %) at the end of every stage.

### Claim 19

A method of synthesizing formaldehyde in microchannel apparatus, comprising:
passing methanol into a channel;
wherein the channel comprises a bulk flow path, a formaldehyde synthesis catalyst supported on a mesoporous matrix adjacent to the bulk flow path, and channel walls comprising plural apertures;
passing oxygen through the plural apertures into at least a first stage and a second stage;
wherein the methanol and the oxygen react on the formaldehyde synthesis catalyst in each of the first and second stages;
wherein the oxygen content is controlled such that the molar % of oxygen does not exceed 10% in each of the first and second stages; and
producing a product stream comprising formaldehyde in a yield of at least 90% based on the methanol reactant.

### Claim 20

A method of synthesizing formaldehyde, comprising:
passing methanol and oxygen over a catalyst at a temperature of 250° C. or more; wherein the catalyst comprises a mixed V, Mo oxide on titania support disposed on mesoporous matrix.

### Claim 21 (depends on 20)

The method of claim 20 wherein the mesoporous matrix comprises SBA-15.

### Claim 22 (depends on 10)

The method of claim 10 wherein the mesoporous matrix comprises a structured wall.

### Claim 23 (depends on 15)

The method of claim 15 wherein the mesoporous matrix comprises a structured wall.

### Claim 24 (depends on 20)

The method of claim 20 wherein the catalyst comprises at least 2 weight % V, not including the weight of the mesporous matrix; and
at least 2 weight % Mo, not including the weight of the mesporous matrix.

### Claim 25 (depends on 20)

The method of claim 20 wherein the catalyst comprises 5 to 20 weight % Mo, and 5 to 60 weight % Ti.

### Claim 26 (depends on 16)

The method of claim 16 wherein O2 concentration exiting any stage is 0.01-1% by volume for all stages in the reactor.

### Claim 27 (depends on 16)

The method of claim 16 wherein O2 concentration exiting any stage is 0.05-0.15% by volume for all stages in the reactor.

### Claim 28 (depends on 26)

The method of claim 26 wherein contact times are 1 to 200 ms in each stage.

### Claim 29 (depends on 16)

The method of claim 16 wherein the mesoporous matrix comprises a structured wall.

### Claim 30 (depends on 4)

The method of claim 4 wherein the total oxygen conversion is greater than 99%.

### Claim 31 (depends on 16)

The method of claim 16 wherein the contact time in the first stage is the same as the contact time in the second stage, and wherein the second stage is longer than the first stage.

### Claim 32 (depends on 16)

The method of claim 16 comprising 5 to 60 stages.

### Claim 33 (depends on 16)

The method of claim 16 comprising 30 or less apertures.

### Claim 34 (depends on 3)

The method of claim 3 comprising 30 or less apertures.

### Claim 35 (depends on 15)

The method of claim 15 wherein the formaldehyde synthesis catalyst comprises oxides of Mo, Ti, and V.

### Claim 36 (depends on 15)

The method of claim 15 wherein methanol conversion is at least 80%.

### Claim 37 (depends on 15)

The method of claim 15 wherein methanol conversion is at least 90%.

### Claim 38 (depends on 16)

The method of claim 16 wherein methanol conversion is at least 80%.

### Claim 39 (depends on 38)

The method of claim 38 wherein formaldehyde selectivity is at least 90%.