# US 11,110,423 B2 · Heat dissipating diluent in fixed bed reactors

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- Number: US 11,110,423 B2
- Document ID: US11110423B2
- Status: Granted
- Kind: B2
- Application number: 16/859,246
- Filed: 2020-04-27
- Published: 2020-08-13
- Granted: 2021-09-07
- Earliest claimed: 2015-09-14
- Assignees: NOVA Chemicals (International) S.A.
- Applicants: NOVA Chemicals (International) S.A.
- Inventors: Vasily Simanzhenkov; Kamal Elias Serhal; Shahin Goodarznia
- Web page: https://patentgrep.com/patent/US11110423B2

## CPC

- B01J 8/025: {in a cylindrical shaped bed}
- B01J 8/0453: {the beds being superimposed one above the other}
- B01J 27/0576: {Tellurium; Compounds thereof}
- C07C 2/84: catalytic
- C07C 5/48: with oxygen as an acceptor
- B01J 2208/00061: of the reactants
- B01J 2208/00513: using inert heat absorbing solids in the bed
- C07C 2527/057: Selenium or tellurium; Compounds thereof
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Incorporating into a fixed bed reactor for an exothermal reaction having a catalyst supported on a support having a thermal conductivity typically less than 30 W/mk within the reaction temperature control limits heat dissipative particles having a thermal conductivity of at least 50 W/mk less than 30 W/mk within the reaction temperature control limits helps control the temperature of the reactor bed.

## Claims

### Claim 1

A process for conducting an oxidative dehydrogenation of one or more C2-4 hydrocarbons comprising:
providing a mixed feed of C2-4 hydrocarbons and oxygen in a volume ratio from 70:30 to 95:5;
conducting oxidative dehydrogenation in a fixed bed reactor at a temperature of less than 420° C., a gas hourly space velocity of not less than 280 hr−1 and a pressure of from 0.8 to 102 atmospheres (80 to 1000 kPa) in the presence of a fixed bed of catalyst, the catalyst comprising a mixed metal oxide catalyst having the empirical formula:
VxMoyNbzTemMenOp
wherein Me is a metal selected from Ta, Ti, W, Hf, Zr, Sb and mixtures thereof; x is from 0.1 to 3 provided that when Me is absent x is greater than 0.5; y is from 0.5 to 1.5; z is from 0.001 to 3; m is from 0.001 to 5; n is from 0 to 2; and p is a number to satisfy the valence state of the mixed metal oxide catalyst;
wherein said mixed metal oxide catalyst is supported on one or more of porous silicon dioxide, ignited silicon dioxide, kieselgur, silica gel, porous or nonporous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, aluminum silicate, silicon nitride or silicon carbide;
wherein said fixed bed of catalyst comprises inert non catalytic heat dissipative particles incorporated into the fixed bed of catalyst, in an amount from 5 to 90 wt. %, based on total weight of the catalyst and the inert non catalytic heat dissipative particles in the fixed bed, wherein said particles have a melting point at least 30° C. above the temperature upper control limit of said oxidative dehydrogenation, a particle size of from 0.5 mm to 75 mm and a thermal conductivity of greater than 30 W/mK (watts/meter Kelvin) within the reaction temperature control limits; and
transferring heat from an interior of the fixed bed of catalyst via the inert non catalytic heat dissipative particles to a wall of the fixed bed reactor to increase cooling homogeneity in the fixed bed of catalyst thereby reducing hot spots in the fixed bed of catalyst.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the particles comprise a thermal conductivity of greater than 150 W/mK within the reaction temperature control limits.

### Claim 3 (depends on 2)

The process according to claim 2, wherein the particles comprise at least one of silver, copper, gold, molybdenum, or tungsten.

### Claim 4 (depends on 3)

The process according to claim 3, wherein the particles have a size from 0.5 to 5 mm.

### Claim 5 (depends on 1)

The process according to claim 1, having a conversion of ethane of not less than 90%.

### Claim 6 (depends on 1)

The process according to claim 1, wherein said temperature upper control limit is less than 400° C.

### Claim 7 (depends on 1)

The process according to claim 1, wherein the mixed metal oxide catalyst comprises a crystalline phase comprising the empirical formula Mo1.0V0.25-0.35Te0.1-0.20Nb0.15-0.19Op where d is a number to satisfy the valence of the oxide.

### Claim 8

A method of oxidative dehydrogenation, comprising:
providing a mixed feed of C2-4 hydrocarbons and oxygen at a volume ratio of the C2-4 hydrocarbons to oxygen in a range of 70:30 to 95:5 to a fixed bed reactor comprising a fixed bed of catalyst, the catalyst comprising mixed metal oxide catalyst that is a heterogeneous catalyst having a crystalline phase comprising the empirical formula Mo1.0V0.25-0.35Te0.1-0.20Nb0.15-0.19Op where d is a number to satisfy the valence of the oxide, wherein inert non catalytic heat dissipative particles comprising a particle size in a range of 0.5 millimeters (mm) to 75 mm are incorporated into the fixed bed of catalyst;
conducting oxidative dehydrogenation in the fixed bed reactor at a temperature less than 420° C., a gas hourly space velocity not less than 280 hr−1, and a pressure in a range of 80 kilopascals (kPa) to 1000 kPa in the presence of the fixed bed of catalyst, wherein the inert non catalytic heat dissipative particles comprise a melting point at least 30° C. above a temperature upper control limit of the oxidative dehydrogenation and a thermal conductivity greater than 30 watts/meter Kelvin (W/mK) within reaction temperature control limits; and
transferring heat from an interior of the fixed bed of catalyst via the inert non catalytic heat dissipative particles to a wall of the fixed bed reactor, thereby increasing cooling homogeneity in the fixed bed of catalyst and reducing hot spots in the fixed bed of catalyst.

### Claim 9 (depends on 8)

The method of claim 8, wherein the mixed metal oxide catalyst as the heterogeneous catalyst comprises the empirical formula:
VxMoyNbzTemMenOp
wherein Me is a metal selected from Ta, Ti, W, Hf, Zr, Sb and mixtures thereof; x is from 0.1 to 3 provided that when Me is absent x is greater than 0.5; y is from 0.5 to 1.5; z is from 0.001 to 3; m is from 0.001 to 5; n is from 0 to 2; and p is a number to satisfy the valence state of the mixed metal oxide catalyst.

### Claim 10 (depends on 8)

The method of claim 8, wherein the mixed metal oxide catalyst is supported on at least one of porous silicon dioxide, ignited silicon dioxide, kieselgur, silica gel, porous or nonporous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, aluminum silicate, silicon nitride, or silicon carbide.

### Claim 11 (depends on 8)

The method of claim 8, wherein the inert non catalytic heat dissipative particles comprise metal and a particle size in a range of 0.5 mm to 5 mm, and wherein the inert non catalytic heat dissipative particles comprise a thermal conductivity greater than 150 W/mK within the reaction temperature control limits.

### Claim 12 (depends on 8)

The method of claim 8, wherein the inert non catalytic heat dissipative particles comprise at least one of silver, copper, gold, molybdenum, or tungsten.

### Claim 13 (depends on 8)

The method of claim 8, wherein the oxidative dehydrogenation comprises a conversion of ethane of at least 90%, and wherein the temperature upper control limit is less than 400° C.

### Claim 14

A method of oxidative dehydrogenation, comprising:
providing a mixed feed of C2-4 hydrocarbons and oxygen at a volume ratio of the C2-4 hydrocarbons to oxygen in a range of 70:30 to 95:5 to a fixed bed reactor comprising a fixed bed of catalyst that incorporates inert non catalytic heat dissipative particles into the fixed bed of catalyst, wherein the inert non catalytic heat dissipative particles comprise at least one of silver, copper, gold, molybdenum, or tungsten, and wherein the catalyst comprises mixed metal oxide catalyst comprising the empirical formula:
VxMoyNbzTemMenOp
wherein Me is a metal selected from Ta, Ti, W, Hf, Zr, Sb and mixtures thereof; x is from 0.1 to 3 provided that when Me is absent x is greater than 0.5; y is from 0.5 to 1.5; z is from 0.001 to 3; m is from 0.001 to 5; n is from 0 to 2; and p is a number to satisfy the valence state of the mixed metal oxide catalyst;
conducting oxidative dehydrogenation in the fixed bed reactor at a temperature less than 420° C., a gas hourly space velocity not less than 280 hr−1, and a pressure in a range of 80 kilopascals (kPa) to 1000 kPa in the presence of the fixed bed of catalyst, wherein the inert non catalytic heat dissipative particles comprise a particle size in a range of 0.5 millimeters (mm) to 75 mm, a melting point at least 30° C. above a temperature upper control limit of the oxidative dehydrogenation, and a thermal conductivity greater than 30 watts/meter Kelvin (W/mK) within reaction temperature control limits; and
transferring heat from an interior of the fixed bed of catalyst via the inert non catalytic heat dissipative particles to a wall of the fixed bed reactor to increase cooling homogeneity in the fixed bed of catalyst to reduce hot spots in the fixed bed of catalyst.

### Claim 15 (depends on 14)

The method of claim 14, wherein the mixed metal oxide catalyst comprises a crystalline phase comprising the empirical formula Mo1.0V0.25-0.35Te0.1-0.20Nb0.15-0.19Op where d is a number to satisfy the valence of the oxide.

### Claim 16 (depends on 14)

The method of claim 14, wherein the mixed metal oxide catalyst is supported on at least one of porous silicon dioxide, ignited silicon dioxide, kieselgur, silica gel, porous or nonporous aluminum oxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boron phosphate, zirconium phosphate, aluminum silicate, silicon nitride, or silicon carbide.