# US 2019/0169088 A1 · Hydrocarbon Conversion

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- Number: US 2019/0169088 A1
- Document ID: US20190169088A1
- Status: Published application
- Kind: A1
- Application number: 16/321,729
- Filed: 2017-08-15
- Published: 2019-06-06
- Earliest claimed: 2016-08-31
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Changmin Chun; Dhaval A. Bhandari; Federico Barrai
- Web page: https://patentgrep.com/patent/US20190169088A1

## CPC

- C07C 2/76: by condensation of hydrocarbons with partial elimination of hydrogen
- B01J 6/008: {Pyrolysis reactions (of hydrocarbons C10G9/00)}
- B01J 8/04: the fluid passing successively through two or more beds
- B01J 8/0492: {Feeding reactive fluids (for solid material, see B01J8/0015)}
- B01J 8/0496: {Heating or cooling the reactor}
- B01J 8/067: {Heating or cooling the reactor (B01J8/062 takes precedence)}
- B01J 19/02: Apparatus characterised by being constructed of material selected for its chemically-resistant properties
- B01J 19/2485: {Monolithic reactors}
- C04B 35/5615: {based on titanium silicon carbides}
- C04B 35/5618: {based on titanium aluminium carbides}
- C04B 35/58078: {based on zirconium or hafnium borides}
- C04B 35/58092: {based on refractory metal silicides}
- C10G 9/002: {Cooling of cracked gases}
- C10G 9/26: with discontinuously preheated non-moving solid material, e.g. blast and run
- C10G 11/00: Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils (cracking in direct contact with molten metals or salts C10G9/34)
- C10G 35/02: Thermal reforming
- B01J 2208/00309: with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
- B01J 2208/00353: Non-cryogenic fluids
- B01J 2208/00513: using inert heat absorbing solids in the bed
- B01J 2208/0053: Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
- B01J 2208/00938: Flow distribution elements
- B01J 2208/065: Heating or cooling the reactor
- B01J 2219/00117: with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
- B01J 2219/00123: adding a temperature modifying medium to the reactants
- B01J 2219/00159: controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
- B01J 2219/2413: Two reactions in indirect heat exchange
- B01J 2219/2428: Catalysts coated on the surface of the monolith channels
- B01J 2219/2438: Ceramics
- C04B 2235/3217: Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B 2235/3225: Yttrium oxide or oxide-forming salts thereof
- C04B 2235/3244: Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
- C04B 2235/3418: Silicon oxide, silicic acids or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
- C04B 2235/3813: Refractory metal borides
- C04B 2235/3826: Silicon carbides
- C04B 2235/3843: Titanium carbides
- C04B 2235/3891: Silicides, e.g. molybdenum disilicide, iron silicide
- C10G 2400/20: C2-C4 olefins
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- 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

## Abstract

The invention relates to hydrocarbon conversion, to equipment and materials useful for hydrocarbon conversion, and to processes for carrying out hydrocarbon conversion, e.g., hydrocarbon pyrolysis processes. The hydrocarbon conversion is carried out in a reactor which includes at least one channeled member that comprises refractory and has an open frontal area ≤55%. The refractory can include non-oxide ceramic.

## Claims

### Claim 1

A hydrocarbon conversion process, comprising:
(a) providing a feed comprising hydrocarbon;
(b) providing a channeled member that includes opposed first and second apertures and at least one internal channel, wherein
(i) the second aperture is separated from the first aperture by a flow-path through the channel,
(ii) the channeled member has an open frontal area (OFA) ≤55%,
(iii) the channeled member comprises a refractory which includes one or more of a first ceramic comprising at least one compound represented by the formula Mn+1AXn, a second ceramic comprising at least one compound represented by the formula NiBj, and a third ceramic comprising at least one compound represented by the formula PkQm, and
(iv) M is at least one element selected from Groups 3-6 of the Periodic Table; A is at least one element selected from Groups 13-16 of the Periodic Table; X is carbon and/or nitrogen; N is at least one element selected from Groups 4 and 5 of the Periodic Table; B is boron; P is at least one element selected from Groups 4-10 of the Periodic Table; Q is silicon and/or aluminum; n is 1, 2, or 3; i and k are each a positive integer; j is i+1 or i+2; and m is a positive integer that can be greater than k, less than k, or equal to k;
(c) providing a flow-through reactor having opposed first and second openings and an internal volume, wherein (i) the internal volume includes the channeled member, (ii) the first opening is adjacent to the first aperture, and (iii) the first and second openings are in fluidic communication through the flow path;
(d) during a heating time tH, heating the channeled member to achieve an average temperature (Tav) in the range of from 500° C. to 1400° C., and a peak temperature (Tp), wherein Tp is >Tav; and
(e) during a reaction time tR,
(i) establishing a flow of the feed from the first opening, through the first aperture, and into the internal channel;
(ii) reacting the feed in the channel, wherein Tav decreases by no more than 100° C. during tR; and
(iii) conducting a flow of a reaction product out of the channel, through the second aperture, and away from the reactor via the second opening.

### Claim 2 (depends on 1)

The process of claim 1, wherein M is selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and combinations thereof; A is selected from the group consisting of Al, Si, P, Ga, Ge, As, Cd, In, Sn, Tl, Pb, and combinations thereof; N is selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and combinations thereof; P is selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, and combinations thereof; and m is ≤k.

### Claim 3 (depends on 1)

The process of claim 1, wherein the first ceramic comprises one or more of Ti3SiC2, Ti2AlC, Nb2AlC, Zr2AlC, Ti2AlC, V2AlC, Cr2AlC, Hf2InC, Ti2SC, V2SC, Ti3SiC2, Ti3GeC2, Ti3SnC2, Ti3AlC2, Ti2AlC, Ti2AlN, Ti3AlC, Ti3AlN2, (Nb,Zr)2AlC, (Ti,V)2AlC, (Ti,Nb)2AlC, (Ti,Cr)2AlC, (Ti,Hf)2InC,and (Ti,V)2SC, Ti3(Si,Ge)C2, and Ti3(Sn,Al)C2, Ti2Al(C,N) and Ti3Al(C,N)2; the second ceramic comprises ZrB2 and/or HfB2; and the third ceramic comprises Nb3Al, Nb2Al, NbAl, NbAl3, and MoSi2.

### Claim 4 (depends on 1)

The process of claim 1, wherein (i) the refractory further comprises one or more of intermetalics, oxides, carbides, nitrides, oxycarbides, oxynitrides, and carbonitrides of at least one metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Al, Si, Y, and La, and (ii) the refractory comprises ≥90 wt. % of non-oxide ceramic based on the weight of the refractory.

### Claim 5 (depends on 1)

The process of claim 1, wherein the refractory comprises ≥75 wt. % based on the weight of the refractory of one or more of the first, second, and third ceramics.

### Claim 6 (depends on 1)

The process of claim 1, wherein the refractory has (i) a mass density in the range of from 4100 kg/m3 to 7000 kg/m3, (ii) a thermal conductivity in the range of from 0.5 W/m° K 50 W/m° K, (iii) a coefficient of thermal expansion ≤1×10−5/° K and 2×10−5/° K, and (iii) a specific heat at 300° K in the range of from 0.04 kj/(° K kg) to 1.2 kj/(° K kg).

### Claim 7 (depends on 1)

The process of claim 1, wherein the internal channel has a plurality of substantially parallel passages having a having a passage density in the range of from 77000/m2 to 1.3×106/m2.

### Claim 8 (depends on 1)

The process of claim 1, wherein the channeled member has an average wetted surface area per unit volume in the range of from 1 cm−1 to 100 cm−1.

### Claim 9 (depends on 1)

The process of claim 1, wherein the refractory further comprises a fourth ceramic, wherein the fourth ceramic includes oxide of at least one of Al, Si, Mg, Ca, Fe, Mn, Ni, Co, Cr, Ti, Hf, V, Nb, Ta, Mo, W, Sc, La, Yt, Zr, and Ce.

### Claim 10 (depends on 1)

The process claim of claim 1, wherein (i) the first ceramic comprises ≥90 vol. % of (A) T3SiC2 and/or (B) T2AlC; (ii) the second ceramic comprises ≥10 vol. % SiC, ≥10 vol. % of TaSi2, wherein ≥90% of the remainder of the second ceramic's volume is ZrB2; and (iii) the third ceramic comprises ≥90 vol. % of MoSi2, wherein ≥90% of the remainder of the third ceramic's volume is one or more of silica, alumina, zirconia, and yttria.

### Claim 11 (depends on 1)

The process of claim 1, wherein the flow-through reactor's internal volume includes a second channeled member, wherein the second channeled member has first and second apertures and at least one internal channel, the second aperture is adjacent to the second opening, the internal channel is cooled during tH, the reactor product is conducted though the internal channel of the second channeled member for cooling during tR.

### Claim 12 (depends on 1)

The process of claim 1, wherein the reaction includes one or more of steam reforming, dry (CO2) reforming, pyrolysis, catalytic cracking, dehydrogenation, and dehydration.

### Claim 13 (depends on 1)

The process of claim 1, wherein the flow-through reactor has a first bulk gas temperature profile at the start of tR, a second bulk gas temperature profile at the end of tR, and the first and second bulk gas temperature profiles are substantially congruent.

### Claim 14 (depends on 1)

The process of claim 1, wherein at the start of tR Tp exceeds Tav by at least 10° C., and Tav and Tp each decrease by no more than 75° C. during tR.

### Claim 15 (depends on 1)

The process of claim 1, wherein the feed comprises one or more of ethane, propane, butanes, saturated and unsaturated C6 hydrocarbon, including those derived from one or more of Fischer-Tropsch synthesis products, shale gas, biogas, associated gas, natural gas and mixtures or components thereof, steam cracked gas oil and residues, gas oils, heating oil, jet fuel, diesel, kerosene, gasoline, naphtha (including coker naphtha, steam cracked naphtha, and catalytically cracked naphtha), hydrocrackate, reformate, raffinate reformate, Fischer-Tropsch liquids, natural gasoline, distillate, virgin naphtha, crude oil, atmospheric pipestill bottoms, vacuum pipestill streams including bottoms, wide boiling range naphtha to gas oil condensates, heavy non-virgin hydrocarbon streams from refineries, vacuum gas oils, heavy gas oil, naphtha contaminated with crude, synthetic crudes, shale oils, coal liquefaction products, coal tars, tars, atmospheric resid, heavy residuum, C4-residue admixture, naphtha-residue admixture, cracked feed, coker distillate streams, and hydrocarbon streams derived from plant or animal matter.

### Claim 16 (depends on 1)

The process of claim 1, wherein the reaction includes pyrolysis, the conversion is ≥60 wt. %, the gas residence time in the channel is ≤0.4 second, tR is ≥1 second, the total pressure ≥5 psig, and a hydrocarbon partial pressure of ≥7 psia (48 kPa).

### Claim 17 (depends on 16)

The process of claim 16, wherein (i) the reaction product comprises unconverted feed, coke, methane, acetylene, and C2+ olefin, and (ii) at least a portion of the coke remains in the internal channel as a deposit.

### Claim 18 (depends on 16)

The process of claim 16, wherein at the start of tR, Tav is in the range of from 925° C. to 1075° C.

### Claim 19 (depends on 16)

The process of claim 16, wherein the gas residence time in the channel is in a range of from 0.01 to 0.4 second, and the channeled member includes at least one monolithic honeycomb having a mass ≥1 kg.

### Claim 20 (depends on 16)

The process of claim 16, wherein the tH is ≥1 second, and the heating of step (d) includes reacting a fuel with an oxidant in the internal volume of the flow-through reactor.

### Claim 21

A reverse-flow reactor, comprising:
(a) a first channeled member having open frontal area (OFA) ≤55%, the first channeled member comprising at least one refractory and having opposed first and second apertures and at least one internal channel, wherein
(i) the second aperture is separated from the first aperture by a first flow-path through the channel,
(ii) the refractory includes one or more of a first ceramic comprising at least one compound represented by the formula Mn+1AXn, a second ceramic comprising at least one compound represented by the formula NiBj, and a third ceramic comprising at least one compound represented by the formula PkQm, and
(iii) M is at least one element selected from Groups 3-6 of the Periodic Table, A is at least one element selected from Groups 13-15 of the Periodic Table; X is carbon and/or nitrogen; N is at least one element selected from Groups 4 and 5 of the Periodic Table; B is boron; P is at least one element selected from Groups 4-10 of the Periodic Table; Q is silicon and/or aluminum; n is 1, 2, or 3; i and k are each a positive integer; j is i+1 or i+2; and m is a positive integer that can be greater than k, less than k, or equal to k;
(b) a second channeled member comprising at least one refractory and having opposed first and second apertures and at least one internal channel, the first and second apertures being separated by a second flow-path through the channel,
(c) a reactor vessel having opposed first and second openings and an internal volume, wherein (i) the internal volume includes the first and second channeled members; (ii) the first opening is adjacent to the first aperture of the first channeled member and the second opening is adjacent to the second aperture of the second channeled member, and (iii) the first and second openings are in fluidic communication through the first and second flow-paths;
(d) at least one feed conduit in fluidic communication with the first opening, at least one reaction product conduit in communication with the second opening, at least one fuel conduit in fluidic communication with the second opening, at least one oxidant conduit in fluidic communication with the second opening, and at least one combustion product conduit in fluidic communication with the first opening;
(e) at least one flow controller for
(i) during time interval tR establishing a flow of feed from the feed conduit into the first opening and a flow of a reaction product from the second opening into the reaction product conduit, and
(ii) during a time interval tH establishing a flow of fuel from the fuel conduit into the second opening, establishing a flow of oxidant from the oxidant conduit into the second opening, and establishing a flow of combustion product from the first opening into the combustion product conduit.

### Claim 22 (depends on 21)

The reverse flow reactor of claim 21, wherein the reactor vessel has the form of an elongated tube of circular, elliptical, or polygonal cross section, and wherein the reverse flow reactor further comprises at least one mixer distributor located in a flow path between the second aperture of the first channeled member and the first aperture of the second channeled member.

### Claim 23 (depends on 21)

The reverse flow reactor of claim 21, wherein M is selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and combinations thereof; A is selected from the group consisting of Al, Si, P, Ga, Ge, As, Cd, In, Sn, Tl, Pb, and combinations thereof; N is selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, and combinations thereof; P is selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, and combinations thereof; and m is ≤k.

### Claim 24 (depends on 21)

The reverse flow reactor of claim 21, wherein the first ceramic comprises one or more of Ti3SiC2, Ti2AlC, Nb2AlC, Zr2AlC, Ti2AlC, V2AlC, Cr2AlC, Hf2InC, Ti2SC, V2SC, Ti3SiC2, Ti3GeC2, Ti3SnC2, Ti3AlC2, Ti2AlC, Ti2AlN, Ti3AlC, Ti3AlN2, (Nb,Zr)2AlC, (Ti,V)2AlC, (Ti,Nb)2AlC, (Ti,Cr)2AlC, (Ti,Hf)2InC,and (Ti,V)2SC, Ti3(Si,Ge)C2, and Ti3(Sn,Al)C2, Ti2Al(C,N) and Ti3Al(C,N)2; the second ceramic comprises ZrB2 and/or HfB2; and the third ceramic comprises Nb3Al, Nb2Al, NbAl, NbAl3, and MoSi2.

### Claim 25

A reverse-flow reactor, comprising:
(a) a mixer-distributor comprising at least one refractory and having opposed first and second apertures and at least one internal channel, wherein
(i) the second aperture is separated from the first aperture by a first flow-path through the channel,
(ii) the refractory includes one or more of a first ceramic comprising at least one compound represented by the formula Mn+1AXn, a second ceramic comprising at least one compound represented by the formula NiBj, and a third ceramic comprising at least one compound represented by the formula PkQm, and
(iii) M is at least one element selected from Groups 3-6 of the Periodic Table, A is at least one element selected from Groups 13-15 of the Periodic Table; X is carbon and/or nitrogen; N is at least one element selected from Groups 4 and 5 of the Periodic Table; B is boron; P is at least one element selected from Groups 4-10 of the Periodic Table; Q is silicon and/or aluminum; n is 1, 2, or 3; i and k are each a positive integer; j is i+1 or i+2; and m is a positive integer that can be greater than k, less than k, or equal to k;
(b) a channeled member comprising at least one refractory and having opposed first and second apertures and at least one internal channel, the first and second apertures being separated by a second flow-path through the channel,
(c) a reactor vessel having opposed first and second openings and an internal volume, wherein (i) the internal volume includes the mixer-distributor and the channeled member; (ii) the first opening is adjacent to the first aperture of the channeled member, (ii) the second aperture of the channeled member is adjacent to the first aperture of the mixer-distributor, (iii) the second opening is in fluidic communication with the second aperture of the mixer-distributor, and (iv) the first and second openings are in fluidic communication through the first and second flow-paths;
(d) at least one feed conduit in fluidic communication with the first opening, at least one reaction product conduit in communication with the second opening, at least one fuel conduit in fluidic communication with the second opening, at least one oxidant conduit in fluidic communication with the second opening, and at least one combustion product conduit in fluidic communication with the first opening;
(e) at least one flow controller for
(i) during time interval tR establishing a flow of feed from the feed conduit into the first opening and a flow of a reaction product from the second opening into the reaction product conduit, and
(ii) during a time interval tH establishing a flow of fuel from the fuel conduit into the second opening, establishing a flow of oxidant from the oxidant conduit into the second opening, and establishing a flow of combustion product from the first opening into the combustion product conduit.