# US 2021/0276002 A1 · Processes for Upgrading Alkanes and Alkyl Aromatic Hydrocarbons

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- Number: US 2021/0276002 A1
- Document ID: US20210276002A1
- Status: Published application
- Kind: A1
- Application number: 17/174,078
- Filed: 2021-02-11
- Published: 2021-09-09
- Earliest claimed: 2020-03-06
- Assignees: ExxonMobil Chemical Patents Inc.
- Applicants: ExxonMobil Chemical Patents Inc.
- Inventors: Xiaoying Bao; John S. Coleman
- Web page: https://patentgrep.com/patent/US20210276002A1

## CPC

- C07C 5/3337: {of the platinum group}
- B01J 21/04: Alumina
- B01J 21/066: {Zirconium or hafnium; Oxides or hydroxides thereof}
- B01J 21/10: Magnesium; Oxides or hydroxides thereof
- B01J 23/10: of rare earths
- B01J 23/626: {with tin}
- B01J 23/628: {with lead}
- B01J 35/31: Density
- B01J 38/10: using elemental hydrogen
- B01J 38/32: Indirectly heating or cooling material within regeneration zone or prior to entry into regeneration zone
- C07C 5/367: Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
- C07C 5/417: {of the platinum group}
- C10G 35/09: Bimetallic catalysts in which at least one of the metals is a platinum group metal
- C10G 35/14: according to the "fluidised-bed" technique
- B01J 2235/30: Scanning electron microscopy; Transmission electron microscopy
- C07C 2521/04: Alumina
- C07C 2521/06: Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C 2521/08: Silica
- C07C 2521/10: Magnesium; Oxides or hydroxides thereof
- C07C 2523/02: of the alkali- or alkaline earth metals or beryllium
- C07C 2523/04: Alkali metals
- C07C 2523/10: of rare earths
- C07C 2523/14: of germanium, tin or lead
- C07C 2523/42: Platinum
- C07C 2523/62: with gallium, indium, thallium, germanium, tin or lead
- Y02P 20/52: using catalysts, e.g. selective catalysts
- Y02P 20/584: Recycling of catalysts
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Processes for upgrading a hydrocarbon. The process can include contacting a hydrocarbon-containing feed with fluidized catalyst particles that can include a Group 8-10 element or a compound thereof disposed on a support to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce a coked catalyst and an effluent. The process can also include contacting at least a portion of the coked catalyst particles with an oxidant to effect combustion of at least a portion of the coke to produce regenerated catalyst particles. The process can also include contacting an additional quantity of the hydrocarbon-containing feed with at least a portion of the regenerated catalyst particles to produce additional effluent and re-coked catalyst particles.

## Claims

### Claim 1

A process for upgrading a hydrocarbon, comprising:
(I) contacting a hydrocarbon-containing feed with fluidized catalyst particles comprising a Group 8-10 element disposed on a support within a conversion zone to effect one or more of dehydrogenation, dehydroaromatization, and dehydrocyclization of at least a portion of the hydrocarbon-containing feed to produce a conversion effluent comprising coked catalyst particles, one or more upgraded hydrocarbons, and molecular hydrogen, wherein:
the hydrocarbon-containing feed comprises one or more of C2-C16 linear or branched alkanes, one or more of C4-C16 cyclic alkanes, one or more of C8-C16 alkyl aromatic hydrocarbons, or a mixture thereof;
the hydrocarbon-containing feed and catalyst particles are contacted at a temperature in a range from 300° C. to 900° C., for a time period in a range from 0.1 seconds to 2 minutes, under a hydrocarbon partial pressure of at least 20 kPa-absolute, wherein the hydrocarbon partial pressure is the total partial pressure of any C2-C16 alkanes and any C8-C16 alkyl aromatic hydrocarbons in the hydrocarbon-containing feed;
the catalyst particles comprise from 0.05 wt % to 6 wt % of the Group 8-10 element based on the weight of the support; and
the support comprises:
at least one of: w wt % of a Group 2 element, x wt % of a Group 4 element, y wt % of a Group 12 element, and z wt % of an element having an atomic number of 21, 39, or 57-71, based on the weight of the support, wherein w, x, y, and z are independently in a range from 0 to 100, wherein:
any Group 2 element is associated with a wt % m based on the weight of the support,
any Group 4 element is associated with a wt % n based on the weight of the support,
any group 12 element is associated with a wt % p based on the weight of the support, and
any element having an atomic number of 21, 39, or 57-71 is associated with a wt % q based on the weight of the support,
m, n, p, and q are independently a number that is in a range from 1 to 100, and
a sum of w/m+x/n+y/p+z/p is ≥1, based on the weight of the support;
the one or more upgraded hydrocarbons comprise a dehydrogenated hydrocarbon, a dehydroaromatized hydrocarbon, a dehydrocylized hydrocarbon, or a mixture thereof;
(II) obtaining from the conversion effluent a first gaseous stream rich in the one or more upgraded hydrocarbons and the molecular hydrogen and a first particle stream rich in the coked catalyst particles;
(III) contacting at least a portion of the coked catalyst particles in the first particle stream with an oxidant in a combustion zone to effect combustion of at least a portion of the coke to produce a combustion effluent comprising regenerated catalyst particles lean in coke and a combustion gas;
(IV) obtaining from the combustion effluent a second gaseous stream rich in the combustion gas and a second particle stream rich in the regenerated catalyst particles; and
(V) contacting an additional quantity of the hydrocarbon-containing feed with fluidized regenerated catalyst particles to produce additional conversion effluent comprising re-coked catalyst particles, additional one or more upgraded hydrocarbons, and additional molecular hydrogen.

### Claim 2 (depends on 1)

The process of claim 1, further comprising, after step (IV) and before step (V), the following step:
(IVa) contacting at least a portion of the regenerated catalyst particles with a reducing gas to produce regenerated and reduced catalyst particles, wherein the additional quantity of the hydrocarbon-containing feed is contacted with fluidized regenerated and reduced catalyst particles in step (V).

### Claim 3 (depends on 2)

The process of claim 2, wherein in step (IVa), at least one of the following is met:
(i) the regenerated catalyst particles and reducing gas are contacted at a temperature in a range from 450° C. to 900° C., preferably 600° C. to 900° C., more preferably 620° C. to 900° C., more preferably 650° C. to 850° C., or more preferably from 670° C. to 800° C.; and
(ii) the regenerated catalyst particles and reducing gas are contacted under a reducing gas partial pressure in a range from 20 kPa-absolute to 1,000 kPa-absolute, preferably from 50 kPa-absolute to 500 kPa-absolute, or more preferably from 70 kPa-absolute to 300 kPa-absolute.

### Claim 4 (depends on 2)

The process of claim 2, wherein at least a portion of the Group 8-10 element in the regenerated and reduced catalyst particles is in the elemental state.

### Claim 5 (depends on 1)

The process of claim 1, wherein a cycle time from the contacting the hydrocarbon-containing feed with the catalyst particles in step (I) to the contacting the additional quantity of the hydrocarbon-containing feed with the regenerated and reduced catalyst particles in step (V) is ≤70 minutes, preferably from 1 minute to 70 minutes, or more preferably from 5 minutes to 45 minutes.

### Claim 6 (depends on 1)

The process of claim 1, wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted with one another in the presence of steam at an amount in a range from 0.1 vol % to 50 vol %, preferably from 0.5 vol % to 30 vol %, or more preferably from 1 vol % to 15 vol %, based on a total volume of any C2-C16 alkanes and any C8-C16 alkyl aromatic hydrocarbons in the hydrocarbon-containing feed.

### Claim 7 (depends on 1)

The process of claim 1, wherein the support comprises the Group 2 element, and wherein in step (I), the hydrocarbon-containing feed and the catalyst particles are contacted with one another in the presence of steam at an amount in a range from 0.1 vol % to 50 vol %, preferably from 0.5 vol % to 30 vol %, or more preferably from 1 vol % to 15 vol %, based on a total volume of any C2-C16 alkanes and any C8-C16 alkyl aromatic hydrocarbons in the hydrocarbon-containing feed.

### Claim 8 (depends on 1)

The process of claim 1, wherein the hydrocarbon-containing feed and the catalyst particles are contacted with one another in the absence of any steam or in the presence of less than 0.1 vol % of steam based on a total volume of any C2-C16 alkanes and any C8-C16 alkyl aromatic hydrocarbons in the hydrocarbon-containing feed.

### Claim 9 (depends on 1)

The process of claim 1, wherein the hydrocarbon-containing feed comprises propane, wherein the upgraded hydrocarbon comprises propylene, and wherein contacting the hydrocarbon-containing feed with the catalyst particles in step (I) has a propylene yield of at least 52%, or at least 62%, or at least 72% at a propylene selectivity of ≥75%, ≥80%, ≥85%, ≥90%, or ≥95%.

### Claim 10 (depends on 1)

The process of claim 1, wherein the hydrocarbon-containing feed comprises ≥70 vol % of propane, based on a total volume of the hydrocarbon-containing feed, wherein the hydrocarbon-containing feed and catalyst particles are contacted under a propane partial pressure of at least 40 kPa-absolute, and wherein contacting the hydrocarbon-containing feed with the catalyst particles in step (I) has a propylene yield of at least 52%, or at least 62%, or at least 72% at a propylene selectivity of ≥75%, ≥80%, ≥85%, ≥90%, or ≥95%.

### Claim 11 (depends on 1)

The process of claim 1, wherein in step (I), at least one of the following is met:
(i) the hydrocarbon-containing feed and the catalyst particles are contacted at a temperature in a range from 600° C. to 900° C., preferably from 600° C. to 800° C., more preferably from 650° C. to 750° C., or more preferably from 670° C. to 720° C.; and
(ii), the hydrocarbon-containing feed and the catalyst particles are contacted under a hydrocarbon partial pressure in a range from 20 kPa-absolute to 1,000 kPa-absolute, preferably from 50 kPa-absolute to 500 kPa-absolute, or more preferably 70 kPa-absolute to 300 kPa-absolute.

### Claim 12 (depends on 1)

The process of claim 1, wherein in step (III), at least one of the following is met:
(i) the coked catalyst particles and oxidant are contacted at a temperature in a range from 600° C. to 1,100° C., preferably from 650° C. to 1,000° C., more preferably from 700° C. to 900° C., or more preferably from 750° C. to 850° C.; and
(ii) the coked catalyst particles and oxidant are contacted under an oxidant partial pressure in a range from 20 kPa-absolute to 1,000 kPa-absolute, preferably from 50 kPa-absolute to 500 kPa-absolute, or more preferably from 100 kPa-absolute to 300 kPa-absolute.

### Claim 13 (depends on 1)

The process of claim 1, wherein the catalyst particles further comprise a promoter, and wherein the promoter comprises Sn, Ga, Zn, Ge, In, Re, Ag, Au, Cu, a combination thereof, or a mixture thereof.

### Claim 14 (depends on 1)

The process of claim 1, wherein the catalyst particles further comprise an alkali metal element selected from Li, Na, K, Rb, Cs, and combinations and mixtures thereof disposed on the support, the catalyst particles comprise up to 5 wt % of the alkali metal element based on the total weight of the support.

### Claim 15 (depends on 1)

The process of claim 1, wherein m, n, p, and q are each equal to 1, 15, or 30, or wherein m=1, n=15, p=15, and q=1.

### Claim 16 (depends on 1)

The process of claim 1, wherein a molar ratio of a combined amount of any Group 2 element, any Group 4 element, any Group 12 element, and any element having an atomic number of 21, 39, or 57-71 to the Group 8-10 element is at least 0.18, at least 0.19, at least 0.24, or at least 0.29.

### Claim 17 (depends on 1)

The process of claim 1, wherein the support further comprises at least one compound comprising at least one metal element or metalloid element selected from Groups 5, 6, 7, 11, 13, 14, 15, and 16.

### Claim 18 (depends on 1)

The process of claim 1, wherein at least one of the following is met:
(i) the hydrocarbon-containing feed and catalyst particles are contacted in step (I) for a time period in a range from 0.1 seconds to 1.5 minutes, preferably from of 0.5 seconds to 1 minute, or more preferably from 1 seconds to 30 seconds;
(ii) a weight ratio of the catalyst particles to a combined amount of any C2-C16 alkanes and any C8-C16 aromatic hydrocarbons is in a range from 1 to 150, preferably from 5 to 100, or more preferably from 10 to 80; and
(iii) the hydrocarbon-containing feed contacts the catalyst in step (I) at a weight hourly space velocity in a range from 0.1 hr−1 to 100 hr−1, preferably from 0.2 hr−1 to 64 hr−1, or more preferably from 0.4 hr−1 to 32 hr−1, based on the weight of any C2-C16 alkanes and any C8-C16 aromatic hydrocarbons in the hydrocarbon-containing feed.

### Claim 19 (depends on 1)

The process of claim 1, wherein the catalyst particles are in the form of a dense turbulent fluidized bed when contacted with the hydrocarbon-containing feed.

### Claim 20 (depends on 1)

The process of claim 1, wherein the conversion zone is disposed within a riser reactor or a down reactor.

### Claim 21 (depends on 1)

The process of claim 1, wherein a first portion of the coked catalyst particles in first particle stream rich in the coked catalyst particles is contacted with the oxidant in the combustion zone in step (II), and wherein a second portion of the coked catalyst particles in the first particle stream rich in the coked catalyst particles is contacted with the additional quantity of the hydrocarbon-containing feed in step (V).

### Claim 22 (depends on 1)

The process of claim 1, further comprising:
removing a portion of the catalyst particles from the conversion zone during contact of the hydrocarbon-containing feed with the fluidized catalyst particles during step (I);
heating the portion of the catalyst particles removed from the conversion zone to produce heated catalyst particles; and
feeding the heated catalyst particles into the conversion zone to contact the hydrocarbon-containing feed.

### Claim 23 (depends on 1)

The process of claim 1, further comprising supplying heat to the catalyst particles within the conversion zone during contact of the catalyst particles with the hydrocarbon-containing feed.

### Claim 24 (depends on 1)

The process of claim 1, wherein the catalyst particles have a particle density in a range from 0.5 g/cm3 to 3 g/cm3, 0.7 g/cm3 to 2 g/cm3, or 0.8 g/cm3 to 1.4 g/cm3.

### Claim 25 (depends on 1)

The process of claim 1, wherein the catalyst particles have a size and particle density that are consistent with a Geldart A definition.