# US 11,299,443 B2 · Distillate production from olefins in moving bed reactors

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- Number: US 11,299,443 B2
- Document ID: US11299443B2
- Status: Granted
- Kind: B2
- Application number: 16/910,027
- Filed: 2020-06-23
- Published: 2021-10-07
- Granted: 2022-04-12
- Earliest claimed: 2020-04-03
- Assignees: ExxonMobil Research and Engineering Company
- Applicants: ExxonMobil Research and Engineering Company
- Inventors: Arsam Behkish; Lei Zhang; Brandon J. O'Neill; Mark A. Deimund; Alice Lin
- Web page: https://patentgrep.com/patent/US11299443B2

## CPC

- C07C 2/12: with crystalline alumino-silicates {or with catalysts comprising} molecular sieves
- B01J 8/005: {Separating solid material from the gas/liquid stream (separation processes per se B01D)}
- B01J 8/085: {Feeding reactive fluids (for solid material, see B01J8/0015)}
- B01J 29/703: {MRE-type, e.g. ZSM-48}
- B01J 29/90: Regeneration or reactivation
- B01J 38/02: Heat treatment
- C10G 50/00: Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
- B01J 2208/00752: Feeding
- C07C 2529/70: of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- 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

## Abstract

Systems and methods are provided for oligomerization of olefins to distillate boiling range products while also recycling naphtha boiling range olefins as part of the feed. By performing the olefin oligomerization while also recycling naphtha boiling range olefins, it has been discovered that the resulting distillate boiling range products can have an unexpected improvement in diesel combustion quality, such as an unexpected improvement in cetane rating. In order to manage coke formation and maintain consistent activity profile for the oligomerization catalyst, the reaction can be performed in a moving bed reactor. Additional temperature control can be maintained by the recycling of the naphtha boiling range portions of the oligomerization product back to the reactor.

## Claims

### Claim 1

A method for upgrading a feed to form distillate boiling range compounds, comprising:
passing a catalyst flow comprising an olefin oligomerization catalyst into a first moving bed reactor of a plurality of serially connected moving bed reactors, the olefin oligomerization catalyst comprising a 1-D 10-member ring zeolite;
exposing an olefin-containing feed comprising C3-C8 olefins and a recycle stream comprising at least 20 wt % C5+ olefins to the catalyst flow in the plurality of moving bed reactors under olefin oligomerization conditions to form an oligomerized effluent, the olefin oligomerization conditions comprising substantially adiabatic operation of the plurality of moving bed reactors and an average reactor temperature of 170° C.-190° C.;
separating the oligomerized effluent to form a distillate boiling range fraction and one or more lower boiling fractions, the one or more lower boiling fractions comprising the recycle stream;
wherein exposing the olefin-containing feed and the recycle stream to the catalyst flow in the plurality of serially connected moving bed reactors comprises:
passing the catalyst flow comprising a catalyst into a first moving bed reactor of the plurality of serially connected moving bed reactors;
exposing the feed and the recycle stream to the catalyst flow in the first moving bed reactor under first olefin oligomerization conditions to form a partially reacted effluent, a temperature differential between the first reactor feed inlet and the first reactor effluent outlet being 85° C. or less;
stripping the catalyst flow with a first stripping fluid to separate at least a portion of the first partially reacted effluent from the catalyst flow, the at least a portion of the first partially reacted effluent comprising a liquid phase effluent portion and a vapor phase effluent portion;
passing the stripped catalyst flow into a second moving bed reactor of the plurality of serially connected moving bed reactors;
passing the liquid phase effluent portion into the second moving bed reactor as a substantially axial flow; and
exposing the vapor phase effluent portion to the stripped catalyst flow in the presence of the liquid effluent portion in the second moving bed reactor under second olefin oligomerization conditions to form the oligomerized effluent.

### Claim 2 (depends on 1)

The method of claim 1, wherein the olefin oligomerization conditions comprise a temperature differential across a moving bed reactor of 85° C. or less.

### Claim 3 (depends on 1)

The method of claim 1, wherein the olefin oligomerization catalyst comprises ZSM-48.

### Claim 4 (depends on 1)

The method of claim 1, wherein the olefin-containing feed comprises 60 wt % or more of C3-C5 olefins relative to a weight of olefins in the olefin-containing feed.

### Claim 5 (depends on 1)

The method of claim 1, wherein the olefin-containing feed comprises 5.0 wt % or less of C2 olefins relative to a weight of olefins in the olefin-containing feed, or wherein the olefin-containing feed comprises 5.0 wt % or less of water relative to a weight of the olefin-containing feed, or a combination thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein exposing the olefin-containing feed and the recycle stream to the catalyst flow comprises exposing the olefin-containing feed, the recycle stream, and a non-reactive co-feed to the catalyst flow.

### Claim 7 (depends on 6)

The method of claim 6, wherein a volume ratio of the recycle stream to the non-reactive co-feed is between 0.2 and 10.

### Claim 8 (depends on 1)

The method of claim 1, wherein the recycle stream comprises 90 wt % or more of 177° C.-compounds.

### Claim 9 (depends on 1)

The method of claim 1, wherein the recycle stream comprises 90 wt % or more of compounds having a boiling range of 30° C. to 177° C.

### Claim 10 (depends on 1)

The method of claim 1, wherein the recycle stream comprises 20 wt % or more of olefins relative to a weight of the recycle stream.

### Claim 11 (depends on 1)

The method of claim 1, wherein the recycle stream comprises 20 wt % or more of C5+ olefins relative to a weight of the recycle stream.

### Claim 12 (depends on 1)

The method of claim 1, wherein the recycle stream comprises 20 wt % or more of C6+ olefins relative to a weight of the recycle stream.

### Claim 13 (depends on 1)

The method of claim 1, wherein a molar ratio of olefins in the olefin-containing feed to olefins in the recycle stream is 0.5 to 2.0.

### Claim 14 (depends on 1)

The method of claim 1, wherein the olefin oligomerization conditions comprise an olefin partial pressure in the first moving bed reactor of 200 psig to 300 psig (1.4 MPa-g to 2.1 MPa-g).

### Claim 15 (depends on 1)

The method of claim 1, wherein the olefin oligomerization conditions comprise a partial pressure of olefins from the feed in the first moving bed reactor of 200 psig to 300 psig (1.4 MPa-g to 2.1 MPa-g).

### Claim 16 (depends on 1)

The method of claim 1, further comprising:
separating spent catalyst from the second effluent; and
passing the spent catalyst into a regenerator to form regenerated catalyst,
wherein at least a portion of the catalyst flow comprises regenerated catalyst.

### Claim 17 (depends on 1)

The method of claim 1, wherein the stripped catalyst flow into the second moving bed reactor forms a catalyst bed having a top surface comprising one or more cones at an angle of repose of the catalyst in the stripped catalyst flow, and wherein passing the liquid phase effluent portion into the second moving bed reactor comprises contacting at least a portion of the liquid phase effluent portion with the one or more cones.

### Claim 18 (depends on 1)

The method of claim 1, wherein the vapor flow within the second moving bed reactor comprises an axial vapor flow, or wherein the vapor flow within the second moving bed reactor comprises a radial vapor flow.

### Claim 19 (depends on 1)

The method of claim 1, wherein the plurality of serially connected moving bed reactors comprises a vertical stack, and wherein the stripped catalyst flow is passed into the second reactor without passing through a catalyst flow controller.