# US 10,479,740 B2 · Process to prepare propylene

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- Number: US 10,479,740 B2
- Document ID: US10479740B2
- Status: Granted
- Kind: B2
- Application number: 15/737,830
- Filed: 2016-06-23
- Published: 2019-01-03
- Granted: 2019-11-19
- Earliest claimed: 2015-06-23
- Assignees: Gasolfin B.V.
- Applicants: Gasolfin B.V.
- Inventors: Hubertus Wilhelmus Albertus Dries
- Web page: https://patentgrep.com/patent/US10479740B2

## CPC

- C07C 4/06: Catalytic processes {(C07C4/025 takes precedence)}
- B01J 21/04: Alumina
- B01J 21/08: Silica
- B01J 21/12: Silica and alumina
- B01J 23/26: Chromium
- B01J 23/42: Platinum
- B01J 23/626: {with tin}
- B01J 29/18: of the mordenite type
- B01J 29/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J 29/7007: {Zeolite Beta}
- B01J 29/7015: {CHA-type, e.g. Chabazite, LZ-218}
- B01J 29/85: Silicoaluminophosphates [SAPO compounds]
- B01J 35/19: {Catalysts containing parts with different compositions}
- B01J 37/28: Phosphorising
- C07C 5/3337: {of the platinum group}
- C07C 5/48: with oxygen as an acceptor
- C10G 7/08: Azeotropic or extractive distillation (refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents C10G21/00)
- C10G 11/05: Crystalline alumino-silicates, e.g. molecular sieves
- C10G 11/10: with stationary catalyst bed
- C10G 11/18: according to the "fluidised-bed" technique
- C10G 35/04: Catalytic reforming
- C10G 35/065: {containing crystalline zeolitic molecular sieves, other than aluminosilicates}
- C10G 35/095: containing crystalline alumino-silicates, e.g. molecular sieves {(C10G35/065 takes precedence)}
- C10G 35/14: according to the "fluidised-bed" technique
- C07C 2521/04: Alumina
- C07C 2523/42: Platinum
- C07C 2523/62: with gallium, indium, thallium, germanium, tin or lead
- C07C 2529/40: of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C 2529/85: Silicoaluminophosphates (SAPO compounds)
- C10G 2300/1088: Olefins
- C10G 2300/1096: Aromatics or polyaromatics
- C10G 2300/4081: Recycling aspects
- C10G 2400/20: C2-C4 olefins
- Y02P 20/52: using catalysts, e.g. selective catalysts
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- 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

The invention is directed to a process to prepare propylene from a mixture of hydrocarbons by performing the following steps. (a) extracting aromatics from the mixture of hydrocarbons thereby obtaining a mixture of hydrocarbons poor in aromatics, (b) contacting the mixture obtained in step (a) with a heterogeneous cracking catalyst as present in a fixed bed thereby obtaining a cracked effluent, (c) separating propylene from the cracked effluent thereby also obtaining a higher boiling fraction, (d) recycling part of the higher boiling fraction to step (b) and at least 5 wt % of the higher boiling fraction to step (a).

## Claims

### Claim 1

A process to prepare propylene from a mixture of hydrocarbons by performing the following steps:
(a) extracting aromatics from the mixture of hydrocarbons thereby obtaining a resulting mixture of hydrocarbons poor in aromatics,
(b) contacting the resulting mixture obtained in step (a) with a mixture of a heterogenous cracking catalyst and a heterogeneous dehydrogenation catalyst in a fixed bed thereby obtaining a cracked effluent,
(c) separating propylene from the cracked effluent thereby also obtaining a higher boiling fraction, and
(d) recycling a first recycle stream comprising between 10 and 30 wt % of the higher boiling fraction to step (a) and a second recycle stream comprising a portion of the higher boiling fraction to step (b), wherein the first recycle stream and the second recycle stream each comprise aromatic compounds originating from the higher boiling fraction.

### Claim 2 (depends on 1)

The process according to claim 1, wherein the mixture of hydrocarbons comprises any one of:
(a) between 1 and 70 wt % olefins having 4 or more carbon atoms;
(b) between 1 and 20 wt % olefins having 4 or more carbon atoms; or
(c) a mixture of paraffins, olefins, naphthenes, and aromatic compounds comprising more than 90 wt % hydrocarbons boiling between 35 and 250° C.

### Claim 3 (depends on 2)

The process according to claim 2, wherein the mixture of hydrocarbons comprises a light straight run naphtha and/or a fraction isolated from an effluent of any one or more of the following processes: Fluid Catalytic Cracking, Catalytic Polymerization, Hydrotreating, Hydrocracking and Delayed Coking.

### Claim 4 (depends on 3)

The process according to claim 3, wherein the mixture of hydrocarbons comprises:
(a) a light straight run naphtha; or
(b) a fraction isolated from the effluent of a Fluid Catalytic Cracking process.

### Claim 5 (depends on 1)

The process according to claim 1, wherein step (b) is performed by contacting the resulting mixture obtained in step (a) with the heterogenous cracking catalyst to produce an intermediate mixture of hydrocarbons and contacting the intermediate mixture with the heterogenous dehydrogenation catalyst in the fixed bed to produce the cracked effluent from which propylene is separated in step (c).

### Claim 6 (depends on 5)

The process according to claim 5, wherein the heterogeneous dehydrogenation catalyst comprises any one or more of:
a. (i) a transition metal or a noble metal, (ii) one or more additive components, and (iii) a carrier;
b. an oxydehydrogenation catalyst; and
c. in that the one or more packed beds comprise a separate solid oxygen source catalyst particle.

### Claim 7 (depends on 6)

The process according to claim 6, wherein the transition metal is Cr or the noble metal Pt.

### Claim 8 (depends on 6)

The process according to claim 6, wherein the oxydehydrogenation catalyst, or the separate solid oxygen source catalyst particle, or both, comprises a reducible metal oxide of at least a transition metal.

### Claim 9 (depends on 1)

The process according to claim 1, wherein step (b) is performed at a temperature between 300 and 750° C. and an absolute pressure between 0.1 and 10 MPa and a Weight hourly space velocity (WHSV) higher than and including 50/hour.

### Claim 10 (depends on 9)

The process according to claim 9, wherein the temperature is between 450 and 600° C.,
wherein the absolute pressure is between 0.1 and 0.5 MPa, and wherein the Weight hourly space velocity (WHSV)is higher than 100/hour.

### Claim 11 (depends on 1)

The process according to claim 1, wherein in step (b) the resulting mixture obtained in step (a) is contacted with the mixture of the heterogenous cracking catalyst and the heterogenous dehydrogenation catalyst in the presence of dilution steam.

### Claim 12 (depends on 1)

The process according to claim 1, wherein the heterogeneous cracking catalyst comprises an acidic material.

### Claim 13 (depends on 12)

The process according to claim 12, wherein the acidic material is a molecular sieve, or an amorphous or semi-crystalline material chosen from the group of alumina, boehmite alumina, gamma alumina, theta alumina, silica alumina, silica-titania, silica-tungsten, silica phosphorous, and silica-alumina-phosphorous.

### Claim 14 (depends on 13)

The process according to claim 13, wherein the molecular sieve is selected from the structure types consisting of: BEA, CHA, MOR, MFI, MEL, IMF and TUN.

### Claim 15 (depends on 1)

The process according to claim 1, wherein the heterogeneous cracking catalyst:
a. further comprises a carrier which does not have strong acidic sites, or
b. does not comprise a molecular sieve and does comprise a material having strong acid sites.

### Claim 16 (depends on 1)

The process according to claim 1, wherein the heterogeneous cracking catalyst and the heterogeneous dehydrogenation catalyst are separate catalyst particles.

### Claim 17 (depends on 1)

The process according to claim 1, wherein the cracking catalyst and the dehydrogenation catalyst are present in one packed bed.

### Claim 18 (depends on 1)

The process according to claim 1, wherein resulting the mixture obtained in step
(a) has an aromatics content of less than 20 wt %.