# US 10,118,167 B2 · Methods for regenerating sulfur-contaminated aromatization catalysts

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- Number: US 10,118,167 B2
- Document ID: US10118167B2
- Status: Granted
- Kind: B2
- Application number: 15/384,353
- Filed: 2016-12-20
- Published: 2018-06-21
- Granted: 2018-11-06
- Earliest claimed: 2016-12-20
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Ryan W. Snell
- Web page: https://patentgrep.com/patent/US10118167B2

## CPC

- B01J 29/90: Regeneration or reactivation
- B01J 23/42: Platinum
- B01J 23/58: with alkali- or alkaline earth metals
- B01J 27/10: Chlorides
- B01J 27/12: Fluorides
- B01J 27/138: with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
- B01J 29/62: Noble metals
- B01J 29/74: Noble metals
- B01J 35/615: {100-500 m2/g}
- B01J 35/633: {less than 0.5 ml/g}
- B01J 37/0018: {Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)}
- B01J 37/0201: {Impregnation}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/0213: {Preparation of the impregnating solution}
- B01J 37/06: Washing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/08: Heat treatment {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/24: Chlorinating
- B01J 37/26: Fluorinating
- B01J 37/30: Ion-exchange
- B01J 38/02: Heat treatment
- B01J 38/12: Treating with free oxygen-containing gas
- B01J 38/14: with control of oxygen content in oxidation gas
- B01J 38/48: Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J 38/54: halogen-containing
- B01J 38/64: using alkaline material; using salts
- C07C 5/325: {of the platinum group}
- C07C 5/417: {of the platinum group}
- C10G 35/095: containing crystalline alumino-silicates, e.g. molecular sieves {(C10G35/065 takes precedence)}
- C10G 45/70: with catalysts containing platinum group metals or compounds thereof
- B01J 2229/42: Addition of matrix or binder particles
- B01J 2229/64: in or on refractory materials
- C07C 2529/62: Noble metals
- C10G 2300/4081: Recycling aspects
- C10G 2400/30: Aromatics
- Y02P 20/52: using catalysts, e.g. selective catalysts
- Y02P 20/584: Recycling of catalysts
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- 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

Methods for regenerating a sulfur-contaminated catalyst are disclosed. Such methods may employ a step of washing the sulfur-contaminated catalyst with an aqueous solution containing an alkali metal, followed by contacting the washed catalyst with a halogen solution containing chlorine and fluorine.

## Claims

### Claim 1

A method for regenerating a sulfur-contaminated catalyst comprising a transition metal and a catalyst support, the method comprising:
(1) washing the sulfur-contaminated catalyst with an aqueous solution, the aqueous solution optionally comprising an alkali metal, to produce a washed catalyst; and
(2) contacting the washed catalyst with a halogen solution comprising chlorine and fluorine to produce a halogenated catalyst.

### Claim 2 (depends on 1)

The method of claim 1, wherein the aqueous solution comprises the alkali metal.

### Claim 3 (depends on 2)

The method of claim 2, wherein:
the transition metal comprises platinum;
the catalyst support comprises a KL-zeolite and a support matrix comprising alumina, silica, a mixed oxide thereof, or a mixture thereof; and
the sulfur-contaminated catalyst comprises:
from about 100 ppmw to about 1000 ppmw sulfur;
from about 0.05 wt. % to about 2 wt. % chlorine; and
from about 0.05 wt. % to about 2 wt. % fluorine.

### Claim 4 (depends on 3)

The method of claim 3, wherein the sulfur-contaminated catalyst contains less than about 0.1 wt. % of barium.

### Claim 5 (depends on 1)

The method of claim 1, wherein the aqueous solution comprises a salt of potassium, rubidium, cesium, or any combination thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein:
step (1) comprises from 2 to 8 washing cycles;
each washing cycle is conducted independently at a washing temperature in a range from about 20° C. to about 95° C. and for a time period in a range from about 5 minutes to about 2 hours; and
each washing cycle is conducted independently with either an aqueous solution comprising the alkali metal or an aqueous solution that does not contain an alkali metal.

### Claim 7 (depends on 6)

The method of claim 6, wherein a ratio of the weight of the aqueous solution to the weight of the sulfur-contaminated catalyst in each washing cycle independently is in a range from about 0.4:1 to about 10:1.

### Claim 8 (depends on 1)

The method of claim 1, wherein the halogen solution comprises a chlorine-containing compound, a fluorine-containing compound, and water.

### Claim 9 (depends on 1)

The method of claim 1, wherein the halogen solution comprises:
from about 0.01 wt. % to about 10 wt. % chlorine; and
from about 0.01 wt. % to about 10 wt. % fluorine.

### Claim 10 (depends on 1)

The method of claim 1, wherein the halogenated catalyst comprises:
from about 0.5 wt. % to about 2 wt. % platinum;
a catalyst support comprising a KL-zeolite and a support matrix comprising alumina, silica, a mixed oxide thereof, or a mixture thereof;
from about 0.5 wt. % to about 5 wt. % chlorine; and
from about 0.5 wt. % to about 5 wt. % fluorine.

### Claim 11 (depends on 10)

The method of claim 10, wherein the halogenated catalyst contains less than about 0.1 wt. % of barium.

### Claim 12 (depends on 1)

The method of claim 1, wherein the method removes at least about 25% of the sulfur from the sulfur-contaminated catalyst, based on the difference in the ppmw of sulfur in the halogenated catalyst and the sulfur-contaminated catalyst.

### Claim 13 (depends on 1)

The method of claim 1, further comprising a drying step after step (2), a calcination step after step (2), or both a drying step and a calcination step after step (2).

### Claim 14 (depends on 1)

The method of claim 1, further comprising a carbon burn step before step (1), after step (1), or both before and after step (1).

### Claim 15 (depends on 1)

The method of claim 1, wherein the halogenated catalyst is characterized by:
a TEOR (end of run temperature) within about 70° F. of the TEOR of a fresh reference catalyst;
a FR (fouling rate) in a range from about 0.05° F./hr to about 0.6° F./hr; and
an aromatics selectivity in a range from about 0.88 to about 0.94.

### Claim 16 (depends on 1)

The method of claim 1, further comprising a reducing step after the halogenation step, the reducing step comprising contacting the halogenated catalyst with a reducing gas stream comprising molecular hydrogen to produce a reactivated catalyst.

### Claim 17 (depends on 16)

The method of claim 16, wherein the reactivated catalyst is characterized by:
a TEOR (end of run temperature) within about 55° F. of the TEOR of a fresh reference catalyst;
a FR (fouling rate) in a range from about 0.1° F./hr to about 0.5° F./hr; and
an aromatics selectivity in a range from about 0.89 to about 0.94.

### Claim 18

A reforming method comprising:
(A) contacting a hydrocarbon feed with an aromatization catalyst comprising a transition metal and a catalyst support under reforming conditions in a reactor system to produce an aromatic product;
(B) contacting a sulfur-contaminated hydrocarbon feed with the aromatization catalyst for a time period sufficient to form a sulfur-contaminated catalyst;
(C) washing the sulfur-contaminated catalyst with an aqueous solution to produce a washed catalyst, the aqueous solution optionally comprising an alkali metal; and
(D) contacting the washed catalyst with a halogen solution comprising chlorine and fluorine to produce a halogenated catalyst.

### Claim 19 (depends on 18)

The method of claim 18, wherein the reforming method is an in situ process.

### Claim 20 (depends on 18)

The method of claim 18, wherein at least one of steps (C) and (D) is performed in a vessel external to the reactor system.

### Claim 21 (depends on 18)

The method of claim 18, wherein:
the transition metal comprises platinum;
the catalyst support comprises a KL-zeolite and a support matrix comprising alumina, silica, a mixed oxide thereof, or a mixture thereof; and
the sulfur-contaminated catalyst comprises:
from about 100 ppmw to about 1000 ppmw sulfur;
from greater than 0 wt. % to about 5 wt. % chlorine; and
from greater than 0 wt. % to about 5 wt. % fluorine.

### Claim 22 (depends on 21)

The method of claim 21, wherein the sulfur-contaminated catalyst contains less than about 0.1 wt. % of barium.

### Claim 23 (depends on 21)

The method of claim 21, wherein the aqueous solution comprises a salt of potassium, rubidium, cesium, or any combination thereof.

### Claim 24 (depends on 18)

The method of claim 18, wherein the halogenated catalyst comprises:
from about 0.5 wt. % to about 2 wt. % platinum;
a catalyst support comprising a KL-zeolite and a support matrix comprising alumina, silica, a mixed oxide thereof, or a mixture thereof;
from about 0.5 wt. % to about 5 wt. % chlorine; and
from about 0.5 wt. % to about 5 wt. % fluorine.

### Claim 25

A method for regenerating a sulfur-contaminated catalyst comprising a transition metal and a catalyst support, the method comprising:
(1) washing the sulfur-contaminated catalyst with an aqueous solution, the aqueous solution optionally comprising an alkali metal, to produce a washed catalyst;
(2) contacting the washed catalyst with a halogen solution comprising chlorine and fluorine to produce a halogenated catalyst; and
(3) drying and calcining the halogenated catalyst to produce a regenerated catalyst.

### Claim 26 (depends on 25)

The method of claim 25, wherein:
the transition metal comprises platinum; and
the catalyst support comprises a KL-zeolite and a support matrix comprising alumina, silica, a mixed oxide thereof, or a mixture thereof.

### Claim 27 (depends on 26)

The method of claim 26, wherein the aqueous solution comprises potassium.

### Claim 28 (depends on 26)

The method of claim 26, wherein the halogen solution comprises a chlorine-containing compound, a fluorine-containing compound, and water.

### Claim 29 (depends on 26)

The method of claim 26, wherein the method removes from about 25% to about 95% of the sulfur from the sulfur-contaminated catalyst, based on the difference in the ppmw of sulfur in the regenerated catalyst and the sulfur-contaminated catalyst.

### Claim 30 (depends on 26)

The method of claim 26, wherein:
the sulfur-contaminated catalyst comprises:
at least about 100 ppmw sulfur; and
less than about 0.1 wt. % of barium; and
the regenerated catalyst comprises:
from about 0.5 wt. % to about 2 wt. % platinum;
from about 0.5 wt. % to about 5 wt. % chlorine; and
from about 0.5 wt. % to about 5 wt. % fluorine.

### Claim 31 (depends on 26)

The method of claim 26, wherein:
drying comprises subjecting the halogenated catalyst to a drying temperature in a range from about 15° C. to about 200° C. at a sub-atmospheric pressure; and
calcining comprises subjecting the halogenated catalyst to a calcination temperature in a range from about 200° C. to about 800° C. for a time period in a range from about 30 minutes to about 8 hours.

### Claim 32 (depends on 26)

The method of claim 26, wherein the regenerated catalyst is characterized by:
a FR (fouling rate) in a range from about 0.05° F./hr to about 0.6° F./hr; and
an aromatics selectivity in a range from about 0.88 to about 0.94.

### Claim 33 (depends on 26)

The method of claim 26, further comprising a reducing step after the drying and calcining step, the reducing step comprising contacting the regenerated catalyst with a reducing gas stream comprising molecular hydrogen to produce a reactivated catalyst; wherein the reactivated catalyst is characterized by a FR (fouling rate) in a range from about 0.1° F./hr to about 0.5° F./hr, and an aromatics selectivity in a range from about 0.89 to about 0.94.

### Claim 34

A method for regenerating a sulfur-contaminated catalyst comprising a transition metal and a catalyst support, the method comprising:
(a) washing the sulfur-contaminated catalyst with an aqueous solution, the aqueous solution optionally comprising an alkali metal, to produce a washed catalyst;
(b) contacting the washed catalyst with a decoking gas stream comprising oxygen to produce a decoked catalyst containing less than about 1 wt. % carbon; and
(c) contacting the decoked catalyst with a halogen solution comprising chlorine and fluorine to produce a halogenated catalyst.

### Claim 35 (depends on 34)

The method of claim 34, wherein step (b) is conducted at a peak decoking temperature in a range from about 150° C. to about 600° C.

### Claim 36 (depends on 34)

The method of claim 34, wherein:
the transition metal comprises platinum;
the catalyst support comprises a KL-zeolite and a support matrix comprising alumina, silica, a mixed oxide thereof, or a mixture thereof;
the sulfur-contaminated catalyst comprises:
at least about 100 ppmw sulfur; and
less than about 0.1 wt. % of barium; and
the halogenated catalyst comprises:
from about 0.1 wt. % to about 10 wt. % platinum;
from about 0.1 wt. % to about 10 wt. % chlorine; and
from about 0.1 wt. % to about 10 wt. % fluorine.

### Claim 37 (depends on 36)

The method of claim 36, wherein:
the aqueous solution comprises a salt of potassium, rubidium, cesium, or any combination thereof; and
the halogen solution comprises a chlorine-containing compound, a fluorine-containing compound, and water.

### Claim 38 (depends on 36)

The method of claim 36, wherein the method removes from about 25% to about 95% of the sulfur from the sulfur-contaminated catalyst, based on the difference in the ppmw of sulfur in the halogenated catalyst and the sulfur-contaminated catalyst.

### Claim 39 (depends on 36)

The method of claim 36, further comprising a step of drying and calcining the halogenated catalyst to produce a regenerated catalyst.

### Claim 40 (depends on 39)

The method of claim 39, further comprising a reducing step, the reducing step comprising contacting the regenerated catalyst with a reducing gas stream comprising molecular hydrogen to produce a reactivated catalyst.