# US 9,040,765 B2 · Methods and apparatuses for isomerization of paraffins

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- Number: US 9,040,765 B2
- Document ID: US9040765B2
- Status: Granted
- Kind: B2
- Application number: 13/434,703
- Filed: 2012-03-29
- Published: 2013-10-03
- Granted: 2015-05-26
- Earliest claimed: 2012-03-29
- Assignees: Uop LLC
- Applicants: Lynn H. Rice
- Inventors: Lynn H. Rice
- Web page: https://patentgrep.com/patent/US9040765B2

## CPC

- C10G 45/60: characterised by the catalyst used
- C10G 45/58: to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins (C10G32/00 takes precedence; improving or increasing the octane number or aromatic content of naphtha C10G35/00)
- C10G 2300/1081: Alkanes
- C10G 2300/70: Catalyst aspects
- C10G 2300/703: Activation
- 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

Embodiments of methods and apparatuses for isomerization of paraffins are provided. In one example, a method comprises the steps of separating an isomerization effluent into a product stream that comprises branched paraffins and a stabilizer vapor stream that comprises HCl, H2, and C6-hydrocarbons. C6-hydrocarbons are removed from the stabilizer overhead vapor stream to form a HCl and H2-rich stream. An isomerization catalyst is activated using at least a portion of the HCl and H2-rich stream to form a chloride-promoted isomerization catalyst. A paraffin feed stream is contacted with the chloride-promoted isomerization catalyst in the presence of hydrogen for isomerization of the paraffins.

## Claims

### Claim 1

A method for isomerization of paraffins, the method comprising the steps of:
separating an isomerization effluent into a product stream that comprises branched and un-branched paraffins and a stabilizer vapor stream that comprises HCl, H2, and C6-hydrocarbons;
separating the stabilizer vapor stream into a net gas vapor comprising HCl, H2, and C5-hydrocarbons and a liquid stream that comprises C2- and C3+ hydrocarbon;
separating the net gas vapor into a C5-hydrocarbons-rich phase and a HCl and H2-rich stream in a chiller;
activating an isomerization catalyst using at least a portion of the HCl and H2-rich stream to form a chloride-promoted isomerization catalyst, wherein at least the portion of the HCl and H2-rich stream is directly recycled from separation of the net gas vapor to activating the isomerization catalyst; and
contacting a paraffin feed stream with the chloride-promoted isomerization catalyst in the presence of hydrogen for isomerization of the paraffins.

### Claim 2 (depends on 1)

The method of claim 1, wherein the step of separating the isomerization effluent comprises separating the isomerization effluent at a stabilizer temperature of from about 65 to about 165° C.

### Claim 3 (depends on 1)

The method of claim 1, wherein the step of forming the net gas vapor comprises separating the stabilizer vapor stream and the C5-hydrocarbons-rich phase at a separation temperature of from about 30 to about 60° C.

### Claim 4 (depends on 3)

The method of claim 3, wherein the step of forming the net gas vapor comprises separating the stabilizer vapor stream and the C5-hydrocarbons-rich phase at a pressure of from about 700 to about 2,100 kPa gauge.

### Claim 5 (depends on 1)

The method of claim 1, further comprising the step of:
dividing the HCl and H2-rich stream into a recycle portion and a treatment portion, wherein the step of activating comprises activating the isomerization catalyst using the recycle portion of the HCl and H2-rich stream.

### Claim 6 (depends on 5)

The method of claim 5, further comprising the step of:
neutralizing the treatment portion of the HCl and H2-rich stream with a caustic.

### Claim 7 (depends on 6)

A method of claim 6, further comprising the step of:
heating the treatment portion of the HCl and H2-rich stream to a temperature of from about 30 to about 70° C. prior to the step of neutralizing.

### Claim 8 (depends on 1)

The method of claim 1, wherein the step of separating the net gas vapor comprises separating the net gas vapor at a separation temperature of from about −40 to about 5° C.

### Claim 9 (depends on 1)

The method of claim 1, wherein the step of separating the net gas vapor comprises separating the net gas vapor at a separation pressure of from about 700 to about 2,100 kPa gauge.

### Claim 10 (depends on 1)

The method of claim 1, further comprising the step of:
separating at least a portion of the liquid stream into a C2-hydrocarbon-rich stream and a LPG stream that comprises C3 and C4 hydrocarbons.

### Claim 11 (depends on 10)

The method of claim 10, wherein the step of separating the at least a portion of the liquid stream comprises separating the at least the portion of the liquid stream at a separation temperature of from about 65 to about 120° C.

### Claim 12 (depends on 10)

The method of claim 10, wherein the step of separating the at least a portion of the liquid stream comprises separating the at least the portion of the liquid stream at a separation pressure of from about 1,000 to about 2,000 kPa gauge.

### Claim 13 (depends on 10)

The method of claim 10, further comprising the step of:
combining the C2-hydrocarbon-rich stream with the stabilizer vapor stream to form a combined stream, and wherein the step of forming the net gas vapor comprises separating the combined stream and the C5-hydrocarbons-rich phase into the net gas vapor and the liquid stream.

### Claim 14

A method for isomerization of paraffins, the method comprising the steps of:
activating an isomerization catalyst in a reactor operating at isomerization conditions to form a chloride-promoted isomerization catalyst, wherein the isomerization catalyst is activated with HCl generated from a chloride promoter stream and from a HCl and H2-rich recycle stream;
contacting a paraffin feed stream comprising un-branched paraffins with the chloride-promoted isomerization catalyst in the reactor in the presence of hydrogen to form an isomerization effluent comprising branched paraffins, HCl, H2, and other C7-hydrocarbons;
introducing the isomerization effluent to a stabilizer at stabilization conditions to form a product stream that comprises branched and un-branched paraffins and a stabilizer vapor stream that comprises HCl, H2, and C6-hydrocarbons;
separating the stabilizer vapor stream in a separator at first separation conditions into a net gas vapor that comprises HCl, H2 and C5-hydrocarbons and a liquid stream that comprises C2- and C3+ hydrocarbons;
separating the net gas vapor in a chiller at second separation conditions into a C5-hydrocarbons-rich phase and a HCl and H2-rich stream; and
directly recycling at least a portion of the HCl and H2-rich stream back to the reactor as the HCl and H2-rich recycle stream.

### Claim 15 (depends on 14)

The method of claim 14, further comprising the steps of:
dividing the HCl and H2-rich stream into a recycle portion and a treatment portion, wherein the step of recycling comprises recycling the recycle portion of the HCl and H2-rich stream back to the reactor; and
introducing the treatment portion of the HCl and H2-rich stream to a scrubber to neutralize HCl with a caustic.

### Claim 16 (depends on 14)

The method of claim 14, wherein the step of separating the net gas vapor comprises introducing the net gas vapor to the chiller for indirect heat exchange with a refrigerant.

### Claim 17 (depends on 16)

The method of claim 16, wherein the step of introducing the net gas vapor comprises cooling the net gas vapor to a temperature of from about −40 to about 5° C.

### Claim 18 (depends on 14)

The method of claim 14, further comprising the step of:
separating at least a portion of the liquid stream in a LPG stripper at third separation conditions into a C2-hydrocarbon-rich stream and a LPG stream that comprises C3 and C4 hydrocarbons.

### Claim 19 (depends on 18)

The method of claim 18, further comprising the step of:
introducing the C2-hydrocarbon-rich stream to the stabilizer vapor stream upstream of the separator to form a combined stream, and wherein the step of forming the net gas vapor comprises separating the combined stream and the C5-hydrocarbons-rich phase in the separator into the net gas vapor and the liquid stream.