# US 11,306,043 B2 · Method for preparing paraffin

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- Number: US 11,306,043 B2
- Document ID: US11306043B2
- Status: Granted
- Kind: B2
- Application number: 16/959,305
- Filed: 2018-11-09
- Published: 2020-11-26
- Granted: 2022-04-19
- Earliest claimed: 2018-01-02
- Assignees: SK Innovation Co., Ltd.; SK Global Chemical Co., Ltd.
- Applicants: SK Innovation Co., Ltd.; SK Global Chemical Co., Ltd.
- Inventors: Sungreal Son; Jisun Choi; Chansaem Park; Hyo Seung Park; In Hyoup Song; Woo Sung Jung; Jae Suk Choi; Daehyun Choo
- Web page: https://patentgrep.com/patent/US11306043B2

## CPC

- C07C 5/03: of non-aromatic carbon-to-carbon double bonds
- C10G 45/00: Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- B01J 21/04: Alumina
- B01J 23/755: Nickel
- C07C 7/04: by distillation
- C07C 7/12: by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
- C07C 7/14: by crystallisation; Purification or separation of the crystals
- C07C 9/22: with more than fifteen carbon atoms
- B01J 23/42: Platinum
- B01J 23/44: Palladium
- B01J 23/462: {Ruthenium}
- B01J 23/464: {Rhodium}
- C07C 2521/04: Alumina
- C07C 2523/42: Platinum
- C07C 2523/44: Palladium
- C07C 2523/46: Ruthenium, rhodium, osmium or iridium
- C07C 2523/755: Nickel
- C10G 2300/1088: Olefins
- 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
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

The present invention relates to a method for preparing paraffin, and can provide a method for preparing paraffin including a hydrogenation step of by-products of a process for preparing linear alpha olefins. Since the method for preparing paraffin of the present invention can convert the by-products of the process for preparing linear alpha olefins to paraffin at a high conversion ratio, it is possible to increase the added value of the by-products.

## Claims

### Claim 1

A preparation method of a paraffin, the method comprising:
performing a linear α-olefin preparation process to prepare a linear α-olefin and by-products comprising 30 to 95 mol % of a branched olefin, 0 to 50 mol % of a linear internal olefin, and a balance of other by-products comprising iso-paraffin, n-paraffin, naphthene, or a combination thereof, based on a total of 100 mol % of the by-products;
providing a feed comprising the by-products; and
hydrogenating the feed,
wherein the branched olefin comprise a C10 branched olefin and a C12 branched olefin, and
wherein the linear a-olefin preparation process comprises a step of oligomerizing an olefin monomer in the presence of a transition metal catalyst comprising an acetylacetonate-based ligand represented by the following Chemical Formula 2, and a heteroatom ligand having a P—C—C—P skeleton structure represented by the following Chemical Formula 3 or a P—N—P skeleton structure represented by the following Chemical Formula 4:
wherein
R46 to R48 are independently of one another hydrogen, a halogen, (C6-C20)aryl, (C6-C20)ar(C1-C10)alkyl, (C1-C10)alkyl, halo(C1-C10)alkyl, (C6-C20)ar(C2-C10)alkenyl, (C2-C10)alkenyl, (C6-C20)ar(C2-C10)alkynyl, (C2-C10)alkynyl, (C1-C10)alkoxy, (C6-C20)aryloxy, (C1-C10)alkylcarbonyloxy, (C2-C10)alkenylcarbonyloxy, (C2-C10)alkynylcarbonyloxy, (C3-C7)cycloalkyl, (C1-C10)alkylsilyl, (C2-C10)alkenylsilyl, fluorine-substituted (C2-C10)alkynylsilyl, (C6-C20)arylsilyl, (C3-C20)heteroaryl, or 5- to 7-membered heterocycloalkyl;
the aryl, aralkyl, alkyl, aralkenyl, alkenyl, aralkynyl, alkynyl, alkoxy, aryloxy, cycloalkyl, heteroaryl, and heterocycloalkyl of R46 to R48 may be further substituted by one or more selected from the group consisting of (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10)alkoxy, (C6-C20)aryl, (C6-C20)aryloxy, and halogens;
R51 to R54 are independently of one another (C6-C20)aryl, (C6-C20)ar(C1-C10)alkyl, (C6-C20)ar(C2-C10)alkenyl, (C6-C20)ar(C2-C10)alkynyl, (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10)alkoxy, (C6-C20)aryloxy, (C1-C10)alkoxycarbonyl, (C1-C10)alkylcarbonyloxy, (C2-C10)alkenylcarbonyloxy, (C2-C10)alkynylcarbonyloxy, aminocarbonyl, (C1-C10)alkylcarbonylamino, (C2-C10)alkenylcarbonylamino, (C2-C10)alkynylcarbonylamino, (C3-C7)cycloalkyl, thio(C1-C10)alkyl, thio(C2-C10)alkenyl, thio(C2-C10)alkynyl, (C1-C10)alkylsilyl, (C2-C10)alkenylsilyl, (C2-C10)alkynylsilyl, (C6-C20)arylsilyl, 5- to 7-membered heterocycloalkyl, or —NR61R62, and R61 and R62 are independently of each other (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C6-C20)aryl, di(C1-C10)alkylamino, di(C2-C10)alkenylamino, or di(C2-C10)alkynylamino;
the aryl, aralkyl, aralkenyl, aralkynyl, alkyl, alkenyl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkyl, heteroaryl, and heterocycloalkyl of R51 to R54 may be further substituted by one or more selected from the group consisting of (C1-C10)alkyl, (C2-C10)alkenyl, (C2-C10)alkynyl, (C1-C10)alkoxy, (C6-C20)aryloxy, di(C1-C10)alkylamino, di(C2-C10)alkenylamino and di(C2-C10)alkynylamino; and
R55 and R56 are independently of each other hydrocarbyl or substituted hydrocarbyl, or R55 and R56 may be bonded to each other via hydrocarbylene, substituted hydrocarbylene, heterohydrocarbylene, or substituted heterohydrocarbylene to form a ring.

### Claim 2 (depends on 1)

The preparation method of paraffin of claim 1, wherein the feed is directly hydrogenated.

### Claim 3 (depends on 1)

The preparation method of paraffin of claim 1, wherein the by-products include 60 to 95 mol % of the branched olefin and 1 to 20 mol % of the linear internal olefin.

### Claim 4 (depends on 1)

The preparation method of paraffin of claim 1, wherein the hydrogenating is performed in a trickle bed reactor.

### Claim 5 (depends on 4)

The preparation method of paraffin of claim 4, wherein the feed flows into the trickle bed reactor in a liquid phase, a space velocity (SV) at which the feed flows in is 0.1 to 4 h−1, and the SV is calculated by dividing an inflow rate (m3/h) of the liquid feed by a reaction volume (m3) in the trickle bed reactor.

### Claim 6 (depends on 1)

The preparation method of paraffin of claim 1, wherein the hydrogenating is performed at a temperature of 100 to 200° C. under a pressure of 10 to 100 kg/cm2g under a metal catalyst selected from the group consisting of nickel (Ni), platinum (Pt), palladium (Pd), rhodium (Rh), ruthenium (Ru), and an alloy containing two or more thereof.

### Claim 7 (depends on 1)

The preparation method of paraffin of claim 1, further comprising: after the hydrogenating, separating a prepared paraffin from a reaction product of the hydrogenation reaction.

### Claim 8 (depends on 1)

The preparation method of paraffin of claim 1, further comprising: after the hydrogenating, separating iso-paraffin from the prepared paraffin.

### Claim 9 (depends on 1)

The preparation method of paraffin of claim 1, further comprising: after the oligomerizing, introducing a catalyst deactivator to a reaction product of the oligomerization reaction.

### Claim 10 (depends on 9)

The preparation method of paraffin of claim 9, wherein the catalyst deactivator comprises an oxygen-containing inorganic material which is in a gaseous state at 25° C. and 1 atm, or an organic compound which includes one or more of functional groups containing at least one selected from the group consisting of H2O, 2-ethylhexanol, oxygen, phosphorus, nitrogen, and sulfur, and has a number average molecular weight of 400 or more.

### Claim 11 (depends on 10)

The preparation method of paraffin of claim 10, wherein the catalyst deactivator comprises an oxygen-containing inorganic material which is in a gaseous state at 25° C. and 1 atm; or an organic compound which includes one or more of functional groups containing at least one selected from the group consisting of oxygen, phosphorus, nitrogen, and sulfur, and has a number average molecular weight of 400 or more.

### Claim 12 (depends on 11)

The preparation method of paraffin of claim 11, wherein the oxygen-containing inorganic material is O2, CO2, CO, NO, NO2, N2O, N2O3, N2O4, N2O5, SO2, SO3, or a mixture thereof.