# US 2014/0155665 A1 · Steamcracking bio-naphtha produced from complex mixtures of natural occurring fats and oils

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- Number: US 2014/0155665 A1
- Document ID: US20140155665A1
- Status: Published application
- Kind: A1
- Application number: 14/095,530
- Filed: 2013-12-03
- Published: 2014-06-05
- Earliest claimed: 2009-07-27
- Assignees: Total Petrochemicals Research Feluy
- Applicants: Total Petrochemicals Research Feluy
- Inventors: Walter Vermeiren; Nicolas Van Gyseghem
- Web page: https://patentgrep.com/patent/US20140155665A1

## CPC

- C10G 3/50: {in the presence of hydrogen, hydrogen donors or hydrogen generating compounds}
- C07C 1/2078: {by a transformation in which at least one -C(=O)-O- moiety is eliminated}
- C07C 1/22: by reduction
- C07C 4/04: Thermal processes {(C07C4/025 takes precedence)}
- C10G 3/42: {Catalytic treatment}
- C10G 3/45: {containing iron group metals or compounds thereof}
- C10G 3/46: {in combination with chromium, molybdenum, tungsten metals or compounds thereof}
- C10G 3/49: {containing crystalline aluminosilicates, e.g. molecular sieves}
- C10G 9/00: Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C11B 3/12: by distillation
- C11B 3/14: with the use of indifferent gases or vapours, e.g. steam
- C11B 13/02: from soap stock
- C11C 3/12: by hydrogenation
- C10G 2300/1007: Used oils
- C10G 2300/1014: of vegetal origin
- C10G 2300/1018: of animal origin
- C10G 2300/805: Water
- C10G 2300/807: Steam
- C10G 2400/02: Gasoline
- C10G 2400/20: C2-C4 olefins
- C10G 2400/22: Higher olefins
- C10G 2400/30: Aromatics
- Y02P 30/20: using bio-feedstock
- 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
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C11B: PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES (drying-oils C09F)
- C11C: FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

A process for making a bio-naphtha and optionally bio-propane from a complex mixture of natural occurring fats & oils, wherein said complex mixture is subjected to a refining treatment for removing the major part of non-triglyceride and non-fatty acid components, thereby obtaining refined fats & oils; said refined fats & oils are transformed into linear or substantially linear paraffin's as the bio-naphtha by an hydrodeoxygenation or from said refined fats & oils are obtained fatty acids that are transformed into linear or substantially linear paraffin's as the bio-naphtha by hydrodeoxygenation or decarboxylation of the free fatty acids or from said refined fats & oils are obtained fatty acids soaps that are transformed into linear or substantially linear paraffin's as the bio-naphtha by decarboxylation of the soaps.

## Claims

### Claim at position 1

1-11. (canceled)

### Claim 12

A process of using a bio-naphtha as a direct feedstock of a steamcracker comprising:
steamcracking a hydrocarbon feedstock comprising bio-naphtha, wherein the bio-naptha is obtained from a complex mixture of natural occurring fats & oils, wherein said complex mixture is subjected to a refining treatment for removing a major part of non-triglyceride and non-fatty acid components, thereby obtaining refined fats & oils; and wherein:
said refined fats & oils are transformed into linear or substantially linear paraffins as the bio-naphtha by hydrodeoxygenation; or
from said refined fats & oils are obtained fatty acids that are transformed into linear or substantially linear paraffins as the bio-naphtha by hydrodeoxygenation or decarboxylation of free fatty acids; or
from said refined fats & oils are obtained fatty acid soaps that are transformed into linear or substantially linear paraffins as the bio-naphtha by decarboxylation of the fatty acid soaps;
wherein the hydrocarbon feedstock optionally comprises bio-propane, or wherein the bio-naphtha is optionally blended with at least a conventional feedstock selected among LPG, naphtha and gasoil;
obtaining cracked products including bio-ethylene, bio-propylene, bio-butadiene, bio-isoprene, bio-cyclopentadiene and bio-piperylenes, bio-benzene, bio-toluene, bio-xylene and bio-gasoline;
wherein in the steamcracking process the hydrocarbon feedstock is mixed with steam in a ratio of 0.3 to 0.45 kg steam per kg hydrocarbon feedstock.

### Claim 13 (depends on 12)

The process of claim 12, wherein the hydrocarbon feedstock is mixed with steam in a ratio of 0.3 to 0.4 kg steam per kg hydrocarbon feedstock.

### Claim 14 (depends on 12)

The process of claim 12, wherein the hydrocarbon feedstock is heated up to a temperature of 750-950° C. and steamcracked for a residence time of 0.05 to 0.5 seconds.

### Claim 15 (depends on 12)

The process of claim 12, wherein the hydrocarbon feedstock is heated up to a temperature of 750-950° C. and steamcracked for a residence time of 0.05 to 0.15 seconds.

### Claim 16 (depends on 12)

The process of claim 12, wherein the obtained cracked products exhibit an ethylene to methane weight ratio of at least 3.

### Claim 17 (depends on 12)

The process of claim 12, wherein the bio-propane is also obtained from the complex mixture of natural occurring fats & oils.

### Claim 18 (depends on 12)

The process of claim 12, wherein the complex mixture of natural occurring fats & oils is selected among vegetable oils and animal fats.

### Claim 19 (depends on 12)

The process of claim 12, wherein the fatty acids are obtained by physical refining, including a steam distillation or vacuum distillation of fats & oils;
or the fatty acids are obtained by hydrolysis of triglycerides of the fats & oils;
or the fatty acids are obtained by acidulation of soaps.

### Claim 20 (depends on 12)

The process of claim 12, wherein the fatty acid soaps are obtained by:
saponification of fats & oils;
or by the chemical refining, including neutralisation of free fatty acids, present in the fats & oils;
or neutralisation of fatty acids, obtained from hydrolysis of the fats & oils.

### Claim 21 (depends on 12)

The process of claim 12, wherein the refined fats & oils are transformed into linear or substantially linear paraffins as the bio-naphtha together with the bio-propane by hydrodeoxygenation in the presence of hydrogen and at least one catalyst selected among Ni, Mo, Co, NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW oxides or sulphides, optionally supported on high surface area carbon, alumina, silica, titania or zirconia.

### Claim 22 (depends on 21)

The process of claim 21, wherein the hydrodeoxygenation is carried out at a temperature from 200 to 500° C., under a pressure from 1 MPa to 10 MPa and with a hydrogen to feed ratio from 100 to 2000 Nl/l.

### Claim 23 (depends on 12)

The process of claim 12, wherein the refined fats & oils are transformed into linear or substantially linear paraffins as the bio-naphtha by hydrolysis of the fats & oils into glycerol and fatty acids, removal of the glycerol;
or by physical refining, including a steam distillation or a vacuum distillation of fats & oils;
or by acidulation of soaps and hydrodeoxygenation or decarboxylation of the fatty acids, said hydrodeoxygenation or decarboxylation being conducted in the presence of hydrogen and at least one catalyst selected among Ni, Mo, Co, NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW and CoMoW oxides or sulphides, optionally supported on high surface area carbon, alumina, silica, titania or zirconia; or group 10 and group 11 metals or alloy mixtures supported on high surface area carbon, magnesia, zinc-oxide, spinels, perovskites, calciumsilicates, alumina, silica or silica-alumina or mixtures of the latter.

### Claim 24 (depends on 12)

The process of claim 12, wherein the refined fats & oils are transformed into linear or substantially linear paraffins as the bio-naphtha by hydrolysis of the fats & oils into glycerol and fatty acids, removal of the glycerol;
or by physical refining, including a steam distillation or a vacuum distillation of fats & oils;
or by acidulation of soaps and decarboxylation of the fatty acids that is carried out on basic oxides, alkaline earth oxides, lanthanide oxides, zinc-oxide, spinels, perovskites, calciumsilicates, either as bulk material or dispersed on neutral or basic carriers, on basic zeolites.

### Claim 25 (depends on 12)

The process of claim 12, wherein the hydrodeoxygenation is carried out at a temperature from 200 to 500° C., under a pressure from 1 MPa to 10 MPa and with a hydrogen to feedstock ratio from 100 to 2000 Nl/l;
or wherein the decarboxylation is carried out at a temperature from 100 to 550° C., under a pressure from 0.1 MPa to 10 MPa and with a hydrogen to feedstock ratio from 0 to 2000 Nl/l.

### Claim 26 (depends on 12)

The process of claim 12, wherein the decarboxylation of the fatty acid soaps is carried out at from 100 to 550° C. under pressure from 0.1 Mpa to 10 Mpa and in presence of water.

### Claim 27 (depends on 12)

The process of claim 12, wherein the decarboxylation of the fatty acid soaps is carried out with a water to feedstock ratio of at least 1 mole water per mole of fatty acid soap.

### Claim 28 (depends on 12)

The process of claim 12, wherein the complex mixture of natural occurring fats & oils is selected among inedible oils, highly saturated oils, waste food oils, by-products of the refining of vegetable oils, and mixtures thereof.

### Claim 29 (depends on 12)

The process of claim 12, wherein the non-triglyceride and non-fatty acid components comprise free fatty acids.

### Claim 30

A process comprising:
steamcracking a hydrocarbon feedstock comprising bio-naphtha, wherein the hydrocarbon feedstock is mixed with steam in a ratio of 0.3 to 0.45 kg steam per kg hydrocarbon feedstock during the steamcracking;
wherein the bio-naphtha is obtained from a complex mixture of natural occurring fats & oils, wherein said complex mixture is subjected to a refining treatment for removing a major part of non-triglyceride and non-fatty acid components, thereby obtaining refined fats & oils, and wherein the non-triglyceride and non-fatty acid components comprise free fatty acids.