66 SUSTAINABILITY
TABLE 1: Comparison of bio-based alkanes Biobased Alkanes
Origin
Dodecane Tetradecane Coconut Undecane Tridecane
Paraffins C13-C15 & C15-C19 linear/branched Palm
Biotechnological Isododecane
Biotechnological Hémisqualane
Olive Squalane
Biotechnological Squalane
Sugar Beet Sugarcane Olive Sugarcane myristic (C14) alcohol of RSPO4
INCI
Palm kernel Undecane (and) Tridecane
C13-C15 Alkane C15-C19 Alkane
Isododecane
C13-C15 Alkane Hydrogenated Farnesene
Squalane Squalane
certified palm
kernel oil. In the first three steps of the process, this cut is produced according to the same chemical sequence as the previous one but applied to palm kernel oil (Figure 1, reaction 2). However, the rest of the process is different
because it consists in hydrogenolysing a C12-C14 alcohols cut into alkanes.5
The
hydrogenolysis reaction leads to the breaking of C-O and C-C bonds and produces hydrocarbons with an odd number of carbon atoms, mainly undecane (C11). In fact, the co-products of the process
are glycerine and methanol - which can be recycled in alcoholysis - as well as methane, a gas with a global warming potential 20 to 25 times greater than carbon dioxide. In the end, the saving of atoms of the whole process is about 72% (Table 1). Physicochemically, dodecane/tetradecane
and undecane/tridecane mixtures have relatively low flash points (< 82°C), which is why they are proposed as substitutes for volatile silicones (cyclomethicones), particularly in cosmetic products for make-up, skin and hair care.3,4
However, these ingredients do not fully replicate the properties of cyclomethicones.
The linear and branched bio-based alkanes Linear and branched paraffins from the HVO (hydrotreated vegetable oils) process more recently appeared on the Biofuels market obtained from vegetable oils and RSPO certified palm oil - marketed under the brand name Emogreen, INCI: C13-15 Alkane & C15-C19 Alkane. These paraffins are obtained by the HVO process which, like petroleum cracking,
1. Coconut oil
Methanolysis -Glycerine
Fatty Acids Methyl Esters
Process Coconut Alkanes Conventional chemistry
Conventional chemistry
Conventional chemistry
Synthetic biology + Synthetic chemistry
Synthetic biology + Synthetic chemistry
Conventional chemistry
Synthetic biology + Synthetic chemistry
GMO-based technology
No No
No Yes
Yes
No Yes
Atom
economy 85%
72% 65% 25%
28%
100% 26%
consists of hydrocracking vegetable oils (Figure 1, reaction 3). Developed by the oil companies Neste
Oyj, Total and ENI, this process enables the production of 3rd generation biodiesel by transforming more than 2.5m tonnes of various fats each year in Europe.7, 8
These are mainly
palm oil (RSPO certified or not), by-products from the refining of acidic oils (deodorisation by-products), used cooking oil, tallow and other fats from animal origin. The crude hydrocarbon cuts from the
process are then fractionated by distillation to produce complex mixtures of C13-C15 and C15-C19 hydrocarbons, fractions that are currently used in cosmetics and mechanical lubricants. The by-products of the process are numerous and relatively abundant: water and light gases such as methane, ethane and propane. Again, a mixture of gases with a high global warming potential. In terms of atom economy - a green chemistry criterion - the latter is significantly lower than the previous alkanes (65%, Table 1). It should be noted that C13-C15 and C15-C19
paraffins are still too heavy to replace volatile silicones, particularly cyclomethylpentasiloxane (D5). However, they appear to have textural and sensory properties similar to silicones, which could potentially be incorporated into skin and hair care formulations.6 Squalane has no petrochemical
counterpart. It is a multi-branched C30 alkane. For a long time obtained from shark liver oil, it is now preferred to be extracted from a co-product of olive oil refining. Due to its remarkable properties, squalane is
1. Hydrogenolysis 2. Distillation
-Methanol (CH3 OH) 2. Palm Kernel Oil
Methanolysis -Glycerine
3. Palm Oil Used Cooking Oils (UCO)
Fatty Acids Methyl Esters
1. Hydrogenolysis 2. Distillation
-Methanol (CH3 - [Methane (CH4
Hydrocracking/Isomerisation , Ethane (C2
H6 OH)
Lauryl Alcohol Myristyl Alcohol
Dehydration -H2
O
Agro-industrial
productivity mT/ha 0.21
0.18 2.47 3.25
1.33
0.025 0.66
Upcycled ingredient Volatility
No No
No No
No
Yes No
Yes Yes
No Yes
No
No No
ISO 16128
compliance Yes
Yes Yes No
No
Yes No
Cosmos approved
Yes Yes
Yes No
No
Yes No
one of the most appreciated emollients by cosmetic product formulators: exceptional sensory profile, excellent solvent, spreading and moisturising properties, perfect skin biocompatibility and oxidative hyper-stability. Long produced from squalene-rich shark
liver, it is now mainly obtained from vegetable squalene, a substance abundant in the unsaponifiable matter of olive oil. Squalene is one of the fundamental lipids of the skin. It is synthesised from the sebaceous glands and accounts for 11-13% of total lipids in sebum.9 Squalene is commonly used as an active
ingredient, adjuvant or additive in many health and wellness products such as cosmetics, nutritional supplements and vaccines. Due to its polyunsaturated molecular
structure, squalene is very sensitive to oxidation, which is why it is considered by cosmetic formulators as an unstable substance in air and heat. Also, a hydrogenated derivative will be developed, a technique taken up by the French chemist Sébastien Sabetay, who developed in 1950 the total hydrogenation of squalene into squalane or still called perhydrosqualene and marketed under the name Cosbiol.10, 11 Squalane is nowadays mainly obtained
from a co-product of the refining of olive oil and to a lesser extent sunflower or soybean oil. The co-products of refining vegetable oils have long been a source of active ingredients for cosmetics and nutrition, such as natural vitamin E, phytosterols, waxes (sunflower, rice bran) and lecithins. The co-product of olive oil refining, rich in squalene (5-15%), is generated during the steam
1-Dodecene 1-Tetradecene
Hydrogenation
Coconut Alkanes (VegelightTM
1214)
Lauryl Alcohol Myristyl Alcohol
Hydrogenolysis -Methane(CH4
)
Palm Kernel Undecane + Tridecane (Cetiol UltimateTM
) ), Propane C3 H8 ) ] Figure 1: Production process of linear and branched bio-based alkanes PERSONAL CARE April 2022
www.personalcaremagazine.com
Palm Linear + Branched Paraffins C13-C15/C15-C19 (EmogreenTM
L15/EmogreenTM L19)
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