Insect oil as natural raw material for alcohol production

Abstract

The invention relates to a method for producing fatty alcohols from alternative, renewable natural raw materials, to the use of fatty alcohols for producing surfactant intermediates or surfactants, and to fatty alcohol compositions. More specifically, the present invention describes the transesterification of triglycerides using insect oil, in particular oil from hermetia illucens larvae, as or as part of a feed stream and subsequent hydrogenation to fatty alcohols in the industrially desired carbon range.

Description

Technical Field

[0001] The present invention generally relates to the production of fatty alcohols from alternative, renewable natural raw materials and the use of fatty alcohols for the production of surfactant intermediates or surfactants. More specifically, the present invention describes the use of insect oils, particularly oils from black soldier fly larvae as a feed stream or as a portion of a feed stream for transesterification of triglycerides and subsequent hydrogenation to fatty alcohols in an industrially desirable carbon range.

[0002] Background of the invention and discussion of the prior art

[0003] Surfactant intermediates such as alcohol sulfates, alcohol ether carboxylates, alcohol alkoxylates and alcohol ether sulfates are traditionally manufactured using conventional raw materials such as kerosene, petroleum-derived materials, etc. However, there is an urgent need to discover alternative raw materials that are not derived from fossil fuels.

[0004] Fat and oil containing lipid or triglyceride are known to be important raw materials for producing various industrial products. Known vegetable oils such as coconut oil or palm kernel oil containing this triglyceride have been described as useful raw materials for producing other lipid-derived products in biofuel / biodiesel and non-food product industry (see, for example, WO2018 / 085064A1). US2013 / 0150615A1 describes the method for forming oleochemicals using renewable raw materials such as soybean oil comprising triglyceride. The product produced is a complex mixture, and the mixture contains various compounds, such as C15-18 paraffin, C16-18 acid, C16-18 alcohol, C16 / C18 ester and other byproducts including unconverted triglyceride.

[0005] However, growing crops as a renewable source for oil production (petroleum production) requires large amounts of land, often accompanied by undesirable deforestation. In addition, plants take a long time to reach maturity. Therefore, utilizing these plant-based oils is generally an expensive, less sustainable way of obtaining this raw material, with less favorable life cycle assessments (LCAs).

[0006] Therefore, there is an increasing need to provide alternative feedstocks for the production of industrially important lipid-derived products such as esters, alcohols and various other compounds, which can find application, for example, as surfactant intermediates. Insect farming has been suggested as a viable industry to provide feedstocks for both nutrition and various industrial applications, supporting a green and bio-based economy.

[0007] These insects and their larvae feed on organic waste such as cities and other waste materials, and in this way, significant environmental advantages have been provided in their short lifespan. Insects require less water and the CO2 emissions required for their reproduction are much lower than crop planting. The main product of the industry obtained from insect larvae materials is protein powder, which is mainly used for feeding (feed, feed) and food applications (such as in S.Smetana et al.: "Insect margarine: Processing, sustainability and design", Journal of Cleaner Production, Elsevier, Amsterdam, NL, vol. 264, described in 2020). However, insect larvae, in addition to protein, also contain bio-based oils. These oils are excellent sources of lipids or triglycerides, and it has been shown that after extraction and purification, these lipids can be successfully used in cosmetics and personal care product formulations (P.Falabella et al.: "Lipids from Insects in Cosmetics and for Personal Care Products", Insects 2022, 13 (1), 41, 2021). Examples include lipids extracted from the larvae of the insect species Hermetia illucens, also known as the black soldier fly (BSF), which are successfully used in the formulation of shower gels and soaps.

[0008] It has also been demonstrated that various industrially useful products, such as biodiesel, can be produced from triglycerides obtained from insect oils (see, for example, IN201911037067, KR2021051237), US2012 / 0144732A1, and S. Jung et al.: "Biodiesel production from black soldier fly larvae derived from food waste by non-catalytic transesterification", Energy, Elsevier, Amsterdam, NL, vol. 238, 2021). Summary of the invention

[0009] Purpose of the invention

[0010] The object of the present invention is to provide a process for producing fatty alcohols from fatty acid methyl esters obtained from insect oils.

[0011] Another object of the present invention is to provide a process for producing fatty alcohols having a specific hydrocarbon chain length distribution by transesterification of triglycerides contained in insect oils followed by hydrogenation.

[0012] Another object of the present invention is to provide a fatty alcohol mixture enriched in C12 alcohols from natural sources, wherein less than 5 wt% of the fatty alcohols have 10 or fewer carbon atoms and at least 40 wt%, preferably at least 60 wt% of the fatty alcohols have 12 and 14 carbon atoms, wherein the weight fraction of C14 fatty alcohols is less than one third of the weight fraction of C12 fatty alcohols and / or C14 alcohols outnumber C16 alcohols by weight.

[0013] SUMMARY OF THE INVENTION

[0014] The present invention is defined in the appended claims and provides a process that can be used to produce fatty alcohols from insect oils or combinations of insect oils with other sources. These alcohols can be used to make surfactant intermediates and surfactants, finding application in a wide range of technical fields, such as fabric and home care, personal care and cosmetics, agriculture, general industry and oil and gas recovery.

[0015] In more detail, the method for producing fatty alcohols comprises the following steps:

[0016] i) providing a feed stream comprising fatty acid methyl esters, wherein

[0017] a) at least 5 wt % of the fatty acid methyl esters are obtained from insect oil,

[0018] b) at least 92 wt% of the fatty acid methyl esters obtained from insect oils have an alkyl chain length > C10, and

[0019] c) at least 20 wt% of the fatty acid methyl esters obtained from insect oils have an alkyl chain length in the range of C12 to C14,

[0020] ii) hydrogenating the fatty acid methyl esters of step i) to form fatty alcohols.

[0021] Surprisingly, it has been found that triglycerides obtained from black soldier fly larvae (BSFL) are useful for high yield production of industrially important C 12 -C 14 An excellent feed stream for fatty alcohols, particularly finds application in personal care and home care product formulations.

[0022] The chain length peak is at C12 To C 14 Hydrocarbons in the C-range are often economically challenging to obtain in high yields from alternative sources. Particularly attractive is the fact that the low yield / lack of lower carbon numbers, i.e., C- 10 and below, resulting in a derivatized alcohol product without the attendant odor problems associated with short chain alcohols. This is clearly economically advantageous as no additional fractionation steps are required to remove the undesirable lower carbon alkyl range molecules.

[0023] The present invention further relates to a composition which is a fatty alcohol composition, wherein the composition comprises more than 95 wt% of fatty alcohols, and wherein more than 95 wt% of the fatty alcohols are linear, saturated and have terminal OH groups, wherein

[0024] a) at least 40 wt%, more preferably at least 60 wt% of the fatty alcohols have an alkyl chain length in the range of C12 to C14; and

[0025] b) at least 92 wt%, more preferably at least 95 wt%, most preferably at least 97 wt% of the fatty alcohols have an alkyl chain length > C10; and

[0026] The weight fraction of C14 fatty alcohol is less than one third of the weight fraction of C12 fatty alcohol. The composition can be obtained by the method of the present invention.

[0027] The composition contains only a small amount of alcohols having 10 or fewer carbon atoms. Therefore, the composition is referred to as a fatty alcohol mixture and the alcohols are all referred to as fatty alcohols, regardless of chain length. The fatty alcohols may be linear or branched, and saturated or unsaturated.

[0028] Considering alternative nonionic derivatives of fatty alcohols such as alkoxylates, higher carbon chain length of the alcohol results in lower water solubility. These products generally show lower critical micelle concentration (cmc) values, indicating desirable higher surface activity and enhanced emulsification properties.

[0029] Clearly, products obtained from insect oils have an attractive low environmental footprint and are a sustainable and economical source for the production of hydrocarbon products in the highly desirable carbon range, most notably the fatty alcohol products obtained from black soldier fly larvae disclosed herein, as well as the production of surfactants and other products through further derivatization, including formulations thereof. DETAILED DESCRIPTION

[0030] In many home care, fabric care or personal care formulations, fatty alcohols and their derivatives such as nonionic surfactants (e.g. alkoxylated alcohols) and anionic surfactants (e.g. alcohol ether sulfate, alcohol sulfate, alcohol ether carboxylate) are used. The largest number of products is based on so-called mid-cut alcohols, which are widely used in laundry detergents and cleaning products. It contains alkyl chain lengths mainly in the range of C 12 To C 16 The maximum carbon atom is C 12 Also commonly used, albeit in relatively small amounts, are so-called heavy-cut alcohols, which have predominantly C 16 and C 18 Carbon atom.

[0031] Table 1: Common carbon chain distributions of fatty alcohol compositions used in a wide variety of consumer products.

[0032]

[0033] Typically, fatty alcohols in these carbon chain ranges are obtained from natural sources such as palm oil, palm kernel oil, and coconut oil, or are manufactured based on petrochemical feed streams.

[0034] In addition to various sustainability advantages when using insect oil derived feedstocks, particularly black soldier fly larvae, insect oils may also provide feedstocks with highly desirable surfactant production characteristics, such as carbon distribution within the sought carbon number range.

[0035] The insect oil derived feedstock can be used alone or in blends with various conventional hydrocarbon feedstocks.The feed stream according to the present invention consists of or comprises such an insect oil derived feedstock.

[0036] A method for producing fatty alcohols may comprise a first step of providing a feed stream comprising fatty acid methyl esters, wherein at least 5 wt% of the fatty acid methyl esters are obtained from insect oils, and at least 92 wt% of these fatty acid methyl esters have a carbonyl group>C 10 At least 20 wt%, preferably at least 40 wt%, more preferably at least 60 wt% of the fatty acid methyl esters obtained from insect oils have an alkyl chain length of at least 1. 12To C 14 The feed stream is then hydrogenated to form fatty alcohols. The hydrogenation removes any unsaturation except trace amounts.

[0037] The feed stream preferably comprises at least 80 wt%, more preferably at least 90 wt% and most preferably at least 95 wt% fatty acid methyl esters.

[0038] The invention is further illustrated by the fact that at least 25 wt%, more preferably at least 50 wt%, but most preferably at least 75 wt% of the fatty acid methyl esters are obtained from insect oils.

[0039] According to a preferred embodiment of the present invention, at least 95 wt%, more preferably at least 97 wt% of the fatty acid methyl esters have>C 10 The alkyl chain length is further limited to at least 40 wt%, more preferably at least 60 wt% of the fatty acid methyl esters having an alkyl chain length of at least C 12 To C 14 The alkyl chain length is within the range.

[0040] The method may further comprise combining the feed stream with at least one non-insect derived feed stream comprising fatty acid methyl esters, wherein at least 20 wt % of the fatty acid methyl esters from the non-insect derived oil have a C 12 To C 14 Length of alkyl chain.

[0041] The process for producing fatty alcohols may comprise a feed stream comprising fatty acid methyl esters obtained from insect oils and non-insect derived oils as defined above, wherein at least 20 wt%, more preferably at least 40 wt% and most preferably at least 60 wt% of the fatty acid methyl esters from the non-insect derived oils have a C 12 To C 14 The alkyl chain length is within the range.

[0042] The method may further comprise providing a first stream comprising triglycerides, wherein at least 5 wt% of the triglycerides are obtained from insects, prior to providing the feed stream comprising fatty acid methyl esters, and subsequently transesterifying the first feed stream to form the feed stream comprising fatty acid methyl esters.

[0043] Typically, at least 20 wt%, more preferably at least 40 wt% or most preferably at least 60 wt% of the triglycerides from the first feed stream - for the triglycerides comprising acid groups - have an acid group at C 12 To C 14It is also beneficial that at least 25 wt %, more preferably at least 50 wt % and most preferably at least 75 wt % of the triglycerides are obtained from insects.

[0044] The method may further comprise fractionating the fatty acid methyl esters, for example to form fractionated fatty acid methyl esters obtained from a non-insect derived oil, for example comprising at least 20 wt%, more preferably 40 wt% and most preferably 60 wt% of a fatty acid methyl ester having a C 12 To C 14 A fatty acid methyl ester having an alkyl chain length within a range of about 1 to about 200 μm is prepared, or a feed stream comprising fatty acid methyl esters is formed.

[0045] Fatty acid methyl esters from insect oils and from non-insect derived oils may be combined and then fractionated, or may be separately fractionated and then combined.

[0046] Insect oils derived from black soldier fly larvae (BSFL) form a particularly beneficial feed stream or a particularly beneficial portion of a feed stream.

[0047] According to one embodiment of the present invention, the method provides a fatty alcohol mixture having at least 20 wt%, more preferably at least 40 wt% or most preferably at least 60 wt% of a fatty alcohol having a terminal OH group, having a 12 To C 14 The alkyl chain length of the linear alcohol is in the range of 1:1, and at least 95 wt%, more preferably at least 97 wt%, of the alkyl alcohols having terminal OH groups and having >C 10 A straight chain alcohol with an alkyl chain length of

[0048] These fatty alcohols produced as described above can generally be used to produce surfactant intermediates or surfactants, such as but not limited to alcohol sulfates (alcohol sulfates, alcohol sulfate esters / salts, alcohol sulfate), alcohol alkoxylates, alcohol ether sulfates (alcohol ether sulfates, alcohol ether sulfate esters / salts, alcohol ether sulfate) and / or alcohol ether carboxylates (alcohol ether carboxylates, alcohol ether carboxylates / salts, alcohol ether carboxylate). Olefins and paraffins are also typical products that can be produced from the above-mentioned fatty alcohols.

[0049] The present invention includes methods of converting the fatty alcohols produced as described above to make products such as:

[0050] Olefins and paraffins, by subjecting fatty alcohols to a further hydrogenation step,

[0051] alcohol alkoxylates, usually ethoxylated and / or propoxylated alcohols, by further applying an additional step of alkoxylation of fatty alcohols,

[0052] Alcohol sulfates, produced by sulfating fatty alcohols,

[0053] alcohol ether sulfates, prepared by first alkoxylating, preferably ethoxylating and / or propoxylating, fatty alcohols and then sulfating the resulting alkoxylated alcohols, and

[0054] Alcohol ether carboxylates, by first alkoxylating, preferably ethoxylating and / or propoxylating, fatty alcohols and then carboxymethylating the resulting alkoxylated alcohols.

[0055] The term "insect" as used herein may refer to insects, their larvae, or both. Furthermore, the term "insect oil" as used herein refers to a triglyceride composition obtained from insects, insect larvae, or a mixture thereof. Furthermore, the term "insect oil" may also refer to a mixture of insect oils obtained from different insects. The terms "insect oil" and "insect fat" may be used interchangeably, and the term "insect oil" does not necessarily mean that the "insect oil" is in a liquid state at room temperature (25° C.), and may also be solid / non-flowing at room temperature.

[0056] Insect oil derived fatty alcohols and their derivatives, including but not limited to surfactants (e.g., alkoxylated alcohols, alcohol sulfates, alcohol alkoxysulfates, ether carboxylates, carboxylated alcohol alkoxylates), esters and paraffins, can be used in detergent compositions, including but not limited to liquid laundry detergents, gel detergents, single or multi-phase unit dose detergents, laundry powders, detergent compositions incorporated into fiber products, laundry pretreatment products, fabric softener compositions, liquid hand dishwashing compositions, solid or liquid automatic dishwashing detergents, hard surface cleaners, and mixtures thereof. Further uses of the above products can be found in various personal care products for hair and / or skin care applications including, but not limited to, leave-in and rinse-off compositions, sunscreens, shampoos, conditioners, body washes and oils, makeup, creams and lotions, lipsticks, deodorants and antiperspirants.

[0057] Other application areas of the above products can be used for industrial purposes, including but not limited to emulsions, suspensions and dispersions, fire-fighting foams, agricultural chemical preparations, such as insecticides, pesticides and plant protection solutions, metalworking fluids, lubricating fluids, products for the production of oil and gas (including but not limited to oil recovery formulations, fracturing fluids, and foaming, cleaning and cementing products), household or industrial paints, inks and coatings, paper industry additives, adhesives and asphalt additives, etc.

[0058] Suitable insect oils that can be used to synthesize the described fatty alcohols include, but are not limited to, Hermetia illucens or black soldier fly (BSF), more specifically, black soldier fly larvae (BSFL).

[0059] Experimental Section

[0060] Various oils with different triglyceride contents were used to illustrate the manufacture of fatty alcohols and related derivatives, as shown in Table 2.

[0061] Table 2 :Fatty acid composition of triglycerides from different sources (determined by GC)

[0062]

[0063] Insect oil (BSFL): Commercially available from Hexafly

[0064] Coconut oil: Commercially available from Gustav Heess GmbH

[0065] Palm kernel oil: commercially available from KLK Oleo, Emmerich, Germany

[0066] All raw materials were dried under vacuum and stored under 0.3 nm molecular sieves. In addition, a drying tube filled with CaCl2 was used.

[0067] To produce fatty acid methyl esters, the oils shown in Table 2 above were subjected to the transesterification procedure as described below.

[0068] General transesterification procedure:

[0069] · Fill the flask with oil.

[0070] • Solid NaOMe (1 wt%) was dissolved in excess MeOH (same volume as oil) and added while stirring under N2 atmosphere.

[0071] The reaction mixture was heated to about 65°C and refluxed for 2.5 hours.

[0072] • Upon completion, the mixture was cooled to 0°C and quenched with aqueous hydrochloric acid to reach a pH of 7.

[0073] - Excess MeOH was removed under reduced pressure.

[0074] In order to obtain fatty acid methyl esters with higher purity, the resulting product was mixed with the same amount of NaCl aqueous solution (10%). After phase separation, the product was obtained as the upper organic phase.

[0075] The methyl ester compositions obtained for the various feed streams are shown in Table 3.

[0076] Table 3 : Methyl ester composition, IO-ME: insect oil after interesterification; CO-ME: coconut oil after interesterification; PKO-ME: palm kernel oil after interesterification

[0077]

[0078] IO = insect oil; CO = coconut oil; PKO = palm kernel oil; ME = methyl ester

[0079] It will be clear to those skilled in the art that combinations of feedstocks may also be processed according to the invention and methyl esters may be produced from blends of insect oils and other triglyceride sources.

[0080] Table 4 : Methyl ester compositions of blends of insect oil (IO) and palm kernel oil (PKO) in different proportions after transesterification

[0081]

[0082] IO = insect oil; PKO = palm kernel oil; ME = methyl ester

[0083] Often, it is desirable to have a composition enriched in a particular carbon chain length as exemplified in Table 1. For these cases, it is common practice to fractionate the methyl esters. 10 ) as small as possible, which is an additional advantage, in order to reduce the energy required for the distillation step and to reduce the amount of by-products produced.

[0084] Fractionation

[0085] The methyl ester solution is filtered and fractionated under reduced pressure to obtain various fractions of fatty acid methyl esters, depending on their boiling points (K. Schwetlick, Organikum Wiley-VCH, Vol. 23, p. 46-54, 2009).

[0086] The following fractions were prepared:

[0087] Table 5 : Methyl ester composition obtained after fractionation

[0088]

[0089] IO = insect oil; CO = coconut oil; PKO = palm kernel oil; MEF = fractionated methyl esters

[0090] The methyl esters obtained from the various oils were fractionated as shown in Table 5. Examples A and B were fractionated to maximize C 12 The amount of carbon chain, removing most of the longer (C 16 and above) carbon chain length and shorter (C 10 On the other hand, Examples C, D and E were fractionated under more efficient conditions to separate only the majority of the longer chain lengths (C 16 and above) carbon chain length, thereby obtaining 12 and C 14 As can be seen, the amount of unwanted shorter alkyl chains found in Examples A and C is significantly less than in Examples B, D and E. This means that advantageously, one separation step can be skipped for insect oil derived methyl esters, which is necessary for vegetable oils such as palm kernel oil or coconut oil to remove these C 10 and shorter chain methyl esters below.

[0091] The various methyl ester feed streams were subsequently hydrogenated to provide fatty alcohols. The carbon distribution was therefore the same as in Table 5.

[0092] General method of hydrogenation:

[0093] In a typical experiment, 5-10 g of a copper-based hydrogenation catalyst was placed in a fixed basket in a 300 ml volume autoclave. The catalyst was then reduced in a hydrogen-nitrogen gas phase at 200° C. for 5 hours.

[0094] After cooling the reactor, 50-100 ml of pure fatty acid methyl ester feed is added to the autoclave under a nitrogen inert atmosphere. The hydrogenation reaction is carried out under a pure hydrogen atmosphere at 220-240°C and 250-300 bar for 5-15 hours. After cooling and nitrogen neutralization, the product is filtered to remove catalyst residues and then analyzed by gas chromatography.

[0095] The following results are obtained:

[0096] Table 6 :Fatty alcohols (FA) produced from fatty acid methyl esters

[0097]

[0098] IO = insect oil; CO = coconut oil; PKO = palm kernel oil; FA = fatty alcohol

[0099] Method Description Odor characteristics: Sensory analysis ranking was performed by a panel of 17 testers (n=17) according to DIN ISO 8587:2006. The samples were provided in special smell test glasses which did not allow any induction by the color or appearance of the samples.

[0100] The testers must rate the odor characteristics of all samples from 1 to 3, where 1 is the most pleasant odor and 3 is the least pleasant odor. The results are expressed as the total number of ratings, which is the sum of the ratings of all testers for the corresponding samples. The lower the total number of ratings, the more pleasant the odor characteristics are. The average is the total number of ratings divided by the number of testers n.

[0101] Table 7: Ranking of odor characteristics of three fatty alcohols derived from insect oil, palm kernel oil, and coconut oil.

[0102]

[0103] IO = insect oil; CO = coconut oil; PKO = palm kernel oil; FA = fatty alcohol

[0104] Surprisingly, it was found that the odor characteristics of the insect oil derived alcohols were superior to the two plant oil derived alcohols. The results are more meaningful if the variance is analyzed using the Friedman Test and the significance of the differences is determined according to 8.2.3ff of DIN ISO 8587:2006.

[0105] To do this, the least significant difference (LSD) is calculated:

[0106]

[0107] Where n: number of testers

[0108] p: sample size

[0109] z: coefficient of deviation

[0110] LSD is a measure of the variance between samples obtained from a result set where there is a certain probability that these samples cannot be distinguished. For a significant result, this probability must be as low as 5%, and for a highly significant result, this probability must be as low as 1%.

[0111] For a 5% probability that the samples cannot be distinguished, z = 1.96, and for a 1% probability, z = 2.576 (Yates, Fisher, Table III, p. 55 in Statistical Tables for biological, Agricultural and Medical Research, 6 th ed., Oliver and Boyd, Edinburgh 1963).

[0112] This results in LSD(5%)=11.4 and LSD(1%)=15.0.

[0113] According to Table 7, the difference between the total number of grades of IO-FA and PKO-FA is 36-23 = 13. Therefore, it is higher than LSD (5%) = 11.4, so this result is significant.

[0114] According to Table 7, the difference between the total number of fractions of IO-FA and CO-FA is 43-23 = 20. Therefore, it is higher than LSD (1%) = 15.0, so the result is highly significant.

[0115] In addition, alcohol ethoxylates (ethoxylation grade = 9) were prepared from some of the fatty alcohols produced according to the invention.

[0116] General ethoxylation procedure:

[0117] Fatty alcohol obtained from bio-oil and aqueous KOH (50%) catalyst (0.15 wt%) were charged to a laboratory ethoxylation reactor. The remaining water was stripped for 120 minutes at 120°C, 300 mbar pressure and nitrogen flow.

[0118] Thereafter, the reaction temperature was raised to 160° C. and nitrogen was added. The calculated amount of ethylene oxide (EO) was added continuously until all the EO was added. After complete addition of EO, the mixture was boiled until the pressure remained constant at 160° C. Subsequently, free EO was removed under reduced pressure at 80° C., 50 mbar and nitrogen flow for 90 minutes. The product was discharged from the reactor.

[0119] The following properties of specific alkoxylated alcohols were determined and are shown in Table 8.

[0120] Method Description:

[0121] • Cloud point: According to DIN EN 1890, the cloud point is determined visually by cooling the temperature of a solution of 10% surfactant in 25% BDG aqueous solution until the solution becomes clear.

[0122] · Surface tension: The surface tension of the surfactant solution was measured according to DIN EN 14370 at 25° C. using a plate tensiometer Krüss K100.

[0123] Wetting behavior: For the cotton disc test (DIN EN 1772), a cotton fabric with a diameter of 30 mm is immersed in the surfactant solution using clamps. The wetting time is the duration until the cotton fabric starts to sink: this occurs when the disc fully wets the filaments. A typical concentration of the surfactant is 1 g / L deionized water. The Dravestest (ASTM D2281-10) apparatus consists of a tall cylinder containing an alcohol ethoxylate solution (1 g / L in deionized water) in which a cotton skein is connected to a string stirrup at the bottom of the cylinder. The time required for the cotton skein to wet and sink, and for the string stirrup to loosen, is recorded as the sinking time.

[0124] Phase behavior: The phase behavior was determined by mixing the surfactant and water at the specified concentration in steps of 10%. The phase state of each mixture was determined visually at room temperature. The phase state was distinguished according to clear liquid, cloudy liquid, cloudy non-homogeneous, gel and solid.

[0125] Table 8 : Properties of some ethoxylated alcohols (ethoxylation grade = 9)

[0126]

[0127] IO = insect oil; PKO = palm kernel oil; AE9 = alcohol ethoxylate, ethoxylation grade = 9

[0128] While both ethoxylated alcohols show similar cloud points, the insect oil derived ethoxylate has lower surface tension and improved wetting behavior.

[0129] The wetting times for both the cotton disc test and the Draves test are expressed as relative differences in seconds to the palm kernel oil ethoxylate as a benchmark. Negative values ​​indicate shorter times and improved wetting behavior.

[0130] ΔWetting time [Δs] = Wetting time (palm kernel oil ethoxylate) [s] - Wetting time (test substance) [s].

[0131] Furthermore, the ethoxylated alcohol prepared from insect oil (IO-AE9) showed less gel formation when compared to a similar product prepared from palm kernel oil (PKO-AE9).

[0132] Further derivatives from the alcohols, such as alcohol sulfates, olefins and alkanes, and from the alkoxylated alcohols, such as alcohol ether sulfates and alcohol ether carboxylates, are prepared according to the following general method:

[0133] General procedure for the production of further derivatives:

[0134] General procedure for the dehydration of fatty alcohols to form olefins and paraffins:

[0135] The specific conditions depend on the fatty alcohol mixture to be dehydrated. A typical process is described in US10654765 B2, where 2474 g of 1-hexadecanol (NACOL 16) is mixed with 500 g of Al2O3 and a solvent such as xylene in a flask equipped with a water separator. The flask is heated to 295°C for 4.5 hours. The linear olefin, hexadecene, is distilled under vacuum. The product is a mixture of alpha-olefins and internal olefins.

[0136] To produce paraffin products, the olefins produced above were hydrogenated according to a prior art hydrogenation process as described in US 10654765 B2, wherein 685 g of hexadecene obtained above were hydrogenated at 98° C. over a heterogeneous Ni-containing catalyst at 20 bar H2 pressure for 7 hours and filtered after cooling.

[0137] General Procedure for Sulfation of Fatty Alcohols / Ethoxylated Alcohols:

[0138] The sulfation of the alkoxylated alcohol / alcohol is usually carried out in a continuous falling film reactor maintained at a temperature of 45°C to 75°C, using sulfur trioxide diluted with air (e.g., 3-7% SO3 mole fraction in process air) as the sulfating agent. The molar ratio of SO3 to the raw material is usually maintained in the range of 0.8 to 1.2:1. The resulting sulfation product is transferred to a neutralization loop and neutralized with an organic or inorganic base at 30°C to 60°C. Solvents or water may be added during the neutralization step to reduce viscosity during mixing / neutralization (Organic Process Research & Development 1998, 2, 194-202).

[0139] General Procedure for Carboxymethylation of Alkoxylated Alcohols:

[0140] The ethoxylate is placed in a flask and heated to 80°C under vacuum and 20 mbar. NaOH (50%, aqueous, 2.1 equivalents) and monochloroacetic acid (80%, aqueous, 1 equivalent) are slowly added by a metering pump. Acid and base are added simultaneously. The water produced by the reaction and the water from the acid / base are removed under reduced pressure (20 mbar). The dosing time takes about 2.5 hours. After the addition, the mixture is stirred at 80°C and 20 mbar for 3 hours. The reaction mixture is then adjusted to a pH value of 1-2 at 80°C with 10% H2SO4 and stirred for about 1 hour. It is transferred to a heatable separating funnel (80°C) and the organic phase and the aqueous phase are separated.

Claims

1. A method for producing fatty alcohols, comprising the following steps: i) providing a feed stream comprising fatty acid methyl esters, wherein a) at least 5 wt% of the fatty acid methyl esters are obtained from insect oils, b) at least 92 wt% of said fatty acid methyl esters obtained from said insect oil have an alkyl chain length > C10, and c) at least 20 wt% of said fatty acid methyl esters obtained from said insect oil have an alkyl chain length ranging from C12 to C14, ii) hydrogenating the fatty acid methyl ester of step i) to form fatty alcohol.

2. The process according to claim 1, wherein the feed stream comprises at least 80 wt%, more preferably at least 90 wt% and most preferably at least 95 wt% fatty acid methyl esters.

3. The process according to at least one of the preceding claims, wherein at least 25 wt%, more preferably at least 50 wt%, most preferably at least 75 wt% of the fatty acid methyl esters are obtained from the insect oil.

4. The method according to at least one of the preceding claims, wherein i) at least 95 wt%, more preferably at least 97 wt% of the fatty acid methyl esters have an alkyl chain length > C10, and ii) at least 40 wt%, more preferably at least 60 wt% of the fatty acid methyl esters have an alkyl chain length in the range of C12 to C14.

5. The process according to at least one of the preceding claims, wherein the feed stream comprises fatty acid methyl esters obtained from the insect oil and fatty acid methyl esters obtained from non-insect derived oils, wherein at least 20 wt%, preferably at least 40 wt%, most preferably at least 60 wt% of the fatty acid methyl esters from the non-insect derived oils have an alkyl chain length in the range of C12 to C14.

6. The process according to claim 1 , wherein before providing the feed stream comprising fatty acid methyl esters, i) providing a first feed stream comprising triglycerides, wherein at least 5 wt% of said triglycerides are obtained from insects, ii) transesterifying said first feed stream to form said feed stream comprising fatty acid methyl esters.

7. The process of claim 6, wherein the triglycerides from the first feed stream comprise at least 20 wt% of acid groups having an alkyl chain length in the range of C12 to C14.

8. The process according to at least one of claims 6 or 7, wherein the triglycerides from the first feed stream comprise at least 40 wt%, more preferably at least 60 wt% of acid groups having an alkyl chain length in the range of C12 to C14.

9. The process according to at least one of claims 6 to 8, wherein at least 25 wt%, more preferably at least 50 wt%, most preferably at least 75 wt% of the triglycerides from the first feed stream are obtained from insects.

10. The process according to at least one of the preceding claims, wherein the feed stream further comprises non-insect derived fatty acid methyl esters, preferably obtained from palm kernel oil and / or coconut oil.

11. The process according to at least one of the preceding claims, wherein the fatty acid methyl esters are fractionated or wherein fatty acid methyl esters from insect oils and non-insect derived fatty acid methyl esters are fractionated separately and then combined to form the feed stream.

12. The process according to claim 11, wherein the fatty acid methyl esters are fractionated to comprise a stream wherein at least 20 wt%, preferably at least 40 wt%, more preferably at least 60 wt% and most preferably at least 80 wt% of the fatty acid methyl esters have an alkyl chain length in the range of C12 to C14.

13. The method according to at least one of the preceding claims, wherein the insect oil originates from black soldier fly larvae or the insects are black soldier fly larvae.

14. Use of a fatty alcohol produced by the process according to at least one of the preceding claims for the production of surfactant intermediates or surfactants.

15. Use of fatty alcohol according to claim 14, wherein the surfactant intermediate or the surfactant is selected from olefins, alkanes, alcohol sulfates, alcohol alkoxylates, alcohol ether sulfates, alcohol ether carboxylates and mixtures thereof.

16. Process for converting fatty alcohols produced by the process of at least one of claims 1 to 13 into: a) paraffins, by subjecting the fatty alcohols to a further hydrogenation step, b) alcohol alkoxylates, preferably ethoxylated and / or propoxylated alcohols, by further applying an additional step of alkoxylating the fatty alcohols, c) alcohol sulfates, produced by sulfating the fatty alcohols, d) alcohol ether sulfates by first alkoxylating the fatty alcohols, preferably ethoxylating and / or propoxylating the fatty alcohols, and subsequently sulfating the resulting alkoxylated alcohols, e) Alcohol ether carboxylates by first alkoxylating the fatty alcohol, preferably ethoxylating and / or propoxylating the fatty alcohol, and subsequently carboxymethylating the resulting alkoxylated alcohol.

17. A fatty alcohol composition obtainable by the process according to at least one of claims 1 to 13, wherein a) at least 40 wt%, more preferably at least 60 wt% of the fatty alcohols have an alkyl chain length in the range of C12 to C14; and b) at least 92 wt%, more preferably at least 95 wt%, most preferably at least 97 wt% of said fatty alcohols have an alkyl chain length > C10.

18. Fatty alcohol composition according to claim 17, wherein the weight fraction of C14 fatty alcohol is preferably less than one third of the weight fraction of C12 fatty alcohol and / or C14 alcohol exceeds C16 alcohol in quantity by weight.

19. A fatty alcohol composition, wherein the composition comprises more than 95 wt% of fatty alcohols and wherein more than 95 wt% of the fatty alcohols are linear, saturated and have terminal hydroxyl groups, wherein a) at least 40 wt%, more preferably at least 60 wt% of the fatty alcohols have an alkyl chain length in the range of C12 to C14; and b) at least 92 wt%, more preferably at least 95 wt%, most preferably at least 97 wt% of said fatty alcohols have an alkyl chain length > C10; and The weight fraction of the C14 fatty alcohol is less than one third of the weight fraction of the C12 fatty alcohol and / or the C14 alcohol exceeds the C16 alcohol in quantity by weight.

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