FI20205374A1 - Bio-based synthetic paraffin wax - Google Patents

Abstract

A method of using a bio-based synthetic paraffin wax comprising at least 50 w% of a mixture of n-alkanes having carbon chains of 23 to 43 carbon atoms is disclosed. Uses as a candle wax, in artificial firelogs, in heating briquettes or heating pellets, in lighter blocks, in gel fuels, for waxing candle wicks, for impregnating porous materials, for coating, for lubricating, for electrical insulation, as a process aid in rubber, as a binder, as a hydrophobization agent in sizing compositions, as an additive in lubricants, in personal care products, in adhesives, or for infiltrating and/or embedding tissue samples are provided.

Description

BIO-BASED SYNTHETIC PARAFFIN WAX

FIELD The present disclosure relates to a method of using a bio-based synthetic paraffin wax. Further, — the present disclosure relates to a method for manufacturing a combustible solid or gelatinous product, to a combustible solid or gelatinous product, and to a candle, comprising the bio-based synthetic paraffin wax.

BACKGROUND Candles are sources of light with one or more combustible wick surrounded by a burning mass — which is solid or semisolid at room temperature (20 °C to 27 °C), as defined by RAL-GZ041 quality assurance for candles. Candles may be grouped based on the type e.g. into paraffin candles, stearin candles, beeswax candles, and self-extinguishing candles. Oil lights on the other hand are defined as consisting of a solid burning mass and a wick that are surrounded by an inflexible container. Various carbonaceous materials are known usable as components in the — burning mass of candles and oil lights, for example paraffin wax, stearin, beeswax, hardened animal and vegetable oils, unhardened animal and vegetable oils, solid animal and vegetable fat, solid fatty acids and solid hydrocarbon compounds, as listed in RAL-GZ041. In ancient times candles were made from renewable materials such as tallow, beeswax, whale fat etc. These materials had their limitations, including limited availability, high cost, undesired — burning behavior including formation of smoke and soot, and offensive smell. Petroleum-based paraffin wax that was first created in 1830, marked a major advancement in candlemaking o technology, as it burned more cleanly and reliably than tallow candles, and was cheaper to N produce. Nowadays petroleum-based paraffin wax is a widely used candle component. It is a S soft colorless solid, typically derived from petroleum, coal or shale oil, and consists of a mixture 3 25 of hydrocarbon molecules containing 20 to 40 carbon atoms. While petroleum-based paraffin E waxes typically contain mostly n-paraffins (in chemistry, paraffin is used synonymously with 3 alkanes), also iso-paraffins, naphthenes and aromatics may be present. A typical petroleum- D based paraffin wax is solid at room temperature and begins to melt above about 37 ”C, and its S boiling point is above 370 ”C. The feedstocks for petroleum-based paraffin wax includes slack wax, which is a mixture of oil and wax, a byproduct from the refining of lubricating oil. Petroleum-based paraffin wax is sold in either liquid or solid form. Pure petroleum-based paraffin wax is relatively brittle at room temperature. In industrial applications it is often useful to modify the crystal properties of the petroleum-based paraffin wax, usually by adding additives, such as EVA copolymers, microcrystalline wax, or forms of polyethylene. The modification results in a modified petroleum-based paraffin wax having higher viscosity, smaller crystalline structure, and modified functional properties. While petroleum-based materials are well available for the time being, their supply is expected to become more and more limited, accompanied by increased price, before their complete extinction. There is also a strong consumer demand for bio-based candles as an environmentally friendly, or greener, alternative to petroleum-based paraffin candles. While the circle is closing — in this respect, a simply returning to the ancient renewable materials is not an option from safety, availability and cost point of view. For environmental, economical, and regulatory reasons, a high motivation exists to produce advanced waxes from renewable sources. Vegetable oils are abundantly available in most parts of the world, at relatively low cost, and various alternatives based on them have already been provided. For example the following four major components are known to be used for manufacturing bio-based wax compositions especially for use in candles: partially and fully hydrogenated vegetable oils (PHVO and FHVO, respectively); free fatty acids (FFA); polyol fatty acid partial esters (PFAPE), such as glycerin mono- and di-stearates; and catalytic trans-esterification products of PHVO, FHVO or PFAPE. While partial hydrogenation of vegetable oil means hydrogenating some of the — unsaturations present in the fatty acid chains of the vegetable oil, full hydrogenation means hydrogenating essentially all of the unsaturations so as to obtain >99% saturated vegetable oil. The FHVOs are typically firmer than PHVOs, and may also be more stable towards e.g. oxidation, or other reactions. One of the most commonly used vegetable oil for partial or full N hydrogenation is soybean oil, partially hydrogenated soybean oil being referred to as soywax.

N x 25 Often the melting, solidification, crystallization, textural and/or combustion properties of 2 individual vegetable waxes are insufficient for obtaining candles with desired safety, aesthetic I and other characteristics, and complex combinations of different components are needed. For 3 example free fatty acids, paraffins, and additional vegetable oils with different melting and 2 solidification properties may be added to the vegetable wax compositions so as to improve the S 30 characteristics of candles made therefrom. There are multitude of publications disclosing complex combinations of different components for use in candles, as thoroughly reviewed in the background section of e.g. WO11028744:

US6063144 discloses candle compositions of vegetable oil, stearic acid, hydrogenated castor oil, and vegetable-derived wax (such as candelilla wax), US6214918 discloses candle compositions of paraffin wax, soybean oil, and a branched hydrocarbon compatibilizer/binding agent; US6284007 and US6497735 disclose candle compositions of petroleum wax and vegetable lipid components, that include vegetable oil or fatty acid/vegetable oil mixtures;

US6503285 and US20050060927 disclose candle compositions of PHVO and PFAPE, such as fatty acid monoesters of glycerol and/or sorbitan; US6599334 and US20070282000 disclose candle compositions of PHVO with additional amounts of synthetic wax, such as poly(alphaolefins), and a second hydrogenated vegetable or petroleum oil; US6645261 discloses candle compositions of PHVO of several different solid fat index with different degrees of hydrogenation, and palmitic acid; US6730137 discloses candle compositions of paraffin wax and FHVO having a low free fatty acid content, US6770104 discloses candle compositions of PHVO, FHVO and PFAPE having a low free acid content; US6773469 discloses candle compositions of PHVO, PFAPE, and fatty acids such as palmitic acid;

US6773548 discloses candle compositions of PHVO, stearic acid, and a creamy vegetable liquid shortening; US6797020 discloses candle compositions of FHVO and several PHVOs of varied degrees of hydrogenation in combinations with PFAPE having a low fatty acid content;

US6824572 and US7217301 disclose candle compositions of PHVO and fatty acids, such as palmitic and stearic acids; US7128766 discloses candle compositions of FHVO and PHVO,

— which includes both soy and palm oil in the same formulation, and poly(alphaolefins) and glycerin mono-stearate used as compatibilizers, while paraffin wax, beewax, or carnauba wax is added optionally; US7192457 discloses candle compositions of products of catalytic trans-

esterification of vegetable oils, FHVO, and PHVO having a low fatty acid content;

US20030046860 discloses candle compositions of FHVO, PHVO, fatty acids, and esters of

S 25 — fatty acids that include PFAPE, canola methyl esters, propylene glycol monoesters, sorbitan x tristearate, and mixtures thereof; US20030061760 discloses candle compositions of FHVO,

x PHVO, stearic acid, a plant-derived surfactant, and microcrystalline petroleum/paraffin wax;

I US20040200136 discloses candle compositions of PHVO, stearic acid, a plant-derived a

+ surfactant, petroleum, and natural waxes; US20040250464 discloses liquid candle e 30 compositions of PHVO and hardening agent selected from the group consisting of fatty acids,

N stearin, cetyl alcohol, arachidyl alcohol, and myricyl alcohol and their mixtures;

N US20060042157 discloses candle compositions of PHVO, shea butter, and vegetable oil, such as olive oil; US20060272200 discloses candle compositions of PHVO, trans-esterified PHVO,

PFAPE, such as mono- and diglycerides, trans-esterified PFAPE, such as mono- and diglycerides, and optionally mineral wax and insect wax; and US20070039237 discloses candle compositions of PHVO having a blend of soy and palm, PFAPE, and other waxes, such as beeswax, carnauba wax, petroleum, wax, and Montana wax, used as migration inhibitors. Also WO11028744 discloses a multicomponent wax composition. The composition comprises non-hydrogenated epoxy product such as epoxides of vegetable oils, fatty acid esters or tall oil fatty acid esters, and at least one of paraffin waxes, hydrogenated tallow and fats, waxes of FHVOs and PHVOs, fatty acids, PFAPE, products of trans-esterification of FHVOs and PHVOs, products of trans-esterification of PFAPE. Other approaches to provide bio-based wax compositions usable in candles include preparing — special derivatives using complex, multistep processes. For example US20080281115 discloses preparation of compositions of chemically modified partially hydrogenated vegetable oil (PHVO) by a three-step process that includes a) epoxidation, b) ring-opening through acid- catalyzed hydrolysis to convert the epoxide into the hydroxylate, and c) esterification of the hydroxyl-groups with the use of fatty acid anhydride using butyric anhydride in methylene — chloride solvent. While most of the approaches rely on fatty acid based materials having carbon chain length of typical fatty acids, usually ranging from C14 to C22 depending on the source of triglyceride oil, some approaches aim at providing components with longer carbon chain length while still possessing polar character. For example WO19070422 discloses a renewable ketone wax comprising > 50 w% C40-C90 ketones and paraffin content < 10 w%, usable in candle compositions, and personal care products. The manufacturing method involves coupling unsaturated carbon chains by basic catalyst followed by oligomerization by acidic catalyst, and o distillation/extraction. It is said that the obtained ketone waxes preferably do not undergo O further processing that would saturate the olefin linkages present in the carbon chain or remove x 25 oxygen from the ketone wax. These ketone waxes are said to have unexpected properties 2 relative to waxes derived from other/conventional sources. The oxygen content and polarity are x said to be unique: higher than for petroleum-based wax and lower than for renewable ester wax. x Notwithstanding the above publications, there is a continuous need for bio-based wax 3 compositions usable in candles, and in other applications.

O N 30 SUMMARY

The object of the present disclosure is to alleviate or even eliminate some of the disadvantages existing in the prior art.

According to a first aspect of the present disclosure, a method of using a bio-based synthetic paraffin wax characterized by what is presented in claim 1, is provided. The bio-based synthetic 5 paraffin wax comprising at least 50 w% of a mixture of n-alkanes having carbon chains of 23 to 43 carbon atoms, is usable as a candle wax, in artificial firelogs, in heating briquettes or heating pellets, in lighter blocks, in gel fuels, for waxing candle wicks, for impregnating porous materials, for coating, for lubricating, for electrical insulation, as a process aid in rubber, as a binder, as a hydrophobization agent in sizing compositions, as an additive in lubricants, in — personal care products, in adhesives, or for infiltrating and/or embedding tissue samples.

The bio-based synthetic paraffin wax as specified in the present disclosure may be manufactured for example as disclosed in WO2007068795, W02007068796, W02007068797, W02016062868, WO2018234187, WO2018234188, WO2018234189, the disclosures of which are herein incorporated by reference in their entirety.

— There are many different compounds of different origin and composition known as wax. Based on origin, waxes can be grouped into petroleum waxes and natural waxes, such as insect, animal, and vegetable wax. The beeswax and carnauba wax (palm tree) are composed of high molecular weight esters with some acids, alcohols, and hydrocarbons. Synthetic waxes are manufactured by chemical synthesis from a variety of chemical compounds, such as alcohols, polyethylene glycols, esters, hydrocarbons and chlorinated hydrocarbons. Ester-like waxes are produced from fatty acids and amines instead of fatty acids and alcohols. Synthetic hydrocarbon waxes may be produced by Fischer-Tropsch process and by the polyethylene manufacturing a process. The term mineral wax may be applied to any wax of mineral origin, such as montan S wax, lignite wax, peat wax, and petroleum wax. The bio-based synthetic paraffin wax as x 25 — specified in the present disclosure is distinguished from these conventionally used waxes by 2 being based on biological materials, but synthetized and thus a non-naturally occurring material I unlike beeswax, fatty acids and triglycerides. Furthermore, the bio-based synthetic paraffin wax 3 as specified in the present disclosure has a high n-alkane content, >95 w% or >99 w% or even 2 >99.5 w%, thus being paraffinic and more resistant towards deterioration e.g. by hydrolysis and O 30 oxygenation compared to fatty acid esters, partially or fully hydrogenated vegetable oils, ketones etc. The bio-based synthetic paraffin waxes as specified in the present disclosure are solid at room temperature.

As used herein, “bio-based” generally refers to the renewable, biological content or origin of the bio-based synthetic paraffin wax. Carbon atoms of biological origin comprise a higher number of '*C isotopes compared to carbon atoms of fossil origin. Therefore, it is possible to distinguish e.g. paraffins of renewable origin from fossil paraffins by analysing the ratio of PC and !"C isotopes. By analysing the ratio of PC and !*C isotopes it can also be determined whether or not the carbon content of a synthetic paraffin wax is of biological origin in full, or partly, or whether the carbon content of the synthetic paraffin wax is fully of fossil origin. Thus, a particular ratio of said isotopes can be used as a "tag" to identify bio-based carbon content of the wax and to differentiate it from fossil waxes. An example of a suitable method for analysing — the content of carbon from biological or renewable sources is ASTM D 6866-12. Preferably at least the n-alkanes of the bio-based synthetic paraffin wax have a fully renewable, bio-based carbon content. While the synthetic paraffin wax of the present disclosure is referred to as being bio-based, it should be understood that e.g. some additives of fossil origin may be incorporated in the bio-based synthetic paraffin wax composition as optional components, without deviating from the scope of the present disclosure. On the other hand some additives optionally incorporated in the bio-based synthetic paraffin wax may have fully bio-based carbon content, such as glycerides, fatty acids, partially or fully hydrogenated vegetable oils, beeswax, carnauba wax, shellac wax, etc. Most preferably essentially the whole carbon content of the bio-based synthetic paraffin wax originates from renewable, biological sources, thereby providing most effective increase in renewable, bio-based content when used for replacing materials of fossil origin in the applications proposed herein.

The bio-based synthetic paraffin wax usable in the present disclosure comprises at least 50 w% of a mixture of n-alkanes having carbon chains of 23 to 43 carbon atoms. These bio-based o synthetic paraffin waxes are solid at room temperature, which is beneficial for various N 25 — applications, for example for use in candles. Furthermore, the n-paraffins of the bio-based S synthetic paraffin wax have long enough carbon chains to increase the flash point of the wax, 3 thereby facilitating safe handling and use in various applications. The bio-based synthetic E paraffin wax has good compatibility with various other materials commonly used in the 3 specified applications, e.g. with stearin conventionally used in candles, without phase D 30 separation. This is believed to be due to the presence of a mixture of different n-alkanes in the O bio-based synthetic paraffin wax, instead of a single n-alkane. The bio-based synthetic paraffin wax may be used in the specified applications as the sole paraffinic wax component, or even as the sole wax component, or in combination with other wax compositions. The bio-based synthetic paraffin wax may be used concurrently or in combination with any typical supplements, further additives and/or materials that are conventionally used in the specified applications. Such supplements, further additives, and materials are well known for a person skilled in the respective field of application.

According to a second aspect of the present disclosure, a method for manufacturing a combustible solid or gelatinous product characterized by what is presented in claim 12, is provided. The method for manufacturing a combustible solid or gelatinous product comprises: providing a bio-based synthetic paraffin wax as specified in the present disclosure; and forming a combustible solid product by compression molding the bio-based synthetic paraffin wax, preferably in a softened state, or by casting the bio-based synthetic paraffin wax in a molten state followed by cooling, or forming a combustible gelatinous product by admixing the bio- based synthetic paraffin wax with a liquid fuel, preferably with an alcohol or a paraffinic liquid fuel.

According to a third aspect of the present disclosure, a combustible solid or gelatinous product characterized by what is presented in claim 14, is provided. The combustible solid or gelatinous product comprises a bio-based synthetic paraffin wax as specified in the present disclosure. According to a fourth aspect of the present disclosure, a candle comprising a bio-based synthetic paraffin wax as specified in the present disclosure, characterized by what is presented in claim 15, is provided. The candle comprises the bio-based synthetic paraffin wax; a wick; and optionally one or more candle wax additives selected from fragrances; dyes; pigments; UV light absorbers; insect repellants; color stabilizers; antioxidants; glyceryl tristearate; saturated fatty acids such as stearic acid, palmitic acid, myristic acid, or arachidic acid; fatty acid mono- or a diglycerides; partially hydrogenated vegetable oils; fully hydrogenated vegetable oils; beeswax; S carnauba wax; shellac wax; and poly(alphaolefins).

S 25 — Further advantages and embodiments of the present disclosure are described and exemplified 3 in the following Detailed Description. The embodiments and advantages mentioned in this E: specification relate, where applicable, to the method of using a bio-based synthetic paraffin x wax, to the method for manufacturing a combustible solid or gelatinous product, to the 3 combustible solid or gelatinous product, as well as to the candle, even though it is not always ES 30 specifically mentioned.

DETAILED DESCRIPTION

The inventors surprisingly found out that the renewable bio-based content may be effectively increased in various applications and products by using a bio-based synthetic paraffin wax as specified in the present disclosure for replacing materials of fossil origin. This is especially beneficial for reducing carbon footprint of the specified applications and products, including greenhouse gas emissions involved in their manufacture and use. Furthermore, the inventors found out that some end-product properties may be modified or even improved by replacing bio-based natural and/or non-paraffinic materials with the bio-based synthetic paraffin wax. Without wishing to be bound by a theory it is believed that the improved stability of the bio- based synthetic paraffin wax and/or its higher content of carbon chains of increased length positively contribute to the end-product properties.

Reference will now be made in detail to the embodiments of the present disclosure. The present disclosure relates to a method of using a bio-based synthetic paraffin wax comprising at least 50 w% of a mixture of n-alkanes having carbon chains of 23 to 43 carbon atoms, as a candle wax, in artificial firelogs, in heating briquettes or heating pellets, in lighter — blocks, in gel fuels, for waxing candle wicks, for impregnating porous materials, for coating, for lubricating, for electrical insulation, as a process aid in rubber, as a binder, as a hydrophobization agent in sizing compositions, as an additive in lubricants, in personal care products, in adhesives, or for infiltrating and/or embedding tissue samples. In several such applications use of the bio-based synthetic paraffin wax of the present disclosure can provide significant advantages. The bio-based synthetic paraffin wax is advantageously used in various combustible solid or gelatinous products such as candles, artificial firelogs, heating briquettes, heating pellets, lighter blocks, gel fuels, candle wicks etc. In these applications the bio-based synthetic paraffin wax may provide not only favorable burning characteristics but also binding, N dust-reducing, friction-reducing, flowability-improving, water-repelling, hydrophobizing 5 25 and/or rheology modifying effects. When used for impregnating porous materials, such as for = impregnating wood, paper or board, yarns or fabrics, the bio-based synthetic paraffin wax may 7 contribute for example to the desired water resistance/repellency and hydrophobicity of the E impregnated material. When used for coating different surfaces, such as for coating fertilizers, = feed or food e.g. fruit or cheese, or paper or board to provide e.g. wax paper, or molds to provide S 30 easier release, or snowboards to improve gliding, the bio-based synthetic paraffin wax may S contribute for example to the desired water resistance, water-repelling, anti-caking, dust- reducing, friction-reducing, flowability, release, oil-proofing, and barrier characteristics e.g. against odours and gases, as well as smoothness and gloss of the coated surfaces. The bio-based synthetic paraffin wax is a good insulator and thus suitable for electrical insulation. Incorporating the bio-based synthetic paraffin wax as a process aid into a rubber composition may provide internal lubrication, mill and mold release, improved compound flow and ozone barrier, as the wax blooms or migrates to the rubber surface creating a friction decreasing and ozone barrier film on the surface. The bio-based synthetic paraffin wax may also be used as a hydrophobization agent in sizing compositions for paper and board, especially for surface sizing. It may also be functionalized or formulated to improve retention on fibers and usability in internal sizing compositions for paper and board. The bio-based synthetic paraffin wax may also be used as an additive (or component) in lubricants, enhancing e.g. lubricant performance at elevated temperatures. The bio-based synthetic paraffin wax may also be used in personal care products including cosmetics, creams, baby creams, shampoos, body lotions, lipsticks, lip and skin ointments, for example for providing moisturizing or rheology-modifying effect. Further application areas for the bio-based synthetic paraffin wax include adhesives, especially hot-melt adhesives. The bio-based synthetic paraffin wax may also be used for infiltrating and/or embedding tissue samples for histological analysis. Usually tissues, after fixation and dehydration process, are not sufficiently hard to cut into thin sections, but need to be infiltrated and embedded in a suitable medium such as paraffin, usually with the help of vacuum. In this way sufficiently hard blocks are obtained to facilitate cutting of sections of only few microns. The infiltration and embedding of tissues may be done by using the same medium, or by using — two different mediums.

In some embodiments, the bio-based synthetic paraffin wax has a slip melting point of about 50 °C to about 90 °C, at 1 atm, preferably about 55 °C to about 85 °C, at 1 atm, more preferably of about 60 °C to about 80 °C, at 1 atm. N The slip melting point (SMP), or slip point, is a conventional definition of the melting point of 5 25 a waxy solid. In brief, it is determined by casting a 10 mm column of the waxy solid in a glass = tube with a specified internal diameter and length, and then immersing the tube in a 7 temperature-controlled water bath. The slip point is the temperature at which the solid column S begins to rise in the tube due to buoyancy, as the outside surface of the solid column is molten. = This method is commonly used for fats and waxes that are often mixtures of compounds with S 30 a range of molecular masses, without well-defined melting points. As used in the present N disclosure, by slip melting point is referred to slip melting point values as determined according to ISO 6321-02. The slip melting point of the bio-based synthetic paraffin wax as specified in the present disclosure is advantageous for applications and products used at room temperature, such as for use in candles.

While the slip melting point of the bio-based synthetic paraffin wax is not directly comparable with melting temperatures of individual, pure C23-C43 n-alkanes, the table below is provided for illustrating the effect of increasing carbon chain length as well as the even/uneven number of carbons on the melting temperatures.

Alkane | Melting point, | Alkane Melting point, | Alkane Melting point, eT fe TT att Costis2 54 Coes Jo |CIMMO0 [78 CosHSS 645 [CMa 7s [ooe In some embodiments, the bio-based synthetic paraffin wax comprises at most 10w% of components having a boiling point of 300 °C or less, at 1 atm.

These embodiments may provide a higher flash point to the wax and thus improved safety, especially beneficial in high- temperature applications.

In some embodiments, the bio-based synthetic paraffin wax comprises at most 10w% of components having a boiling point of 600 °C or more, at 1 atm.

These embodiments may provide improved processability without requiring as high S temperatures, contain less unmelt clots when molten, and facilitate wider usability with less s 15 defects e.g. in impregnation and coating applications. 3 In some embodiments, the bio-based synthetic paraffin wax comprises at least 70w% of I components having a boiling point in the range of 370 — 545 °C, at 1 atm. a X In some embodiments, the bio-based synthetic paraffin wax comprises at least 60w%, or at least D 70w% or at least 80w%o, preferably at least 90w%, of the mixture of n-alkanes having carbon O 20 chains of 23 to 43 carbon atoms.

In some embodiments, the bio-based synthetic paraffin wax comprises at least 60w%, preferably at least 70w%, of a mixture of n-alkanes having carbon chains of 31 to 39, preferably

31 to 35, carbon atoms.

In some embodiments, the bio-based synthetic paraffin wax comprises at least 60w% of n-alkane having carbon chain of 31 carbon atoms.

In some embodiments, the bio-based synthetic paraffin wax comprises less than 10 w%, preferably less than Sw%, more preferably less than 3w% of isoparaffins.

Too high content of isoparaffins may decrease the slip melting temperature of the bio-based synthetic paraffin wax to an undesired low level, as isoparaffins have lower melting temperatures compared n- paraffins of same carbon number.

In some embodiments, the bio-based synthetic paraffin wax has a flash point of at least 130 °C, preferably at least 140 °C, more preferably at least 150 °C, as determined according to ENISO2719. In some embodiments, the bio-based synthetic paraffin wax has a kinematic viscosity of at most 5 mm?/s at 100°C as determined according to ENISO3104. In some embodiments, the bio-based synthetic paraffin wax has a kinematic viscosity of at most 8 mm?/s at 80°C as determined according to ENISO3104. In some embodiments, the bio-based synthetic paraffin wax has a kinematic viscosity of at most 20 mm?/s at 40°C as determined according to ENISO3104. In some embodiments, the bio-based synthetic paraffin wax is essentially free from aromatic compounds.

Neither the feedstocks nor the manufacturing methods of the bio-based synthetic paraffin waxes requires presence of aromatics.

In some embodiments, the bio-based synthetic paraffin wax is obtainable by a process comprising: providing a feedstock comprising fatty acid compounds having fatty acid carbon chains of 12 to 22 carbon atoms; subjecting the feedstock to catalytic ketonization to obtain a O ketone stream comprising ketones of 23 to 43 carbon atoms; subjecting at least part of the O ketone stream to catalytic deoxygenation, preferably catalytic hydrodeoxygenation, to obtain a 3 deoxygenation effluent comprising a mixture of n-alkanes having carbon chains of 23 to 43 2 25 — carbon atoms; separating at least gases and water from the ketone stream and/or deoxygenation E effluent; and recovering the remaining deoxygenation effluent as the bio-based synthetic + paraffin wax.

Preferably the bio-based synthetic paraffin wax is obtained by the above specified & process.

As used herein, fatty acid carbon chain of 23 to 43 carbon atoms refers to the total ä carbon number of the fatty acid portion of the fatty acid compound, any other carbon atoms such as those present in glycerol or C1-C5 alkyl alcohol portion are omitted.

Bio-based synthetic paraffin waxes according to these embodiments have a beneficial, narrow carbon chain distribution, sometimes no more than 5 carbons wide, and an extremely low content of volatile organic compounds (VOC). Thus, the bio-based synthetic paraffin waxes according to these embodiments may also have a narrow distillation range. The narrow carbon number and distillation range may provide more coherent and controllable properties to the bio-based synthetic paraffin wax that may be desired in many applications. In some further embodiments the remaining deoxygenation effluent may be subjected to one or more fractionation steps, especially to one or more distillation steps, to provide a bio-based synthetic paraffin wax having even narrower carbon chain distribution, as may be desired for some of the applications of the present disclosure.

Generally, the bio-based synthetic paraffin wax as specified in the present disclosure may be manufactured as disclosed in WO02007068795, W02007068796, W02007068797, W02016062868, WO2018234187, WO2018234188, or WO2018234189, the disclosures of which are herein incorporated by reference in their entirety. The manufacture of the bio-based synthetic paraffin wax as specified in the present disclosure does not include a separate isomerization step, as disclosed in these references. The feedstocks, the catalytic ketonization catalysts and/or conditions, and the catalytic deoxygenation, especially hydrodeoxygenation, catalysts and/or conditions for manufacturing the bio-based synthetic paraffin wax as specified in the present disclosure may be selected as disclosed in WO2007068795, W02007068796, WO02007068797, WO02016062868, WO02018234187, WO2018234188, and/or in WO02018234189. Alternatively, any of said materials and/or conditions may be modified according to availability and/or preferences as long as the bio-based synthetic paraffin wax as specified herein is obtained. Such modifications are well known for a person skilled in the art. Feedstocks of the above specified process have a substantial effect on the composition and N distillation range of the bio-based synthetic paraffin wax. For example for feedstocks 5 25 comprising fatty acid compounds having fatty acid carbon chains of 16, 18, 20 and 22 carbon = atoms, typical carbon chains of the obtained n-alkanes, when two fatty acids of same carbon 7 chain length are combined, are respectively of 31, 35, 39, and 43 carbon atoms, and when two E fatty acids of different carbon chain length are combined, the obtained n-alkanes have carbon = chains of 33, 35, 37, 39, and 41 carbon atoms. For obtaining bio-based synthetic paraffin waxes S 30 having even narrower carbon chain distributions, the feedstocks comprising fatty acid S compounds may be fractionated by distillation before subjecting to the catalytic ketonization. In some embodiments, the feedstock of the above specified process comprises at least S0w%, preferably at least 70 w%, more preferably at least 85w%, of fatty acid compounds having fatty acid carbon chains of 12 to 22 carbon atoms, preferably of 16 to 20 carbon atoms. In some embodiments, the fatty acid compounds comprise free fatty acids, salts of fatty acids, fatty acid mono-, di- or triglycerides, esters of fatty acids and C1-C5 alkyl alcohols, fatty acid anhydrides, fatty alcohols, fatty aldehydes, or any combinations thereof.

Examples of feedstocks suitable for use in the above specified process include one or more of vegetable oils such as rapeseed oil, canola oil, soybean oil, coconut oil, sunflower oil, palm oil, palm kernel oil, peanut oil, linseed oil, sesame oil, maize oil, poppy seed oil, cottonseed oil, soy oil, tall oil, colza oil, hemp oil, corn oil, castor oil, jatropha oil, jojoba oil, olive oil, flaxseed oil, camelina oil, safflower oil, babassu oil, seed oil of any of Brassica species or subspecies, — such as Brassica carinata seed oil, Brassica juncea seed oil, Brassica oleracea seed oil, Brassica nigra seed oil, Brassica napus seed oil, Brassica rapa seed oil, Brassica hirta seed oil and Brassica alba seed oil, and rice bran oil, or fractions or residues of said vegetable oils such as palm olein, palm stearin, palm fatty acid distillate (PFAD), purified tall oil, tall oil fatty acids, tall oil resin acids, and used cooking oil of vegetable origin; animal fats such as tallow, lard, — yellow grease, brown grease, fish fat such as baltic herring oil, salmon oil, herring oil, tuna oil, anchovy oil, sardine oil, and mackerel oil, poultry fat, and used cooking oil of animal origin; microbial oils, such as algal lipids, fungal lipids and bacterial lipids. Suitable fatty acid compounds may also be obtained by transesterifying fatty acid glycerides in the presence of an alkyl alcohol, especially C1-C5 alkyl alcohol, to obtain transesterification effluent containing the corresponding fatty acid alkyl ester and crude glycerol, and/or by hydrolyzing fatty acid glycerides to obtain a hydrolysis effluent containing free fatty acids and crude glycerol; and by recovering the fatty acid alkyl ester from the transesterification effluent and/or the free fatty acids from the hydrolysis effluent.

O O In some embodiments, the bio-based synthetic paraffin wax is supplemented with one or more 3 25 additives selected from fragrances; dyes; pigments; UV light absorbers; insect repellants; color 2 stabilizers; antioxidants; glyceryl tristearate; saturated fatty acids such as stearic acid, palmitic I acid, myristic acid, or arachidic acid; fatty acid mono- or diglycerides; partially hydrogenated 3 vegetable oils; fully hydrogenated vegetable oils; beeswax; carnauba wax; shellac wax; and 2 poly(alphaolefins), as may be desired for the intended application. ES 30 The present disclosure relates to a method for manufacturing a combustible solid or gelatinous product comprising: providing a bio-based synthetic paraffin wax as specified in the present disclosure; and forming a combustible solid product by compression molding the bio-based synthetic paraffin wax, preferably in a softened state, or by casting the bio-based synthetic paraffin wax in a molten state followed by cooling, or forming a combustible gelatinous product by admixing the bio-based synthetic paraffin wax with a liquid fuel, preferably alcohol or paraffinic liquid fuel, such as ethanol, isopropyl alcohol or diesel.

As used herein, combustible refers to products that are intended for combustion.

In these products the bio-based synthetic paraffin wax may function primarily as a burning mass (like in candles and lighter blocks), as a binder and a water-repellant that also reduces friction, dusting and improves flowability (like in briquettes and pellets), and/or as a rheology modifier (like in gel fuels). The bio-based synthetic paraffin wax is especially advantageous in combustible solid or gelatinous products — because it may provide binding, dust-reducing, friction-reducing, flowability, hydrophobizing, water-repelling and/or rheology modifying effects in addition to the favorable burning characteristics.

In some embodiments, one or more combustible solid further material is incorporated in the combustible solid or gelatinous product.

Examples of such combustible solid further materials include wick, wood chips, saw dust, wood powder, bark, straw, manure, — cellulosic and/or lignocellulosic fibers, other natural fibers, organic synthetic fibers, and combinations thereof.

Manufacturing of candles, artificial firelogs, heating briguettes or heating pellets typically involves incorporation of one or more of combustible solid further materials.

This may be effected for example by casting the bio-based synthetic paraffin wax in a molten state as an admixture with the combustible solid further material, or pouring the molten wax into a mold containing the combustible solid further material.

Alternatively, the combustible solid further material may be incorporated in the combustible product by compression molding it together with comminuted bio-based synthetic paraffin wax, for example as processed into chips or granules.

Lighter blocks a.k.a ignition blocks or fire starters are conveniently manufactured by compression molding or casting the bio-based synthetic paraffin wax.

Gel S 25 — fuels usable e.g. in indoor and outdoor gel fuel fireplaces are manufactured by admixing the x bio-based synthetic paraffin wax with a liguid fuel, preferably alcohol or paraffinic liguid fuel, x such as ethanol, isopropyl alcohol or diesel.

Any technique or processing known in the art I suitable for this purpose may be used.

In the gel fuels the bio-based synthetic paraffin wax acts a + as a rheology modifier increasing viscosity, and reducing e.g. spillage and splattering of the n 30 liquid fuel. 5 The present disclosure relates to a combustible solid or gelatinous product, preferably a combustible solid product, comprising a bio-based synthetic paraffin wax as specified in the present disclosure.

The present disclosure relates to a candle comprising a bio-based synthetic paraffin wax as specified in the present disclosure, and a wick. In some embodiments, the candle further comprises one or more candle wax additives selected from fragrances; dyes; pigments; UV light absorbers; insect repellants; color stabilizers; antioxidants; glyceryl tristearate; saturated fatty acids such as stearic acid, palmitic acid, myristic acid, or arachidic acid; fatty acid mono- or diglycerides; partially hydrogenated vegetable oils; fully hydrogenated vegetable oils; beeswax; carnauba wax; shellac wax; and poly(alphaolefins). Suitable additives for candle compositions are described e.g. in US6063144 and US6503285. When present, the amount of total additives in the composition is generally in the range from

0.01 w% to 20 w%, e.g., from 0.5 w% to 10 w% or from 1 w% to 5 w%, based on the total weight of the candle. Suitable pigments and dyes include titanium dioxide, zinc oxide white, copper, bronze, aluminum metal powders and flakes, phthalocyanine blue, phthalocyanine green, yellow and red pigments of the benzimide azolone group, etc. The fragrance may be synthetic or a naturally derived oil, such as oil of basil, bergamot, bitter orange, citrus, lemon, mandarin, caraway, cedar leaf, clove leaf, cedar wood, geranium, jasmine, lavender, orange, origanum, rosemary, petitgrain, white cedar, patchouli lavandin, neroli, vanilla, rose, etc. Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percentages are based on weight, and all test methods are current as of the filing date of this disclosure. The weight percentages in connection with hydrocarbons, may be measured for — example using field ionization mass spectrometry (FI-MS). The embodiments of the present disclosure described in this specification may be combined, in whole or in part, with each other to form further embodiment(s) of the present disclosure. o Further, the particular features or characteristics illustrated or described in connection with O various embodiments may be combined, in whole or in part, with the features or characteristics x 25 of one or more other embodiments without limitation. Such modifications and variations are 2 intended to be included within the scope of the present disclosure. A method of using, a method I for manufacturing, a combustible solid or gelatinous product, or a candle, to which the present 3 disclosure is related, may comprise at least one of the embodiments of the present disclosure e described in this specification.

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N N 30 EXAMPLES In the following, the present disclosure will be described in more detail. The description below discloses some embodiments and examples of the present disclosure in such detail that a person skilled in the art is able to utilize the present disclosure. Not all steps of the embodiments are discussed in detail, as many of the steps will be obvious for the person skilled in the art based on this specification. The following examples were carried out in a small-scale testing laboratory; however, a person skilled in the art is able to scale the examples as desired.

Unless otherwise stated, the data in percent or ratios are always percent by weight, or weight ratios, respectively. Preparation of the bio-based synthetic paraffin wax The bio-based synthetic paraffin wax used in the tests was produced according to the principles disclosed in WO2016062868 examples 1 and 2. In brief, a fatty feedstock of PFAD was provided comprising free fatty acids and fatty acid glycerides, majority of the fatty acids having a carbon chain length of C16, or C18. The feedstock was subjected to a catalytic ketonization to obtain ketones similarly as in WO2016062868 example 1, but using CO2-containing gas- atmosphere. The ketones were subjected to a catalytic hydrodeoxygenation, and gases and water were removed (as in WO2016062868 example 2). The resulting mixture of n-alkanes, that contained mainly C31, C33 and C35 n-alkanes, was determined to have a slip melting point above 60 °C, which is of good level for applications and products used at room temperature, such as for use in candles. The obtained n-alkane mixture was subjected to various tests relevant for use as bio-based synthetic paraffin wax in candles, such as in tealights. The test procedures and results are reported below.

— While the n-alkane mixture, obtained as described above, was used as such as the bio-based synthetic paraffin wax in the following tests, the properties of said wax could be further tailored for example by removing lower boiling paraffins to further increase flash point, and/or by S removing a fraction having highest boiling point so as to improve e.g. colour and stability, as s residual impurities (if any) tend to reside in the highest boiling fraction. 3 25 — Tests relating to candle quality specifications according to RAL-GZ041 quality assurance for z candles a 3 The properties of the bio-based synthetic paraffin wax were tested, and compared to the D requirements for paraffin wax according to RAL-GZ041 Appendix 1 - Requirements for raw S materials and additives to protect health (see table 1 below).

Table.

Odour ASTMDI1834 No distinctive | No distinctive noticeable atypical odours* tmn PAH content by UV method below the | not present** adsorption limit of Ph. Eur 7th edition monograph 1034 Sulphur content DIN EN ISO 20884 max | 2.1 mg/kg *

EE Solvent remainders: Benzene max 0.5 | not present™* a N.D. = not determined * Modified test used: odour of solid paraffin sample was evaluated by 1 person ** No aromatic solvents are utilized in the production process, and thus they are not present. ~ Determined according to ASTMD7039 Based on the results reported in table 1, the bio-based synthetic paraffin wax is in conformity with the tested RAL-GZ041 Appendix 1 requirements set forth for paraffin wax for use in candles. Elemental analysis of the bio-based synthetic paraffin wax S 10 The bio-based synthetic paraffin wax was subjected to an elemental analysis using ICP (see N table 2 below).

S 2 Table 2. Content of elements in the bio-based synthetic paraffin wax (ICP analysis) ä k m Metals and other elements contained in candle base materials may result in undesirable changes because of their catalytic activity, and there may also be indoor air limits for some elements. Based on the results reported in table 2, the bio-based synthetic paraffin wax contains very low or even undetectable amounts of metals, and may thus be expected to exhibit good stability against metal-catalysed reactions. This may be especially beneficial when the bio-based synthetic paraffin wax is used in candles admixed with less stable candle compositions such as with vegetable and animal fats and oils. The low/negligible metal content improves also safety during processing and use, and may be crucial especially for indoor use of combustible — products. Furthermore, elevated metals content might also cause colouring of the wax that could be regarded as a defect in untinted products, but could also affect tinting of the burning mass, or cause bending of the color when preparing tinted candles. S Physical parameters of the bio-based synthetic paraffin wax S Flash point, boiling range and kinematic viscosity at various temperatures of the bio-based 3 15 — synthetic paraffin wax were measured. The results are reported in table 3 below.

T a Table 3. Test results of key physical parameters of the bio-based synthetic paraffin wax <

Based on the results reported in table 3 above, it can be concluded that the bio-based synthetic paraffin wax exhibits sufficiently high flash point to facilitate safe use in the applications specified in the present disclosure. Furthermore, the bio-based synthetic paraffin wax exhibits a very low kinematic viscosity already at temperatures well below the flash point. For most applications there is no need to heat the wax to 100°C, as already when heated e.g. to 80°C the kinematic viscosity of the molten wax is low enough enabling e.g. impregnation of materials having very fine pores. It is beneficial that the molten wax exhibits such low kinematic viscosities at temperatures that do not damage materials to be contacted with the molten wax. The low kinematic viscosity of the molten wax at the typical processing temperatures may reduce formation of bubbles and other defects when manufacturing products using the wax. Candle casting and burning tests using different materials The materials listed in table 4 were used in the candle casting and burning tests. Table 4. Materials used in the candle casting and burning tests. Test Materials Material description Slip melting point, oe ee TTT s N Bio-based synthetic paraffin wax | paraffin wax obtained by ketonizing | 63.5 ky TTT imusta | 3 15

T a Sample materials were molten in oven at temperature slightly above the melting point. 10 g of = each sample material was poured in a metal tea light container with a wick positioned in the S middle. The cast candles were let to cool down and solidify. Burning tests were carried out in N ventilated hood and the burning behaviour inspected for set parameters as well filmed. Average results of 2 parallel test candles are reported in table 5.

Table 5. Sample Slip melting | Visual inspection Burning time | Residues = after ans [pue | mee tn CRI 54.5 Natural white 21 Small flame Yellowish when melt CR2 58.5 White 27 5.34 EE jona 1 | Generally, desired properties for candles include steady burning behavior, and burning time that is long enough to allow controlled burning. On the other hand the amount of residues after burning tend to increase upon prolonged burning time, so the burning time should be sufficiently limited so as to avoid increased residues after burning. Candles with elevated melting point may be regarded desired as their appearance may be less affected by direct sunlight, warm weather or hot climate, during storage, transportation and use. Additionally, the basic color of the material should not prevent tinting, or cause bending of the color when — preparing tinted candles. All sample materials could be easily formed into tealight candles. The optical and technical requirements were good for all candles: Surfaces were free of bubbles, crack, chips and damage; o colour shades were acceptable; the candles burnt with bright, calm flame, the wick exhibited N medium curvature, and no visible soot was released. <+ = 15 Among the tested materials, the bio-based synthetic paraffin wax had the highest slip melting 7 point. The bio-based synthetic paraffin wax exhibited similar burning time, and amount of a residues after burning, as the commercial references CR1, CR3 and CR4. Commercial reference = CR2 exhibited prolonged burning time resulting in increased residues after burning.

LO N A further series of candle casting and burning tests were conducted as above to verify suitability - 20 of the bio-based synthetic paraffin wax for use in blends. 10 g of materials or material mixtures as indicated in table 6 were cast to form tealight candles. The commercial paraffin used in the tests was a mineral paraffin wax typical for use in candles. The candles were burned, and burning time and residues evaluated. Table 6. Blending tests to verify compatibility Commercial BSPW CRI CR2 CR3 Burning time Residue paraffin [wt%] =[wt%] [wt%] |[wt%] [min/g] after [wt%] burning [g] 100 16 0.52 E r L - ET 04 | 55 E - La i. EG; 05 W TtT | J Hy 04 i G E m | 15 ETT i 50 - + 5 EX: 5 Based on the results reported in above table 6, the bio-based synthetic paraffin wax is well compatible with the tested wax materials in altering blend ratios, and can thus be utilized without any limitations as a component in candle wax blends to reduce their carbon footprint. While the above tests were conducted primarily in view of use in candles, the results obviously show usability of the bio-based synthetic paraffin wax in the other applications and products, as set forth in the present disclosure.

It is obvious to a person skilled in the art that with the advancement of technology, that the o basic idea of the present disclosure may be implemented in various ways. The present disclosure

N S and its embodiments are thus not limited to the examples described above, instead, they may x vary within the scope of the claims. o © 15

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Claims (15)

1. A method of using a bio-based synthetic paraffin wax comprising at least 50 w% of a mixture of n-alkanes having carbon chains of 23 to 43 carbon atoms, as a candle wax, in artificial firelogs, in heating briquettes or heating pellets, in lighter blocks, in gel fuels, for waxing candle wicks, for impregnating porous materials, for coating, for lubricating, for electrical insulation, as a process aid in rubber, as a binder, as a hydrophobization agent in sizing compositions, as an additive in lubricants, in personal care products, in adhesives, or for infiltrating and/or embedding tissue samples.

2. The method of claim 1, wherein the bio-based synthetic paraffin wax has a slip melting point of about 50 °C to about 90 °C, at 1 atm, preferably about 55 °C to about 85 °C, at 1 atm, more preferably of about 60 °C to about 80 °C, at 1 atm.

3. The method of claim 1 or 2, wherein the bio-based synthetic paraffin wax comprises at most 10w% of components having a boiling point of 300 °C or less, at 1 atm, and optionally at most 10w% of components having a boiling point of 600 °C or more, at 1 atm.

4 The method of any one of claims 1 - 3, wherein the bio-based synthetic paraffin wax comprises at least 70w% of components having a boiling point in the range of 370 — 545 °C, at 1 atm.

5. The method of any one of claims 1 - 4, wherein the bio-based synthetic paraffin wax comprises at least 80w%, preferably at least 90w%, of the mixture of n-alkanes having carbon — chains of 23 to 43 carbon atoms.

6. The method of any one of claims 1 - 5, wherein the bio-based synthetic paraffin wax Q comprises at least 60w%, preferably at least 70w%, of a mixture of n-alkanes having carbon

O 5 chains of 31 to 35 carbon atoms.

O 2 7. The method of any one of claims 1 - 6, wherein the bio-based synthetic paraffin wax has a I 25 — flash point of at least 130 °C, preferably at least 140 °C, more preferably at least 150 °C. a N 8. The method of any one of claims 1 - 7, wherein the bio-based synthetic paraffin wax is n S obtainable by a process comprising: providing a feedstock comprising fatty acid compounds S having fatty acid carbon chains of 12 to 22 carbon atoms; subjecting the feedstock to catalytic ketonization to obtain a ketone stream comprising ketones of 23 to 43 carbon atoms; subjecting at least part of the ketone stream to catalytic deoxygenation, preferably catalytic hydrodeoxygenation, to obtain a deoxygenation effluent comprising a mixture of n-alkanes having carbon chains of 23 to 43 carbon atoms; separating at least gases and water from the ketone stream and/or deoxygenation effluent; and recovering the remaining deoxygenation effluent as the bio-based synthetic paraffin wax.

9. The method of claim 8, wherein the feedstock comprises at least S0w%, preferably at least 70 w%, more preferably at least 85w%, of fatty acid compounds having fatty acid carbon chains of 12 to 22 carbon atoms, preferably of 16 to 20 carbon atoms.

10. The method of claim 8 or 9, wherein the fatty acid compounds comprise free fatty acids, salts of fatty acids, fatty acid mono-, di- or triglycerides, esters of fatty acids and C1-C5 alkyl alcohols, fatty acid anhydrides, fatty alcohols, fatty aldehydes, or any combinations thereof.

11. The method of any one of claims 1 - 10, wherein the bio-based synthetic paraffin wax is supplemented with one or more additives selected from fragrances; dyes; pigments; UV light absorbers; insect repellants; color stabilizers; antioxidants; glyceryl tristearate; saturated fatty acids such as stearic acid, palmitic acid, myristic acid, or arachidic acid; fatty acid mono- or —diglycerides; partially hydrogenated vegetable oils; fully hydrogenated vegetable oils; beeswax; carnauba wax; shellac wax; and poly(alphaolefins).

12. A method for manufacturing a combustible solid or gelatinous product comprising: providing a bio-based synthetic paraffin wax as defined in any one of claims 1 — 11; and forming a combustible solid product by compression molding the bio-based synthetic paraffin wax, preferably in a softened state, or by casting the bio-based synthetic paraffin wax in a molten state followed by cooling, or forming a combustible gelatinous product by admixing the bio- based synthetic paraffin wax with a liquid fuel.

O S

13. The method of claim 12, wherein one or more combustible solid further material is

N < incorporated in the combustible solid or gelatinous product.

O 3 25

14. A combustible solid or gelatinous product, comprising a bio-based synthetic paraffin wax E as defined in any one of claims 1-11. =

15. A candle comprising a bio-based synthetic paraffin wax as defined in any one of claims 1- S 10, a wick and optionally one or more candle wax additives selected from fragrances; dyes; N pigments; UV light absorbers; insect repellants; color stabilizers; antioxidants; glyceryl — tristearate; saturated fatty acids such as stearic acid, palmitic acid, myristic acid, or arachidic acid; fatty acid mono- or diglycerides; partially hydrogenated vegetable oils; fully hydrogenated vegetable oils; beeswax; carnauba wax; shellac wax; and poly(alphaolefins).

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