NL1037217C

NL1037217C - Combustible materials.

Info

Publication number: NL1037217C
Application number: NL1037217A
Authority: NL
Inventors: Erik Alexander Bijpost
Original assignee: Holland Novochem B V
Priority date: 2008-08-21
Filing date: 2009-08-21
Publication date: 2010-03-10
Also published as: NL1035853C

Description

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Titel: COMBUSTIBLE MATERIALS

INTRODUCTION

Fireplaces have been used in homes over the years for providing heat as well as to provide a desired ambience. While 5 wood and coal have been the primary fuels for burning in fireplaces, there is an increasing demand for either manufactured or artificial fireplace logs. These logs are typically easier to purchase and store, provide better heating values than wood or coal, are easier to light, safer to use 10 with virtually no maintenance during burning, and can be used to build fires of a known duration, generally from 2 hours to more than 4 hours. Artificial firelogs are typically manufactured by combining a carrier material, usually particles of cellulosic origin, with a combustible 15 binder/fuel. The cellulosic material may be sawdust, or a mixture of sawdust with other combustible materials of varying proportion. The binder/fuel typically consists of a suitable blend of waxes, typically a flammable wax such as paraffin or slack wax, flammable vegetable oils, such as stearic and/or 20 palmitic acid or other fatty acids or esters which can be used either alone or in combination with other combustible materials. Additives providing desired combustion characteristics, appearance, and other attributes may be combined with the basic ingredients. Such additives may 25 include chemicals designed to color or otherwise modify or retard the flame, add aroma or crackling sounds or otherwise change the burning characteristics to more closely mimic the burning of natural logs. Following thorough mixing of the raw materials, the resulting mixture is formed into suitable, log- 1037217 '2 like shapes by extrusion, molding or compression, in either a batch or continuous process.

Firelog base waxes should have physical characteristics (e.g. melting point and hardness) that allow the material to 5 be readily formed into firelogs having a pleasing appearance and/or feel to the touch, as well as having desirable olfactory properties. Artificial firelogs are typically manufactured from blends of about 50% to about 60% (by weight) petroleum waxes and about 40% to 50% (by weight) cellulosic 10 fibers. The petroleum wax, which may include paraffin wax or slack wax by way of example, provides the principal fuel content for the firelog and contains about twice the BTU (British thermal unit) energy value per unit mass as the cellulosic fibers.

15 In recent years, there has been dramatic inflation in the cost of petroleum products, including refined products, such as petroleum waxes. Consequently, the application of petroleum-based products is much less economic for firelog manufacturers. Furthermore, paraffin wax material is derived 20 from non-renewable petroleum fossil fuel, and thus the byproducts of burning such fuel can contribute to the Greenhouse Effect.

In addition, the last decade has shown that the amount of waste material has increased rapidly due to both higher 25 consumption and higher production. Moreover, the availability of crude oil slowly starts to be limited. It means that it is absolutely necessary to find applications turning waste material into valuable products. It finally should lead to a strong reduction of crude oil use, whilst giving room for 30 sustainable alternatives. This problem is valid for many industries.

The most common binder component of synthetic firelogs is a petroleum slack wax or a synthetic polymer of high molecular weight which provides good adhesion with cellulosic fibers.

35 Saturated fatty acids, such as palmitic or stearic acids, can 3 be used to raise the melting point of the wax blend or to solidify the binder. Unsaturated, oily fatty acids are generally excluded because they are liquid at room temperature and lack the binding characteristics required for firelogs. A 5 liquid or soft wax binder material, such as that disclosed in U.S. Patent No. 4,326,854, must be solidified with the fibres using chemical processes, such as polymerization or neutralization in order to form a firelog, which can significantly increase the cost and complexity of production. 10 WO 2008/076456 teaches an artificial firelog comprising a combustible cellulosic material and a combustible nonpetroleum wax, derived from a plant oil, a vegetable oil, an animal fat, a rosin, a pitch and combinations thereof. As a result more environmental friendly artificial firelogs can be 15 produced. However, the prices of natural oils are increasing very rapidly due to the use as starting material for the production biodiesel.

A pricewise friendly alternative is offered by using corn by-products from ethanol production, marketed under the brand 20 name alluma™. Typically these corn-based mixtures comprise starch, yeast cells and proteins. These compounds possess a significantly lower energy value than the traditional petroleum waxes, owing the lower carbon content in the molecules. In addition, proteins contain nitrogen atoms, which 25 can be upon combustion transformed into NOx compounds. These products are known to be toxic.

The last few years, Applicant has put a lot of effort in turning waste material into petroleum and paraffin wax alternatives, especially towards developing protective 30 coatings for fertilizers (e.g. W02006/091076). Recently,

Applicant has filed a patent describing the use of polymers originating from fats and natural oil, e.g. polymeric biodiesel distillation residues. Such products appeared to be excellent mineral oil/wax alternatives in several 35 applications, ranging from fertilizer coatings, carrier for 4 pigments, cokes density improver to defoamer. The research has clearly demonstrated the attractive possibilities of the polymers.

5 OBJECTIVE OF THE INVENTION

It is obvious that there is a need for more affordable, efficient and low toxic binder materials for the production of artificial firelogs. In addition, it is advantageous when 10 extra additives can be admixed to provide other characteristics, e.g. the addition of sodium bicarbonate can give rise to lowering the CO emission upon burning the firelog (WO 02/0904.72) .

15 DESCRIPTION OF THE INVENTION

The invention relates to a method, composition and products providing new firelogs having (a) 30% to about 70% by weight of a combustible non-petroleum additive and (b) about 20 30% to about 70% by weight of combustible cellulosic or fibre material constituent, possibly admixed with a petroleum wax, saturated fatty acid or salt, for a total of about 100 parts.

The non-petroleum additives of choice are selected from 25 polymers with the formula ((FA)p - X))q (I) in which FA consists of C8 - C24 fatty alkyl, containing 0 to 5, preferably 0 to 3, C=C groups in de carbon chain, 30 X is a polar group selected from-C(0)OH, -C(0)0R, -NH2, -

NHC(O)R', NHC(0)OH, -OH, -COR

p = 1 to 1000, preferably 1 to 3, q = 1 tot 1000, preferably 2 to 5, on the understanding that p and q are not simultaneously 35 equal to 1, 5 R is a lower alkyl group, R' is H or a lower alkyl group.

Such polymers are based on unsaturated monomers, 5 containing fatty alkyl groups. Depending on the position of the unsaturation the product contains linear or branched chains, and the product can be a di-, tri-, oligo-, or polymer. For clarity the products are called polymers.

Valuable polymers appeared to originate from compounds in 10 which R and R' are equal or different from CH3, C2H5, C3H7, C4H9, C5Hh, pentaerytritol group, glycerol group, or a ether bond.

Preferably de FA group comprises an unsaturated Ci4-C22 fatty alkyl, containing 0 to 5, preferably 0 to 3, C=C groups in the alkyl chain.

15 Another objective is the application of distillation residues, in particular polymers (polymers comprise both oligo- and polymers), from the production of biodiesel and comparable products, such as fatty acids, fatty alcohols, fatty amines, fatty amides, fatty carbamates and fatty ethers.

20 Applicant has found that these distillation residues contains polymers according abovementioned formula (I) and can serve well as raw material for firelogs. The polymer is preferably originating from the bottom fraction of the biodiesel distillation process.

25 The polymers claimed can further be obtained via synthetic routes, especially by distillation of either an ester or salt from the corresponding (monomeric) fatty acid, fatty alcohol, fatty amine, fatty amide, fatty carbamate, or fatty ether, containing 8-24 C-atoms.

30 Another method comprises polymerization of the original fatty monomers via known polymerization processes, preferably a radical-initiated polymerization (see e.g. WO2008/136661).

In addition, 'yellow grease' appeared to be an attractive raw material for firelogs. Yellow grease consists mainly of 6 old and used domestic fats and oils, such as deep fat, originating from either vegetable or animal sources.

The polymers claimed are usually well-available and affordable, while they are hardly applied yet on industrial 5 scale other than a cheap fuel source. Owing to the high carbon level, the energy value of these esters is high.

Moreover, applicant has found that the selected fatty polymers can be admixed with the traditional petroleum waxes. The solidification properties of the firelog end product can 10 further be adjusted by using saturated fatty acids, such as palmitic acid and stearic acid and mixtures thereof. Surprisingly, up to 10% (w/w) inorganic salts, such as sodium bicarbonate can be dissolved in the fatty polymers. WO 02/090472 claims that this specific salt decrease the CO 15 emission upon combusting a firelog. In addition, it appeared that the addition of either sodium hydroxide or potassium hydroxide to the polymers leads to a strong increase of the viscosity. Moreover, the flame retardation can be adjusted by admixing various compounds, such as used deep fat and 20 inorganic salts. Consequently, the application of fatty polymers as firelog constituent offers the producer very attractive opportunities: it matches with the traditional petroleum waxes, whereas it can also be tuned at wish by addition of e.g. used deep fat or inorganic salts.

25 Examples of combustible cellulosic or fiber material that may be used include, without limitation, wood particles, pulp, shavings or chips, sawdust, ground bark, peat, shredded paper or cardboard, waxed cardboard, charcoal powder, sphagnum moss, and agricultural waste materials such as straw, grass 30 clippings, leaves, cotton linter, rice hulls, peanut, almond, walnut or other nut shells and hulls, distillers grain or other cereal grain by-products and coffee grounds, and blends of any two or more of the foregoing.

The petroleum wax of a firelog material may be derived 35 from a variety of sources, including without limitation those 7 having a petroleum or non-petroleum base. A petroleum wax can contain one or more suitable wax or waxy materials, including without limitation combustible paraffin's, petrolatum's, microcrystalline and waxy crude oils, consisting of any one of 5 the following, in whole or part of a blend, including; slack wax, scale wax, residual wax, olefins, and resins.

The invention will be explained below with a number of examples, with the use of methods which are representative for handling and testing of the new raw materials for artificial 10 firelogs. These examples exclusively serve to explain and not to limit the claimed protective scope of the present invention.

EXAMPLES

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To test the potential of new raw materials, artificial firelogs have been prepared on lab scale. The procedure starts by admixing saw dust (110 mesh) with fatty polymers, possibly followed by petroleum wax, saturated fatty acid (or its metal 20 salt), inorganic salt or mixtures thereof (total amount of 20 grams) in a glass beaker at a temperature of approximately 90 °C. The components are thoroughly mixed by means of a spatula. The mixture is warmed up to 90 °C for 30 minutes and again thoroughly mixed. A plastic cylinder with a diameter of 3.0 cm 25 and a length of 14 cm is filled with the combustible mixture. Afterwards a piston is put in the cylinder at a pressure of 2 bar for 1 minute. The resulting firelog (3 cm high, 3 cm diameter) is allowed to cool down to room temperature and subjected to a 5 minute burning test (Table 1). A mixture of 30 saw dust and slack wax is used as reference.

Table 1. Compositions and characteristics of several firelogs

Raw materials Ratio Results 8

Reference: Saw dust, slack 50/50 Stable firelog.

wax (m.p. 65 °C, oil content After 5 minutes 25% (w/w)) burning, 2 mm of firelog outside is black.

Saw dust, used deep fat 50/50 Stable firelog.

(polymerized triglyceride 10% After 5 minutes (w/w), triglycerides 80% burning only half (w/w), fatty acid 10% (w/w)) of the cylinder is burned (flame retardation).

Saw dust, biodiesel polymer 50/50 Stable firelog.

ester residue (polymerized After 5 minutes ' triglyceride 30% (w/w), non- burning, 6 mm of hydrolysable 50% (w/w), long firelog outside chain methyl ester 20% (w/w)) is black.

Saw dust, used deep fat, 50/25/25 Stable firelog.

biodiesel polymer fatty ester After 5 minutes residue burning, 2 mm of firelog outside is black.

Saw dust, biodiesel polymer 50/25/25 Stable firelog.

fatty ester residue, slack After 5 minutes wax burning, 2 mm of firelog outside is black.

Saw dust, biodiesel polymer 50/50 Stable firelog.

fatty ester residue, After 5 minutes petrolatum (m.p. 85 °C, oil burning, 2 mm of content 10% (w/w/)) firelog outside is black.

Saw dust, biodiesel polymer 50/25/25 Stable firelog, fatty ester residue, some cracks, saturated stearic acid After 5 minutes 9 burning, 3 mm of firelog outside is black.

Saw dust, biodiesel polymer 50/25/25 Stable firelog. fatty ester residue, After 5 minutes magnesium stearate burning, 2 mm of firelog outside is black.

Saw dust, biodiesel polymer 50/48/2 Stable firelog. fatty ester residue, sodium After 5 minutes bicarbonate burning, 2 mm of firelog outside is black.

Saw dust, biodiesel polymer 50/45/5 Stable firelog.

fatty ester residue, sodium Upon burning, the hydroxide (33% aq) flame strongly retarded.

Saw dust, biodiesel polymer 50/45/5 Stable firelog.

fatty ester residue, Upon burning, the potassium hydroxide (50% aq) flame strongly retarded.

Saw dust, pentaerythritol 50/50 Stable firelog.

tetrastearate ester After 5 minutes burning, 3 mm of firelog outside is black.

Saw dust, sorbitan 50/50 Stable firelog.

tristearate ester After 5 minutes burning, 3 mm of firelog outside is black.

It can be concluded that a wide range of polymers originating from fatty components, such as used deep fat, 10.

fatty esters and its polymerized distillation residues, act as good binders and combustion additives for artificial firelogs. It has been shown that the physical properties of fatty polymers can further be adjusted by either admixing other 5 fatty esters or addition of petroleum waxes, saturated fatty acids, saturated fatty acid salts and/or inorganic salts.

1037217

Claims

A combustible material containing a combination of combustible cellulose and combustible polymer compounds of formula ((FA) p - X) q (I) 5 wherein FA is a saturated or unsaturated C 8 -C 24 fatty alkyl, having from 0 to 5, with preferably from 0 to 3, C = C groups in the chain, X is a radical selected from -C (O) 0 H, -C (O) O R, -NH 2, -NHC (O) R ', NHC ( O) OH, -OH, -COR p = 1 to 1000, preferably from 1 to 3, q = 1 to 1000, preferably from 2 to 5, provided that p and q are not both equal to 1 at the same time, 15. is a lower alkyl group, R 'is H or is a lower alkyl group.

Material according to claim 1, wherein the combustible material consists of 30 to 70% (m / m) cellulose, 30 to 70% (m / m) polymer compound of formula (I), with a final total of 100% (m / m) m).

3. Material according to one or more of claims 1 to 2, wherein the material is further provided with a petroleum wax or mixtures thereof.

Material according to one or more of claims 1 to 3, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compound of formula (I) and 0.1 30 to 70% (m / m) petroleum wax, with a final total of 100% (m / m).

R 'is H or a lower alkyl group, wherein a residual stream containing vegetable oils, animal fat, or recycled fat is subjected to transesterification in a manner known for the production of biodiesel, the product thus obtained being distilled for removal of a fraction suitable as biodiesel, and isolating the residual bottom fraction thus obtained to obtain a fraction containing polymer compounds of formula (I), which compounds are optionally subjected to functionalization into amine, amide, ether or carbamate compounds.

5. Material according to one or more of claims 1 to 4, wherein the material is further provided with a saturated fatty acid, in particular hexadecanic acid, octadecanic acid or mixtures thereof.

Material according to one or more of claims 1 to 5, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compound of formula (I) and 0, 1 to 70% (m / m) saturated fatty acid, with a final total of 100% (m / m).

A material according to any one of claims 1 to 6, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compound of formula (I), 0.1 up to 70% (m / m) petroleum and 0.1 to 70% (m / m) saturated fatty acid, with a final total of 100% (m / m). 15

Material according to one or more of claims 1 to 7, wherein the material further comprises a metal salt of a fatty acid, in particular aluminum stearate and magnesium stearate or mixtures thereof. 20

A material according to any one of claims 1 to 8, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compound of formula (I) and 0.1 up to 70% (m / m) metal salts of fatty acid, with a final total of 100% (m / m).

A material according to any one of claims 1 to 9, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compound of formula (I), 0.1 up to 70% (m / m) petroleum, 0.1 to 70% (m / m) saturated fatty acid and 0.1 to 70% (m / m) metal salts of fatty acid, with a final total of 100% (m / m) m).

11. Material according to one or more of claims 1 to 10, wherein the material is further provided with an inorganic salt or mixtures thereof.

12. Material according to one or more of claims 1 to 11, wherein the material consists of 30 to 70% (m / m) cellulose, 30 to 70% (m / m) polymer compound of formula (I) and 0.1 to 10% (m / m) inorganic salt, with a final total of 100% (m / m).

A material according to any one of claims 1 to 12, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compound of formula (I), 0, 1 to 70% (m / m) petroleum wax, 0.1 to 70% (m / m) saturated fatty acid, 0.1 to 70% (m / m) metal salts of fatty acid and 0.1 to 10% (m / m) m) inorganic salt, with a final total of 100% (m / m).

A material according to any one of claims 11 to 13, wherein the inorganic salt contains sodium bicarbonate.

15. Material according to one or more of claims 11 to 14, wherein the inorganic salt contains a hydroxide, in particular sodium hydroxide and potassium hydroxide.

Material according to one or more of claims 1 to 15, wherein the flammable cellulose comes from an organic source, in particular wood flour and sawdust. 25

Material according to one or more of claims 1 to 16, wherein the polymer compound is 'yellow grease', in particular fatty acid ester derivatives containing frying fat waste. 30

The material of any one of claims 1 to 17, wherein R and R ', which may be the same or different, are CH 3, C 2 H 5, C 3 H 7, C 4 H 9, C 5 HU, pentaerythritol radical, glycerol radical, or an ether bond. 35

A material according to any one of claims 1 to 18, wherein FA is a saturated or unsaturated, C14 -C22 fatty alkyl, having from 0 to 5, preferably 0 to 3, C = C groups in the chain.

A material according to any one of claims 1 to 19, wherein the polymer compound of formula (I) is from the bottom fraction of the biodiesel distillation process.

A material according to any one of claims 1 to 20, wherein the polymer compound of formula (I) is obtained by distillation of an ester or salt of a corresponding fatty acid, fatty alcohol, fatty amine, fatty amide, fatty ether, or fatty carbamate with 8-24 C atoms.

A material according to any one of claims 1 to 21, wherein the polymer compound of formula (I) is obtained by polymerization of the corresponding monomer.

23. Material according to claim 22, wherein the polymer compound of formula (I) is obtainable by radically-initiated polymerization of the corresponding monomer.

24. A method for making combustible material wherein a mixture is made of a combustible cellulose and combustible polymer compounds of formula (I), ((FA) p - X) q (I) wherein

A method according to claim 24, wherein the combustible material consists of 30 to 70% (m / m) cellulose, 30 to 70% (m / m) polymer compounds of formula (I), with an egg total of 100% (m / m) m).

26. Method according to one or more of claims 24 to 25, wherein the material is further provided with a petroleum wax or mixtures thereof.

A method according to any one of claims 24 to 26, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compounds of formula (I) and 0.1 30 to 70% (m / m) petroleum wax, with a final total of 100% (m / m).

28. Method according to one or more of claims 24 to 27, wherein the material is furthermore provided with a saturated fatty acid, in particular hexadecanic acid, octadecanic acid or mixtures thereof.

A method according to any one of claims 24 to 28, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compounds of formula (I) and 0, 1 to 70% (m / m) saturated fatty acid, with a final total of 100% (m / m). 5

A method according to any one of claims 24 to 29, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compounds of formula (I), 0.1 up to 70% (m / m) petroleum and 0.1 to 70% (m / m) saturated fatty acid, with a final total of 100% (m / m).

FA is a C8 -C24 fatty alkyl, saturated or unsaturated, with C = C groups in the chain from 0 to 5, preferably from 0 to 3, X is a radical selected from -C (O) OH , -C (O) R, -NH 2, NHC (O) R ', NHC (O) OH, -OH, -COR, p = 1 to 1000, preferably 1 to 3, q = 1 to 1000, at preferably 2 to 5, with the proviso that p and q are not both simultaneously equal to 1, R is a lower alkyl group,

31. Method according to one or more of claims 24 to 30, wherein the material is further provided with a metal salt of a fatty acid, in particular aluminum stearate and magnesium stearate or mixtures thereof.

A method according to any one of claims 24 to 31, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compounds of formula (I) and 0.1 20 to 70% (m / m) metal salts of fatty acid, with a final total of 100% (m / m).

A method according to any one of claims 24 to 32, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70% (m / m) polymer compounds of formula (I), 0, 1 to 70% (m / m) petroleum wax, 0.1 to 70% (m / m) saturated fatty acid and 0.1 to 70% (m / m) metal salts of fatty acid, with a final total of 100% (m / m) m).

The method of any one of claims 24 to 33, wherein the material further comprises an inorganic salt or mixtures thereof.

A method according to any of claims 24 to 34, wherein the material consists of 30 to 70% (m / m) cellulose, 30 to 70% (m / m) polymer compounds of formula (I) and 0.1 to 10% (m / m) inorganic salt, with a final total of 100% (m / m).

A method according to any one of claims 24 to 35, wherein the material consists of 30 to 70% (m / m) cellulose, 0.1 to 70%. (. M / m) polymer compounds of formula (I), 0.1 to 70% (m / m) petroleum wax, 0.1 to 70% (m / m) saturated fatty acid, 0.1 to 70% (m / m) metal salts of fatty acid and 0.1 to 10% (m / m) inorganic salt, with a final total of 100% (m / m).

The method of any one of claims 34 to 36, wherein the inorganic salt contains sodium bicarbonate. 10

A method according to any one of claims 34 to 37, wherein the inorganic salt contains a hydroxide, in particular sodium hydroxide and potassium hydroxide.

The method of any one of claims 24 to 38, wherein the combustible cellulose is from an organic source, in particular wood flour and sawdust.

40. A method according to any one of claims 24 to 39, wherein the polymer compound is 'yellow grease', in particular fatty acid ester derivatives containing frying fat waste.

41. Material obtainable by the method according to one or more of claims 24 to 40.

42. Method for making a combustible product, wherein use is made of a material according to one or more of claims 1 to 23 and 41 or of a material obtained according to the method according to one or more of claims 24 to 40, wherein the material is pressed, preferably in a mold, and the material is allowed to cure to a product with the desired shape.

A product obtainable according to the method of claim 42.

The product of claim 43, wherein the product is a hearth block. r '1 03 72 17