FR3075812A1 - COMBUSTIBLE COMPOSITION FROM BIOMASS, USE OF BIOMASS COMPOSITION AS FUEL AND PROCESS FOR PREPARATION - Google Patents

Abstract

The present invention relates to a fuel composition derived from biomass, in particular liquid biomass, and a process for preparing this fuel composition. The combustible composition comprises: from 10 to 50% by weight of pitch of tall oil, at least one compound derived from the treatment of wood, in particular of resinous wood, chosen from a compound derived from a terpene and an ester of rosin. This combustible composition is particularly suitable for being burned in industrial combustion plants.

Description

FUEL COMPOSITION FROM BIOMASS, USE OF A COMPOSITION FROM BIOMASS AS FUEL, AND METHOD OF PREPARATION

TECHNICAL AREA

The present invention relates to a combustible composition derived from biomass, in particular liquid biomass, the use of a liquid composition comprising pitch of tall oil as a fuel and a process for preparing the combustible composition.

Combustible combustion includes tall oil pitch (“tall oil pitch” in English terminology) as well as fluxing compounds.

The combustible composition of the present invention is more particularly suitable for use in combustion plants consuming exclusively, alone or in mixture, natural gas, liquefied petroleum gases, heating oil, coal, heavy fuel oils, biomass. It is therefore not a fuel.

In particular, the combustible composition of the present invention can be used in combustion plants classified in section 2910 A (and a fortiori 2910 B and 2910 C) of the nomenclature of installations classified for environmental protection (ICPE nomenclature). defined in decree No. 2013-814 of September 11, 2013, published in the Official Journal of the French Republic of September 13, 2013.

BACKGROUND ART The petroleum refining industry, at least in Western Europe, tends to decrease the production of heavy fuel oil due to the fall in demand. This decrease is linked to the switch to alternative energy sources by customers, notably natural gas, as well as to environmental constraints which tend to limit the quantities of NOx, SO2 and dust emitted into the atmosphere. To comply with the most stringent regulatory requirements, high-power combustion plants should use fuel oil free from nitrogen, sulfur and ash or smoke treatment techniques, which is not economically viable by compared to other energies, such as natural gas for example.

In addition, heavy fuel oil generally needs to be stored at a temperature close to 50 ° C in order to make it pumpable and must be sprayed at a temperature between 85 and 130 ° C depending on the burner technology, in connection with the viscosity of the product. These heating steps represent a significant energy consumption.

In addition, the flash point of heavy fuel oil (typically between 70 and 120 ° C) close to its processing temperature, can generate additional constraints in terms of safety (explosive atmospheres).

Research has therefore been carried out in order to obtain alternative fuels for heavy fuel oil which are less restrictive during their implementation and which make it possible to meet the increasingly high requirements relating to the atmospheric emissions resulting from its combustion.

There are thus fuel compositions based on heavy fuel oil and products produced from biomass, such as for example the fuel compositions produced by the applicant and described in documents WO2013 / 098524 and WO2014 / 102492. The combustible compositions described in WO2013 / 098524 are a mixture of heavy fuel oil and tall oil or a neutralizing oil (composition of fatty acids neutralized by a base then acidified), tall oil and oil neutralization to stabilize the fuel composition. The compositions described in WO2014 / 102492 are mixtures of a neutralization paste and a heavy fuel of petroleum origin. These different fuel compositions are not, however, entirely derived from biomass.

There are also combustible compositions composed of tall oil pitch and one or more solvents such as light pine oil and / or turpentine. Such compositions are called "pitch of diluted tall oil" or "diluted pitch" in the remainder of the present application. The addition of solvent to the pitch of tall oil is necessary to lower the viscosity of the pitch of pure tall oil and thus make it manipulable for combustion (pumping, storage, circulation in the preparation loops ... ). However, the presence of solvent significantly increases the cost of the composition.

There is therefore a need for a substitute fuel for heavy fuel oil which is less restrictive during its implementation, which makes it possible to achieve the increasingly high requirements relating to atmospheric emissions resulting from its combustion and which is entirely derived from biomass, at a lower cost.

BRIEF SUMMARY OF THE INVENTION

The applicant proposes a composition, in particular liquid, used as fuel. This composition can replace an oil, in particular to be burned in an industrial boiler or an industrial oven instead of an oil. The Applicant proposes, in particular, a combustible composition, in particular a liquid composition, directly obtained from biomass and which can replace a fuel oil, in particular to be burned in an industrial boiler or an industrial oven instead of an oil. "Directly from biomass" means that it does not contain fossil fuel. This does not exclude the fact that this composition may contain other products, for example additives, not derived from biomass.

A first subject of the invention thus relates to a combustible composition, in particular a liquid composition, comprising from 10 to 50% by mass of tall oil pitch, and at least one compound resulting from the treatment of wood, in particular of resinous wood, chosen from a compound derived from a terpene and a compound derived from rosin, here a rosin ester.

Such a composition has the advantage of being derived solely from biomass: it does not include fossil fuel components. The pitch of tall oil is the product recovered at the bottom of the column during the fractionation of crude tall oil by distillation, crude tall oil being a product resulting from the manufacture of paper by the Kraft process. Rosin ester is a rosin derivative which can also be obtained from the distillation of crude tall oil from a softwood or which can come from the processing of gemstones or strains of wood, especially softwood. . The terpenes used are derived from the treatment of wood, in particular coniferous, in particular from the essence of stationery recovered during the Kraft process or from the essence of turpentine recovered by distillation of the gem.

The composition also has the advantage of emitting low emissions during combustion, respecting high environmental constraints. Finally, its cost is low, the pitch of tall oil and the derivatives of terpenes and / or rosin, which play the role of fluxing agent, being by-products of the treatment of wood, in particular resinous, for example of the paper industry.

Advantageously, the combustible composition comprises at least one compound derived from a terpene and at least one rosin ester.

The combustible composition according to the invention may comprise at least one of the following characteristics, preferably both: a content of compound (s) derived from a terpene of 5 to 30% m; a rosin ester content of 5 to 30% m.

Advantageously, the combustible composition can comprise at least one other product originating from the manufacture of paper, in particular by the Kraft process, chosen from a product resulting from the distillation of crude tall oil, such as for example a distilled tall oil ( DTO) and a light fraction of tall oil.

The combustible composition can then comprise at least one of the following characteristics: a content of light fraction of tall oil from 1 to 30% m, a content of distilled tall oil from 1 to 20% m. Advantageously, the combustible composition can also comprise toluene in a content less than or equal to 0.1% by mass.

The combustible composition according to the invention may also comprise one or more additives, preferably chosen from: - a combustion additive having the effect of reducing dust emissions; these are generally additives containing metal salts (iron or / and calcium or / and cerium) dissolved in a matrix of fatty acids and hydrocarbons, - an additive having the effect of improving stability; these additives generally contain dispersing agents dissolved in a matrix of fatty acids and hydrocarbons.

The total content of additives) of the combustible composition can be from 0.01 to 0.5% m, preferably from 0.2 to 0.05% m.

Advantageously, the combustible composition may have at least one of the following characteristics: a pour point less than or equal to -10 ° C, preferably less than or equal to -12 ° C, a viscosity at 100 ° C ranging from 10 to 20 cSt, a flash point greater than or equal to 70 ° C, preferably greater than or equal to 80 ° C, an acid number less than or equal to 80mgKOH / g, preferably less than or equal to 75mgKOH / g, an ash content less than or equal to 0.1% by mass, preferably less than or equal to 0.05% by mass, a metal content less than or equal to 250 mg / kg, preferably less than or equal to 150 mg / kg, more preferably less or equal to 50 mg / kg, a nitrogen content less than or equal to 0.08% by mass, preferably less than or equal to 0.04% by mass, a water content less than or equal to 0.5% by mass, preferably less than or equal to 0.4% by mass.

According to a particular embodiment, the composition according to the invention, used as fuel, consists solely of compounds and products originating from the manufacture of paper, in particular by the Kraft process and / or of compounds and products originating from the treatment of wood, in particular of coniferous wood, and optionally of one or more additives as described above. The products from papermaking are as follows: tall oil pitch, compound (s) derived from a terpene, rosin ester (s) and at least one other product derived from the distillation of crude tall oil, especially chosen from distilled tall oil and a light fraction of tall oil. These products are preferably produced from the processing of softwoods. The compound (s) derived from a terpene and rosin ester (s) can also come from other wood treatments, in particular resinous, such as the treatment of the gemstone and the strains of wood. The invention also relates to the use of the composition described above as a fuel.

The composition used as fuel of the present invention is capable of being obtained by the preparation process described below.

Another object of the invention is a process for the preparation of a combustible composition, in particular a liquid composition, obtained from biomass comprising: the mixing of tall oil pitch with at least one compound derived from the treatment of wood, in particular wood resinous chosen from a compound derived from a terpene and a compound derived from rosin, here a rosin ester, the pitch content of tall oil in the composition being from 10 to 50% by mass.

Advantageously, the method also comprises, during the mixing step, the addition of at least one other product originating from the manufacture of paper, in particular by the Kraft process, chosen from a product resulting from the distillation of crude tall oil, such as for example distilled tall oil and a light fraction of tall oil.

The contents in the various products and the products are as described above for the composition according to the invention.

Another subject of the invention relates to a method of combustion of a combustible composition in a combustion installation, in particular of the 2910A or 2910B or 2910C type according to the ICPE nomenclature, in which the combustible composition according to l is burned as fuel. invention or directly obtained by the preparation process according to the invention. The composition according to the invention can burn while respecting the regulatory constraints on emission without requiring recourse to costly smoke treatments.

DETAILED DESCRIPTION OF THE INVENTION

The Kraft process is a wood transformation process which isolates on one side the pulp of wood useful for the paper industry and on the other a black liquor containing in particular crude tall oil.

During the Kraft process, wood chips are usually heated in the presence of sodium sulfide in an alkaline aqueous solution (white liquor). This treatment is generally done at a temperature of 130 to 180 ° C, under pressure for 2 to 5 hours following the essence of the wood in a device sometimes called "digester".

We obtain paper pulp immersed in a black liquor. After separation of the black liquor and decantation, we observe the formation of an alkaline upper layer called soap ("tall oil soap"), which can be isolated from the black liquor.

This tall oil soap is then acidified, for example with sulfuric acid, to produce the crude tall oil. Crude tall oil consists mainly of resin acids, fatty acids and non-saponifiable compounds. Insufficient acidification can lead to a crude tall oil containing metal salts, usually sodium. This characteristic is linked to the fact that tall oil mainly comprises hydrocarbon compounds functionalized with organic acids, essentially carboxylic acids, sometimes phenols. Tall oil also includes non-saponifiable sterols, fatty alcohols and other derivatives of alkylated hydrocarbons.

The rest of the black liquor is reduced by evaporation. The gases recovered during this evaporation as well as those recovered during the heating of the wood in the white liquor contain terpene essences. The crude essences recovered by condensation of these gases, also called stationery essences or "Crude sulfate turpentine" (CST) in English terminology, essentially contain the following compounds: a-pinene, β-pinene, Δ3 carene, myrcene, dipentene and possibly less common derivatives, such as camphene and others. These terpenes can be separated by fractionation. Tall oil, otherwise known as tall oil, is a liquid byproduct of the Kraft wood processing process. Tall oil is mainly obtained when using softwoods (conifers) in the Kraft process. The products from the distillation of crude tall oil are generally used as bases in the chemical industry and for the manufacture of glues and adhesives.

An average tall crude oil has an acid number (TAN: total acid number, in mg of KOH per g of product) between 30 and 100, more generally between 50 and 80 (limits included).

When heated, the crude tall oil can be separated (by distillation) to obtain: - a light oil (column head) - fatty acids (TOFA), - a distilled tall oil (“distilled tall oil”) DTO), mixture of fatty acids and resin acids, - resin acids (rosin or "rosin" in English), - a heavy phase or residue, which cannot be distilled, called tall oil pitch oil pitch). The pitch of tall oil contains a small amount of fatty and resin acids and a significant amount of unsaponifiables.

The terpenes and the rosin whose derivative compounds are used in the present invention can come from the treatment of wood, in particular of softwoods. By resinous wood is meant a species of wood secreting resin.

This treatment of wood can be a Kraft process as described above or a treatment of the gem obtained by gemming. As part of the Kraft process, terpenes and rosin can come from the distillation of crude tall oil (see above).

Tapping is an operation which involves wounding the bark of a softwood in order to harvest the gem or resin. The gem then undergoes distillation to obtain: - water (about 10% m), - turpentine (about 70% m), which generally contains a-pinene, β-pinene, sesquiterpenes and oxidizing products, - rosin (solid product, around 20% m) containing resin acids and neutral components.

Rosin can also be obtained by solvent extraction of wood stumps, especially softwood.

Tall oil pitch

As described above, tall oil pitch is a product obtained from the production of paper by the Kraft process, in particular from softwood. This is the residue from the fractionation of crude tall oil obtained by processing softwood using the Kraft process.

The pitch pitch content of tall oil in the composition according to the invention is from 10 to 50% m, advantageously from 10 to 40% m, preferably from 10 to 35% m.

Due to its relatively high content of nitrogen and metals, it may be preferable not to exceed a content of 40% m.

Compound (s) derived from a terpene

The composition according to the invention may contain from 5 to 30% m of compound (s) derived from a terpene, advantageously from 10 to 30% m, preferably from 15 to 30% m.

The terpenes considered are those resulting from the treatment of wood, especially resinous. These are the compounds present in paper essences, in particular from the transformation of wood by the Kraft process. They are contained in the gases recovered during the Kraft process previously mentioned. It can also be the compounds present in the essence of turpentine obtained by distillation of the gem of a resinous wood.

These terpenes can thus be chosen from: α-pinene, β-pinene, Δ3 carene, myrcene, dipentene, camphene or other monoterpenes. Advantageously, they are chosen from: α-pinene, β-pinene, Δ3 hull.

These different terpenes can be separated by fractionation.

Terpene derivatives can be derived from the isomerization and polymerization of the previously mentioned terpenes, in order to obtain terpenes and polyterpenes.

Preferably, the compounds derived from a terpene are chosen from terpenes and polyterpenes of formula (CsHsjn where n is an integer from 2 to 12.

Advantageously, the combustible composition according to the invention comprises a mixture of terpenes of formula (CsHsjn with integer n from 2 to 12.

In particular, this mixture of terpenes mainly comprises (more than 50% m) of triterpenes (n = 6), in particular the mixture mainly comprises triterpenes and diterpenes. For example, this mixture can comprise approximately (from 1 to 3%) 7% m of diterpenes, 85% m of triterpenes and 0 to 4% m of other terpenes.

Terpenoids can be viewed as modified terpenes with added or removed methyl groups, or added oxygen atoms. Like terpenes, terpenoids can be classified according to their number (n) of isoprene units. In one embodiment, the compound or compounds derived from the terpene can be chosen from terpenoids, with a number n of isoprene units from 2 to 12, and the terpenes and polyterpenes previously described.

Rosin compound) derivative: rosin esters

Rosin derivatives are rosin esters.

Rosin (or rosin, “rosin” in English) is a mixture mainly comprising organic acids called rosin acids or resin acids which correspond to the crude formula C20H30O2 (mainly acids of abietic type and of pimaric type). The proportion of different resin acids in rosin is variable depending on the species of softwood from which rosin was obtained. For example, rosin can contain 85 to 95% m of resin acids.

In general, rosin consists mainly of abietic acid, from 50% to 80% m, and in a lesser proportion of dihydroabietic acid, from 5% to 30% m and primaric acid, from 5% to 30% m.

Rosin can also contain the following acids: isoprimaric acid, palustriic acid, neoabietic acid. C20 abietic acid tends to polymerize and can thus form polymers of C40, C60, .... Dihydroabietic acid is the hydrogenated form of abietic acid, and therefore can no longer polymerize.

Rosin can be recovered as a by-product of papermaking as a product of the distillation of crude tall oil from the Kraft process, especially during the processing of softwood (tall oil rosin). Rosin can also come from the distillation of the gem (rosin from gem) or from the treatment of strains of resinous wood (rosin from wood). The composition according to the invention may comprise a content of compound (s) derived from rosin from 5 to 30% m, advantageously from 5 to 25% m, preferably from 10 to 20% m.

Rosin derivatives can be derived from the esterification of rosin acids. The esterification of rosin makes it soluble in organic solvents. This esterification can be carried out in the presence of alcohols such as glycerol, pentaerythritol, triethylene glycol and methanol.

Advantageously, the rosin derivatives are chosen from a rosin ester of pentaerythritol and a rosin ester of glycerol.

The composition according to the invention may in particular comprise at least two rosin esters, each for example in a content of 1 to 10% m.

Tall oil distilled ÎDTO)

This distillate corresponds to a cut resulting from the distillation of a crude tall oil, in particular resulting from the transformation of resinous wood by the Kraft process.

The tall oil distillate is a lighter cut than the pitch of tall oil and heavier than the fraction containing tall oil fatty acids.

The composition according to the invention can comprise from 1 to 20% m of DTO, advantageously from 1 to 15% m, preferably from there 10% m.

Light fraction of tall oil

This light fraction of tall oil (also called light oil in the present application) corresponds to the top fractions of the distillation of a crude tall oil, in particular resulting from the transformation of softwoods by the Kraft process. This light fraction generally corresponds to volatile compounds.

The composition according to the invention can comprise from 1 to 30% m of this light fraction, advantageously from 1 to 25% m, preferably from 10 to 20% m.

Preparation of the composition

The composition according to the invention is obtained by mixing the constituents previously described, in the proportions described. The different constituents can be added one after the other, in no particular order, or together in one or more installments.

Advantageously, in order to improve the homogeneity of the mixture obtained, this step is carried out with stirring, for example mechanical and / or by recirculation.

In order to facilitate mixing and improve its homogeneity, the components of the mixture can be heated prior to mixing. In particular, the pitch of tall oil can be heated to a temperature of 40 to 70 ° C, preferably from 50 to 60 ° C. EXAMPLES Example 1

Table 1 shows some physico-chemical characteristics of a sample of tall oil pitch.

Tables 2 and 3 show the same physico-chemical characteristics for the following products:

Product A: combustible composition according to the invention,

Product B: pitch of diluted tall oil,

Product C: TBTS (Very Low Sulfur) fuel oil, not additive.

Product B comprises from 70 to 80% m of pitch of tall oil and from 20 to 30% m of flux consisting of light pine oils and / or turpentine. Light pine oil can be defined as a light fraction recovered at the top of the column during the distillation of crude tall oil. Its flash point is between 40 and 70 ° C (terminals included).

Product A comprises: from 10 to 40% m of pitch of tall oil: this proportion is relatively low because of the high viscosity of the pitch and also of its relatively high content of metals and nitrogen. The pitch of tall oil is charged with it since it comes from the bottom of the distillation of crude tall oil; from 10 to 30% m of terpenes of formula (CsHsJn with integer n from 2 to 12 (preferably mainly terpenes with n = 4 or 6), free of heteroatom (S, N, O, metals), their presence can helping to reduce atmospheric emissions of pollutants, from 1 to 10% m of rosin esters of pentaerythritol. These esters have a low acidity (from 15 to 30 mgKOH / g) making it possible to counterbalance the acidity provided by the light fraction and distilled tall oil richer in fatty acids than tall oil pitch, from 1 to 10% m of rosin glycerol esters: these esters have good heat stability which improves the stability of finished product, the fuel can be stored in a warmed tank for several months before use, and can promote the miscibility of terpenes in tall oil pitch from 1 to 20% m of light oils (light fractions) tal oil distillation l crude: these oils have a low viscosity and a low metal content, from 1 to 10% m of distilled tall oil (DTO), which has a low viscosity and few metals, toluene (<0.1% m), it can help increase PCI and stabilize aromatics.

Table 1

_

Table 2

(*): specifications imposed by the CSR 500 for heavy fuel oil. These specifications are established by the Chambre Syndicale du Raffinage in France.

Table 3

Note: a lower pour point (-15 ° C) of the composition according to the invention compared to that observed for the diluted pitch (B: 20 ° C). This makes it possible to envisage storage with less heating and therefore energy savings and ease of implementation.

A lower viscosity of the composition (A) compared to the diluted pitch (B), which makes it possible to burn it with lower temperatures in the feeding and spraying circuits. This results in energy savings and ease of implementation.

A lower flash point of the composition (A) compared to that of the diluted pitch (B), which allows an easier lighting and an ease of implementation.

A lower ash content of the composition (A) compared to the diluted pitch (B), which allows a reduction in particle emissions, facilitates compliance with the emission limit values without having to resort to expensive smoke treatments and delicate operations. This also allows a reduction in deposits in combustion plants, causing lower yields and requiring sweeping operations (shutdown of operations).

A lower nitrogen content for composition (A) compared to diluted pitch (B) and heavy fuel oil (C), which allows a theoretical reduction of at least 46% of NOx emissions of combustible origin, facilitates compliance with emission limit values without having to resort to expensive and delicate smoke treatment operations.

Lower metal contents of the composition (A) compared to the diluted pitch (B), mainly Na, K, Fe and Ca. These metals combine with sulfates to form salts which foul the smoke circuits (economizers ) and are poisons for any smoke treatment catalysts present.

Example 2: Pilot combustion test

Products A, B, C, the characteristics of which are shown in Tables 2 and 3, have been tested.

Each product is burned separately in a 1 MW smoke tube boiler, 1 mechanical spray burner without assistance. Atmospheric emissions are analyzed continuously by means of analyzers placed in the flue gas outlet, at the outlet of the fireplace.

Table 4 below shows the combustion conditions for this test as well as the combustion efficiency and the measured emissions.

The combustion of the composition according to the invention (A) has a yield similar to that of heavy fuel oil (C) and slightly higher than diluted pitch (B).

The spray temperature used for the composition according to the invention (A) is significantly reduced compared to the other products (B) and (C).

It is also noted that the NOx and dust emissions of the composition according to the invention are lower than the emissions of the other products, a significant drop being observed for NOx.

Table 4

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m3 (n): normal cubic meters, measured at P = 101.3kPa and T = 273K

Claims (12)

1. A combustible composition, in particular a liquid composition, comprising: from 10 to 50% by mass of tall oil pitch, at least one compound obtained from the treatment of wood, in particular resinous wood, chosen from a compound derived from a terpene and a rosin ester. 2. Combustible composition according to claim 1, characterized in that it comprises at least one of the following characteristics: a content of compound (s) derived from a terpene of 5 to 30% m, an ester content of rosin from 5 to 30% m. 3. Combustible composition according to claim 1 or 2, characterized in that it further comprises at least one other product originating from the manufacture of paper, in particular by the Kraft process, chosen from a product resulting from the distillation of crude tall oil, such as for example distilled tall oil and a light fraction of tall oil. 4. Combustible composition according to claim 3, characterized in that it comprises at least one of the following characteristics: a content of light tall oil fraction of 1 to 30% m, a distillate content of 1 to 20% m . 5. Combustible composition according to any one of claims 1 to 4, characterized in that it comprises toluene in a content less than or equal to 0.1% by mass. 6. A combustible composition according to any one of claims 1 to 5, in which the compound derived from a terpene is chosen from terpenes and polyterpenes of formula (CsHsjn where n is an integer from 2 to 12. 7. A combustible composition according to any one of claims 1 to 6 comprising at least one of the following characteristics: a pour point less than or equal to -10 ° C, a viscosity at 100 ° C from 10 to 20 cSt, a flash point greater than or equal to 70 ° C, an acid number less than or equal to 80 mgKOH / g, an ash content less than or equal to 0.1% by mass, a metal content less than or equal to 250 mg / kg, a content in nitrogen less than or equal to 0.08% by mass, a water content less than or equal to 0.5% by mass. 8. Use as fuel of a composition of products chosen from products obtained from the manufacture of paper, in particular by the Kraft process, and products derived from the treatment of wood, in particular of softwood, said composition comprising: from 10 to 50 % by mass of tall oil pitch, at least one compound obtained from the treatment of wood, in particular resinous wood, chosen from a compound derived from a terpene and a rosin ester. 9. Use according to claim 8, characterized in that the composition also comprises at least one other product originating from the manufacture of paper, in particular by the Kraft process, chosen from a product resulting from the distillation of crude tall oil, such as for example a distilled tall oil and a light fraction of tall oil. 10. A method of preparing a combustible composition from biomass comprising: mixing tall oil pitch with at least one compound obtained from the treatment of wood, in particular resinous wood, chosen from a compound derived from a terpene and a rosin ester, the pitch content of tall oil in the composition being 10 to 50% by mass. 11. The preparation method according to claim 10, further comprising during the mixing step, the addition of at least one other product originating from the manufacture of paper, in particular by the Kraft process, chosen from a product derived from distillation of crude tall oil, such as for example distilled tall oil and a light fraction of tall oil. 12. A method of combustion of a fuel in a combustion installation, in which a combustible composition according to any one of claims 1 to 7 is burned or a fuel directly obtained by the method according to any of claims 10 or 11 .