CN111303952A

CN111303952A - Pulp suspension comprising calcined wood particles

Info

Publication number: CN111303952A
Application number: CN201910976787.8A
Authority: CN
Inventors: B.帕瓦格奥; 齐玲; J-C.卡斯坦; R.塔德莫里; H.费伊; R.格雷塞尔
Original assignee: Rhodia Operations SAS
Current assignee: Rhodia Operations SAS
Priority date: 2014-12-23
Filing date: 2014-12-23
Publication date: 2020-06-19
Also published as: WO2016101113A1; EP3237586A1; US20170349848A1; CN107207980A; EP3237586A4

Abstract

A slurry suspension comprising: a) having an average diameter D comprised between 0.1 and 200 μm₅₀The carbonaceous material particles of (a); b) a nonionic surfactant; c) an aqueous phase; and d) an organic phase.

Description

Pulp suspension comprising calcined wood particles

The present application is a divisional application of the following applications: application date: 12 month 23 year 2014; application No.: 2014800843513(PCT/CN 2014/094571); the invention name is as follows: "slurry suspension comprising calcined wood particles".

Technical Field

The present invention relates to the field of slurry suspensions comprising particles of carbonaceous material intended for use as liquid combustibles.

Background

In order to reduce the emission of sulphur from the combustion of fuels polluting the environment and to comply with regulations concerning fuel consumption, refineries provide fuels available with a low sulphur content consisting of refined heavy fuels of diesel. However, due to the expensive processes, these fuel alternatives are generally more expensive than those that are less refined.

In addition, due to anticipated crude oil shortages due to natural reserves decline, it is more urgent than ever to find some effective alternatives to reduce the portion of fossil-based energy sources.

Some alternatives to further refining fuels are to replace stone-based combustibles with biofuels, which development is generally aimed at designing new catalytic processes to convert solid biomass into liquid fuels. However, this destructive process is often compromised by the competitive price of making biofuels from biomass or making biofuels.

Some other alternatives have recently been proposed to increase the renewable fuel fraction in fuel compositions. For example, coal/water slurry (CWS) based technologies, in which coal is dispersed into water, provide liquid fuels that are compatible with existing liquid boilers.

However, a disadvantage of coal/water slurries is that water is inert to combustion and therefore reduces the gross calorific value of the aqueous coal or bio-coal suspension.

Another alternative that can be explored is the use of torrefied biomass for the production of renewable energy with cost competitive features, and primarily for transportation in view of being a high energy density material compared to white, unburnt biomass.

This "thermally treated biomass" provides interesting properties such as low sulfur content, low nitrogen content, and excellent combustion properties.

Furthermore, the torrefied biomass is an inert material, as compared to the unbaked, white biomass, and the material acquires hydrophobic properties due to the loss of oxygen during the torrefaction process.

There remains a need in the art to provide liquid combustible formulations that produce low sulfur emissions, with fossil-based energy sources accounting for only a reduced portion.

More particularly, because carbonaceous materials provide good combustion characteristics, there remains a need in the art to provide suspensions comprising the carbonaceous materials in a liquid carrier that are uniformly and stably dispersed.

Furthermore, there remains a need in the art to provide liquid combustible formulations that are compatible with existing systems (such as engines and boilers).

Disclosure of Invention

A first aspect of the invention relates to a pulp suspension comprising:

(a) having an average diameter D comprised between 0.1 and 200 μm₅₀The carbonaceous material particles of (a);

(b) a nonionic surfactant;

(c) an aqueous phase; and

(d) and (4) an organic phase. (REV 1)

Another aspect of the invention relates to a method for preparing a pulp suspension according to the invention, comprising the steps of:

i. mixing at least ingredients (b), (c) and (d) to form an emulsion;

mixing component (a) with the emulsion obtained in step i to form a slurry suspension. (REV 16)

Another aspect of the invention relates to a method for generating electricity, the method comprising combusting a slurry suspension according to the invention. (REV 18)

Yet another aspect of the invention relates to the use of a nonionic surfactant for stabilizing a liquid composition comprising a polymer having a mean diameter D comprised between 0.1 μm and 200 μm₅₀The use of an emulsion of carbonaceous material particles of (a). (REV 19)

Detailed Description

The inventors have surprisingly found that particles of carbonaceous material can be added to an emulsion, in particular an oil-in-water emulsion, to obtain a stable and uniformly dispersed slurry suspension that can be further used as a liquid biofuel for combustion.

Emulsions, particularly oil-in-water emulsions, are stabilized by the presence of nonionic surfactants.

Slurry suspension

Accordingly, a first aspect of the present invention relates to a pulp suspension comprising:

(b) a nonionic surfactant;

(c) an aqueous phase; and

(d) and (4) an organic phase. (REV 1)

Within the scope of the present invention, the term "suspension" refers to a system comprising particles of carbonaceous material (i.e. solid material) dispersed as particles having a size larger than colloidal in a liquid phase comprising an aqueous phase, an organic phase and a non-ionic surfactant.

In certain embodiments, the term "suspension" refers to a system (emulsion state) comprising an emulsion (i.e., liquid phase) having carbonaceous material particles dispersed therein.

In certain embodiments, the term "suspension" refers to a system in which the aqueous liquid phase and the organic liquid phase are separate phases and do not form an emulsion; the carbonaceous material particles are dispersed in these liquid phases (non-emulsion state).

Within the scope of the present invention, the term "about" refers to a value that may vary from the value mentioned by +/-10%.

Particles of carbonaceous material

Within the scope of the present invention, the term "carbonaceous material" refers to a material containing a significant amount of carbon.

The carbon content of carbonaceous material particles useful for the present invention is typically more than 30 wt.%, based on the total weight of the carbonaceous material particles; it is often more than 40 wt.%. It is preferably more than 45 wt.%, more preferably more than 50 wt.%, based on the total weight of the carbonaceous material particles. On the other hand, it is typically up to 90 wt.%, and often up to 80 wt.%, based on the total weight of the carbonaceous material particles. It can be up to the total weight of the carbonaceous material particles70 wt.% or even up to 60 wt.%. Certain useful ranges for the carbon content of the carbonaceous material particles useful in the present invention are from about 40 wt.% to about 80 wt.%, or from about 45 wt.% to about 75 wt.%, based on the total weight of the carbonaceous material particles. The carbon content of the carbonaceous material particles can be determined by any method known to those skilled in the art. For example, it may be determined by: drying the carbonaceous material particles in an oven at 100 ℃ for 12h (to remove water and other volatiles), then holding the dried particles in a dryer (to avoid moisture absorption), then burning the carbonaceous material particles in a combustion furnace under conditions that are capable of converting substantially all (when not all) of the carbon content of the carbonaceous material particles to carbon dioxide, then detecting by infrared (by CO formed via combustion)₂) The C content was quantified.

In one embodiment, the carbonaceous material particles are selected from the group consisting of plant biomass, coal, coke, graphite, charcoal, bio-coal, and mixtures thereof. (REV 3)

According to the present invention, the plant biomass comprises lignocellulosic fibres and may be provided by any plant, wood and crop susceptible to providing a suitable biomass.

Plants such as miscanthus, switchgrass, hemp; wood such as poplar, bamboo, eucalyptus, oil palm, willow, pine, oak, gum, aspen, beech, coconut and spruce; and crops such as corn, sorghum, sugar cane and sugar beet are suitable for practicing the present invention.

In certain embodiments, the plant biomass is selected from the group comprising plants or parts thereof, such as leaves, stems, roots, including crops or parts thereof; wood, wood chips or sawdust; straw; bark of tree; grass; forestry residues; agricultural residues such as corn cobs, corn stover, wheat straw, bamboo grass, vine cane (vineshoot), bagasse, sorghum bagasse, almond hulls, sunflower seed hulls, and mixtures thereof.

In certain embodiments, the plant biomass is subjected to a treatment to remove its moisture content, such treatment being dry heat treatment, steam explosion, vacuum evaporation, hydrothermal carbonization, or any suitable treatment known from the prior art.

The dry heat treatment process may include treating the starting biomass at a temperature below the maximum temperature of 200 ℃ to 500 ℃ for a period of time from several minutes to several hours.

In certain embodiments, the dry heat treatment consists of calcination at a temperature ranging from about 280 ℃ to about 320 ℃ for a time period ranging from 1min to 15min, preferably from 2min to 8 min.

In certain preferred embodiments, the plant biomass is a torrefied plant biomass, preferably a torrefied wood particle. (claim 4)

In certain embodiments, the carbonaceous material is coal, such as anthracite, semi-anthracite, charcoal, solvent refined coal, medium and high volatile bituminous coal, sub-bituminous coal, and lignite.

In certain embodiments, the carbonaceous material is coke, such as petroleum coke, high temperature coke, foundry coke, low temperature coke, medium temperature coke, pitch coke, or any product obtained by carbonizing coal, pitch, petroleum residue, and certain other carbonaceous materials.

In some embodiments, a mixture of coal and petroleum coke may be used in the present invention.

When referring to "carbonaceous material particles," one will understand that the particles have a low moisture content or are anhydrous. By "low water content", one can understand water contents as high as 20% by weight compared to the weight of the starting material. Thus, up to 20% by weight of water includes water contents of 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% and 20% by weight as compared to the weight of the starting material.

Within the scope of the present invention, the expression "particles of carbonaceous material" means particles of carbonaceous material in the solid state.

The carbonaceous material particles encompassed by the present invention are obtained after fine wet or dry milling of the carbonaceous material using a mill. When wet milling is performed, the carbonaceous material particles may be further treated to undergo a dry heat treatment aimed at reducing their moisture content to a maximum of 20%. In contrast, when dry milling is carried out, the carbonaceous material particles according to the invention have a moisture content of at most 20% by weight, as compared to the weight of the starting material.

In certain embodiments, the carbonaceous material particles provide the following size distribution:

-D₁₀is comprised between 1 and 50 μm, and

-D₉₀is comprised between 50 and 500 μm. (REV 5)

Within the scope of the present invention, the size of the particles may be measured by any suitable average value known from the prior art.

In a preferred embodiment, the size distribution of the particles is measured by the mean value of the laser diffraction of the dry dispersion in view of the principles and basic rules specified in ISO 13320:2009 (E).

In practice, analysis was performed using a Helos H1302 laser diffraction sensor (Sympatec, germany). The detector focal length is chosen such that its passband covers the size range of the carbonaceous material particles to be analyzed. For example, an R4 detector (0.5 μm to 350 μm) is particularly well suited when analyzing ground torrefied biomass.

The carbonaceous material particles were dispersed under pressure in a stream of dry nitrogen using a dry dispersion unit (Rodos, naproxa, germany).

The optimum operating conditions were experimentally sought to obtain a good dispersion of particles without breaking in the eductor. In practice, when analyzing carbonaceous material particles in the form of milled torrefied biomass, the nitrogen pressure is about 100kPa (1 bar) and the low pressure (depression) represents about 4kPa (40 mbar).

The carbonaceous material particles are fed using a vibratory trough. The feed rate was adjusted to obtain an optical concentration between 2% and 10%. In practice, the total mass of the sample containing the carbonaceous material particles to be analyzed is in the range from about 1g to about 10g, preferably about 5 g.

Laser diffraction data were acquired and analyzed using windows 5 software (napatch, n.pa, germany).

In one embodiment, the carbonaceous material particles represent between 5% and 50% by weight of the total weight of the suspension. (REV 6)

Nonionic surfactant

Within the scope of the present invention, the nonionic surfactant may be selected from the group consisting of ether-based nonionic surfactants, ester-based nonionic surfactants, amine-based or amide-based nonionic surfactants, and fluorosurfactants. (REV7)

a) Ether-based nonionic surfactant

Among the ether-based nonionic surfactants, one may cite carboxylic acid-based nonionic surfactants, alcohol-based nonionic surfactants, glycoside-based nonionic surfactants, fatty alcohol-based nonionic surfactants, and ethers of silicone nonionic surfactants.

The nonionic emulsifiers of interest according to the present invention can be represented by ethers of carboxylic acids having the following formula (1):

R1-O-(R2–O)y-CH2-COOH(1)，

wherein R1 is C8-C20 alkyl, C8-C20 alkylphenyl or C8-C20 alkenyl, R2 is C2-C10 alkylene, such as-CH 2-CH2-, -CH2-CH2-CH2-, or mixtures thereof, and y ranges from 2 to 50.

In certain embodiments, the ether of a carboxylic acid is represented by a compound having formula (1), wherein R2 is C2 or C3 alkylene.

In particular, the ethers of carboxylic acid-based nonionic surfactants are preferably represented by polyoxyethylene nonionic surfactants (- (CH2-CH2-O) -), polyoxypropylene nonionic surfactants (- (CH2-CH2-CH2-O) -), polyoxyethylene-polyoxypropylene nonionic surfactants.

The polyoxyethylene nonionic surfactant may include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene alkyl ether.

Among polyoxyethylene alkyl ethers, one may cite compounds such as polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene oleyl ether, polyoxyethylene stearyl ether, and polyoxyethylene isostearyl ether.

Among polyoxyethylene alkylphenyl ethers, one may cite compounds such as polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether and dialkylphenoxypoly (ethyleneoxy) ethanol.

Among polyoxyethylene polyoxypropylene alkyl ethers, one may cite compounds such as polyoxyethylene polyoxypropylene cetyl ether, polyoxyethylene polyoxypropylene decyltetradecyl ether.

The alcohol-based nonionic surfactants of interest according to the present invention can be represented by alkoxylated alcohols.

Within the scope of the present invention, the term "alkoxylated" depends on the presence of oxyalkylene units, wherein the total number of these units is generally in the range from 2 to 50, preferably from 3 to 25, preferably from 4 to 12, preferably from 2 to 10, most preferably from 2 to 6, or preferably from 10 to 50, most preferably from 10 to 35.

Alkoxylated alcohols of interest may be represented by compounds having the following general formula (2):

R1-O-(R2–O)y-H(2)

wherein R1 is a C6-C30 hydrocarbon group, R2 is a C2-C10 alkylene group, such as-CH 2-CH2-, -CH2-CH2-CH2-, or mixtures thereof, and y ranges from 2 to 50.

Preferably, the alkoxylated alcohol may be represented by a compound having the following general formula (3):

R3-O-(R2–O)y-H(3)

wherein R3 is C8-C20 alkyl or C8-C20 alkenyl, R2 is C2-C10 alkylene, such as-CH 2-CH2-, -CH2-CH2-CH2-, or mixtures thereof, and y ranges from 2 to 50, or

Alternatively, the alkoxylated alcohol has the following formula (4):

wherein R4 is C4-C20 alkyl, in particular R4 is octyl (C8) or nonyl (C9),

is p-phenylene, R2 is C2-C10 alkylene, for example-CH 2-CH2-, -CH2-CH2-CH 2-or mixtures thereof, and y ranges from 2 to 50.

Analogous alcohols can be prepared by reaction with [2, 4-6-tri- (tert-butyl)]-phenyl replacing in formula (4) above

And (4) obtaining.

Examples of alkoxylated alcohols suitable as nonionic surfactants according to the present invention are condensation products of (i) from 2 to 50 moles of at least one C2-C3 alkylene oxide, such as ethylene oxide, with (ii) one mole of an ethylenically saturated or unsaturated fatty alcohol, especially a C8-C20 alcohol selected from lauryl alcohol, myristyl alcohol, palmityl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol, linolenyl alcohol, oxo alcohols and mixtures thereof.

Further examples of alkoxylated alcohols suitable as nonionic surfactants according to the present invention are the condensation products of (i) from 2 to 50 moles of at least one C2-C3 alkylene oxide, such as ethylene oxide, with one mole of n-octylphenol, n-nonylphenol and mixtures thereof.

The alkoxylated alcohol may be under the trade name

(Atlas Chemical Co.))),

(Clariant) and

(BASF) available commercially.

The glycosidic nonionic surfactant may comprise a long chain alkyl polyglucoside obtained by condensation of a) a long chain alcohol containing from about 6 to about 25 carbon atoms with b) glucose or a glucose-containing polymer. In practice, such compounds may be alkylpolyglycosides and alkylpolysaccharides such as decyl glucoside, octyl glucoside or decyl maltoside.

In certain embodiments, the ether-based nonionic surfactant is an alkoxylated phenolic surfactant. (REV 8)

In certain embodiments, the alkoxylated phenolic surfactant is selected from the group consisting of alkoxylated alkylphenols, alkoxylated alkylarylphenols, alkoxylated sulfated and/or phosphate alkylphenols, and alkoxylated sulfated and/or phosphate alkylarylphenols. (REV 9)

Suitable alkoxylated phenol compounds comprise an oxyalkylene group, which oxyalkylene group can be, for example, an oxyethylene group, an oxypropylene group, or an oxyethylene/oxypropylene group (i.e., ethoxy-propoxylated group).

The number of oxyalkylene units, such as Oxyethylene (OE) units and/or Oxypropylene (OP) units, in the alkoxylated phenol compound is typically between 2 and 100, depending on the desired HLB (hydrophilic/lipophilic balance). More particularly, the number of OE and/or OP units is comprised between 2 and 50. Preferably, the number of OE and/or OP units is comprised between 5 and 50.

The alkoxylated phenol compounds suitable for the present invention may comprise one, two, or three linear or branched hydrocarbyl groups attached to the phenol group, the hydrocarbyl group or groups preferably comprising from 4 to 50 carbon atoms, more preferably comprising from 4 to 12 carbon atoms. Such hydrocarbyl groups are preferably hydrocarbyl groups selected from the group consisting of: alkyl groups such as tert-butyl, or isobutyl, aryl groups, alkylaryl groups, and arylalkyl groups, which may contain heteroatoms such as N, O or S. The alkyl portion of the alkylaryl or arylalkyl group can be a C1-C6 alkyl moiety. The hydrocarbyl group may notably be represented by phenyl or phenethyl.

The alkoxylated phenol compound may also contain functional groups attached to the alkoxylated chain, such as phosphate (PO4-M +), sulfate (SO4-M +), sulfonate (SO3-M +), or carboxylate (COO-M +). M + may be a cation including, but not limited to, H +, Na +, NH4+, K +, or Li +.

Suitable salts are, for example, metal salts, such as salts of alkali metals or alkaline earth metals, for example sodium, potassium, calcium or magnesium; or salts with ammonia or organic amines, such as morpholine, piperidine, pyrrolidine, mono-, di-or tri-lower alkylamines, for example ethyl-, diethyl-, triethyl-or dimethyl-propylamine, or mono-, di-or tri-hydroxy-lower alkylamines, for example mono-, di-or tri-ethanolamine.

The alkoxylated phenol compound may notably be a compound having the following formula (5):

wherein:

-R1, R2 and R3, independently of each other, are hydrogen or a linear or branched hydrocarbon radical, preferably containing from 4 to 50 carbon atoms, preferably containing from 4 to 12 carbon atoms;

-R4 is a divalent linear or branched alkylene group containing from 2 to 8 carbon atoms, preferably 2 or 3 carbon atoms; r4 can be a mixture of several different alkylene groups;

-n is an integer comprised between 2 and 100, preferably comprised between 2 and 50;

-R5 is H, OH, alkoxy, Phosphate (PO)₄ ^-M⁺) Sulfate (SO)₄ ^-M⁺) Sulfonate (SO)₃ ^-M⁺) Or a Carboxylate (COO)^-M⁺)；M⁺If present, is a cation, including but not limited to H⁺、Na⁺、NH₄ ⁺、K⁺Or Li⁺。

As represented in formula (5), R1, R2, and R3 are hydrogen or a linear or branched hydrocarbon group attached to the phenyl structure. R1, R2 and R3, independently of each other, may be alkyl, such as tert-butyl, butyl or isobutyl, aryl, alkylaryl, or arylalkyl groups, which may contain heteroatoms, such as N, O or S. The alkyl portion of the alkylaryl or arylalkyl group can be a C1-C6 alkyl moiety. R1, R2 and R3 may be, independently of one another, especially phenyl or phenethyl.

When R5 is alkoxy, it can be, for example, C1-C6 alkoxy, such as-OCH 3, -OC2H5, -OC3H7, -OC4H9, -OC5H11, or-OC 6H 13.

Suitable alkoxylated phenolic compounds may be selected in particular from the group consisting of:

alkoxylated alkylphenols, which may be, for example, C₆-C₁₆Alkanols, such as alkoxylated octylphenols, alkoxylated lauryl phenols and alkoxylated nonylphenols, such as polyethoxylated octylphenols and polyethoxylated nonylphenols;

alkoxylated alkylaryl phenols which may be, for example, alkoxylated mono-, di-or tristyrylphenols, such as polyethoxylated tristyrylphenols;

-alkoxylated sulfated and/or phosphate alkylphenols; and

alkoxylated sulfated and/or phosphate alkylarylphenols, such as ethoxylated and/or propoxylated, sulfated and/or phosphated mono-, di-or tristyrylphenols, ethoxylated polyarylphenol ether phosphates.

Tristyrylphenol ethoxylates for other uses are disclosed, for example, by U.S. patent No. 6,146,570, published PCT patent application nos. WO 98/012921 and WO 98/045212, which are incorporated herein by reference.

The alkoxylated phenol compounds of the present invention may be selected in particular from the group consisting of: nonylphenol ethoxylated with 2 OE units; nonylphenol ethoxylated with 4 OE units; nonylphenol ethoxylated with 6 OE units; nonylphenol ethoxylated with 9 OE units; nonylphenol ethoxylated with 25 OE + OP units; nonylphenol ethoxylated with 30 OE + OP units; nonylphenol ethoxylated with 40 OE + OP units; nonylphenol ethoxylated with 55 OE + OP units; nonylphenol ethoxylated with 80 OE + OP units; bis (1-phenylethyl) phenol ethoxylated with 5 OE units; bis (1-phenylethyl) phenol ethoxylated with 7 OE units; di (1-phenylethyl) phenol ethoxylated with 10 OE units; tris (1-phenylethyl) phenol ethoxylated with 8 OE units; tris (1-phenylethyl) phenol ethoxylated with 16 OE units; tris (1-phenylethyl) phenol ethoxylated with 20 OE units; tris (1-phenylethyl) phenol ethoxylated with 25 OE units; tris (1-phenylethyl) phenol ethoxylated with 40 OE units; tris (1-phenylethyl) phenol ethoxy-propoxylated with 25 OE + OP units; ethoxylated and sulfated bis (1-phenylethyl) phenol containing 5 OE units; ethoxylated and sulfated bis (1-phenylethyl) phenol containing 7 OE units; ethoxylated and sulfated bis (1-phenylethyl) phenol containing 15 OE units; ethoxylated and sulfated bis (1-phenylethyl) phenol comprising 16 OE units; ethoxylated and sulfated tris (1-phenylethyl) phenol containing 16 OE units; and ethoxylated and phosphorylated tris (1-phenylethyl) phenol containing 16 OE units.

In fact, the alkoxylated phenolic surfactants according to the invention may be selected from:

ethoxylates of tristyrylphenol, such as are commercially available

BSU；

CY8；

S25 (Solvay);

ethoxylates of alcohols, such as are commercially available

LA 12/80；

LA12；

BC 720；

BC 630；

BC 639 (Rhodia);

ethoxylates of alkylphenols, such as the commercially available products

RC 630；

DM530；

RC 620；

CO 610；

CO 630；

CO 660；

CO710；

CO 710 (suwei).

In practice, the siloxane surfactant includes polydimethylsiloxanes modified at one or more side chains, one terminus, both termini, and combinations thereof. As an example of modification, the polydimethylsiloxane may be modified with a polyether group, such as a polyoxyethylene group or a polyoxyethylene polyoxypropylene group.

b) Ester-based nonionic surfactant

Among the ester-based nonionic emulsifiers of interest, one can cite alkoxylated oils and fats. These compounds include the ethoxylated and/or propoxylated derivatives of lanolin (lanolin) or castor oil. Lanolin is the common name for waxes containing a mixture of esters of high molecular weight alcohols and fatty acids and polyesters. Castor oil is a mixture of triglycerides of fatty acids.

Other examples of ester-based nonionic emulsifiers may be represented by alkoxylated acids, such as compounds represented by monoesters and diesters.

Monoesters of interest can be represented by compounds having the following general formula (6):

wherein R1 is C₆-C₃₀Hydrocarbyl radical, R2 is C₂-C₁₀Alkylene radicals, e.g. CH₂-CH₂-、-CH₂-CH₂-CH₂-or a mixture thereof, and y ranges from 2 to 50.

Preferably, the monoester may be represented by a compound having the following general formula (7):

wherein R3 is C₈-C₂₀Alkyl or C₈-C₂₀Alkenyl, R2 is C₂-C₁₀Alkylene radicals, e.g. CH₂-CH₂-、-CH₂-CH₂-CH₂-or a mixture thereof, and y ranges from 2 to 50.

Examples of alkoxylated acid monoesters are the condensation products of from 2 to 50 moles, especially from 4 to 16 moles, of an alkylene oxide, such as ethylene oxide, with one mole of a saturated or unsaturated fatty acid selected from lauric, myristic, palmitic, stearic, oleic, linoleic and linolenic acids.

Examples thereof are

A product which is a condensate of about 4 to 5mol of oxyethylene units with lauric acid and/or myristic acid (Cognis, corning, germany). The corresponding propoxylated and/or butylated fatty acids may also be included on purposeIn the alkoxylated acid monoesters of the above.

Interesting diesters can be represented by compounds having the following general formula (8):

wherein R1 and R3 are independently C₆-C₃₀Hydrocarbyl radical, R2 is C₂-C₁₀Alkylene radicals, e.g. CH₂-CH₂-、-CH₂-CH₂-CH₂-or a mixture thereof, and y ranges from 2 to 50. Preferably, the diester of interest may be represented by a compound having the following general formula (9):

wherein R4 and R5 are independently C₈-C₂₀Alkyl or C₈-C₂₀Alkenyl, R2 is C₂-C₁₀Alkylene radicals, e.g. CH₂-CH₂-、-CH₂-CH₂-CH₂-or a mixture thereof, and y ranges from 2 to 50.

Other examples of useful ester-based nonionic emulsifiers can be represented by alkoxylated glycols such as alkoxylated ethylene glycol esters and alkoxylated propylene glycol esters.

The alkoxylated ethylene glycol ester may be represented by a compound having the following general formula (10):

wherein R1 is C₈-C₂₀Alkyl or C₈-C₂₀Alkenyl, R2 is C₂-C₁₀Alkylene radicals, e.g. CH₂-CH₂-、-CH₂-CH₂-CH₂-or a mixture thereof, and y ranges from 2 to 50.

The alkoxylated propylene glycol ester may be represented by a compound having the following general formula (11):

Alkoxylated esters of monoglycerides, dialkoxylated esters of diglycerides and trialkoxyated esters of triglycerides, which are the reaction product of glycerol or one of its derivatives with a carboxylic acid comprising from 8 to 20 carbon atoms and comprising a total of from 6 to 60 oxyalkylene units, may also be interesting compounds.

Among the non-limiting ester-based nonionic surfactants, there may be mentioned polyoxyethylene alkyl esters, polyoxyethylene glycerin fatty acid esters, polyoxyethylene castor oil, hydrogenated castor oil, polyoxyethylene sorbitol fatty acid esters, polyethylene glycol fatty acid esters, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, propylene glycol fatty acid esters, sucrose fatty acid esters, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, polyglycerol fatty acid esters, propylene glycol fatty acid esters, polyoxyethylene castor oil, polyoxyethylene hardened oil fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene, Sucrose fatty acid ester, polyoxyalkylenated fatty acid ester, oxyalkylenated alkyl polyglycoside, alkyl glucoside ester.

Among polyoxyethylene glycerin fatty acid esters, in particular, polyoxyethylene hydrogenated castor oil, polyoxyethylene glycerin monostearate, polyoxyethylene glycerin monooleate, and polyoxyethylene glycerin monoisostearate are cited.

Among polyoxyethylene sorbitan fatty acid esters, one may cite polyoxyethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate.

Among polyoxyethylene sorbitol fatty acid esters, one may cite polyoxyethylene sorbitol monolaurate.

Among the polyethylene glycol fatty acid esters, one may cite polyethylene glycol monostearate, polyethylene glycol monooleate and polyethylene glycol monolaurate.

c) Amine or amide based nonionic surfactants

An example of the amine-based nonionic surfactant may be an amine oxide surfactant having the following general formula (11):

wherein the arrow is a semipolar bond (N)⁺-O^-) Conventional representation of (a); and R1, R2, and R3 can be aliphatic, aromatic, heterocyclic, alicyclic, or a combination thereof. In practice, R1 is C₈To C₂₄Alkyl groups of (a); r2 and R3 are C₁To C₃Alkyl or hydroxyalkyl or mixtures thereof; r2 and R3 may be linked to each other, for example, through an oxygen or nitrogen atom to form a cyclic structure.

In certain embodiments, R1 is selected from the group consisting of octyl, decyl, dodecyl, isododecyl, coconut oil, and tallow alkyl di- (lower alkyl) groups.

In practice, these compounds are referred to as octyldimethylamine oxide, nonyldimethylamine oxide, decyldimethylamine oxide, undecyldimethylamine oxide, dodecyldimethylamine oxide, isododecyldimethylamine oxide, tridecyldimethylamine oxide, tetradecyldimethylamine oxide, pentadecyldimethylamine oxide, hexadecyldimethylammonium oxide, heptadecyldimethylamine oxide, octadecyldimethylamine oxide, dodecyldipropylamine oxide, tetradecyldimethylamine oxide, hexadecyldipropylamine oxide, tetradecyldibutylamine oxide, octadecyldibutylamine oxide, bis (2-hydroxyethyl) dodecylamine oxide, bis (2-hydroxyethyl) -3-dodecyloxy-1-hydroxypropylamine oxide, dimethyl- (2-hydroxydodecyl) amine oxide, decyldimethylamine oxide, dodecyldimethylamine oxide, 3,6, 9-trioctadecyl dimethyl amine oxide and 3-dodecyloxy-2-hydroxypropyl bis- (2-hydroxyethyl) amine oxide.

Further examples of amine-based nonionic emulsifiers of interest according to the invention can be represented by alkoxylated amines, such as dialkoxylated primary amines and monoalkoxylated secondary amines.

Dialkoxylated primary amines of interest can be represented by compounds of formula (12) as follows:

wherein R1 is C₈-C₂₀Alkyl or C₈-C₂₀Alkenyl, R2 and R3 are independently C₂-C₁₀Alkylene radicals, e.g. CH₂-CH₂-、-CH₂-CH₂-CH₂-or mixtures thereof, and y' independently range from 2 to 50;

the monoalkoxylated tertiary amine may be represented by a compound having the following general formula (13):

wherein R1 and R3 are independently C₈-C₂₀Alkyl or C₈-C₂₀Alkenyl, R2 is C₂-C₁₀Alkylene radicals, e.g. CH₂-CH₂-、-CH₂-CH₂-CH₂-or a mixture thereof, and y ranges from 2 to 50.

Among the amido nonionic surfactants, there may be mentioned aldehyde diamide (aldolamide), fatty acid alkanolamide, polyoxyethylene alkylamide, and polyoxyethylene fatty acid amide.

In some embodiments, the alkanolamide surfactants include, but are not limited to, cocamide DEA, lauryldiethanolamide, lauramide DEA, cocamide DEA, lauramide DEA.

Further examples of amido nonionic emulsifiers of interest according to the present invention may be represented by alkoxylated alkanolamides, such as alkoxylated monoalkanolamines and dialkoxylated dialkanolamines.

The alkoxylated monoalkanolamide may be represented by a compound of formula (14) as follows:

The dialkoxylated dialkanolamide may be represented by a compound having formula (15) as follows:

wherein R1 is C₈-C₂₀Alkyl or C₈-C₂₀Alkenyl, R2 and R3 are independently C₂-C₁₀Alkylene radicals, e.g. CH₂-CH₂-、-CH₂-CH₂-CH₂-or mixtures thereof, and y' range independently from each other from 2 to 50.

d) Fluorosurfactants

In general, fluorosurfactants can be characterized by the level of fluorine in the molecule, which can result from copolymerization of partially or fully fluorinated alkylene oxide with non-fluorinated alkylene oxide, or by reaction of a fluorine-containing reactant with poly (alkylene oxide) to provide a fluorine content to the end groups.

In the first case, the oligomer or polymer comprises, in addition to the oxyalkylene groups, a certain amount of corresponding groups having one or more fluorine atoms, i.e. in the case of ethylene oxide as alkylene oxide, these compounds comprise- (CH2-CH2-O) -units and- (CH2-aXa-CH2-bXb-O) -units, where X represents fluorine and at least one of a or b represents an integer of at least 1.

In some cases, the fluorosurfactant can be represented by a compound having the following general formula (16):

F(CF₂-CF₂)_x-CH₂-CH₂-O-(CH₂-CH₂-O)_y-R (16)

wherein R is H or alkoxy, and x and y have values in the range from 1 to 50, preferably in the range from 1 to 30 and particularly preferably x and y are up to 20.

Products of this type having a weight-average molecular weight of up to 2000, preferably up to 1500 and even more preferably up to 1000 are of particular interest. The ratio of x to y (x/y) is not particularly limited and may be selected within a wide range. Many fluorosurfactants of this type are available from DuPont under the trade name DuPont

Are available.

Another group of fluorosurfactants includes CFs having six or fewer groups₂And end-capped at one end with fluorine and bound to a polymer such as that available under the trade name dupont

Commercially available delivery systems such as polymers or surfactants.

In certain embodiments, the nonionic surfactant represents from 0.1% to 5% by weight of the total weight of the suspension. (REV 10)

In certain embodiments, the nonionic surfactant has an HLB comprised between about 10 and about 14, preferably an HLB of about 12. (REV 11)

Nonionic surfactants having an HLB ranging from about 10 to about 14 are hydrophilic, i.e., readily dispersible in the aqueous phase. Aqueous phase

In a particular embodiment, the aqueous phase consists of water.

In certain embodiments, the aqueous phase comprises water and at least one hydrophilic additive.

Suitable hydrophilic additives may include, but are not limited to, mono-alcohols having 2 to 8 carbon atoms, such as ethanol and isopropanol, and polyols, such as glycerol, glycols, pentanediol, propylene glycol, butanediol, isoprene glycol, and polyethylene glycols such as PEG-8.

In certain embodiments, the at least one hydrophilic additive may represent from 0.01% to 10%, preferably from 0.1% to 1%, by weight of the total weight of the suspension.

The lower amount of aqueous phase contained in the suspension reduces the amount of material (i.e., water) that is inert with respect to combustion, as compared to a coal/water slurry (CWS).

In certain embodiments, the aqueous phase represents between 10% to 30% by weight of the total weight of the suspension. (REV 12)

Organic phase

In certain embodiments, the organic phase is selected from the group consisting of fossil-based liquids or derivatives thereof, biomass-based liquids, synthetic organic liquids or derivatives thereof, and mixtures thereof. (REV 13)

In certain embodiments, the fossil-based liquid is a petroleum-based liquid or a derivative thereof. (REV 14)

In certain embodiments, fossil-based liquids according to the present disclosure may be crude petroleum and crude petroleum derivative products produced from its processes, for example, by refineries. As examples of products from oil refineries one may cite diesel fuel, fuel oil, Furnace Fuel Oil (FFO), gasoline, Heavy Fuel Oil (HFO), Intermediate Fuel Oil (IFO), jet fuel, Marine Diesel Oil (MDO), bunker fuel oil (MFO), bunker gasoline (MGO), naval special grade fuel oil (NSFO) and mixtures thereof.

In certain embodiments, biomass-based liquids according to the present disclosure may be algal biofuels, bioethanol, biodiesel, biofuel gasoline, biomethanol, coconut oil, green diesel, palm oil, vegetable oil, and mixtures thereof.

In certain embodiments, biodiesel suitable for use in the present invention may comprise palm oil, i.e., malaysia biodiesel or LOF biodiesel, the latter of which has been used in the examples herein. The malaysia liquid biodiesel composition comprises a biodiesel composition derived from palm stearin, a biodiesel composition derived from palm oil methyl ester and a biodiesel composition derived from waste cooking oil.

In certain embodiments, the organic phase comprises a synthetic fuel notably derived from biomass and/or fossil agents.

Within the scope of the present invention, the organic phase may comprise aliphatic hydrocarbons, such as, for example, hexane, heptane, octane or nonane; inert alicyclic hydrocarbons such as cyclohexane, cyclopentane or cycloheptane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, or liquid cycloalkanes; alcohols such as butanol, ethanol, methanol or propanol; and mixtures thereof.

The presence of the organic phase contained in the suspension increases the amount of readily combustible material as compared to a coal/water slurry (CWS). Thus, the slurry suspension according to the invention provides excellent burning characteristics, in particular a good gross calorific value.

In a certain embodiment, the organic phase represents between 50% and 75% by weight of the total weight of the suspension. (REV 15)

Emulsion and method of making

In one aspect of the invention, the slurry suspension may be in the form of an emulsion, i.e., an oil-in-water (O/W) emulsion or a water-in-oil (W/O) emulsion.

The emulsion may be prepared according to common general knowledge known in the art. In practice, the preparation of the emulsion may comprise the separate preparation of a homogeneous aqueous phase and a homogeneous organic phase.

In certain embodiments, a nonionic surfactant having an HLB ranging from about 10 to about 14 is dispersed in the aqueous phase.

At this stage, a direct oil-in-water (O/W) emulsion can be prepared by introducing the organic phase into the continuous aqueous phase with stirring. A direct O/W emulsion is thus obtained and represents a discontinuous organic phase dispersed in a continuous aqueous phase.

Conversely, a water-in-oil (W/O) emulsion is obtained by introducing the aqueous phase into the organic phase via stirring. At the end of the process, the inverse W/O emulsion is therefore represented by a discontinuous aqueous phase dispersed in a continuous organic phase. Other known specific preparation methods may also be used.

In certain embodiments, the suspension is an oil-in-water emulsion. (REV 2)

In certain embodiments, the weight ratio of the aqueous phase to the organic phase is in a range from a ratio of 1/7.5 to a ratio of 1/1.65, preferably from a ratio of 1/4 to a ratio of 1/2.

In certain embodiments, when the nonionic surfactant is mixed in the aqueous phase, the weight ratio of the nonionic surfactant to the aqueous phase is in a range from the ratio of 1/100 to the ratio of 1/7, preferably the ratio of 1/25 to the ratio of 1/8.

These ratios are particularly useful for providing stable emulsions and for effectively and uniformly dispersing the carbonaceous material particles in the aqueous phase.

One or more additional ingredients

The suspensions of the invention may also contain one or more additional ingredients, such as conventional ingredients known in the art. Non-limiting examples of such ingredients may be humectants, wetting agents, rheological additives, alkalis, corrosion inhibitors, foam inhibitors, stabilizers, and biocidal preservatives.

When present in the suspension, the additional ingredients represent from 0.001% to 5%, preferably from 0.01% to 1% by weight of the total weight of the suspension.

Method of producing a composite material

In another aspect, the present invention relates to a method for preparing a slurry suspension according to the present invention, the method comprising the steps of:

i. mixing at least ingredients (b), (c) and (d) to form an emulsion;

In certain embodiments, the emulsion is an oil-in-water emulsion. (REV 17)

In certain embodiments, the method for preparing a slurry suspension according to the present invention comprises the steps of:

i1. mixing at least the nonionic surfactant (b) and the aqueous phase (c);

i2. mixing the organic phase (d) to the mixture obtained in step i1. to form an oil-in-water emulsion;

mixing the carbonaceous material particles (a) with the oil-in-water emulsion obtained in step i2. to form a slurry suspension.

In these embodiments, the nonionic surfactant is preferably added to the aqueous phase prior to forming the emulsion because nonionic surfactants having an HLB ranging from about 10 to about 14 readily disperse in the aqueous phase.

Furthermore, it was observed that the presence of the non-ionic surfactant facilitated the dispersion of the carbonaceous material particles in the aqueous phase.

In certain embodiments, an oil-in-water emulsion as described above is obtained, and the carbonaceous material particles are dispersed in the continuous aqueous phase between the organic phase droplets.

Without wishing to be bound by theory, in the case of an oil-in-water (O/W) emulsion, the lipophilic portion of the nonionic surfactant may advantageously form an interaction with the hydrophobic surface of the carbonaceous material particles, while the hydrophilic portion of the nonionic surfactant will facilitate dispersion in the continuous aqueous phase. Thus, these carbonaceous material particles are uniformly dispersed into the continuous aqueous phase and their precipitation in the emulsion is significantly delayed.

In addition, these carbonaceous material particles are dispersed between the droplets of the organic phase, which creates surface tension that keeps the droplets of the organic phase uniformly dispersed into the continuous aqueous phase

For these reasons, these carbonaceous material particles can behave like surfactants because they keep the droplets uniformly dispersed into the continuous aqueous phase and coalescence of the organic phase is significantly delayed.

In another aspect, the invention relates to a method for generating electricity, the method comprising combusting a slurry suspension (REV 18) according to the invention.

Use of

In another aspect, the invention also relates to the use of a non-ionic surfactant for stabilizing a composition comprising a polymer having a mean diameter D comprised between 0.1 μm and 200 μm₅₀The use of an emulsion of carbonaceous material particles of (a). (REV 19)

In certain embodiments, the emulsion is an oil-in-water emulsion. (REV 20)

The inventors have observed that the suspension according to the invention is capable of forming a stable emulsion (e.g. an oil-in-water emulsion) for a period of at least 2 weeks.

However, after a longer period of time, the suspension in the form of an emulsion may return to a state of non-emulsion suspension, i.e. after settling and/or separation of the aqueous and organic phases has taken place. The suspension may be further manipulated in a manner to form a stable emulsion for another period of time of at least 2 weeks.

The stable emulsions according to the invention can be advantageously used in already available internal combustion engines, or only slight modifications of these existing engines are necessary.

Examples of the invention

Example 1: preparation of fired wood particles

The calcined wood chips are obtained by calcination and the platelets have an average size of centimeter dimensions. The calcined wood chips were ground according to a dry milling protocol to obtain particles having an average size of 300 μm to 1 mm. These granules in powder form were then dry milled by using a Retsch ZM200 dry mill with the following characteristics: grid 120 μm, speed 18000rpm, 25 ℃, nitrogen purge, in 10min each 80 g. At the end of the milling process, the particles showed the following particle size distribution measured with a neopataxel laser diffraction sensor: d₁₀＝6μm；D₅₀＝23μm；D₉₀＝60μm。

Example 2: slurry suspension comprising water/diesel/calcined wood particles

By first mixing 20% wt of water, 63% of Diesel oil (Shell V-Power Diesel CAS number: 68334-30-5) and 2% wt of Diesel oil

BSU (nonionic surfactant) makes stable oil-in-water (O/W) emulsions at room temperature. A surfactant (SoprophorBSU; HLB ═ 12) is added to water, which readily wets the wood particles.

15% wt of the calcined wood particles according to example 1 (25 μm) were then added and mixed with the first mixture to obtain a stable dispersion. An oil-in-water (o/w) emulsion is obtained with the fired wood particles in the continuous phase. It was observed that the calcined wood particles were trapped between the droplets in the continuous phase, which prevented them from settling. At the same time, the fired wood particles appear to act as an emulsifier, preventing coalescence of these droplets.

The number of days until the emulsion became unstable was determined by visual inspection of each sample once a day. Emulsion-based slurries are said to be unstable if:

coalescence leads to the formation of an oil layer on top of the slurry.

Creaming (grinding) leads to phase separation, forming wood and a water layer at the bottom of the container.

Precipitation results in a solid layer at the bottom of the vessel.

In this case, the emulsion remained stable for a long period of time with 15% of the calcined wood, 20% of water and 2% of Soprophor BSU. Illustratively, the slurry emulsion remains stable after a storage period of two weeks or more.

Thus, the formulation of emulsions made from calcined wood, water and diesel stabilized with nonionic surfactants is feasible.

Claims

1. A slurry suspension comprising:

(a) having an average diameter D between 0.1 and 200 μm₅₀The carbonaceous material particles of (a);

(b) a nonionic surfactant;

(c) an aqueous phase; and

(d) the organic phase is mixed with the water to be purified,

wherein the nonionic surfactant is an alkoxylated phenol compound having the formula (5):

wherein:

-R1, R2 and R3, independently of each other, are hydrogen or a linear or branched hydrocarbon radical containing from 4 to 50 carbon atoms;

-R4 is a divalent linear or branched alkylene group containing from 2 to 8 carbon atoms; and

-R5 is H, OH, alkoxy, Phosphate (PO)₄ ^-M⁺) Sulfate (SO)₄ ^-M⁺) Sulfonate (SO)₃ ^-M⁺) Or a Carboxylate (COO)^-M⁺) M + is a cation;

-n is an integer comprised between 2 and 100.

2. The suspension according to claim 1, wherein R1, R2 and R3, independently of each other, are linear or branched hydrocarbon groups.

3. The suspension of claim 2, wherein R1, R2, and R3, independently of each other, are aryl groups.

4. The suspension of claim 1, wherein R4 is a divalent linear or branched alkylene group containing 2 or 3 carbon atoms.

5. The suspension of claim 1, wherein R5 is H, OH or alkoxy.

6. The suspension of claim 5, wherein R5 is an OH group.

7. The suspension according to claim 1, wherein R1, R2 and R3 are aryl groups, R4 is a divalent linear or branched alkylene group containing 2 or 3 carbon atoms, R5 is an OH group.

8. The suspension according to claim 1, wherein the non-ionic surfactant is an alkoxylated mono-, di-or tristyrylphenol.

9. The suspension according to claim 8, wherein the non-ionic surfactant is an alkoxylated tristyrylphenol.

10. The suspension according to claim 9, wherein the non-ionic surfactant is a tristyrylphenol ethoxylate.

11. The suspension according to any one of claims 1 to 10, wherein the suspension is an oil-in-water emulsion.

12. The suspension according to any one of claims 1 to 10, wherein the particles of carbonaceous material are selected from the group comprising vegetable biomass, coal, coke, graphite, charcoal, bio-coal and mixtures thereof.

13. The suspension of claim 12, wherein the carbonaceous material particles are fired wood particles.

14. A suspension according to any one of claims 1 to 10, wherein the particles of carbonaceous material provide the following size distribution:

-D₁₀is comprised between 1 and 50 μm, and

-D₉₀is comprised between 50 and 500 μm.

15. A suspension according to any one of claims 1 to 10, wherein the particles of carbonaceous material represent between 5% and 50% by weight of the total weight of the suspension.

16. The suspension according to any one of claims 1 to 10, wherein the non-ionic surfactant represents from 0.1 to 5% by weight of the total weight of the suspension.

17. The suspension according to any one of claims 1 to 10, wherein the non-ionic surfactant has an HLB comprised between 10 and 14.

18. Suspension according to any one of claims 1 to 10, in which the aqueous phase represents between 10% and 30% by weight of the total weight of the suspension.

19. The suspension according to any one of claims 1 to 10, wherein the organic phase is selected from the group comprising fossil based liquids or derivatives thereof, biomass based liquids, synthetic organic liquids or derivatives thereof, and mixtures thereof.

20. The suspension of claim 19, wherein the organic phase is a petroleum-based liquid or derivative thereof.

21. The suspension according to any one of claims 1 to 10, wherein the organic phase represents between 50% and 75% by weight of the total weight of the suspension.

22. A method for preparing a slurry suspension according to any one of claims 1 to 21, comprising the steps of:

i. mixing at least ingredients (b), (c) and (d) to form an emulsion;

mixing component (a) with the emulsion obtained in step i to form a slurry suspension.

23. The method of claim 22, wherein the emulsion is an oil-in-water emulsion.

24. A method for generating electricity, the method comprising combusting the slurry suspension of any one of claims 1 to 21.

25. The nonionic surfactant is used forStable containing particles having an average diameter D comprised between 0.1 and 200 μm₅₀The use of an emulsion of carbonaceous material particles of (1), the nonionic surfactant being an alkoxylated phenolic compound having the formula (5):

wherein:

-n is an integer comprised between 2 and 100.

26. The use according to claim 25, wherein R1, R2 and R3 are aryl groups, R4 is a divalent linear or branched alkylene group containing 2 or 3 carbon atoms, and R5 is an OH group.

27. Use according to claim 25 or 26, wherein the non-ionic surfactant is an alkoxylated tristyrylphenol.

28. Use according to any one of claims 25 to 27, wherein the emulsion is an oil-in-water emulsion.