U.S. patent application number 15/539246 was filed with the patent office on 2017-12-07 for slurry suspension comprising torrefied wood particles.
The applicant listed for this patent is RHODIA OPERATIONS. Invention is credited to Jean-Christophe CASTAING, Helene FAY, Robert GRESSER, Bertrand PAVAGEAU, Ling QI, Rawad TADMOURI.
Application Number | 20170349848 15/539246 |
Document ID | / |
Family ID | 56148857 |
Filed Date | 2017-12-07 |
United States Patent
Application |
20170349848 |
Kind Code |
A1 |
PAVAGEAU; Bertrand ; et
al. |
December 7, 2017 |
SLURRY SUSPENSION COMPRISING TORREFIED WOOD PARTICLES
Abstract
A slurry suspension comprises: a) carbonaceous material
particles having an average diameter D.sub.50 comprised between 0.1
.mu.m and 200 .mu.m; b) a non-ionic surfactant; c) an aqueous
phase; and d) an organic phase.
Inventors: |
PAVAGEAU; Bertrand;
(Villenave d'Ornon, FR) ; QI; Ling; (Shanghai,
CN) ; CASTAING; Jean-Christophe; (Sevres, FR)
; TADMOURI; Rawad; (Bordeaux, FR) ; FAY;
Helene; (Bordeaux, FR) ; GRESSER; Robert;
(Vernouillet, FR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
RHODIA OPERATIONS |
Paris |
|
FR |
|
|
Family ID: |
56148857 |
Appl. No.: |
15/539246 |
Filed: |
December 23, 2014 |
PCT Filed: |
December 23, 2014 |
PCT NO: |
PCT/CN2014/094571 |
371 Date: |
June 23, 2017 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C10L 2290/28 20130101;
C10L 1/2683 20130101; C10L 1/2475 20130101; C10L 1/324 20130101;
C10L 9/083 20130101; Y02E 50/10 20130101; Y02E 50/15 20130101; C10L
10/18 20130101; C10L 5/447 20130101; C10L 2250/082 20130101; C10L
2250/06 20130101; Y02E 50/30 20130101; C10L 2290/24 20130101; C10L
1/1985 20130101 |
International
Class: |
C10L 1/32 20060101
C10L001/32; C10L 10/18 20060101 C10L010/18; C10L 5/44 20060101
C10L005/44; C10L 9/08 20060101 C10L009/08 |
Claims
1. A slurry suspension comprising: (a) carbonaceous material
particles having an average diameter D.sub.50 from 0.1 .mu.m to 200
.mu.m; (b) a non-ionic surfactant; (c) an aqueous phase; and (d) an
organic phase.
2. The suspension according to claim 1 wherein said suspension is
an oil-in-water emulsion.
3. The suspension according to claim 1 wherein said carbonaceous
material particles are selected from a group consisting of a
vegetal biomass, a coal, a coke, a graphite, a char, a biocoal and
a mixture thereof.
4. The suspension according to claim 3 wherein the vegetal biomass
is a torrefied vegetal biomass.
5. The suspension according to claim 1 wherein carbonaceous
material particles provide the size distribution as follows:
D.sub.10 is from 1 to 50 .mu.m, and D.sub.90 is from 50 to 500
.mu.m.
6. The suspension according to claim 1 wherein the carbonaceous
material particles represent from 5% to 50% by weight of the total
weight of the suspension.
7. The suspension according to claim 1 wherein the non-ionic
surfactant is selected from a group consisting of ether-based
non-ionic surfactants, ester-based non-ionic surfactants,
amine-based and amide-based non-ionic surfactants, and
fluoro-surfactants.
8. The suspension according to claim 7 wherein the ether-based
non-ionic surfactant is an alkoxylated phenol surfactant.
9. The suspension according to claim 8 wherein the alkoxylated
phenol surfactant is selected from a group comprising consisting of
an alkoxylated alkylphenol, an alkoxylated alkylarylphenol, an
alkoxylated sulfated and/or phosphate alkylphenol and alkoxylated
sulfated and/or phosphate alkylarylphenol.
10. The suspension according to claim 1 wherein the non-ionic
surfactant represents from 0.1% to 5% by weight of the total weight
of the suspension.
11. The suspension according to claim 1 wherein the non-ionic
surfactant has an HLB from about 10 to about 14.
12. The suspension according to claim 1 wherein the aqueous phase
represents from 10 to 30% by weight of the total weight of the
suspension.
13. The suspension according to claim 1 wherein the organic phase
is selected from a group consisting of a fossil-based liquid and a
derivative thereof, a biomass-based liquid, a synthetic organic
liquid and a derivative thereof, and a mixture thereof.
14. The suspension according to claim 13 wherein the fossil-based
liquid is a petroleum-based liquid or a derivative thereof.
15. The suspension according to claim 1 wherein the organic phase
represents from 50% to 75% by weight of the total weight of the
suspension.
16. A method for the preparation of a slurry suspension according
to claim 1, the method comprising the steps of: i. mixing at least
ingredients (b), (c) and (d) to form an emulsion; ii. mixing
ingredient (a) with the emulsion obtained in step i. to form a
slurry suspension.
17. The method according to claim 16, wherein the emulsion is an
oil-in-water emulsion.
18. A method for generating power, the method comprising combustion
of the slurry suspension according to claim 1.
19. A method for stabilizing an emulsion comprising carbonaceous
material particles having an average diameter D.sub.50 from 0.1
.mu.m to 200 .mu.m, the method comprising using a non-ionic
surfactant.
20. The method according to claim 19, wherein the emulsion is an
oil-in-water emulsion.
21. The suspension according to claim 4, wherein torrefied vegetal
biomass is torrefied wood particles.
22. The suspension according to claim 3, wherein said carbonaceous
material particles are biocoal.
23. The suspension according to claim 3, wherein said carbonaceous
material particles are coal.
24. The suspension according to claim 23, wherein the coal is
selected from a group consisting of anthracite, semi-anthracite,
charcoal, solvent refined coal, medium and high-volatile
bituminous, sub-bituminous and lignite coals.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to the field of slurry
suspensions comprising carbonaceous material particles intended to
be used as a liquid combustible.
STATE OF THE ART
[0002] In order to reduce the emission of sulphur from the
combustion of fuel, which pollutes the environment, and be
compatible with the Regulations relating to fuel consumption, oil
refineries rendered available low sulphur content fuel, made up
with refined heavy fuel of diesel fuel. However, due to a costly
process, these fuel alternatives are usually more expensive than
the less refined ones.
[0003] In addition, because of the expected shortage of crude oil
due to the decline in natural reserves, it is more than ever urgent
to find some efficient alternatives to reduce the portion of
fossil-based energy sources.
[0004] Some alternatives to further refined fuel have consisted in
replacing fossil-based combustible with biofuels, which development
usually aims to design new catalytic process to convert solid
biomass into liquid fuel. However, this disruptive process usually
suffers for competitive price to make biofuel or biofuel from
biomass.
[0005] Some other alternatives were recently proposed to increase
the renewable fuel part in fuel compositions. For example, a
technology based on a coal/water slurry (CWS), for which the coal
is dispersed into water, provides a liquid fuel compatible with
existing liquid boilers.
[0006] However, the disadvantage of coal/water slurries is that the
water is inert to combustion, and therefore reduces the gross
calorific value of aqueous coal or biocoal suspensions.
[0007] Another alternative that may be explored is the use of
torrefied biomass for producing renewable energy with
cost-competitive aspects and mainly for transportation regarding
the high energy density material compared to white untorrefied
biomass.
[0008] This "thermal processed biomass" offers interesting
properties, such as low sulphur content, low nitrogen content, and
excellent combustion properties.
[0009] Furthermore, torrefied biomass is an inert material as
compared to untorrefied, white, biomass and the material get
hydrophobic properties due to the loss of oxygen during the
torrefaction process.
[0010] There is still a need in the art for the provision of liquid
combustible formulations resulting in low sulphur emission, for
which the fossil-based energy source accounts for only a reduced
portion.
[0011] More particularly, because carbonaceous materials offer good
combustion properties, there is still a need in the art for the
provision of suspension comprising said carbonaceous materials in a
liquid vehicle, said suspension being homogeneously and stably
dispersed.
[0012] Further, there is still a need in the art for providing
liquid combustible formulations that are compatible with the
existing systems, such as engines and boilers.
SUMMARY OF THE INVENTION
[0013] A first aspect of the invention relates to a slurry
suspension comprising:
[0014] (a) carbonaceous material particles having an average
diameter D.sub.50 comprised between 0.1 .mu.m and 200 .mu.m;
[0015] (b) a non-ionic surfactant;
[0016] (c) an aqueous phase; and
[0017] (d) an organic phase. (REV 1)
[0018] Another aspect of the invention relates to a method for the
preparation of a slurry suspension according to the invention
comprising the steps of:
[0019] i. mixing at least ingredients (b), (c) and (d) to form an
emulsion;
[0020] ii. mixing ingredient (a) with the emulsion obtained in step
i. to form a slurry suspension. (REV 16)
[0021] Another aspect of the invention relates to a method for
generating power comprising combustion of the slurry suspension
according to the instant invention. (REV 18)
[0022] A still another aspect of the invention relates to a use of
a non-ionic surfactant to stabilize an emulsion comprising
carbonaceous material particles having an average diameter D.sub.50
comprised between 0.1 .mu.M and 200 .mu.m. (REV 19)
DETAILED DESCRIPTION OF THE INVENTION
[0023] The inventors surprisingly found that carbonaceous material
particles may be added to an emulsion, in particular an
oil-in-water emulsion, in order to obtain a stable and
homogeneously dispersed slurry suspension that can be further used
as a liquid biofuel for combustion.
[0024] The emulsion, in particular an oil-in-water emulsion, is
stabilized by the presence of a non-ionic surfactant.
[0025] Slurry Suspension
[0026] Hence, a first aspect of the invention relates to a slurry
suspension comprising:
(a) carbonaceous material particles having an average diameter
D.sub.50 comprised between 0.1 .mu.m and 200 .mu.m; (b) a non-ionic
surfactant; (c) an aqueous phase; and (d) an organic phase. (REV
1)
[0027] Within the scope of the invention the term "suspension"
refers to a system comprising carbonaceous material particles, i.e.
a solid material, dispersed in a liquid phase comprising an aqueous
phase, an organic phase and a non-ionic surfactant, in particles of
larger than colloidal size.
[0028] In certain embodiments, the term "suspension" refers to a
system comprising an emulsion, i.e. a liquid phase, in which are
dispersed the carbonaceous material particles (emulsion state).
[0029] In certain embodiments, the term "suspension" refers to a
system wherein an aqueous liquid phase and an organic liquid phase
are separate phases and do not form an emulsion; the carbonaceous
material particles being dispersed in these liquid phases
(non-emulsion state).
[0030] Within the scope of the present invention, the term "about"
refers to a value that may vary from +/-10% from said mentioned
value.
Carbonaceous Material Particles
[0031] Within the scope of the instant invention, the term
"carbonaceous material" refers to a material containing a large
content of carbon.
[0032] The carbon content of carbonaceous material particles useful
for the present invention typically exceeds 30 wt. %, based on the
total weight of the carbonaceous material particles; it is often
above 40 wt. %. It is preferably above 45 wt. %, more preferably
above 50 wt. %, based on the total weight of the carbonaceous
material particles. On the other hand, it is typically of at most
90 wt. %, and often of at most 80 wt. %, based on the total weight
of the carbonaceous material particles. It can be of at most 70 wt.
% or even of at most 60 wt. %, based on the total weight of the
carbonaceous material particles. Certain useful ranges for the
carbon content of carbonaceous material particles useful for the
present invention are either 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 materials particles. The carbon content of the
carbonaceous material particles can be determined by any method
known to the skilled person. For example, it can be determined by
drying the carbonaceous material particles for 12 h at 100.degree.
C. in an oven (to remove water and other volatiles), then keeping
the dried particles in a dessicator (to avoid water pickup), then
burning the carbonaceous materials particles in a burning oven
under conditions capable of converting essentially the whole (when
not, the whole) carbon content of the carbonaceous materials
particles into carbon dioxide, then quantifying the C content
(through the CO.sub.2 formed by the combustion) by infrared
detection.
[0033] In one embodiment, the carbonaceous material particles are
selected in a group comprising a vegetal biomass, a coal, a coke, a
graphite, a char, a biocoal and a mixture thereof (REV 3)
[0034] According to the present invention, a vegetal biomass
comprises ligno-cellulosic fibers, and may be provided by any
plant, wood and crop susceptible to provide suitable biomass.
[0035] Plants such as miscanthus, switchgrass, hemp; woods such as
poplar, bamboo, eucalyptus, oil palm, willow, pine, oak, gum,
aspen, beech, coconut tree and spruce; and crops such as corn,
sorghum, sugarcane and beet are suitable for implementing the
instant invention.
[0036] In certain embodiments, the vegetal biomass is selected in a
group comprising a plant or a part thereof, e.g. leave, stem, root,
including a crop or a part thereof; a wood, a wood chip or a wood
sawdust; a straw; a bark; a grass; a forestry residue; an
agricultural waste such as corn cobs, corn stover, corn stalk,
wheat straw, bamboo grass, vine shoot, sugar cane bagasse, sorghum
bagasse, almond shell, sunflower seed hull and a mixture
thereof.
[0037] In certain embodiments, the vegetal biomass has been
subjected to a treatment in order to remove its water content, such
treatment being a dry heat treatment, steam explosion, vacuum
evaporation, hydrothermal carbonization, or any suitable treatment
known from the state of the art.
[0038] A dry heat treatment method may encompass a treatment of the
starting biomass at a temperature below 200.degree. C. to a maximum
temperature of 500.degree. C., for a period of time from several
minutes to several hours.
[0039] In certain embodiments, the dry heat treatment consists of
torrefaction, which is performed at a temperature ranging from
about 280.degree. C. to about 320.degree. C., for a period of time
ranging from 1 min to 15 min, preferably from 2 min to 8 min.
[0040] In certain preferred embodiments, the vegetal biomass is a
torrefied vegetal biomass, preferably torrefied wood particles.
(claim 4)
[0041] In certain embodiments, the carbonaceous material is coal,
such as anthracite, semi-anthracite, charcoal, solvent refined
coal, medium and high-volatile bituminous, sub-bituminous, and
lignite coals.
[0042] 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 carbonization of coal, pitch, petroleum
residues, and certain other carbonaceous materials.
[0043] In certain embodiments, mixtures of coal and petroleum coke
can be used in this invention.
[0044] When referring to "carbonaceous material particles", one may
understand that said particles have low water content or are
water-less. By "low water content", one may understand a water
content that is at most 20% in weight as compared to the weight of
the starting material. Hence, at most 20% in weight of water
encompasses a water content of 0%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%,
9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% and 20% in
weight as compared to the weight of the starting material.
[0045] Within the scope of the invention, the expression
"carbonaceous material particles" refers to particles of a
carbonaceous material in a solid state.
[0046] The carbonaceous material particles encompassed by the
invention are obtained after a fine wet or dry grinding of the
carbonaceous material, using a grinding mill. When performing a wet
grinding, the carbonaceous material particles may be further
handled as to undergo a dry heat treatment intended to reduce its
water content to a maximum of 20%. Oppositely, when performing a
dry grinding, the carbonaceous material particles according to the
invention have a water content of a maximum of 20% in weight as
compared to the weight of the starting material.
[0047] In certain embodiments, the carbonaceous material particles
provide the size distribution as follows: [0048] D.sub.10 is
comprised between 1 and 50 .mu.m, and [0049] D.sub.90 is comprised
between 50 and 500 .mu.m. (REV 5)
[0050] Within the scope of the invention, the size of the particles
may be measured by any suitable mean known from the state of the
art.
[0051] In preferred embodiments, the size distribution of the
particles is measured by the mean of laser diffraction by dry
dispersion, respecting the principles and basic rules set out in
ISO 13320:2009 (E).
[0052] In practice, the analysis is performed using a Helos H1302
laser diffraction sensor (Sympatec, Germany). The detector of the
focal length is selected so that its pass band covers the size
range of the carbonaceous material particles to be analysed. For
example, when analysing a milled torrefied biomass, R4 detector
(0.5 .mu.m to 350 .mu.m) is particularly well adapted.
[0053] The carbonaceous material particles are dispersed in a
stream of dry nitrogen under pressure using a dry dispersing unit
(Rodos, Sympatec, Germany).
[0054] The optimum operating conditions are sought experimentally
to obtain a good dispersion of particles, without crushing in the
ejector. In practice, when analysing carbonaceous material
particles in the form of ground torrefied biomass, the nitrogen
pressure is about 100 kPa (1 bar) and the depression represents
about 4 kPa (40 mbar).
[0055] The carbonaceous material particles are fed using a
vibrating chute. The feed rate is adjusted so as to obtain an
optical concentration between 2% and 10%. In practice the total
mass of the sample containing the carbonaceous material particles
to be analysed ranges from about 1 g to about 10 g, preferably
about 5 g.
[0056] Laser diffraction data were acquired and analysed using the
Windox 5 software (Sympatec, Germany).
[0057] In one embodiment, the carbonaceous material particles
represent between 5% to 50% by weight of the total weight of the
suspension. (REV 6)
[0058] Non-Ionic Surfactant
[0059] Within the scope of the present invention, a non-ionic
surfactant may be selected in a group comprising ether-based
non-ionic surfactants, ester-based non-ionic surfactants,
amine-based or amide-based non-ionic surfactants and
fluro-surfactants. (REV 7)
[0060] a) Ether-Based Non-Ionic Surfactants
[0061] Among the ether-based non-ionic surfactants, one may cite
ether of carboxylic acids-based non-ionic surfactant, alcohol-based
non-ionic surfactant, oside-based non-ionic surfactants, fatty
alcohol-based non-ionic surfactants and silicone non-ionic
surfactants.
[0062] Non-ionic emulsifiers of interest in accordance with the
present invention may be represented by ether of carboxylic acids
of formula (1) as follows:
R1-O--(R2-O)y-CH2-COOH (1),
[0063] wherein R1 is C8-C20 alkyl, C8-C20 alkyl phenyl or C8-C20
alkenyl, R2 is C2-C10 alkylene, for example --CH2-CH2-,
--CH2-CH2-CH2- or a mixture thereof, and y ranges from 2 to 50.
[0064] In certain embodiments, ether of carboxylic acids are
represented by a compound of formula (1), wherein R2 is a C2 or C3
alkylene.
[0065] In particular, ether of carboxylic acids-based non-ionic
surfactants are preferably represented by polyoxyethylene-based
non-ionic surfactants (--(CH2-CH2-O)--), polyoxypropylene-based
non-ionic surfactants (--(CH2-CH2-CH2-O)--),
polyoxyethylene-polyoxypropylene-based non-ionic surfactants.
[0066] A polyoxyethylene-based nonionic surfactant may comprise a
polyoxyethylene alkyl ether, a polyoxyethylene alkyl phenyl ether,
a polyoxyethylene polyoxypropylene alkyl ether.
[0067] 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, polyoxyethylene isostearyl
ether.
[0068] Among polyoxyethylene alkyl phenyl ethers, one may cite
compounds such as polyoxyethylene octylphenyl ether,
polyoxyethylene nonylphenyl ether and dialkylphenoxy
poly(ethyleneoxy) ethanol.
[0069] Among polyoxyethylene polyoxypropylene alkyl ether, one may
cite compounds such as polyoxyethylene polyoxypropylene cetyl
ether, polyoxyethylene polyoxypropylene decyltetradecyl ether.
[0070] Alcohol-based non-ionic surfactant of interest in accordance
with the present invention may be represented by alkoxylated
alcohols.
[0071] Within the scope of the present invention, the term
"alkoxylated" relies upon the presence of oxyalkylene units, for
which the total number of these units generally ranges 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.
[0072] Alkoxylated alcohols of interest may be represented by a
compound of the general formula (2) as follows:
R1-O--(R2-O)y-H (2)
[0073] wherein R1 is C6-C30 hydrocarbyl, R2 is C2-C10 alkylene, for
example --CH2-CH2-, --CH2-CH2-CH2- or a mixture thereof, and y
ranges from 2 to 50.
[0074] Preferably, alkoxylated alcohols may be represented by a
compound of the general formula (3) as follows:
R3-O--(R2-O)y-H (3)
[0075] wherein R3 is C8-C20 alkyl or C8-C20 alkenyl, R2 is C2-C10
alkylene, for example --CH2-CH2-, --CH2-CH2-CH2- or a mixture
thereof, and y ranges from 2 to 50, or
[0076] Alternatively, alkoxylated alcohols are of formula (4) as
follows:
R4-.phi.-O--(R2-O)y-H (4)
[0077] wherein R4 is C4-C20 alkyl, in particular, R4 is octyl (C8)
or nonyl (C9), .phi. is p-phenylene, R2 is C2-C10 alkylene, for
example --CH2-CH2-, --CH2-CH2-CH2- or a mixture thereof, and y
ranges from 2 to 50.
[0078] Similar alcohols can be obtained by replacing R4-.phi. in
the above formula (4) by [2,4-6-tri-(t-butyl)]-phenyl.
[0079] Examples of alkoxylated alcohols suitable as a non-ionic
surfactant, according to the invention, are the products of the
condensation of (i) from 2 to 50 moles of at least one C2-C3
alkylene oxide, such as ethylene oxide, with (ii) a mole of an
ethylenically saturated or unsaturated fatty alcohol, especially a
C8-C20 alcohol chosen from lauryl alcohol, myristyl alcohol,
palmityl alcohol, stearyl alcohol, oleyl alcohol, linoleyl alcohol,
linolenyl alcohol, oxoalcohols and mixtures thereof.
[0080] Other examples of alkoxylated alcohols suitable as a
non-ionic surfactant, according to the invention, are the products
of condensation of (i) from 2 to 50 moles of at least one C2-C3
alkylene oxide, such as ethylene oxide, with a mole of
n-octylphenol, n-nonylphenol and mixtures thereof.
[0081] Alcoxylated alcohols may be commercially available under the
tradenames Brij.RTM. (Atlas Chemical Co.), Genapol.RTM. (Clariant)
and Lutensol.RTM. (BASF).
[0082] Oside-based nonionic surfactants may comprise long chain
alkyl polyglucosides, which are obtained by the condensation of a)
a long chain alcohol containing from about 6 to about 25 carbon
atoms, with b) a glucose or glucose containing polymer. In practice
such a compound may be alkyl polyglycosides and alkyl
polysaccharides, such as decyl glucoside, octyl glucoside or decyl
maltoside.
[0083] In certain embodiments, the ether-based non-ionic surfactant
is an alkoxylated phenol surfactant. (REV 8)
[0084] In certain embodiments, the alkoxylated phenol surfactant is
chosen in a group comprising an alkoxylated alkylphenol, an
alkoxylated alkylarylphenol, an alkoxylated sulfated and/or
phosphate alkylphenol and alkoxylated sulfated and/or phosphate
alkylarylphenol. (REV 9)
[0085] An alkoxylated phenol compound that is suitable comprises an
oxyalkylene group that may be for instance an oxyethylene group, an
oxypropylene group, or an oxyethylene/oxypropylene group (i.e.
ethoxy-propoxylated group).
[0086] The number of oxyalkylene units, such as the number of
oxyethylene (OE) units and/or oxypropylene (OP) units, in the
alkoxylated phenol compound is normally between 2 and 100 depending
on the desired HLB (hydrophile/lipophile 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.
[0087] Alkoxylated phenol compounds suitable for the present
invention may comprise one, two or three linear or branched
hydrocarbon group(s), preferably comprising from 4 to 50 carbon
atoms, more preferably comprising from 4 to 12 carbon atoms,
connected to the phenol group. This hydrocarbon group is preferably
a hydrocarbon group chosen in the group consisting of an alkyl
group, such as tert-butyl, butyl, or isobutyl; an aryl group; an
alkylaryl group; and an arylalkyl group, which may comprise a
heteroatom such as N, O or S. The alkyl moiety of the alkylaryl
group or the arylalkyl group may be a C1-C6 alkyl moiety.
Hydrocarbon group may notably be represented by a phenyl group or a
phenylethyl group.
[0088] Alkoxylated phenol compounds may also comprise a functional
group connected 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+.
[0089] Suitable salts are, for example, metal salts, such as alkali
metal or alkaline earth metal salts, e.g. sodium, potassium calcium
or magnesium salts, or salts with ammonia or an organic amine, such
as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower
alkylamine, for example ethyl-, diethyl-, triethyl- or
dimethyl-propylamine, or a mono-, di- or tri-hydroxy-lower
alkylamine, for example mono-, di- or tri-ethanolamine.
[0090] Alkoxylated phenol compounds may notably be a compound of
formula (5) as follows:
##STR00001##
wherein: [0091] R1, R2 and R3 are, independently from each other, a
hydrogen or a linear or branched hydrocarbon group, preferably
comprising from 4 to 50 carbon atoms, preferably comprising from 4
to 12 carbon atoms; [0092] R4 is a divalent linear or branched
alkylene radical comprising from 2 to 8 carbon atoms, preferably 2
or 3 carbon atoms; R4 may be a mixture of several different
alkylene radicals; [0093] n is an integer comprised between 2 and
100, preferably comprised between 2 and 50; [0094] R5 is H, OH,
alkoxy group, phosphate (PO.sub.4.sup.-M.sup.+), sulfate
(SO.sub.4.sup.- M.sup.+), sulfonate (SO.sub.3.sup.- M.sup.+) or
carboxylate (COO.sup.- M.sup.+); M.sup.+ if present is a cation
including but not limited to H.sup.+, Na.sup.+, NH.sub.4.sup.+,
K.sup.+ or Li.sup.+.
[0095] As expressed in formula (5), R1 R2 and R3 are hydrogen or
linear or branched hydrocarbon group connected to the phenyl
structure. R1 R2 and R3 may be, independently from each other,
alkyl group, such as tert-butyl, butyl, or isobutyl; aryl group;
alkylaryl group; or arylalkyl group, which may comprise a
heteroatom such as N, O or S. The alkyl part of alkylaryl group or
arylalkyl group may be a C1-C6 alkyl part. R1 R2 and R3 may notably
be, independently from each other, phenyl group or a phenylethyl
group.
[0096] When R5 is an alkoxy group, it may be for instance a C1-C6
alkoxy group, such as --OCH3, --OC2H5, --OC3H7, --OC4H9, --OC5H11,
or --OC6H13.
[0097] Suitable alkoxylated phenol compounds may notably be chosen
in the group consisting of: [0098] alkoxylated alkylphenol that may
be e.g. a C.sub.6-C.sub.16-alkanol such as alkoxylated octylphenol,
alkoxylated laurylphenols and alkoxylated nonyl phenol, such as
polyethoxylated octylphenols and polyethoxylated nonylphenols;
[0099] alkoxylated alkylarylphenol that may be e.g. an alkoxylated
mono-, di- or tristyrylphenol, such as polyethoxylated
tristyrylphenol; [0100] Alkoxylated sulfated and/or phosphate
alkylphenol; and [0101] Alkoxylated sulfated and/or phosphate
alkylarylphenol, such as ethoxylated and/or propoxylated, sulfated
and/or phosphated, mono-, di- or tristyrylphenols, ethoxylated
polyarylphenol ether phosphate.
[0102] Tristyrylphenol ethoxylates, for other uses, are for
instance disclosed by U.S. Pat. No. 6,146,570, published PCT patent
application number WO 98/012921 and WO 98/045212, incorporated
herein by reference.
[0103] Alkoxylated phenol compounds of the present invention may
notably be chosen in 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 ethoxy-propoxylated with
25 OE+OP units; nonylphenol ethoxy-propoxylated with 30 OE+OP
units; nonylphenol ethoxy-propoxylated with 40 OE+OP units;
nonylphenol ethoxy-propoxylated with 55 OE+OP units; nonylphenol
ethoxy-propoxylated with 80 OE+OP units; di(1-phenylethyl)phenol
ethoxylated with 5 OE units; di(1-phenylethyl)phenol ethoxylated
with 7 OE units; di(1-phenylethyl)phenol ethoxylated with 10 OE
units; tri(1-phenylethyl)phenol ethoxylated with 8 OE units;
tri(1-phenylethyl)phenol ethoxylated with 16 OE units;
tri(1-phenylethyl)phenol ethoxylated with 20 OE units;
tri(1-phenylethyl)phenol ethoxylated with 25 OE units;
tri(1-phenylethyl)phenol ethoxylated with 40 OE units;
tri(1-phenylethyl) phenols ethoxy-propoxylated with 25 OE+OP units;
ethoxylated and sulfated di(1-phenylethyl)phenol comprising 5 OE
units; ethoxylated and sulfated di(1-phenylethyl)phenol comprising
7 OE units; ethoxylated and sulfated di(1-phenylethyl)phenol
comprising 15 OE units; ethoxylated and sulfated
di(1-phenylethyl)phenol comprising 16 OE units; ethoxylated and
sulfated tri(1-phenylethyl)phenol comprising 16 OE units; and
ethoxylated and phosphated tri(1-phenylethyl)phenol comprising 16
OE units.
[0104] In practice, alkoxylated phenol surfactants according to the
invention may be selected among: [0105] Tristyryl phenol
ethoxylates, such as the commercially available products
Soprophor.RTM. BSU; Soprophor.RTM. CY8; Soprophor.RTM. S25
(Solvay); [0106] Alcool Ethoxylates, such as the commercially
available products Rhodasurf.RTM. LA 12/80; Rhodasurf 0 LA 12;
Rhodasurf 0 BC 720; Rhodasurf 0 BC 630; Rhodasurf 0 BC 639
(Rhodia); [0107] Alkyl Phenol Ethoxylate such as the commercially
available products Igepal.RTM. RC 630; Igepal.RTM. DM 530;
Igepal.RTM. RC 620; Igepal.RTM. CO 610; Igepal.RTM. CO 630;
Igepal.RTM. CO 660; Igepal.RTM. CO 710; Igepal.RTM. CO 710
(Solvay).
[0108] In practice, silicone surfactants comprise
polydimethylsiloxane that is modified on side-chain(s), one
extremity, both extremities and combination thereof. As an example
of modifications, the polydimethylsiloxane may be modified by a
polyether group, such as a polyoxyethylene group or a
polyoxyethylene polyoxypropylene group.
[0109] b) Ester-Based Non-Ionic Surfactants
[0110] Among ester-based non-ionic emulsifiers of interest, one may
cite alkoxylated oils and fats. These compounds encompass
ethoxylated and/or propoxylated derivatives of lanolin (wool fat)
or of castor oil. Lanolin is the generic name of a wax containing a
mixture of esters and polyesters of high-molecular-weight alcohols
and fatty acids. Castor oil is a mixture of a triglyceride of fatty
acids.
[0111] Other examples of ester-based non-ionic emulsifiers may be
represented alkoxylated acids, such as the compounds represented by
monoesters and diesters.
[0112] Monoesters of interest may be represented by a compound of
the general formula (6) as follows:
##STR00002##
wherein R1 is C.sub.6-C.sub.30 hydrocarbyl, R2 is C.sub.2-C.sub.10
alkylene, for example --CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--CH.sub.2-- or a mixture thereof, and y ranges
from 2 to 50.
[0113] Preferably, monoesters may be represented by a compound of
the general formula (7) as follows:
##STR00003##
wherein R3 is C.sub.8-C.sub.20 alkyl or C.sub.8-C.sub.20 alkenyl,
R2 is C.sub.2-C.sub.10 alkylene, for example
--CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2-- or a
mixture thereof, and y ranges from 2 to 50.
[0114] Examples of alkoxylated acids monoesters are the
condensation products of from 2 to 50 moles (in particular, from 4
to 16 moles) of an alkylene oxide (such as ethylene oxide) with one
mole of a saturated or unsaturated fatty acid chosen from lauric
acid, myristic acid, palmitic acid, stearic acid, oleic acid,
linoleic acid and linolenic acid. An example thereof is
Deplastol.RTM. product which is a condensate of about 4-5 mol
oxyethylene units with lauric acid and/or myristic acid (Cognis,
Germany). Corresponding propoxylated and/or butylated fatty acids
may also be included in the alkoxylated acids monoesters of
interest.
[0115] Diesters of interest may be represented by a compound of the
general formula (8) as follows:
##STR00004##
[0116] wherein R1 and R3 are independently a C.sub.6-C.sub.30
hydrocarbyl, R2 is C.sub.2-C.sub.10 alkylene, for example
--CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2-- or a
mixture thereof, and y ranges from 2 to 50. Preferably, diesters of
interest may be represented by a compound of the general formula
(9) as follows:
##STR00005##
wherein R4 and R5 are independently C.sub.8-C.sub.20 alkyl or
C.sub.8-C.sub.20 alkenyl, R2 is C.sub.2-C.sub.10 alkylene, for
example --CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2-- or
a mixture thereof, and y ranges from 2 to 50.
[0117] Other examples of ester-based non-ionic emulsifiers of
interest may represented by alkoxylated glycol, such as alkoxylated
ethylene glycol esters and alkoxylated propylene glycol esters.
[0118] Alkoxylated ethylene glycol esters may be represented by a
compound of the general formula (10) as follows:
##STR00006##
wherein R1 is C.sub.8-C.sub.20 alkyl or C.sub.8-C.sub.20 alkenyl,
R2 is C.sub.2-C.sub.10 alkylene, for example
--CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2-- or a
mixture thereof, and y ranges from 2 to 50.
[0119] Alkoxylated propylene glycol esters may be represented by a
compound of the general formula (11) as follows:
##STR00007##
wherein R1 is C.sub.8-C.sub.20 alkyl or C.sub.8-C.sub.20 alkenyl,
R2 is C.sub.2-C.sub.10 alkylene, for example
--CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2-- or a
mixture thereof and y ranges from 2 to 50.
[0120] Alkoxylated esters of monoglycerides, dialkoxylated esters
of diglycerides and trialkoxylated esters of triglycerides may also
be compounds of interest, said esters being the reaction products
of glycerol, or one of its derivatives, with a carboxylic acid
comprising from 8 to 20 carbon atoms and comprise in total from 6
to 60 oxyalkylene units.
[0121] Among the non limitating ester-based non-ionic surfactants,
one may cite polyoxyethylene alkylesters, polyoxyethyleneglycerine
aliphatic acid esters, polyoxyethylene castor oil, hydrogenated
castor oil, polyoxyethylene sorbitol aliphatic acid esters,
polyethylene glycols aliphatic acid esters, aliphatic acid
monoglycerides, polyglycerine aliphatic acid esters, sorbitan
aliphatic acid esters, polyoxyethylene sorbitan aliphatic esters,
propylene glycol aliphatic acid esters, cane sugar aliphatic acid
esters, polyethylene glycol fatty acid esters, sorbitan fatty acid
esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene
sorbit fatty acid esters, glycerin fatty acid esters,
polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid
esters, propylene glycol fatty acid esters, polyoxyethylene castor
oil, polyoxyethylene cured castor oil, polyoxyethylene cured castor
oil fatty acid ester, sucrose fatty acid esters, polyoxyalkylenated
fatty acid esters, oxyalkylenated alkyl polyglycosides, alkyl
glucoside esters.
[0122] In particular, among polyoxyethylene glycerin fatty acid
esters, one may cite polyoxyethylene hydrogenated castor oil,
polyoxyethylene castor oil, polyoxyethylene glyceryl monostearate,
polyoxyethylene glyceryl monooleate, and polyoxyethylene glyceryl
monoisostearate.
[0123] Among polyoxyethylene sorbitan fatty acid esters, one may
cite polyoxyethylene sorbitan monostearate and polyoxyethylene
sorbitan monooleate.
[0124] Among polyoxyethylene sorbitol fatty acid esters, one may
cite polyoxyethylene sorbitol monolaurate.
[0125] Among polyethylene glycol fatty acid esters, one may cite
polyethylene glycol monostearate, polyethylene glycol monooleate
and polyethylene glycol monolaurate.
[0126] c) Amine-Based or Amide-Based Non-Ionic Surfactants
[0127] Examples of amine-based non-ionic surfactants may be amine
oxide surfactants of the general formula (11) as follows:
##STR00008##
wherein the arrow is a conventional representation of a semi-polar
bond (N.sup.+--O.sup.-); and, R1, R2, and R3 may be aliphatic,
aromatic, heterocyclic, alicyclic, or combinations thereof. In
practice, R1 is an alkyl radical in C.sub.8 to C.sub.24; R2 and R3
are alkyl or hydroxyalkyl in C.sub.1 to C.sub.3 or a mixture
thereof; R2 and R3 can be attached to each other, e.g. through an
oxygen or nitrogen atom, to form a ring structure.
[0128] In certain embodiments, R1 is selected from the group
comprising octyl, decyl, dodecyl, isododecyl, coconut and tallow
alkyl di-(lower alkyl) radicals.
[0129] In practice, these compounds are known as octyldimethylamine
oxide, nonyldimethylamine oxide, decyldimethylamine oxide,
undecyldimethylamine oxide, dodecyldimethylamine oxide,
iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,
tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,
hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,
octadecyldimethylaine oxide, dodecyldipropylamine oxide,
tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,
tetradecyldibutylamine oxide, octadecyldibutylamine oxide,
bis(2-hydroxyethyl)dodecylamine oxide,
bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,
dimethyl-(2-hydroxydodecyl)amine oxide,
3,6,9-trioctadecyldimethylamine oxide and
3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethy)amine oxide.
[0130] Other examples of amine-based non-ionic emulsifiers of
interest in accordance with the present invention may be
represented by alkoxylated amines, such as dialkoxylated primary
amines and monoalkoxylated secondary amines.
[0131] Dialkoxylated primary amines of interest may be represented
by a compound of formula (12) as follows:
##STR00009##
wherein R1 is C.sub.8-C.sub.20 alkyl or C.sub.8-C.sub.20 alkenyl,
R2 and R3 independently are C.sub.2-C.sub.10 alkylene, for example
--CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2-- or a
mixture thereof, and y and y' range independently from 2 to 50;
[0132] Monoalkoxylated tertiary amines may be represented by a
compound of general formula (13) as follows:
##STR00010##
wherein R1 and R3 independently are C.sub.8-C.sub.20 alkyl or
C.sub.8-C.sub.20 alkenyl, R2 is C.sub.2-C.sub.10 alkylene, for
example --CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2-- or
a mixture thereof and y ranges from 2 to 50.
[0133] Among the amide-based non-ionic surfactants, one may cite
aldobionamides, aliphatic acid alkanolamides, polyoxyethylene
alkylamides, polyoxyethylene aliphatic acid amides.
[0134] In some embodiments, the alkanolamide surfactants include,
but are not limited to, cocamide DEA, lauryl diethanolamide,
lauramide DEA, cocamide DEA, lauramide DEA.
[0135] Other examples of amide-based non-ionic emulsifiers of
interest in accordance with the present invention may be
represented by alkoxylated alkanolamides, such as alkoxylated
monoalkanolamides and dialkoxylated dialkanolamides.
[0136] Alkoxylated monoalkanolamides may be represented by a
compound of formula (14) as follows:
##STR00011##
wherein R1 is C.sub.8-C.sub.20 alkyl or C.sub.8-C.sub.20 alkenyl,
R2 is C.sub.2-C.sub.10 alkylene, for example
--CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2-- or a
mixture thereof, and y ranges from 2 to 50.
[0137] Dialkoxylated dialkanolamides, may be represented by a
compound of formula (15) as follows:
##STR00012##
wherein R1 is C.sub.8-C.sub.20 alkyl or C.sub.8-C.sub.20 alkenyl,
R2 and R3 independently are C.sub.2-C.sub.10 alkylene, for example
--CH.sub.2--CH.sub.2--, --CH.sub.2--CH.sub.2--CH.sub.2-- or a
mixture thereof, and y and y' independently from each other range
from 2 to 50.
[0138] d) Fluoro-Surfactants
[0139] In general, fluoro-surfactants may be characterized by a
content of fluorine in the molecule, which might either arise from
the copolymerization of a partially or fully fluorinated alkylene
oxide with a non-fluorinated alkylene oxide or by reaction of
fluorine containing reactants with poly(alkylene oxides) thus
providing endgroups with a fluorine content.
[0140] In the first case the oligomer or polymer comprises, in
addition to the oxyalkylene groups, a certain amount of respective
groups having one or more fluorine atom, i.e. in the case of
ethylene oxide as the alkylene oxide these compounds comprise
--(CH2-CH2-O)-- units and --(CH2-aXa-CH2-bXb-O)-- units, wherein X
represents fluorine and at least one of a or b represents an
integer of at least 1.
[0141] In certain cases, fluoro-surfactants may be represented by a
compound of the general formula (16) as follows:
F(CF.sub.2--CF.sub.2).sub.x--CH.sub.2--CH.sub.2--O--(CH.sub.2--CH.sub.2--
-O).sub.y--R (16)
wherein R is H or an alkoxy group and x and y have a value in the
range of from 1 to 50, preferably in the range of from 1 to 30 and
particularly preferred x and y are at most 20. Products of this
type having a weight average molecular weight of at most 2000,
preferably at most 1500 and even more preferably at most 1000 are
of special interest. The ratio of x to y (x/y) is not subject to
specific restrictions and may be selected within a wide range. A
number of fluoro-surfactants of this type is available from DuPont
under the trade name Zonyl.RTM.).
[0142] Another group of fluoro-surfactants includes short chain
molecules having six or less groups CF.sub.2 and terminated at one
end with fluorine and bound to a delivery system such as a polymer
or surfactant as commercially available from Du Pont under the
trade name Capstone.RTM..
[0143] In certain embodiments, the non-ionic surfactant represents
from 0.1% to 5% by weight of the total weight of the suspension.
(REV 10)
[0144] In certain embodiments, the non-ionic surfactant has an HLB
comprised between about 10 to about 14, preferably a HLB of about
12. (REV 11)
[0145] Non-ionic surfactant having an HLB ranging from about 10 to
about 14 are hydrophilic, i.e. are easily dispersible in an aqueous
phase. Aqueous phase
[0146] In one particular embodiment, the aqueous phase consists of
water.
[0147] In certain embodiments, the aqueous phase comprises water
and at least one hydrophilic additive.
[0148] A suitable hydrophilic additive may include, without
limitation, mono-alcohols having 2 to 8 carbon atoms, such as
ethanol and isopropanol, and polyols such as glycerol, glycols,
pentylene glycol, propylene glycol, butylene glycol, isoprene
glycol and polyethylene glycols such as PEG-8.
[0149] 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.
[0150] As compared to the coal/water slurry (CWS), the lower amount
of aqueous phase contained in the suspension reduces the amount of
material that is inert with respect to combustion, namely
water.
[0151] In certain embodiments, the aqueous phase represents between
10 to 30% by weight of the total weight of the suspension. (REV
12)
[0152] Organic Phase
[0153] In certain embodiments, the organic phase is selected in a
group comprising a fossil-based liquid or a derivative thereof, a
biomass-based liquid, a synthetic organic liquid or a derivative
thereof, and a mixture thereof (REV 13)
[0154] In certain embodiments, the fossil-based liquid is a
petroleum-based liquid or a derivative thereof (REV 14)
[0155] In certain embodiments, a fossil-based liquid according to
the invention may be crude oil petroleum and crude oil petroleum
derivative products, e.g. resulting from its process by oil
refineries. As an example product from an oil refinery 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), marine fuel oil (MFO), marine gas oil (MGO), navy special
fuel oil (NSFO) and mixture thereof.
[0156] In certain embodiments, a biomass-based liquid according to
the invention may be algae biofuel, bioethanol, biodiesel, biofuel
gasoline, biomethanol, coconut oil, green diesel, palm oil,
vegetable oil and a mixture thereof.
[0157] In certain embodiments, a biodiesel that is suitable for the
instant invention may comprise palm oil, namely a Malaysian
biodiesel or a LOF biodiesel, which latter has been used in the
examples herein. The said Malaysian liquid biodiesel composition
comprises a biodiesel composition derived from palm stearin, a
biodiesel composition derived from palm oil methylester and a
biodiesel composition derived from waste cooking oil.
[0158] In certain embodiments, the organic phase comprises a
synthetic fuel, notably obtained from biomass and/or fossil
reagents.
[0159] Within the scope of the invention, the organic phase may
comprise aliphatic hydrocarbons such as for instance hexane,
heptane, octane or nonane; inert cycloaliphatic hydrocarbons such
as cyclohexane, cyclopentane or cycloheptane; aromatic hydrocarbons
such as benzene, toluene, ethylbenzene, xylenes, or liquid
naphthenes; alcohols such as butanol, ethanol, methanol or
propanol; and a mixture thereof.
[0160] As compared to the coal/water slurry (CWS), the presence of
an organic phase contained in the suspension increases the amount
of material that is prone to combustion. Hence, the slurry
suspension according to the invention offers excellent combustion
properties, in particular a good gross calorific value.
[0161] In certain embodiment, the organic phase represents between
50% and 75% by weight of the total weight of the suspension. (REV
15)
[0162] Emulsions
[0163] In one aspect of the invention the slurry suspension may be
in the form of an emulsion, namely an oil-in-water (O/W) emulsion
or a water-in-oil (W/O) emulsion.
[0164] An emulsion may be prepared according to the general
knowledge known in the state of the art. In practice, the
preparation of an emulsion may include preparing, separately, a
homogeneous aqueous phase and a homogeneous organic phase.
[0165] In certain embodiments, the non-ionic surfactant having a
HLB ranging from about 10 to about 14 is dispersed in the aqueous
phase.
[0166] At this stage, a direct oil-in-water (O/W) emulsion may be
prepared by introducing the organic phase into the continuous
aqueous phase while stirring. A direct O/W emulsion is hence
obtained and represents a discontinuous organic phase dispersed in
a continuous aqueous phase.
[0167] Oppositely, a water-in-oil (W/O) emulsion, is obtained by
introducing the aqueous phase into the organic phase by stirring.
At the end of this process, the reverse W/O emulsion is therefore
represented by a discontinuous aqueous phase dispersed in a
continuous organic phase. Other known specific methods of
preparation may also be employed.
[0168] In certain embodiments, said suspension is an oil-in-water
emulsion. (REV 2)
[0169] In certain embodiments, the weight ratio of the aqueous
phase to the organic phase is ranging 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.
[0170] In certain embodiments, when the non-ionic surfactant is
mixed in the aqueous phase, the weight ratio of the non-ionic
surfactant to the aqueous phase is ranging from a ratio of 1/100 to
a ratio of 1/7, preferably a ratio of 1/25 to a ratio of 1/8.
[0171] These ratios are particularly suitable for providing a
stable emulsion and for efficiently and homogeneously dispersing
the carbonaceous material particles in the aqueous phase.
[0172] Additional Ingredient(s)
[0173] Suspension of the present invention may also comprise one or
several additional ingredient(s), such as the usual ingredients
known in the field. Non-limitating examples of such ingredients may
be humectants, wetting agents, rheology additives bases, corrosion
inhibitors, foam inhibitors, stabilizers and biocidal
preservatives.
[0174] When present in the suspension, said additional
ingredient(s) represent(s) from 0.001% to 5%, preferably from 0.01%
to 1% by weight of the total weight of the suspension.
[0175] Methods
[0176] In another aspect, the invention relates to a method for the
preparation of a slurry suspension according to the instant
invention comprising the steps of:
[0177] i. mixing at least ingredients (b), (c) and (d) to form an
emulsion;
[0178] ii. mixing ingredient (a) with the emulsion obtained in step
i. to form a slurry suspension. (REV 16)
[0179] In certain embodiments, said emulsion is an oil-in-water
emulsion. (REV 17)
[0180] In certain embodiments, said method for the preparation of a
slurry suspension according to the instant invention comprises the
steps of:
[0181] i1. mixing at least the non-ionic surfactant (b) and the
aqueous phase (c);
[0182] i2. mixing the organic phase (d) to the mix obtained in step
i1. to form an oil-in-water emulsion;
[0183] iii. mixing carbonaceous material particles (a) with the
oil-in-water emulsion obtained in step i2. to form a slurry
suspension.
[0184] In these embodiments, the non-ionic surfactant is preferably
added in the aqueous phase prior to the formation of the emulsion,
as non-ionic surfactants with a HLB ranging from about 10 to about
14 are prone to be easily dispersed in an aqueous phase. Moreover,
it was observed that the presence of a non-ionic surfactant
facilitates the dispersion of the carbonaceous material particles
in the aqueous phase.
[0185] In certain embodiments, an oil-in-water emulsion is obtained
as described above, and the carbonaceous material particles are
dispersed in the continuous aqueous phase in between the droplets
of the organic phase.
[0186] Without wishing to be bound to a theory, in the case of an
oil-in-water (O/W) emulsion, the lipophilic moiety of the non-ionic
surfactant may advantageously form interactions with the
hydrophobic surface of the carbonaceous material particles, whereas
the hydrophilic moiety of the non-ionic surfactant would ease the
dispersion in a continuous aqueous phase. Therefore, the
carbonaceous material particles are homogeneously dispersed into
the continuous aqueous phase and their sedimentation within the
emulsion is significantly delayed.
[0187] In addition, the fact that the carbonaceous material
particles are dispersed in between the droplets of organic phase
creates a surface tension that maintain the droplets of organic
phase homogeneously dispersed into the continuous aqueous phase
[0188] For these reasons, the carbonaceous material particles may
behave as a surfactant, as they keep the droplets homogenously
dispersed into the continuous aqueous phase, and the coalescence of
the organic phase is significantly delayed.
[0189] In another aspect, the invention relates to a method for
generating power comprising combustion of the slurry suspension
according to the instant invention (REV 18).
[0190] Uses
[0191] In another aspect, the invention also relates to the use of
a non-ionic surfactant to stabilize an emulsion comprising
carbonaceous material particles having an average diameter D.sub.50
comprised between 0.1 .mu.M and 200 .mu.m. (REV 19)
[0192] In certain embodiments, said emulsion is an oil-in-water
emulsion. (REV 20)
[0193] The inventors have observed that a suspension according to
the invention is able to form a stable emulsion, for e.g. an
oil-in-water emulsion for a period of time of at least 2 weeks.
[0194] However, after a longer period of time the suspension in the
form of an emulsion may return to a state of a non-emulsion
suspension, i.e. after sedimentation and/or separation of the
aqueous phase and the organic phase, has/have occurred. The
suspension may further be manipulated in a way to form a stable
emulsion for another period of at least 2 weeks.
[0195] The stable emulsion according to the invention may be
advantageously used in already available combustion engine, or with
only minor changes of these existing engines.
Examples
Example 1: Preparation of Torrefied Wood Particles
[0196] The torrefied wood chips are obtained by torrefaction and
chips have cm scale average size. Torrefied wood chips are grinded
following a dry grinding protocol to obtain particles with an
average size of 300 .mu.m to 1 mm. These particles, in the form of
a powder, are subsequently dried milled by using a Retsch ZM200 dry
miller with the following features: grid 120 .mu.M, speed 18000
rpm, 25.degree. C., nitrogen purge, 80 g per batch in 10 min. At
the end of the milling process, particles display a particle size
distribution, measured with Sympatec laser diffraction sensors, as
follows: D.sub.10=6 .mu.m; D.sub.50=23 .mu.m; D.sub.90=60
.mu.m.
Example 2: Slurry Suspension Comprising Water/Diesel/Torrefied Wood
Particles
[0197] A stable oil in water (0/W) emulsion is prepared at room
temperature by first mixing 20% wt of water, 63% of diesel (Shell
V-Power Diesel CAS number: 68334-30-5) and 2% wt of Soprophor.RTM.
BSU (non-ionic surfactant). The fact that the surfactant (Soprophor
BSU; HLB=12) is added to water it wets wood particles easily.
[0198] 15% wt of torrefied wood particles according to example 1
(25 .mu.m) are then added and mixed with the first mixture to
obtain a stable dispersion. An oil-in-water (o/w) emulsion is
obtained with the torrefied wood particles located in the
continuous phase. It can be observed that the torrefied wood
particles get caught between the droplets in the continuous phase,
which prevents them from settling. At the same time, the torrefied
wood particles seem to act as emulsifying agents, preventing the
coalescence of the droplets.
[0199] The number of days until an emulsion was unstable was
determined by visually inspecting each sample once a day. Emulsion
based slurry was termed unstable if: [0200] Coalescence led to the
formation of an oil layer at the top of the slurry. [0201] Creaming
led to phase separation so that a wood and water layer at the
bottom of the vessel was formed. [0202] Sedimentation led to a
solids layer at the bottom of the vessel.
[0203] In this case, with 15% torrefied wood, 20% water and 2%
Soprophor BSU, emulsion remains stable for a long period of time.
Illustratively, the said slurry emulsion remains stable after a
period of time of storage of two weeks or more.
[0204] The formulation of an emulsion made from torrefied wood,
water and diesel, stabilized with the non-ionic surfactant is hence
feasible.
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