CA1184763A

CA1184763A - Coal-oil slurries containing a surfactant

Info

Publication number: CA1184763A
Application number: CA000413379A
Authority: CA
Inventors: Joseph H.Y. Niu; Irving R. Schmolka
Original assignee: BASF Wyandotte Corp
Current assignee: BASF Corp
Priority date: 1981-11-02
Filing date: 1982-10-14
Publication date: 1985-04-02
Also published as: FI823739L; EP0078483A3; FI823739A0; EP0078483A2; US4637822A

Abstract

COAL-OIL SLURRIES CONTAINING A SURFACTANT
Abstract of the Disclosure Unwanted settling in a composition comprising a suspension of fine particles of coal in fuel oil is elimi-nated or substantially reduced by adding an effective amount of a polyoxypropylene-polyoxyethylene copolymer which corresponds to the formula:

Description

7~3 COAL-OIL SLURRIES _ONTAINING A SURFACTANT
Background of the Invention 1. Field of the Invention The present invention relates in general to combustible fuel slurries con~aining liquid hydrocarbon fuel and particulate carbonaceous material, and more particu-larly, to the prevention or substantial reduction of the settling of the particulate carbonaceous material in the liquid hydrocarbon.

2. Description of the Prior Art Xn recent years, the importance of reducing the dependency of the world upon natural gas and liquid hydrocarbon fuels Eor its energy has been dramatically demonstrated. While not constituting a complete solution to this problem, attempts have been made to add solid particu-late carbonaceous material, such as coal, to liquid hydro-carbon fuels because such particulate carbonaceous materials are known to be far more plentiful than liquid fuels.
The idea of using in place of liquid hydrocarbon fuels, such as Bunker C fuel oil, a mixture of such oil and finely divided particles of carbonaceous material, such as bituminous or anthracite coal or lignite, is an old one. In a book published in 1926, Fuels and Their Combustion by Robert T. Haslam et al (McGraw-FIill, New York), there is a discussion on pages 135 and 136 o "colloidal fuel" which is referred to as an emulsion of solid fuel and oil developed by the Submarine Defense Association during World War I.

'763 This reference ~eaches mixing oil with a solid uel, which may be any of the coals from lignite to anthracite, or peat, coke, or wood, provided that at leas~ 2/3 of the dry solid fuel is combustible and that the fuel is pulverized 50 that 95 percent of it will pass through a 100 mesh screen and 85 percent of it will pass through a 200 mesh screenO This reference teaches the use of 30 weight percent of coal, 1.5 or 1.2 percent of l'fixateur" and the remainder fuel oils, such as pressure-still oil or tar or coal tar. It teaches the use as "fixateur" of lime-ro~in~grease (made by heating 8~.5 percent oil, 10 percent rosin, 5 percent lime, and 1.5 percent water) or one of the coal tar distillates, such as creosol.
A considerably more extensive discussion of "colloidal fuel" appears at pages 226-234 of Fuels and Combustion Handbook, edited by Alan J. Johnson and George H.
Auth, published by McGraw-Hill Book Co., New York, in 1951. This reference points out that the term "colloidal fuels" is a misnomer because in common usage, "colloidal solutions" are ones in which the partic].es are between 0.1 micron and 0.001 micron in mean dlameter, whereas in these fuels, there are particles of coal which have been ground so that 100 percent of them will pass through a 100 mesh screen (150 microns) and 90 percent of them will pass through a 200 mesh screen t74 microns).
The Johnson et al reference shows that those skilled in the art have been awar~ of the advantages of 7~3 coal-in-oil fuels: their use makes it possible to preserve petroleum resources, obtain be~ter use of storage space, permit disposal of fines and low rank coals, etc.
This reference also points out that the behavior of a particular coal-in-oil fuel in respect to settling depends on a number of factors. If the fuel can be prepared constantly at the site of use so tha~ there is a mlnimum of storage time, stabilization behavior of the coal-in-oil fuel is not important. If stirring or pumping to provide circulation can be used, again there is not much of a problem. Some mixtures remain stable for months without any additional treatment, particularly when the coal particles are fine, the concentration of the coal is relatively high, and the oil is relatively viscous and/or possesses a high specific gravity. Although it is desirable to use a relatively viscous oil, since this promotes the stability;
the coal-in-oil mixture must not be permitted to become too viscous, because this gives difficulty in connection with pumping the fuel.
The Johnson et al reference also discusses the matter of stabilizers saying:

"~..it is a consensus that, with careful attention to a selection of fuels, pulverization, mixing, and storage, stabilizers can and should be avoided in most cases."
The reference cites the work of Aimison Jonnard, "Colloidal Fuel Development for Industrial Use", Bulletin 48, Kansas State College, Manhattan, Kansas, January 1946, reporting Jonnard's testing of 148 stabilizing agents. Jonnard "concluded that spent alkylation acid was the only one (of the stabilizers tested) with commercial possibilities."
For reasons set forth above, there is considerable renewed interest in the possibility of extending and/or supplementing liquid fuels with solid fuels. Numerous approaches have been taken to the problem of combining a solid particulate carbonaceous material with a liquid hydrocarbon fuel. It has become apparent to those skilled in the art that, if an effective stabilizing agent is found, the usefulness of the concept of using coal-in-oil fuel is greatly improved.
U.S. Patents 3,907,134, issued September 23, 1975 and 4,082,516, issued April 4, 1978, to Grant W. Metzger, disclose the combination of solid particulate carbonaceous material such as powdered coal, a liquid hydrocarbon fuel such as Bunker C (No. 6) fuel oil, a stabilizing agent, preferably starch, and a viscosity reducing agent, prefer-ably a detergent, more preferably soap, in the ~134 patent and anionic surfactants in the '516 patent.
U.S. 4,090,853, issued May 23, 1978, to Clayfield et al, discloses a coal in liquid hydrocarbon fuel product which includes water as a stabilizer and may be further stabilized by the addition of small amounts of surfactants such as anionic surfactants.
U.S. 4,276,054, issued June 30, 1981 to Schmolka et al discloses a coal in liquid hydrocarbon fuel which ~4--7~3 includes as a stabilizer a copolymer which corresponds to the formula:

y[ (C2H4o)m(c3H6o)nH]x wherein Y is the residue of an organic compound having from about 1 to 6 carbon atoms and containing x reactive hydrogen atoms in which x has a value of at least one, m has a value such that the oxyethylene conten~ of the molecule is from about 10 to 40 weight percent and n has a value such that the total molecular weight of the polyoxyalkylene groups is from about 2000 to 6000~
U.S. 4,251,229, issued February 17, 1981, dis-closes a fuel slurry composition comprising a fuel oil, pulverized coal, and an effective amount of a stabilizing agent selected ~rom a group which includes a polyether-type adduct having a molecular weight from 1,000 to 100,000 between a lower alkylene oxide and a compound having at least three active hydrogen atoms selected from the group consisting of an alcohol, an amine, a carboxylic acid and a phenol~
U.S. 4,252,540, issued February 24, 1981, Massaki et al, discloses a stabilizer for mixed fuels of finely divided coal and fuel oil. This stabilizer is a non-ionic surface active agent consisting oE a block copolymer represented by the following general formula:

'7~3 Rlo- (C2H40) 1- (C3H'j)m- (C21l'10)m U.S. 4,130,401, issued ~ecember 19, 1978, discloses combustible fuel slurries prepared by admixing solid particulate carbonaceous material, liquid hydrocarbon fuel, and a wetting agent having an HLB value in the range of 6.5 to 10.
Summary of the Invention Good results in terms of preventing.or subs-tan-tially reducing unwanted settling in compositions comprising a suspen-sion of solid particulate carbonaceous material in A liquid hydrocarbon fuel are obtained by including in the mixture a small ~ut effective amount of a polyoxyethylene-polyoxypropylene copolymer stabilizing agent.
In particu:Lar, the present invention provides a combustible fuel slurry comprising solid particulate carbona-ceous material, liquid hydrocarbon fuel, and a minor slurry sus-pension stabilizing amount of a polyoxyethylene-polyoxypropylene copolymer which corresponds to the formula:

(C2H40) y ~C3I160) X (C3H60) X (C2H4o~ y (C2H4O)y (C3H6O)~ ~ ~ I Y4 in which the values of Xl, X2, X3 and X~ may be the same or ; different, Yl, Y2, Y3 and Y~ ,ay be the same or di:E:Eerent, Yl-~Y2~Y3+Y~I give a total oxyethylene content of -the molecule of from about 10 to 80 weight percent and Xl, X2, X3 and X4 have values such that the total molecular weigh-t of the molecule is from about 1500 to 30,000. This produces a high solids content s-table and _. ~

/' ~~

-combustible fuel slurry comprising solid particulate carbonaceous material, liquid hydrocarbon fuel, and the above described stabilizing agent. In addition, small amounts of water and/or aromatic hydrocarbon solvent have been found to improve antisettling properties in some cases.
Description of ~he Preferred Embodiments -The combustible Euel slurry o~ the present invention is principally comprised o~ a solid particulate carbonaceous material and a liquid hydrocarbon fuel. As used herein, "solid particulate carbonaceous material" shall include such materials as bituminous and anthracite coals, coke, petroleum coke, lignite, charcoal, peat~ etc., and combinations thereof. The expression "liquid hydrocarbon Euel" as used herein shall include crude and refined hydrocarbon based oils, including without limitation by enumeration, petroleum fuel oils, heavy residual oils and crude oils, and the like. More particularly, liquid hydrocarbon fuel oils having a viscosity in the ran~e of about 50 to about 300 seconds Saybolt Universal at 175~F are preferred. Bunker C (No. 6) residual fuel oil is particu-larly useful in the slurry oE the present invention~
It is preferred that the particulate carbonaceous material be powdered or pulverized to a si~e which will ` enable substantially the ent:ire quantity employed in the slurry to pass through a 100 mesh sieve or screen and at least ~0 preferably 100 percent to pass -through a 200 mesh screen; While such screening results in rel~tively small particle si~es, _ _ _ _ _ _ __ __ . ~ , a 7~;3 the particles are considerably larger than colloidal size, and some particles larger than a 200 mesh screen but less than 100 mesh can be tolerated. The cost of pulverizing or grinding coal or the like to a sizP appreciably below 200 mesh, particularly colloidal size, begins to increase dramatically, which could eliminate the economic advantages of the present slurry. It has been found that such addi-tional grinding does not produce any material advantage in the practice of the presen~ invention. For simplicity's sake, the solid particulate carbonaceous material shall be referred to herein as coal although it is to be understood that it includes bituminous and anthracite coals, coke, petroleum coke, lignite, charcoal, peat, etc., and combina~
tions thereof. Similarly, the liquid hydrocarbon fuel will be referred to herein as oil although it is to be understood that it includes petroleum fuel oils, heavy residual oils, crude oils and the like.
In general, the proportion of coal to oil by weight will range Erom about 20:80 to 55 45O In accordance with the prior art, there are indications that is i9 generally difficult to obtain a satisEactory composition whenever the percentage of coal exceeds ~3 percent by weight because the mixture tends to become viscous and too diffi-cult to pump. However, it was found that, with the use of a stabilizer in accordance with the present invention, it i5 possible to obtain a composition which performs satis-factorily even at equal weights of coal and oil and even up 7~3 to 55 percent by weight coal. A pref rred range i9 40 60 to 50:50 coal to oil by weight, neglecting for the present any other ingredients present in minor quantities~
In accordance with the present invention, there is used as a stabilizer at least one polyoxyethylene-polyoxy-propylene copolymer which corresponds to the formula:

(C2~O)y (C3H6O)Xl (C3H6O)X (c2H4o)y H

(C2H~o)y (C3H6)X2 (C3H6O)X (c2H4o)y H

in which the values of Xl, X2, X3 and X4 may be the same or ' 1~ Y2~ Y3 and Y4 may be the same or different, Yl+Y2~Y3+Y~ give a total oxyethylene content of the molecule of from about 10 to 80 weight percent and Xl, X2, X3 and X4 have values such that the total molecular weight of the molecule is from about 1500 to 30,000. Compositions of this type are more particularly described in U.S. Patent No. 2,979,528. In the above formula, the oxypropylene chains optionally, but advantageously, contain small amounts oE ethylene oxide and the oxyethylene chains also optionally, but advantageously, contain small amounts of alkylene oxidas such as propylene oxide and butylene oxide.
The proportion of stabilizer used may ranqe from about 0~05 to 5 percent by weight, preferably 0.1 to 1 percent by weight, of the total of coal, oil, stabilizer and ~,7 .

any other components in the overall composition. In any event, a proportion sufficient to give a substantial stabilizing effect is required and, in most cases, the addition of a proportion greater than about 1.5 percent merely adds to the cost without conferring any corresponding beneit.
Water may be optionally present in the cornposi-tion~ Ordinarily, at least a small proportion of water will be present, because it is common to have water present during the operation of grinding coal as a measure to control the development of dust, and it is difficult/ costly and time-consuming to remove all the water after the grinding operation, before the coal is mixed with the oil.
Thus, water may be present in an amount up to about 10 percent, e.g. ~xom ~bout 0;05 to 10 percent, prcferably up to about 6 percent, by weight taking the total of the coal, water, stabilizer and oil as 100 percen-t.
Also, it has been Eound that the addition of a conventional aromatic hydrocarbon solvent can be useful.
Suitable solvents for this purpose are: toluene, xylene, benzene, chlorobenzene, other sub5tituted aromatic organic solvents, preerably higher boiling aromatic solvents ancl mixtures thereof. The solvent may be employed in an amount from about 0 to 5 and preferably 0.05 to 1.0 percent by weight, taking the total of coal, solvent, and oil as 100 percent.

The stabilizer may be mixed with the other ingredients in any suitable manner. Usually, it is desir~
able to have the fuel oil at a temperature such that the viscosity is relatively low, so that the mixture may be readily stirred. A preferred temperature range i5 about 120-150F. In principle, however, the manner of mixing the stabilizer with the other ingredients is not important, so long as a homogeneous mixture is obtained.
Following are specific, non-limiting examples which are provided to illustrate the instant invention. All parts, percentages and proportions are by weight unless o~herwise indicated.
Example 1 Two 150 gram coke/oil/water mixtures containing by weight 30 percent coke, 67.5 percent oil and 2.5 percent water were prepared by mixing in a Tekmar "Super Dispax System". The petroleum coke was pulverized to 100 percent passing through Zl 200 mesh screen. No. 6 (Bunker C) fuel oil was employed as the liquid hydrocarbon fuel. A stabil-izer sold under the trademark TETRONIC~1307 was then addedto one of the mixtures in amount of 0.20 percent by weight of the total mixture. No stabilizer was added to the other mixture.
The stabilizer was a nonionic surfactant having the following generalized formula:

H(c2H~o)y~c3H6o)x i(C3H6o)x(C2H40)yH
~ N-CH ~CH -N
H(C2H~)y(C3H63X (C3H60)x(C2H40]y The polyoxypropylene groups (x) have a total molecular weight of 5600 and the oxyethylene content (y) is about 70 weight percent of the molecule.
Two aspects of stabilization were investigated, i~e., the settling and redispersing characteristics. The settling was measured by means of a K scan instrument which determined the dielectric constant (pf) of a small section of coke/oil mixture in a 30 millimeter diameter tube which was filled with the mixture to a height of approximately 150 millimeters~
The redispersibility was examined by poking the mixture with a glass rod (10 millimeter diameter). With an easily dispersed mixture, the glass rod will reach the bottom of the tube with little efort.
After 16 days, the coke/oil mixture containing the stabilizer reached an equilibrium and the settled coal was found to redisperse easily. In the coke/oil mixture with no stabilizer, the coke settled in a few days and could not be zo redispersed as evidenced by the fact that the glass rod could only reach half way down the tube.
Example 2 A 150 gram coke/oil mixture is prepared as described in Example 1 with the exception that TETRONIC~702 polyol is substituted for the TETRONIC 1307 polyol stabil-iiL.~L~4'';'~;3 izer. This stabilizer has the same general formula as thestabilizer of Example 1 except that the polyoxypropylene groups (x) have a total molecular weight of 2600 and the oxyethylene content (y) is about 20 weight percent. A
stabilized slurry having good settling and redispersing properties is obtained.
Example 3 A 150 gram coal/oil mixture is prepared as described in Example 1 wherein an average eastern bituminous coal is substituted for the petroleum coke. A stabilized slurry having good set~ling and redispersing properties is obtained.
Example 4 A 150 gram coke/oil mixture is prepared as described in Example 1 with the exception that TETRONIC~1508 polyol is substituted for the TETRONIC 1307 polyol stabil-izer. This stabiLizer has the same general formula as the stabilizer of Example 1 except that the polyoxypropylene groups (x) have a total molecular weight of 6500 and the oxyethyler.e content (y) is about 80 weight percent. A
stabilized slurry having good settling and redispersing properties is obtained.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A combustible fuel slurry comprising solid particulate carbonaceous material, liquid hydrocarbon fuel, and a minor slurry suspension stabilizing amount of a polyoxyethylene-polyoxypropylene copolymer which corresponds to the formula:
in which the values of X1, X2, X3 and X4 may be the same or different, Y1, Y2, Y3 and Y4 may be the same or dif-ferent, Y1+Y2+Y3+Y4 give a total oxyethylene content of the molecule of from about 10 to 80 weight percent and X1, X2, X3 and X4 have values such that the total molecular weight of the molecule is from about 1500 to 30,000.

2. The slurry of claim 1 wherein said carbon-aceous material is petroleum coke.

3. The slurry of claim 2 wherein said petroleum coke is in the form of particles sufficiently fine that 100 percent pass through a 200 mesh screen.

4. The slurry of claim 1 wherein said carbon-aceous material is bituminous coal.

5. The fuel slurry of claim 1 wherein the content of said copolymer ranges from about 0.05 to 5.0 percent by weight of the total composition.

6. The fuel slurry of claim 5 wherein the ratio of said solid particulate carbonaceous material to said liquid hydrocarbon fuel ranges from by weight about 20:80 to 55:45.

7. The fuel slurry of claim 5 wherein said slurry also contains a small but effective amount of water.

8. The fuel slurry of claim 5 wherein said slurry also contains water in amount from about 0.05 to 10 percent by weight.

9. The fuel slurry of claim 6 wherein said slurry also contains a small but effective amount of water.

10. The fuel slurry of claim 6 wherein said slurry also contains water in amount from about 0.05 to 10 percent by weight.