CA1175653A - Composite fluid fuel made of natural cellulose materials and a process of preparation thereof - Google Patents
Composite fluid fuel made of natural cellulose materials and a process of preparation thereofInfo
- Publication number
- CA1175653A CA1175653A CA000388990A CA388990A CA1175653A CA 1175653 A CA1175653 A CA 1175653A CA 000388990 A CA000388990 A CA 000388990A CA 388990 A CA388990 A CA 388990A CA 1175653 A CA1175653 A CA 1175653A
- Authority
- CA
- Canada
- Prior art keywords
- natural cellulose
- cellulose materials
- amount
- fuel
- total weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000446 fuel Substances 0.000 title claims abstract description 43
- 229920002678 cellulose Polymers 0.000 title claims abstract description 34
- 239000001913 cellulose Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 34
- 239000012530 fluid Substances 0.000 title claims abstract description 20
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000295 fuel oil Substances 0.000 claims abstract description 18
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000003350 kerosene Substances 0.000 claims abstract description 10
- 239000013256 coordination polymer Substances 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 17
- 239000006227 byproduct Substances 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 235000013311 vegetables Nutrition 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 244000068988 Glycine max Species 0.000 claims description 2
- 235000010469 Glycine max Nutrition 0.000 claims description 2
- 238000000855 fermentation Methods 0.000 claims description 2
- 230000004151 fermentation Effects 0.000 claims description 2
- 235000015067 sauces Nutrition 0.000 claims description 2
- 235000013405 beer Nutrition 0.000 claims 1
- 230000000875 corresponding effect Effects 0.000 description 9
- 239000003415 peat Substances 0.000 description 9
- 239000002023 wood Substances 0.000 description 9
- 241000209094 Oryza Species 0.000 description 6
- 235000007164 Oryza sativa Nutrition 0.000 description 6
- 238000013019 agitation Methods 0.000 description 6
- 235000009566 rice Nutrition 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- YFGAFXCSLUUJRG-WCCKRBBISA-M sodium;(2s)-2-amino-5-(diaminomethylideneamino)pentanoate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCCN=C(N)N YFGAFXCSLUUJRG-WCCKRBBISA-M 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229940117927 ethylene oxide Drugs 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- BHMLFPOTZYRDKA-IRXDYDNUSA-N (2s)-2-[(s)-(2-iodophenoxy)-phenylmethyl]morpholine Chemical compound IC1=CC=CC=C1O[C@@H](C=1C=CC=CC=1)[C@H]1OCCNC1 BHMLFPOTZYRDKA-IRXDYDNUSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920006184 cellulose methylcellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001246 colloidal dispersion Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000005251 gamma ray Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- GBCAVSYHPPARHX-UHFFFAOYSA-M n'-cyclohexyl-n-[2-(4-methylmorpholin-4-ium-4-yl)ethyl]methanediimine;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1CCCCC1N=C=NCC[N+]1(C)CCOCC1 GBCAVSYHPPARHX-UHFFFAOYSA-M 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108010027322 single cell proteins Proteins 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Liquid Carbonaceous Fuels (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
Abstract
Title of the Invention:
COMPOSITE FLUID FUEL MADE OF NATURAL
CELLULOSE MATERIALS AND A PROCESS OF PREPARATION
THEREOF
Abstract of the Disclosure:
A composite fluid fuel made of natural cellulose materials comprising a natural cellulose material which has been crashed to a size finer than 100 mesh, heavy oil or kerosine in the same amount by weight as that of the natural cellulose materials, surfactant in an amount more than 0.5% to the total weight of the fuel, gelating agent of the botanical origin in an amount from 0.04 to 0.15%
to the total weight of the fuel and water in an amount from 5 to 20% to the total weight of the fuel, and having a viscosity ranging from 100 to 8000 CP.
COMPOSITE FLUID FUEL MADE OF NATURAL
CELLULOSE MATERIALS AND A PROCESS OF PREPARATION
THEREOF
Abstract of the Disclosure:
A composite fluid fuel made of natural cellulose materials comprising a natural cellulose material which has been crashed to a size finer than 100 mesh, heavy oil or kerosine in the same amount by weight as that of the natural cellulose materials, surfactant in an amount more than 0.5% to the total weight of the fuel, gelating agent of the botanical origin in an amount from 0.04 to 0.15%
to the total weight of the fuel and water in an amount from 5 to 20% to the total weight of the fuel, and having a viscosity ranging from 100 to 8000 CP.
Description
75~i;3 ~ackyround of the Invention:
Field of the Invention:
The present invention relates to a composite fluid fuel made of natural cellulose materials and oils and a process of preparation thereof.
Description of Prior Arts:
Nowadays a gaseous fuel of higher than about 7000 calories or a liquid fuel is employed for domestic uses in most modern families. Liquid fuels such as heavy oil or kerosine are us~d for boilers in industries and agricultural uses.
Recently, however, supply of fossil fuels, especially of petroleum, comes short and the price increases rapidly.
~s a result, new resources other than petroleum are eagerly sought for.
An attempt is being made to use natural cellulose materials (natural resources or biomass) directly as a fuel.
For instance, processed fuels such as charcoal, firewoods and "Ogalite" (from rice bran) are now being produced.
However, they are much meager in quantity relative to the total ener~y demand.
Natural cellulose materials themselves are of indefinitely shaped solid and contain a certain water content.
Since they contain oxygen in their chemical constitution, liquifaction of them requires a high temperature and pressure in the presence of a specified catalyst for the purpose of adding hydrogen, as appears in the literature. But further investigation is necessary from the standpoint of the heat evolution and the cost. Natural cellulose materials " ~
~5i~i3 including wood burn with a low absolute heat evolution. Thus, they evolve about 4500 kcal/kg when they are absolutely dried, and about 3000 ~cal~kg when water content is about 30/O~ There~
fore they have only a narrow range of application as a fuel.
The present invention has been made in view of the situation as described above.
Summary of the Invention:
_ It is an object of the present invention to provide a fuel which is (1) in the forrn o~ fluid, thus easy to hand~e and use and (2) evolves heat by more than 7000 kcal/kg, directly from natural cellulose materials or from any convenient by-products from chemical industries employing natural cellulose materials as raw material.
In accordance with the invention, there is thus provided a composite fluid fuel made oE natural cellulose materials comprising a natural cellulose material which has been crashed to a size finer than 100 mesh, a heavy oil or kerosine in the same amount by weight as that of the natural cellulose materials, a neutral surfactant in an arnount of 0.5 to 0.99% to the total weight of the fuel, a vegetable gelating agent in an amount o 0.04 to 0.15% to the total weight of the fuel and water in an amount from 5 to 20% to the total weight of the fuel, and having a neutral pH and a viscosity ranging from 100 to ~000 CP.
The invention also provides, in a further aspect thereof, a method for the preparation of a composite fluid fuel as defined above, which comprises crashing natural cellulose materials or by-products of chemical industries which employ natural cellulose materials as raw material to a size ~iner than 100 mesh, mixing heavy oil or kerosine with the cellulose materials both in almost the same quantities, adding to the mixture a neutral surfactant and a gelating agent of vegetable origin in amounts of 0.5 to 0.99% and 0.04 to 0.15%, respectively, to the total weight of the mixture, adjusting the pH close to neutrality and the water content to 5 to 20% and the viscosity to 100 to 8000 CP.
The present invention intends to provide a "designed clean fuel" in which properties of the fluid fuel such as - 3a -for instance, viscosity, degree of gelation and the heat evolution could be controlled arbitrarily by changing the added amount of water and the natural cellulose materials.
Detailed Description of the Invention-The fluid fuel of this invention contains water and the natural cellulose materials include oxygen atoms in their molecules, 50 that the theoretical air-fuel ratio is smaller than that of coal and the combustion of the fuel is possible in dilutely mixed air. Toxic components are contained in low concentrations in the exhaust gas. A high water content of the gas is even effective for lowering the Nx content.
The natural cellulose materials to be used in this invention include, for instance, forlorn wood, waste wood in lumbermills, waste materials in agricultural industries and processors, peat and rice brans.
By-products in chemical industries which employ natural cellulose materials as raw material include lees from pulp waste liquid, by-products of SCP (Single Cell Protein), methane fermentation and alcohol production, and by-products from be~r and soybean sauce factories.
Neutral and water soluble surfactants are used in this invention. Followings are of general use:
R-(ocH2-clH)m~(oc~2-cH)-oAM
Rl R2 or R-(OCH2-CH) -IOCH -CH) -OH
Rl ,here R = C6 - C20, alkyl, alkenyl, alkylphenyl, alkyl-microalkyl groups;
Rl and R2 = alkyl groups containing C1 ~ C3;
m _ 0, n > 0, m ~ n = 0 - 20;
M = alkali or alkaline earth metal;
A = SO3, PO3, or half of PO2.
For gelating agents of the vegetable origin serve viscous matters obtained from vegetables, such as sodium arginate, CMC and starch paste.
Neutral surfactants should be added at least 0.5 to the total weight to maintain the mixture in a colloidal form. The maximum amount is 0.99%. More amount does not give better results.
The gelating agent of the vegetable origin acts in cooperation with water to adjust the viscosity of formed fuels. Addition of the agent in the amount 0.04 to 0.15%
to the total weight is effective to adjust to 100 to 8000 CP.
The water content i5 adjusted to 5 to 20% to assure the colloidal dispersion and to adjust the viscosity. In this range of water content good combustion property can be obtained with the fluid fuel.
The colloidal mixture can be resulted in by the rapid agitation in a wet mixing process.
Advantages of the fluid fuel of this invention exist first in the fluidity with which the hurning speed could readily be controlled, and second in their high heat content, 7000 to 8500 kcal/kg, which enables the use for a general purpose fuel.
i3 Further advantage is that various natural cellulose materials, by-products from those processings which employ natural cellulose materials as raw material, and peat can be used in this invention. Thus, inexpensi~e fuels could be obtained. The composite fluid fuels produced by the process of this invention are designated below as LOM (lîgnin oil mixture) for those of natural cellulose and as WOM (wood oil mixture) for those of wood.
Description of Preferred Embodimentso This invention will be better understood from the following examples.
Example 1 In the production of single cell protein (SCP), a wood powder is irradiated with gamma ray (10 Mrad total dose) and hydrolyzed with an acid or decomposed by enzyme to obtain saccharides in the first stage, where unreacting cellulose and lignin are obtained as by-product lees in an amount of more than 50% to the total weight. The by-product called B-SCP
contains a large amount of water. The water could be removed largely by pressing or centrifugation, but 20 to 25% of the total water still remains. To the water containing B-SCP in amount of 220 g (165 g of completely dry wooden material and 55 g of water), 200 g of A heavy oil is added, and the whole mixture is agitated in a universal homogenizer at a hlgh speed (500 to 2000 rpm,for example~, to make fine powders of B-SCP which are insoluble (separate under standing). To the separated insoluble mixture, synthetic alcohol (C1l - Cl5) +
3 EO (ethyleneoxide) sulfonate of sodium and water in the 5~3 amount of 35% to the total mixture is added. Further, 5O5 g of a neutral surfactant sold under the trade mark WAIJINOL AS300, by Yokkaichi Chemical Industry, corre-sponding to 0.98% to the sum of B-SCP and a heavy oil, and 10 g of sodium arginate in a 4% aqueous solution, corresponding to about 0.046% to the sum of B-SCP and the heavy oil, were added and further agitated in a high speed (500 to 2000 rpm~. In this way 466.5 cc of a stable fluid fuel was obtained. This fuel was kept standing for about 2 months. ~he viscosi-ty value then estimated was almost the same as that estimated immediately after the production, 1800 CP, e~hibiting the high stability.
The charged amounts, water contents and the evolved heats are shown in Table 1.
i6 _ ~ .
~o _~
~X
~` ~ ._._ .
_, ~ ~
~I~
V
. __ _ _ a) ~ ,, ,, ~ . .
o s~ o o o . ~, __ _ _ _ _ a)~- In ~ ~ ~ o o ~ ~ ~ ~n I~
,, ~
_. . . . o _ E~ ~ r~ o n ~ _ 'a) ~ .
~ ~ un Ln n ~o o o ~ Ln o a) ~ ~ o I~ In ~1 ~ . ~ ~
_ _ _. _ .
tq tq ~ ~ o~ ~ ~ 1:
t~ U U~ ,~
rl ~ .
' ~ ~ O 0 ,, a) u~ U-rl ~ 0 i'~l O ,a ,~
C) O ~ ~1l 0 3 ~1 3 . ,~ U-~I O
~4 ~ ~ X i' ~
C.) ~> ~ O ~ 3 V~l ~¢
U~ (~ ~ 3 0 u~ ~d ~
a) ~._ t~ ~u O
_ _ ~ .
7 a .. ",, ,,i~
5~3 , ~ .. .
(Remarks) Number in the parenthesis refers to moist B-SCP.
True specific gravity was estimated to be 1.5 for the calculation.
* For calculating the heat, 5500 and 11500 kcal/kg were assumed for dried B-SCP and heavy oil, respectively.
Example 2 S~r-~c~ polishing i~ included in the process of manufacturing plyboards. Tiny particles (containing about 7%
water) of a 200 mesh size produced as by-product 3f this operation were mixed with 200 ~ of kerosine. The mixture was treated by agitation with a universal homogenizer Eor a short time.
Immediately followed the addition of sodium salt of phenoxyethanol su]fonate and water by 42.4% to the total weight of the above mixture, 5.5 g (corresponding to 0.82% to the total weight of wood powdex and kerosine) of the neutralized surfactant "Waijinol" SP100, and a 11 g aqueous so:Lution of 10% carboxymethyl-cellulose (CMC~ ~corresponding to 0.028~ to the total weight).
Agitation or 2 minute$ gave 404.5cc of a stable fluid fuel.
The viscosity, 2200 CP, measured immedaitely after the manufacture remained unchanged in 2 month standing time.
The amount of charged matter, water contents and heat evolution observed in this Example are shown in Table 2.
7~3 Table 2 .
Weight ~7olume Volume Heat (~) ~cc1 fracticn ~-~iA~-~ood materialmatter 186 44.65 124 0.30 Kerosine charged 200 48.00 250 0.61 7279 7340 Additives __ Water absorbed on w~od powder 14 Surfactant and l water 5.5 ~30.5 7.35 30.5 0.09 Auxiliary and l water 11 J _ (Remarks) Number in the parenthesis refers to moist wood powder.
True specific gravity was estimated to be 1.5 for the calculation.
* For calculating heat, 4800 and 10700 kcal/kg were assumed for dried wood powder and kerosine, respectively.
Example 3 200 grams of rice bran (containing 3% of water) which llas been crashed into 250 mesh particles with a turbomill was mix~ed with 200 g of A heavy oil and agitated fox a short time with a universal homogenizer. Then followed addition of synthetic alcohol (C12 - C13) + P0/E0 additive of a sulfonic compound and water, corresponding to 21.8~ to the total weight ~t7~j~53 , . ~ , oE the above mixture, 4.5 g (corresponding to 0.89% to the total weight of the bran and the heavy oil) of neutralized surfactant "Waijinol" SA330, and 20 g of a 1% aqueous solution of starch paste ~the paste corresponding to 0.05~ to the total weight). Agitation for 3 minutes gave 428.2cc of a stable fluid fuel. The viscosity, 4900 CP, remained unchanged for 2 months of standing.
The amounts of charged matters, water contents and the heat evolution observed are shown in Table 3.
Table 3 Weight Volume Volume Heat _ (cc) fraction (kcal~ l _ Dried (~ lateUd* Found Rlce bran matter 194 45.30 129,3 0.33 charged _ (200) Heavy oil charged 200 46.70 250 0.64 7308 7100 _ _ _ Additives Water adsorbed on rice bran 6 Surfactant ~ water 8.2 34.2 7.9 7.9 0.03 Auxiliary and water 20.0 _ (Remarks) Number in the parenthesis refers to the moist rice bran.
True specific gravity was assumed to be 1.5 for the calculation.
* For calculating the heats, 4500 and 11500 kcal/kg were assumed for dried rice bran and A heavy oil, respectively.
-- 10 -- ' Example 4 A mixture of 250 g of pulverized peat (containing 28%
of water) and 200 g of A heavy oil was agitated at a high speed for 1 minute in a universal homogenizer. To the resulting mixture were added synthetic alcohol ~Cll - C15) + 3 EO (ethylene oxide) sulfonate of sodium and water in the amount of 35% and 5.5 g (corresponding to 0.94% to the total weight of the peat and the A heavy oil) of neutrali~ed surfactant "Waijinol" SA300 and 8 g (corresponding to 0.11%
to the total weight of the peat and the A heavy oil) of a 5%
aqueous solution of sodium arginate. During 3 minute agitation with a high speed agitator, the viscosity increased gradually and turned into a gel. When the agitation stopped, a mixed fuel in the gel form, 388.1cc in total, was obtained.
The gel state remained stable for 3 months of standing.
The amounts of charged matters, water contents and the evolved heat observed are shown in Table 4.
Table 4 _ _ _ .
Weight Volume IVolume Heat j (%~ (cc) ¦fraction (kcal/kg~ Found _ I lated _ _ Dried Peat charged (250) 38.8 120 1 0.31 ... _ _ .eavy oil charged 200 43.1 250 ¦ 0.646740 6580 _ !
Additives Water absorbed on peat 70 Surfactant and water 5.5 83.5 18.1 18.1 0.05 Auxiliary and water 8 _ ~1 ~ t~J ~' I~ ~ 7--~r3~
~5LIL ,r b~ r~
(Remarks) Number in the parenthesis refers to the moist peat.
True specific gravity was estimated to be 1.5 for the calculation.
* For calculating the heats, 4600 and llS00 kcal/kg were assumed for the dried peat and the A heavy oil.
Field of the Invention:
The present invention relates to a composite fluid fuel made of natural cellulose materials and oils and a process of preparation thereof.
Description of Prior Arts:
Nowadays a gaseous fuel of higher than about 7000 calories or a liquid fuel is employed for domestic uses in most modern families. Liquid fuels such as heavy oil or kerosine are us~d for boilers in industries and agricultural uses.
Recently, however, supply of fossil fuels, especially of petroleum, comes short and the price increases rapidly.
~s a result, new resources other than petroleum are eagerly sought for.
An attempt is being made to use natural cellulose materials (natural resources or biomass) directly as a fuel.
For instance, processed fuels such as charcoal, firewoods and "Ogalite" (from rice bran) are now being produced.
However, they are much meager in quantity relative to the total ener~y demand.
Natural cellulose materials themselves are of indefinitely shaped solid and contain a certain water content.
Since they contain oxygen in their chemical constitution, liquifaction of them requires a high temperature and pressure in the presence of a specified catalyst for the purpose of adding hydrogen, as appears in the literature. But further investigation is necessary from the standpoint of the heat evolution and the cost. Natural cellulose materials " ~
~5i~i3 including wood burn with a low absolute heat evolution. Thus, they evolve about 4500 kcal/kg when they are absolutely dried, and about 3000 ~cal~kg when water content is about 30/O~ There~
fore they have only a narrow range of application as a fuel.
The present invention has been made in view of the situation as described above.
Summary of the Invention:
_ It is an object of the present invention to provide a fuel which is (1) in the forrn o~ fluid, thus easy to hand~e and use and (2) evolves heat by more than 7000 kcal/kg, directly from natural cellulose materials or from any convenient by-products from chemical industries employing natural cellulose materials as raw material.
In accordance with the invention, there is thus provided a composite fluid fuel made oE natural cellulose materials comprising a natural cellulose material which has been crashed to a size finer than 100 mesh, a heavy oil or kerosine in the same amount by weight as that of the natural cellulose materials, a neutral surfactant in an arnount of 0.5 to 0.99% to the total weight of the fuel, a vegetable gelating agent in an amount o 0.04 to 0.15% to the total weight of the fuel and water in an amount from 5 to 20% to the total weight of the fuel, and having a neutral pH and a viscosity ranging from 100 to ~000 CP.
The invention also provides, in a further aspect thereof, a method for the preparation of a composite fluid fuel as defined above, which comprises crashing natural cellulose materials or by-products of chemical industries which employ natural cellulose materials as raw material to a size ~iner than 100 mesh, mixing heavy oil or kerosine with the cellulose materials both in almost the same quantities, adding to the mixture a neutral surfactant and a gelating agent of vegetable origin in amounts of 0.5 to 0.99% and 0.04 to 0.15%, respectively, to the total weight of the mixture, adjusting the pH close to neutrality and the water content to 5 to 20% and the viscosity to 100 to 8000 CP.
The present invention intends to provide a "designed clean fuel" in which properties of the fluid fuel such as - 3a -for instance, viscosity, degree of gelation and the heat evolution could be controlled arbitrarily by changing the added amount of water and the natural cellulose materials.
Detailed Description of the Invention-The fluid fuel of this invention contains water and the natural cellulose materials include oxygen atoms in their molecules, 50 that the theoretical air-fuel ratio is smaller than that of coal and the combustion of the fuel is possible in dilutely mixed air. Toxic components are contained in low concentrations in the exhaust gas. A high water content of the gas is even effective for lowering the Nx content.
The natural cellulose materials to be used in this invention include, for instance, forlorn wood, waste wood in lumbermills, waste materials in agricultural industries and processors, peat and rice brans.
By-products in chemical industries which employ natural cellulose materials as raw material include lees from pulp waste liquid, by-products of SCP (Single Cell Protein), methane fermentation and alcohol production, and by-products from be~r and soybean sauce factories.
Neutral and water soluble surfactants are used in this invention. Followings are of general use:
R-(ocH2-clH)m~(oc~2-cH)-oAM
Rl R2 or R-(OCH2-CH) -IOCH -CH) -OH
Rl ,here R = C6 - C20, alkyl, alkenyl, alkylphenyl, alkyl-microalkyl groups;
Rl and R2 = alkyl groups containing C1 ~ C3;
m _ 0, n > 0, m ~ n = 0 - 20;
M = alkali or alkaline earth metal;
A = SO3, PO3, or half of PO2.
For gelating agents of the vegetable origin serve viscous matters obtained from vegetables, such as sodium arginate, CMC and starch paste.
Neutral surfactants should be added at least 0.5 to the total weight to maintain the mixture in a colloidal form. The maximum amount is 0.99%. More amount does not give better results.
The gelating agent of the vegetable origin acts in cooperation with water to adjust the viscosity of formed fuels. Addition of the agent in the amount 0.04 to 0.15%
to the total weight is effective to adjust to 100 to 8000 CP.
The water content i5 adjusted to 5 to 20% to assure the colloidal dispersion and to adjust the viscosity. In this range of water content good combustion property can be obtained with the fluid fuel.
The colloidal mixture can be resulted in by the rapid agitation in a wet mixing process.
Advantages of the fluid fuel of this invention exist first in the fluidity with which the hurning speed could readily be controlled, and second in their high heat content, 7000 to 8500 kcal/kg, which enables the use for a general purpose fuel.
i3 Further advantage is that various natural cellulose materials, by-products from those processings which employ natural cellulose materials as raw material, and peat can be used in this invention. Thus, inexpensi~e fuels could be obtained. The composite fluid fuels produced by the process of this invention are designated below as LOM (lîgnin oil mixture) for those of natural cellulose and as WOM (wood oil mixture) for those of wood.
Description of Preferred Embodimentso This invention will be better understood from the following examples.
Example 1 In the production of single cell protein (SCP), a wood powder is irradiated with gamma ray (10 Mrad total dose) and hydrolyzed with an acid or decomposed by enzyme to obtain saccharides in the first stage, where unreacting cellulose and lignin are obtained as by-product lees in an amount of more than 50% to the total weight. The by-product called B-SCP
contains a large amount of water. The water could be removed largely by pressing or centrifugation, but 20 to 25% of the total water still remains. To the water containing B-SCP in amount of 220 g (165 g of completely dry wooden material and 55 g of water), 200 g of A heavy oil is added, and the whole mixture is agitated in a universal homogenizer at a hlgh speed (500 to 2000 rpm,for example~, to make fine powders of B-SCP which are insoluble (separate under standing). To the separated insoluble mixture, synthetic alcohol (C1l - Cl5) +
3 EO (ethyleneoxide) sulfonate of sodium and water in the 5~3 amount of 35% to the total mixture is added. Further, 5O5 g of a neutral surfactant sold under the trade mark WAIJINOL AS300, by Yokkaichi Chemical Industry, corre-sponding to 0.98% to the sum of B-SCP and a heavy oil, and 10 g of sodium arginate in a 4% aqueous solution, corresponding to about 0.046% to the sum of B-SCP and the heavy oil, were added and further agitated in a high speed (500 to 2000 rpm~. In this way 466.5 cc of a stable fluid fuel was obtained. This fuel was kept standing for about 2 months. ~he viscosi-ty value then estimated was almost the same as that estimated immediately after the production, 1800 CP, e~hibiting the high stability.
The charged amounts, water contents and the evolved heats are shown in Table 1.
i6 _ ~ .
~o _~
~X
~` ~ ._._ .
_, ~ ~
~I~
V
. __ _ _ a) ~ ,, ,, ~ . .
o s~ o o o . ~, __ _ _ _ _ a)~- In ~ ~ ~ o o ~ ~ ~ ~n I~
,, ~
_. . . . o _ E~ ~ r~ o n ~ _ 'a) ~ .
~ ~ un Ln n ~o o o ~ Ln o a) ~ ~ o I~ In ~1 ~ . ~ ~
_ _ _. _ .
tq tq ~ ~ o~ ~ ~ 1:
t~ U U~ ,~
rl ~ .
' ~ ~ O 0 ,, a) u~ U-rl ~ 0 i'~l O ,a ,~
C) O ~ ~1l 0 3 ~1 3 . ,~ U-~I O
~4 ~ ~ X i' ~
C.) ~> ~ O ~ 3 V~l ~¢
U~ (~ ~ 3 0 u~ ~d ~
a) ~._ t~ ~u O
_ _ ~ .
7 a .. ",, ,,i~
5~3 , ~ .. .
(Remarks) Number in the parenthesis refers to moist B-SCP.
True specific gravity was estimated to be 1.5 for the calculation.
* For calculating the heat, 5500 and 11500 kcal/kg were assumed for dried B-SCP and heavy oil, respectively.
Example 2 S~r-~c~ polishing i~ included in the process of manufacturing plyboards. Tiny particles (containing about 7%
water) of a 200 mesh size produced as by-product 3f this operation were mixed with 200 ~ of kerosine. The mixture was treated by agitation with a universal homogenizer Eor a short time.
Immediately followed the addition of sodium salt of phenoxyethanol su]fonate and water by 42.4% to the total weight of the above mixture, 5.5 g (corresponding to 0.82% to the total weight of wood powdex and kerosine) of the neutralized surfactant "Waijinol" SP100, and a 11 g aqueous so:Lution of 10% carboxymethyl-cellulose (CMC~ ~corresponding to 0.028~ to the total weight).
Agitation or 2 minute$ gave 404.5cc of a stable fluid fuel.
The viscosity, 2200 CP, measured immedaitely after the manufacture remained unchanged in 2 month standing time.
The amount of charged matter, water contents and heat evolution observed in this Example are shown in Table 2.
7~3 Table 2 .
Weight ~7olume Volume Heat (~) ~cc1 fracticn ~-~iA~-~ood materialmatter 186 44.65 124 0.30 Kerosine charged 200 48.00 250 0.61 7279 7340 Additives __ Water absorbed on w~od powder 14 Surfactant and l water 5.5 ~30.5 7.35 30.5 0.09 Auxiliary and l water 11 J _ (Remarks) Number in the parenthesis refers to moist wood powder.
True specific gravity was estimated to be 1.5 for the calculation.
* For calculating heat, 4800 and 10700 kcal/kg were assumed for dried wood powder and kerosine, respectively.
Example 3 200 grams of rice bran (containing 3% of water) which llas been crashed into 250 mesh particles with a turbomill was mix~ed with 200 g of A heavy oil and agitated fox a short time with a universal homogenizer. Then followed addition of synthetic alcohol (C12 - C13) + P0/E0 additive of a sulfonic compound and water, corresponding to 21.8~ to the total weight ~t7~j~53 , . ~ , oE the above mixture, 4.5 g (corresponding to 0.89% to the total weight of the bran and the heavy oil) of neutralized surfactant "Waijinol" SA330, and 20 g of a 1% aqueous solution of starch paste ~the paste corresponding to 0.05~ to the total weight). Agitation for 3 minutes gave 428.2cc of a stable fluid fuel. The viscosity, 4900 CP, remained unchanged for 2 months of standing.
The amounts of charged matters, water contents and the heat evolution observed are shown in Table 3.
Table 3 Weight Volume Volume Heat _ (cc) fraction (kcal~ l _ Dried (~ lateUd* Found Rlce bran matter 194 45.30 129,3 0.33 charged _ (200) Heavy oil charged 200 46.70 250 0.64 7308 7100 _ _ _ Additives Water adsorbed on rice bran 6 Surfactant ~ water 8.2 34.2 7.9 7.9 0.03 Auxiliary and water 20.0 _ (Remarks) Number in the parenthesis refers to the moist rice bran.
True specific gravity was assumed to be 1.5 for the calculation.
* For calculating the heats, 4500 and 11500 kcal/kg were assumed for dried rice bran and A heavy oil, respectively.
-- 10 -- ' Example 4 A mixture of 250 g of pulverized peat (containing 28%
of water) and 200 g of A heavy oil was agitated at a high speed for 1 minute in a universal homogenizer. To the resulting mixture were added synthetic alcohol ~Cll - C15) + 3 EO (ethylene oxide) sulfonate of sodium and water in the amount of 35% and 5.5 g (corresponding to 0.94% to the total weight of the peat and the A heavy oil) of neutrali~ed surfactant "Waijinol" SA300 and 8 g (corresponding to 0.11%
to the total weight of the peat and the A heavy oil) of a 5%
aqueous solution of sodium arginate. During 3 minute agitation with a high speed agitator, the viscosity increased gradually and turned into a gel. When the agitation stopped, a mixed fuel in the gel form, 388.1cc in total, was obtained.
The gel state remained stable for 3 months of standing.
The amounts of charged matters, water contents and the evolved heat observed are shown in Table 4.
Table 4 _ _ _ .
Weight Volume IVolume Heat j (%~ (cc) ¦fraction (kcal/kg~ Found _ I lated _ _ Dried Peat charged (250) 38.8 120 1 0.31 ... _ _ .eavy oil charged 200 43.1 250 ¦ 0.646740 6580 _ !
Additives Water absorbed on peat 70 Surfactant and water 5.5 83.5 18.1 18.1 0.05 Auxiliary and water 8 _ ~1 ~ t~J ~' I~ ~ 7--~r3~
~5LIL ,r b~ r~
(Remarks) Number in the parenthesis refers to the moist peat.
True specific gravity was estimated to be 1.5 for the calculation.
* For calculating the heats, 4600 and llS00 kcal/kg were assumed for the dried peat and the A heavy oil.
Claims (5)
1. A composite fluid fuel made of natural cellulose materials comprising a natural cellulose material which has been crashed to a size finer than 100 mesh, a heavy oil or kerosine in the same amount by weight as that of the natural cellulose materials, a neutral surfactant in an amount of 0.5 to 0.99% to the total weight of the fuel, a vegetable gelating agent in an amount of 0.04 to 0.15% to the total weight of the fuel and water in an amount from 5 to 20% to the total weight of the fuel, and having a neutral pH and a viscosity ranging from 100 to 8000 CP.
2. A composite fluid fuel according to claim 1, wherein the natural cellulose material are by-products from chemical industries which employ natural cellulose materials as raw material.
3. A composite fluid fuel according to claim 1, wherein the surfactant is of the neutral aqueous solution type.
4. A fluid fuel according to claim 2, wherein the by-products from chemical industries which employ natural cellulose materials as raw material are one or more members selected from the group consisting of lees from pulp waste liquid, by-products in SCP, methane fermentation, and alcohol manufacturing and by-products from beer and soybean sauce factories.
5. A process for preparing a composite fluid fuel made of natural cellulose materials, which comprises crashing to a size finer than 100 mesh natural cellulose materials or by-products from chemical industries which employ natural cellulose materials as raw material, mixing to it heavy oil or kerosine in an amount almost the same as that of the foregoing material, adding to the mixture a neutral surfactant and a vegetable gelating agent in amounts of 0.50 to 0.99% and 0.04 to 0.15%, respectively, as expressed relative to the total weight of the mixture, and adjusting the pH nearly to neutrality, the water content to 5 to 20% and the viscosity to 100 to 8000 CP.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15685980A JPS5839479B2 (en) | 1980-11-07 | 1980-11-07 | Natural cellulose-based composite fluid fuel and its manufacturing method |
| JPSHO55-156859 | 1980-11-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1175653A true CA1175653A (en) | 1984-10-09 |
Family
ID=15636936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000388990A Expired CA1175653A (en) | 1980-11-07 | 1981-10-29 | Composite fluid fuel made of natural cellulose materials and a process of preparation thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5839479B2 (en) |
| CA (1) | CA1175653A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4744797A (en) * | 1984-04-21 | 1988-05-17 | Yoshinari Shimada | Mixed fuel of coal powder or the like and heavy oil |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0616629B2 (en) * | 1984-03-28 | 1994-03-02 | 日本電気株式会社 | Loop data transmission system |
| JPS6268179U (en) * | 1985-10-16 | 1987-04-28 |
-
1980
- 1980-11-07 JP JP15685980A patent/JPS5839479B2/en not_active Expired
-
1981
- 1981-10-29 CA CA000388990A patent/CA1175653A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4744797A (en) * | 1984-04-21 | 1988-05-17 | Yoshinari Shimada | Mixed fuel of coal powder or the like and heavy oil |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5780487A (en) | 1982-05-20 |
| JPS5839479B2 (en) | 1983-08-30 |
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