GB2220673A

GB2220673A - Method of improving the flow of oil emulsion fuels

Info

Publication number: GB2220673A
Application number: GB8913361A
Authority: GB
Inventors: Noboru Moriyama; Tsugitoshi Ogura; Akio Hiraki
Original assignee: Kao Corp; Mitsubishi Heavy Industries Ltd
Current assignee: Kao Corp; Mitsubishi Heavy Industries Ltd
Priority date: 1988-06-10
Filing date: 1989-06-09
Publication date: 1990-01-17
Anticipated expiration: 2009-06-09
Also published as: JPH068424B2; CA1339651C; JPH01313591A; GB8913361D0; GB2220673B; CA1339650C

Abstract

An ultraheavy oil emulsion having been deteriorated can be regenerated by adding 0.01 to 2 parts by weight of a nonionic surfactant having a HLB (hydrophile-lipophile balance) value of 2 to 16 based on 100 parts by weight of the fuel and treating the mixture with agitation. The surfactants used are alkylene oxide adducts.

Description

METHOD OF REGENERATING DETERIORATED O/W TYPE ULTRAHEAVY OIL EMULSION FUEL The present invention relates to a method of regenerating a deteriorated O/W type (oil-in-water type) ultraheavy oil emulsion fuel.

CPrior Art z Because of their high reserves, oil sand and bitumen have attracted special attention as fossil fuel resources which do not fall under the category of petroleum, coal, and LNG. With regard to the petroleum as well, asphalt, i.e., residue after removal of oils, such as naphtha, from petroleum through distillation, or residue after heat treatment of asphalt is in surplus. These ultraheavy oils are usually each an oleaginous substance containing about 60 to 70% or more of a high-boiling fraction having a boiling point of 420 to 4500C or above which is a vacuum residue and do not flow in themselves or have a viscosity as high as several tens of thousands of cP or more.For this reason, they are fuels very difficult to handle because when they are used as a fuel without heating at 280 to 3000C, there arise problems with handling and atomization as well as occurrence of clogging of piping. In recent years, an attempt has been made on a reduction in the viscosity of the ultraheavy oil difficult to handle through emulsification thereof in water so that it has a viscosity similar to that of water. In this case, it is known that a surfactant-plays an important role for maintaining in a stable state an emulsion fuel comprising an ultraheavy oil emulsified in water.

An emulsion is a thermodynamically unstable system and broken with the lapse of time. In the case of the above-described ultraheavy emulsion fuel as well, the emulsion is partially broken during storage for a long period of time or during transportation by sea, i.e., deteriorated. When this emulsion is burnt as it is, there occur various unfavorable problems with combustion such as high unburnt combustibles. Furthermore deterioration of the emulsion brings about a lowering in the flowability and an increase in the viscosity to such an extent that it cannot be handled as a flowable liquid, so that it becomes difficult to pump. For this reason, it is important to modify, i.e., regenerate the deteriorated ultraheavy oil prior to combustion into a fuel having high flowability and low unburnt combustibles.

( Summary of the Invention ) The present inventors have found that the two following methods employed in the regeneration of a deteriorated ultraheavy oil emulsion fuel selected depending upon the extent of deterioration enables production of a fuel suitable for combustion, which has led to the completion of the present invention.

(1) Method of regenerating an O/W type ultraheavy oil emulsion fuel deteriorated to such a small extent that it can be pumped and handled as a flowable liquid: 0.01 to 2 parts (by weight; the same shall apply hereinafter), preferably 0.1 to 1 part of a nonionic surfactant having a HLB value of 2 to 16, preferably 10 to 14 and selected from the group consisting of the following surfactants (i) to (vii) is added to 100 parts of an emulsion fuel, and the resulting mixture is agitated with a high shear agitator such as a line mixer, to regenerate the emulsion fuel, thereby preparing an O/W type ultraheavy oil emulsion fuel which can be sufficiently atomized at a high temperature, e.g., 80 to 900C, and has a low unburnt combustibles content.It is preferred from the viewpoint of improving the combustibility that the HLB value and amount of addition of the nonionic surfactant be selected so that the emulsion fuel is of an O/W type at production, storage and transportation temperatures and converted into a W/O type at an atomization temperature.

(i) An alkylene oxide adduct of a compound having a phenolic hydroxyl group1 such as phenol, cresol, butylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, p-cumyphenol, or bisphenol A, wherein the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide.

(ii) An alkylene oxide adduct of a formalin condensate of a compound having a phenolic hydroxyl group, such as alkylphenol, phenol, m-cresol, styrenated phenol, or benzylated phenol, wherein the average degree of condensation is 1.2 to 100, preferably 2 to 20, and the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide.

(iii) A polyalkylene oxide adduct of a compound having a monovalent active group, such as a branched and/or straight-chain aliphatic alcohol or aliphatic amine having 2 to 50 carbon atoms, wherein the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide.

(iv) A product of block or random addition polymerization of ethylene oxide with propylene oxide and/or butylene oxide or styrene oxide.

(v) An alkylene oxide adduct of a polyhydric alcohol such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerin, ethylene glycol, polyethylene glycol, propylene glycol, or polypropylene glycol, or an ester of said polyhydric alcohol with an aliphatic acid having 8 to 18 carbon atoms, wherein the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide.

(vi) An alkylene oxide adduct of a polyamine having a plurality of active hydrogen atoms, such as ethylenediamine, tetraethylenediamine, or polyethyleneimine (molecular weight: 600 to 10,000), wherein the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide.

(vii) A product of addition reaction of an alkylene oxide with a mixture of 1 mol of a triglyceride oil with at least one polyhydric alcohol selected from the group consisting of glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, ethylene glycol, polyethylene glycol having a molecular weight of 1000 or less, propylene glycol, and polypropylene glycol having a molecular weight of 1000 or less and/or 0.1 to 5 mol of water. The alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide.

Among the above-described nonionic surfactants, the most preferable surfactants and the next most preferable surfactants are those belonging to the above-described groups (vii) and (i), respectively.

(2) Method of regenerating a deteriorated O/W type ultraheavy oil emulsion fuel deteriorated to such a great extent that it experiences difficulty in pumping because of high viscosity and cannot be handled as a flowable liquid: 0.01 to 2 parts, preferably 0.08 to 0.6 part of an anionic surfactant selected from the group consisting of the following surfactants (I) to (VII) is added to 10 parts of a highly deteriorated O/W emulsion fuel and mildly agitated to lower the viscosity of the emulsion fuel, and 0.01 to 2 parts, preferably 0.1 to 1 part, based on 100 parts of the emulsion fuel, of a nonionic surfactant having a HLB value of 2 to 16 and selected from the group consisting of the surfactants (i) to (vii) described above in connection with method (1) is added to the resulting mixture, thereby preparing an emulsion fuel which has excellent flowability and can be sufficiently atomized at a high temperature, e.g., 80 to 900C.

Alternatively, 0.05 to 3 parts, preferably 0.3 to 1.5 parts in total of an anionic surfactant selected from the group consisting of the following surfactants (I) to (VII) and a nonionic surfactant having a HLB value of 2 to 16 and selected from the group consisting of the surfactants (i) to (vii) described above in connection with method (1) in an anionic surfactant to nonionic surfactant weight ratio of 100 : 10 to 100 : 1000, preferably 100 : 100 to 100 : 400 may be added to 100 parts by weight of the emulsion fuel, and the resulting mixture may be then agitated, thereby regenerating an emulsion fuel which has excellent flowability and can be sufficiently atomized at a high temperature, e.g., 80 to 900C.The anionic surfactant mainly serves to lower the viscosity of the emulsion fuel, while the nonionic surfactant mainly serves to prevent the emulsion particles from aggregating into larger particles. It is preferred that the HLB value and amount of addition of the nonionic surfactant be selected so that the emulsion fuel is of an O/W type at production, storage and transportation temperatures and converted into a W/O type at an atomization temperature.

(I) A formalin condensate of a sulfonic acid or sulfonic acid salt of an aromatic ring compound such as naphthalene, alkylnaphthalene, alkylphenol, or alkylbenzene, wherein the average degree of condensation is 1.2 to 100, preferably 2 to 20, and the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, magnesium or calcium.

(II) Ligninsulfonic acid, a salt of ligninsulfonic acid, or a derivative thereof, and a formalin condensate of ligninsulfonic acid with a sulfonic acid or an aromatic compound such as naphthalene or alkylnaphthalene and salts thereof, wherein the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, calcium or magnesium and the average degree of condensation is 1.2 to 50, preferably 2 to 20.

(III) Polystyrenesulfonic acid or its salt and a copolymer of styrenesulfonic acid with other copolymerizable monomer and a salt thereof, wherein the molecular weight is 500 to 500,000, preferably 2,000 to 100,000, and the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, calcium or magnesium.

(IV) A polymer of dicyclopentadienesulfonic acid or its salt, wherein the polymer has a molecular weight of 500 to 500,000, preferably 2,000 to 100,000, and the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, calcium or magnesium.

(V) A copolymer of maleic anhydride and/or itaconic anhydride with other copolymerizable monomer and its salt, wherein the molecular weight is 500 to 500,000, preferably 1,500 to 100,000, and the salt is that of ammonium or an alkali metal such as sodium or potassium. Examples of the copolymerizable monomer include olefins (such as ethylene, propylene, butylene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, and hexadecene), styrene, vinyl acetate, acrylic esters, methacrylic acid, and acrylic acid.

(VI) Maleic acid-modified liquid polybutadiene or its salt, wherein the liquid polybutadiene has a molecular weight of 500 to 200,000, preferably 1,000 to 50,000, the degree of modification with maleic acid may be one necessary for dissolution in water, preferably 40 to 70%, and the salt is that of ammonium or an alkali metal such as sodium or potassium.

(VII) The following anionic surfactants each having one or two hydrophilic group in its molecule.

(a) A sulfate of an alcohol having 4 to 18 carbon atoms, wherein the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, magnesium or calcium.

(b) Alkane-, alkene- and/or alkylaryl-sulfonic acid having 4 to 18 carbon atoms, wherein the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, magnesium or calcium.

(c) A sulfate or phosphate of an alkylene oxide adduct of a compound having at least one active hydrogen in its molecule, and its salt, wherein the salt is that of ammonium or an alkali metal such as sodium or potassium.

(d) A sulfosuccinic acid salt which is an ester of a saturated or unsaturated fatty acid having 4 to 22 carbon atoms, wherein the salt is that of ammonium, sodium, or potassium.

(e) Alkyl diphenyl ether disulfonic acid or its salt, wherein the alkyl group is one having 8 to 18 carbon atoms and the salt is that of ammonium, sodium, potassium, magnesium, or calcium.

(f) Rosin acid or its salt, wherein the salt is that of ammonium, sodium, or potassium and which includes a tall oil mixed acid comprising a mixture of rosin acid with a higher fatty acid, and its salt.

(g) An alkane or alkene fatty acid having 4 to 18 carbon atoms and its salt, wherein the salt is that of ammonium, potassium, or sodium.

Among the above-described anionic surfactants, those of the types (I) and (II) are preferable.

The surfactants of the type (I) exhibit a slightly superior performance. In the surfactants of the type (I), no difference in the performance is observed as far as the degree of condensation is 2 or more.

In the surfactants of the type-(II), a modified-lignin having a carboxyl group introduced thereinto instead of a sulfonic acid group exhibited a slightly superior performance. The HLB value of the nonionic surfactant is the same as that of the surfactant used in method (1), i.e., 2 to 16, preferably 10 to 14. Among the nonionic surfactants, the best surfactant and the next best surfactant are those of the types (vii) and (i) described above in connection with method (1), respectively.

In both of the methods (1) and (2), any agitating means may be used. Further, two or more kinds of agitating means may be used in combination. The use of a high shear agitation device is particularly preferable. Examples thereof include a line mixer, a fletching type turbine blade, a propeller blade, a Brumagin-type blade, and a paddle blade.

The oil called "ultraheavy oil" in the present invention includes the following oils which do not flow unless they are heated at a high temperature.

(1) Petroleum-derived asphalt and a mixture thereof with an oil.

(2) Products, intermediate products, and residues of various treatments of petroleum-derived asphalt, and mixtures thereof with an oil.

(3) A high fluid point oil which does not flow at a high temperature, or a crude oil.

(4) Petroleum-derived tar pitch and a mixture thereof with an oil.

(5) Bitumen, Brief Description of the Drawings: Figs. 1 and 2 are each a schematic view of a regeneration apparatus used in Example 3.

1: deteriorated emulsion 2: storage tank 3: agitator 4: heater 5: pump 6, 6': additive 7, 7': static mixer 8, 8': line mixer 9: boiler CExamples3 The present invention will now be described with reference to the following Examples. However, the present invention is not limited to these Examples only.

Example 1 An 800-ml SUS container was charged with 300 g of a slightly deteriorated O/W type ultraheavy oil emulsion fuel and immersed in a heating bath to heat the emulsion fuel to 600C. A predetermined amount of a nonionic surfactant was added thereto. After a given temperature (600C) was reached, the mixture was agitated at 300 rpm with a paddle blade for 5 min. The mixture was further subjected to high shear agitation with a TK homomixer at 6,000 rpm for 2 min to re-emulsify the emulsion fuel, and placed in a thermostatic chamber of 60"C to measure the viscosity. Part of the re-emulsified emulsion fuel was kept at 500C and taken out of the thermostatic chamber to measure the percentage undersize of a 100-mesh sieve.The viscosity was measured with a model VS-AI Vismetron, No. 2 (number of revolutions of the rotor: 60 rpm) manufactured by Shibaura Systems Co., Ltd., while the percentage undersize was determined by putting about 10 g of a sample on a 100-mesh stainless sieve of 100 mmi in an atmosphere of 50 0C, measuring the oversize after 10 min, and calculating the undersize.

The results are shown in Tables 1 and 2.

The above-described slightly deteriorated emulsion fuel is one prepared by adding 0.12 part of ligninsulfonic acid and 0.48 part of polyoxyethylene nonylphenyl ether (HLB value : 15.2) to 100 parts of Middle Eastern petroleum-derived asphalt (penetration: 60 - 80) or Athabasca bitumen (a softening temperature of 12.5 C; occurring in Canada) and agitating the resulting mixture at 750C with a TK homomixer (provided with a low viscosity agitation blade) manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an emulsion fuel, and storing the emulsion fuel at 500C for one month.

The performance was expressed in the descending order of preference: Qo > 0 > A > x.

Table 1

Physical properties at production ao I ~ ~ ~ es Sieve evaluation No.

(%) Viscosity (100-mesh) 3 E < O u) o O un to > ur 0 -C > > > n ether (HLB: ~ ---- 3 74 o 0.10 310 30 0 4 74 " cn o o 250 70 0" " 0 ;Y" OD 5 74 " 0.50 210 75 6 74 " 1.00 220 72 ethylene oxide adduct do,aoo-e of o ,a o o o o 74 glycerin rl > 1 ratio: 1/0.5) 0.05 | &commat;A o sc > ~uo u &commat;QN : = co; X c m ^ E 4J uz S > ~ e N = k O a) 4 < E a4Us v > N X v M b z < N ~ v S | W | r ~ Table 1 (continued)

0 rrrco p 1 uz > oxide adduct (HLB: 12.7) of tallow oil/ 200 73 h O gp) (molar ratio: 1/0.5) 0.30% 10 74 " ,.50 190 78 11 74 : Û ~~ ~ ~ ~ r oQ N ri-(Y oleyl ether 230 72 12 74 (llLB: 12.6) 0.50 O O .0 O O ~ U1 O O Uol ~ h h N O H 4C &commat; =H E O < ~I X U ~ > h n c : n &commat; n h 4J | O ~ 0o &commat; c s4 H aa o as c X ax W n : : c c c JJ fi X X ö ZD Qa Q1 &commat; u O > E 4 ,C v0 C rs fiC 40 X al cs C h oi > h U h h X X X u = ~4 E CO4 v C 4 CO4 OE U C~ c u S v sr v sr or v C40C- > b > > > fi o O ~I N 1 v g Z < < H H Table 2

' Physical properties " Zip Test bitumen Surfactant and amount (%) No. concn. i Sieve evaluation (%) Viscosty (100-mesh) S Qcn vi > N O N VI O 2 1 74 not r added > 3700 0 x cl dlU1 72 rc ao o U 1 r L ho .' ~ esP O O - O O O Oe 0 O O = CS E O U 4J oCv X oo c c es : ax W n : 4 oH iX~ X. c m O > E fi W r ; a . U : o : C X cq C h z X x aX h S O k H &commat; O 4) C a > l É = C4&commat; &commat;~ ~ s E C~ D n U aP v er sr v v w c > b rb b > < n U w E - ~ N In Example 2 An 800-ml SUS container was charged with 300 g of a seriously deteriorated O/W type ultraheavy oil emulsion fuel and immersed in a heating bath to heat the emulsion fuel to 600C. A predetermined amount of an anionic surfactant was added thereto, and the resulting mixture was agitated at 300 rpm with a paddle blade for 5 min. Further, the mixture was subjected to high shear agitation for 2 min at 6,000 rpm with a TK homomixer.A predetermined amount of a nonionic surfactant was added to the emulsion fuel, and the mixture was stirred with a spatula, agitated again with the TK homomixer, and placed in a thermostatic chamber of 600C to measure the viscosity.

Part of the re-emulsified emulsion fuel was kept at 50 C and taken out of the thermostatic chamber to measure the percentage undersize of a 100-mesh sieve.

The viscosity was measured with a model VS-AI Vismetron, No. 2 (number of revolutions of the rotor: 60 rpm) manufactured by Shibaura Systems Co., Ltd., while the percentage undersize was determined by putting about 10 g of a sample on a 100-mesh stainless sieve of 70 mm in an atmosphere of 500C, measuring the oversize after 10 min, and calculating the undersize.

The results are shown in Table 3 and 4.

In the above-described test, the anionic surfactant and the nonionic surfactant were separately added. Next, a mixture of the anionic surfactant with the nonionic surfactant was added instead of the anionic surfactant, and the emulsion fuel was then subjected to high shear agitation at 6,000 rpm with a TK homomixer for 2 min. The viscosity and undersize were measured under the same condition as that described above.

The above-described seriously deteriorated emulsion fuel is one prepared by adding 1.0 part of polyoxyethylene nonylphenyl ether (HLB value: 15.5) to 100 parts of Middle Eastern petroleum-derived asphalt (penetration: 60 - 80) or Athabasca bitumen (a softening temperature of 12.50C; occurring in Canada) and agitating the resulting mixture at 750C with a TK homomixer (Provided with a low viscosity agitation blade) manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an emulsion fuel, and storing the emulsion fuel at 50 C for one month. The viscosity of the emulsion fuel was 500 cP as determined immediately after the production and 7,000 cP one month after the production.

The performance was expressed in the descending order of preference: &commat; > O > A > x. Table 3

- o rlrl Test fi Overall m X < and &commat; sieve evaluation Qlrl o at > undersize (%) X ,1 I P1UIP) c X X X 2 74 system al s b, Q1E--e ~z v O N O e UN U: UZ J UN and VI rr) nonylphenyl ether (HLB: 12.4) rg 0Q 0o U ~e X ffi X O ~ a E;).1 U ma o O < z UO 8 8 88 lln O O 75 1.50 O ZJ O O v z hl (Y CM v) 12 O rl CU 2.00 1,009 25 a U . ~~~ S S S 00000 o Q o (degree of o 000 009n C > r P)C1 ether > X v w4 e~ 3 S ,c c c e O o N O O (IILB: 12.4) (weight ratio: 1/2) O sr fi &commat; H ~ wherein the total amount of both C X N v D C S O W surfactants is > as 0"1: (added in r mixed &commat; < fi 5 a E n w < X s fi e Ç 0.30 370 52 " (0 X Q a 3 s C ~i O4 0 X Ut 0.90 ELlrllll C z 3 W n W C 4J tS C N O O ~l I ^ O = 10 S 4 re X e c 75 3.00 940 27 o c ç s W o ^ < ua o S x X m S S - O W E X c 3 0 m 4 < X X o al t < E U h C ~4 4J m > h Q C ffi O ~l zJ C X 0S &commat; O > X u E W > n > E u c s sr s > h ra O ~ C h O 'O m O fi o S w . 4 J c c ~ = as u n X E &commat; U qX N 1 < rn X m s fi fa e , ~ c t0 E C aj S h U E C S c x < u X X ~ Cr} S X U &commat; V O O O X a1 v c > < < > i S X S X Sm h 44 X fi en cr c X Ll E c o c a X h c O Si 0 3 o en > o o O s n < c m ~ cW X O c o ffi 3 ua fi c u S v v 4 /U O ~ N 1 1 Ez Z Table 3 (cont'd)

c Physical properties Asphalt at production Test cV O Surfactant and amount (%) 0, ~ oP cuiia, Q 4 74 system s rs Ln o k ligninsulfonate and N ~ \9 > N d II h O o c) oil with glycerin (HLB: 12.7) 00 3 O cu is > lo ffi > (added in O mixed system): 0.10% O O o 0.30 350 mQ DSZ m 77 > X oe t Ln 5 74 tn ligninsulfonate and Ipolyoxyethylene vlui O ul Q ul ~ H 3 s 4J J (HLB: 12.4) wherein the 3 C m amount of both Q) L1 is Q w > H H U fi c s and 0.90% while the c I ri O rl Q C LI C) rii cS O E E ratio of U k 4 E E 5 S O - 3 4 U U 5 S aJ U 5 > c I xA (anionic/nonionic) is varied as JJfollow F g L) d a L)d V1 CI D O W = in X mixed system): 1/0.5 200 15 A 1/1 250 ltl X C C (JO Bp i, E f LI II a P rrJ C Q1 3 Q c E ~ 76 c 000 25 A 3 ul > O ao X; c s s o o o w ; c S - fi h c Q 3 fiO c O c U z O t-) ~ 4J tD < X O h Q C *H O U 4w E uk W E W S v X fi C h O < r h H C C O 4J 4 W e s C 5 U 5 rC1 < e X U 5 aX N O JJ h u vz ow eo w fi fi fi uz > . < c H E C H S O u X E c x 4 e fi c X Q 3 > 4 X Q < < o - c 4 S O a ; c e < W X W c > a:1 5 ul G1 E s Ul -,1 H Q Q h c ul > ~ a o c < c n > x . a s 3 U ~ X ~ X = XE g O3 U x 4J cu ~ > v < 8 X Table 3 (cont'd)

o rrJIO U X h 5 W > < Oo Test Asphalt Overall I (%) Viscosit 100-mesh) > &commat; O P)m cn Q)EN 6 7 V)O comprising sodium 20 78 0" tO and h O ~ X Q 5 ~I h ~ and the total amount and o 0 LIO ratio (anionic/nonionic) of both surfactants are 0.90% and 1/4, ffi U 1u N > XU &commat; s C ~ c ax o9 4 s S O ~ X X mS v JJ 9 as W H C : > s : 3 0 5 C t1 X O E al S U X ~ C E 5 S 4 J C U tu U < ffi O X X < c H n S4 C dP s O > X; O O C C11 c C C Qz C < CE ftl C O-rl &commat; 5 C 0 IXI C X W O O O 4 C O4 E C C < eJ Q X X X \ X X X X C S z U Si > ~l X a) 3 X U h C tU C > X X O S~ UX; O H W E W S t JJ O + 4 Q) h O xI JJ =; C = > = U 5 Ql N ce e H 4J X u fi E c x U C U U &commat; H o - U; o e al ; c zm W < W ss 1 4 X fi h 01 > .~{ O ~: C X 5 &commat; ul ~ ffi U7 ta h 0T h 4J 4 C ~ S U oP v ffi c rs U} O J E Z Table 4

c properties o at production Test bitumen Overall 84 and amount (%) No. concn. viscosity Sieve evaluation (%) (cP; at 600c) (100-mesh) 174 not added & 6,00 Q12 2 74 system comprising sodium pl U=X S U1 01 GD E N 1 I ~l O v o aw is varied as follows LIO clC) . ll t1 C O U n k C) 1.50 Dz > o 0 LIO -I LI 800 29 A m m m o O 0 rr 0 3 C r 0 a O S O xn 1 N N G ~ N N and X o vo ether (I!L8: 12.4) wherein the total 00000 of is and Ê s s s x weight ratio EOcr of both surfactants is varied as Y CLrQI fi &commat; U < JJ U W O H U} fi > l S X - > w t c 1fl0 c ew c 19 cus c a c cC - E 1/1 Ql X ttJJ E ffi R c v o, m x 1/4 240 a 78 S o -ri 1/6 700 28 a X Ul X C 3 N w 3 D7 Ul X C 3 4 a C U1 C C O \ O O C O O O JJ C ^ ~ J::l ~I X tJI C n O ~ C C C t H Q C v C ~ 4.l + Q Q . D1 Xt O X { Q Q t1 X zU C Ul aJ C N I 0 14 * 1 S C N O C ~ U v .-4 Q ~I E z IU ~ 111 0 o1 h c 1 0 fi Ul h c ~ fi 0 '4 X Q ffi O > - c X ffi O > - = fi v c X E 44 m > n E W 1 w X O ^i ? O X C O ~ X a O U h Q C): CX ~ h E Q ~l U :: Q = E JJ h :1 X 08 < X > X S X m X E C X 4 h X E c x c S fi 3 41 1 o h S W o o ~I O h O s O O = C ::^ O > al > 4 = U > Q < < 1 > S vi fi X Ul > H H ~ > -~1 0 U al o X > 1 o wJ o U1 Q t1 0 C QZ Q a a ~ ~ D 3 0 I;z 1x1 E C n 2 OS v v S8 C- > > > UX O O .~ N r-l Et z Example 3 Regeneration of a deteriorated emulsion was conducted by making use of regeneration apparatuses shown in Figs. 1 and 2 on a pilot plant scale.

Regeneration by making use of a regeneration apparatus shown in Fig. 1 was conducted by feeding a given amount of a deteriorated emulsion 1 heated at 500C in a storage tank 2 through a circulating pump 5, adding an additive 6, conducting premixing with a static mixer 7, and agitating the emulsion under high shearing with a line mixer 8.

In a regeneration apparatus shown in Fig. 2, in order to add an additive in two stages 6 and 6', static mixers 7 and 7' were connected in series with line mixers 8 and 8' in two systems.

Examples of the regeneration conducted include regeneration of a slightly deteriorated emulsion with a regeneration apparatus shown in Fig. 1 (regeneration 1), regeneration of a seriously deteriorated emulsion through the use of a mixed additive with a regeneration apparatus shown in Fig. 1 (regeneration 2), and regeneration through separate addition of two types of additives with a regeneration apparatus shown in Fig. 2 (regeneration 3). Mechanical conditions for this regeneration are shown in Table 5, while description of the additive and properties of the emulsion before and after the regeneration are shown in Table 6.

As is apparent from the results shown in Table 6, as with Examples 1 and 2, a sufficient effect could be recognized also in the continuous regeneration of a deteriorated emulsion on a pilot plant scale. Table 5: Mechanical conditions for regeneration

Mechanical conditions Number of Regeneration Amount of flow rate of Number of times Number of Temp. revolutions of emulsion circulation of circulation revolutions ( C) agitator of tank (kg) (m/hr) (times) of L/M (rpm) regeneration 1 20000 50 2 3 6 1000 regeneration 2 20000 50 2 3 10 2800 regeneration 3 20000 50 2 3 6 2000 Table 6:Results of regeneration

C of emulsion S1 of Asphalt lil of emulsion CI Viscosity undersize (cP; 600c) (%; 500C) E h ul > > Q P) regeneration c 'CI O , < ~ cn 1 74 u.gen 0.2% 200 72 0 Q) U ri LI 0 Le m yr O 0 O C\ 01 0 y (V O (V re 0m uX m no m a, added in a mixed form E O c cu e cv addition .> 3 74 -riO\U) w ig o vD X H 4 00 4 C Ut0 = ~ ; , E O 4 E O Z ; Z 4 cS S U S sr sr v v v D OC > > rs > > N m c O O OC O O O ax e sk si k C Q Q Q Q X Ç Q c Qc C sC OC O u U r W > mQ Q Ds Q Q C C O c O O uw H O < < O fi ~ fi ; X uz Q z < k h Q O: O O h H E fi = < z tD C h O SJ adJ tD r (U a,J n wJ W ~1 aJ S-l 4J X O Q Q Q c X U] r Note: Emulgen 909 (a product of Kao Corp.): polyoxyethylene nonylphenyl ether (HLB: 12.4) NSF: formalin condensate of sodium naphthalenesulfonate (degree of condensation: 4.1)

Claims

Claims:

1. A method of regenerating a deteriorated O/W type ultraheavy oil emulsion fuel, characterized by adding 0.01 to 2 parts by weight of a nonionic surfactant having a HLB (hydrophile-lipophile balance) value of 2 to 16 and selected from the group consisting of the following surfactants (i) to (vii) to 100 parts by weight of an O/W type ultraheavy oil emulsion fuel deteriorated to such a small extent that it can be pumped and handled as a flowable liquid, and subjecting the resulting mixture to high shear agitation:: (i) an alkylene oxide adduct of a compound having a phenolic hydroxyl group, such as phenol, cresol, butylphenol, octylphenol, nonylphenol, dinonylphenol, dodecylphenol, p-cumylphenol, or bisphenol A, wherein the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide; (ii) an alkylene oxide adduct of a formalin condensate of a compound having a phenolic hydroxyl group, such as alkylphenol, phenol, m-cresol, styrenated phenol, or benzylated phenol, wherein the average degree of condensation is 1.2 to 100 and the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide;; (iii) a polyalkylene oxide adduct of a compound having a monovalent active group, such as a branched and/or straight-chain aliphatic alcohol or aliphatic amine having 2 to 50 carbon atoms, wherein the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide; (iv) a product of block or random addition polymerization of ethylene oxide with propylene oxide and/or butylene oxide or styrene oxide; (v) an alkylene oxide adduct of a polyhydric alcohol such as glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, polyglycerin, ethylene glycol, polyethylene glycol, propylene glycol, or polypropylene glycol, or an ester of said polyhydric alcohol with an aliphatic acid having 8 to 18 carbon atoms, wherein the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide;; (vi) an alkylene oxide adduct of a polyamine having a plurality of active hydrogen atoms, such as ethylenediamine, tetraethylenediamine, or polyethyleneimine (molecular weight: 600 to 10,000), wherein the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide; and (vii) a product of addition reaction of an alkylene oxide with a mixture of 1 mol of a triglyceride oil with at least one polyhydric alcohol selected from the group consisting of glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose, ethylene glycol, polyethylene glycol having a molecular weight of 1000 or less, propylene glycol, and polypropylene glycol having a molecular weight of 1000 or less and/or 0.1 to 5 mol of water, wherein the alkylene oxide is ethylene oxide and/or propylene oxide, butylene oxide, or styrene oxide.

2. A method of regenerating a deteriorated O/W type ultraheavy oil emulsion fuel, characterized by adding 0.01 to 2 parts by weight of an anionic surfactant selected from the group consisting of the following surfactants (I) to (VII) to 100 parts by weight of an O/W type ultraheavy oil emulsion fuel deteriorated to such a great extent that it experiences difficulty in pumping because of high viscosity and cannot be handled as a flowable liquid, lowering the viscosity of said emulsion fuel through mild agitation of the resulting mixture, adding 0.01 to 2 parts by weight, based on 100 parts by weight of said emulsion fuel, of a nonionic surfactant according to claim 1 to the resulting mixture, thereby preparing an emulsion fuel having high flowability; or adding 0.05 to 3 parts by weight in total of an anionic surfactant selected from the group consisting of the following surfactants (I) to (VII) and a nonionic surfactant according to claim 1 in an anionic surfactant to nonionic surfactant weight ratio of 100 : 10 to 100 : 1000 to 100 parts by weight of said emulsion fuel, and agitating the resulting mixture:: (I) a formalin condensate of a sulfonic acid or sulfonic acid salt of an aromatic ring compound such as naphthalene, alkylnaphthalene, alkylphenol, or alkylbenzene, wherein the average degree of condensation is 1.2 to 100 and the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, magnesium or calcium;; (II) ligninsulfonic acid, a salt of ligninsulfonic acid, or a derivative thereof, and a formalin condensate of ligninsulfonic acid with a sulfonic acid of an aromatic compound such as naphthalene or alkylnaphthalene and salts thereof, wherein the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, calcium or magnesium and the average degree of condensation is 1.2 to 50;; (III) polystyrenesulfonic acid or its salt and a copolymer of styrenesulfonic acid with other copolymerizable monomer and a salt thereof, wherein the molecular weight is 500 to 500,000 and the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, calcium or magnesium; (IV) a polymer of dicyclopentadienesulfonic acid or its salt, wherein the polymer has a molecular weight of 500 to 500,000 and the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, calcium or magnesium;; (V) a copolymer of maleic anhydride and/or itaconic anhydride with other copolymerizable monomer and its salt, wherein the molecular weight is 500 to 500,000 and the salt is that of ammonium or an alkali metal such as sodium or potassium; (VI) maleic acid-modified liquid polybutadiene or its salt, wherein the liquid polybutadiene has a molecular weight of 500 to 200,000 and the salt is that of ammonium or an alkali metal such as sodium or potassium; and (VII) the following anionic surfactants each having one or two hydrophilic group in its molecule: (a) a sulfate of an alcohol having 4 to 18 carbon atoms, wherein the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, magnesium or calcium; (b) alkane-, alkene- and/or alkylary-sulfonic acid having 4 to 18 carbon atoms, wherein the salt is that of ammonium, a lower amine such as monoethanolamine, diethanolamine, triethanolamine or triethylamine, or an alkali or alkaline earth metal such as sodium, potassium, magnesium or calcium;; (c) a sulfate or phosphate of an alkylene oxide adduct of a compound having at least one active hydrogen in its molecule, and its salt, wherein the salt is that of ammonium or an alkali metal such as sodium or potassium; (d) a sulfosuccinic acid salt which is an ester of a saturated or unsaturated fatty acid having 4 to 22 carbon atoms, wherein the salt is that of ammonium, sodium, or potassium; (e) alkyl diphenyl ether disulfonic acid or its salt, wherein the alkyl group is one having 8 to 18 carbon atoms and the salt is that of ammonium, sodium, potassium, magnesium, or calcium; (f) rosin acid or its salt, wherein the salt is that of ammonium, sodium, or potassium and which includes a tall oil mixed acid comprising a mixture of rosin acid with a higher fatty acid, and its salt; and (g) an alkane or alkene fatty acid having 4 to 18 carbon atoms and its salt, wherein the salt is that of ammonium, potassium, or sodium.

3. The method as claimed in Claim 1, in which the nonionic surfactant has an HLB value of 10 to 14.

4. The method as claimed in Claim 1, in which the nonionic surfactant is selected from the group consisting of (vii) and (i).

5. The method as claimed in Claim 2, in which the anionic surfactant is selected from the group consisting of (I) and (II).

6. The method as claimed in Claim 2, in which the nonionic surfactant has an HLB value of 10 to 14.

7. The method as claimed in Claim 2, in which the non ionic surfactant is selected from the group consisting of (vii) and (i).