CA1187285A - Zirconium additives for residual fuel oil - Google Patents
Zirconium additives for residual fuel oilInfo
- Publication number
- CA1187285A CA1187285A CA000407533A CA407533A CA1187285A CA 1187285 A CA1187285 A CA 1187285A CA 000407533 A CA000407533 A CA 000407533A CA 407533 A CA407533 A CA 407533A CA 1187285 A CA1187285 A CA 1187285A
- Authority
- CA
- Canada
- Prior art keywords
- fuel oil
- amount
- group
- oil
- salt
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/188—Carboxylic acids; metal salts thereof
- C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
Abstract
ABSTRACT OF THE DISCLOSURE
A process for reducing the amount of particulate matter formed during the combustion of residual fuel oil, particularly No. 6 fuel oil, comprising adding an effec-tive amount of selected oil soluble zirconium salts of an alcohol/phenol or sulfonate to the residual fuel oil prior to combustion.
A process for reducing the amount of particulate matter formed during the combustion of residual fuel oil, particularly No. 6 fuel oil, comprising adding an effec-tive amount of selected oil soluble zirconium salts of an alcohol/phenol or sulfonate to the residual fuel oil prior to combustion.
Description
~ 1 --
2 1. Field of the Invention
3 This invention relates to the use o~ specific ~ zirconium salts in residual fuel oil to reduce the amount of particulate matter formed during combustion.
6 2. Brief Description of the Prior Art 7 Residual fuel oils, including Grades Nos. 4, 5 8 and 6 (ASTM D-396), are widely used in a variety of g industrial heating and steam boiler applications. A
particularly desired fuel oil is No. 6, which is exten-11 sively used by utility and power companies.
12 State and federal EP~ emission standards are 13 currently limiting the use of residual fuels which produce 14 excessive amounts of particulate emission during combus-tion and thus are not in compliance with standards.
16 However, the situation is relati~ely complicated, 17 since state-to-state emission standards tend to be differ-18 ent and compliance by a residual fuel oil in one state may 1~ not necessarily be achieved in another, and further, since standards are continuously subject to change, a fuel oil 21 currently in compliance may not be in compliance in the 22 near future in the same location and under the same 23 end-use conditions.
24 Fuels which tend to produce excessive amounts of ~5 particulate emission generally have one or more character-26 istics associated with them: a sulfur content above about 27 1 percent; a Conradson Carbon Residue (ASTM D-189, also ~8 termed NCon CarbonN in the art) above about 7 percent; or 29 a high asphaltene content. Fuels yielding particulate emissions that surpass the existing standards can't be 31 directly used, but in some cases can be blended in admix-32 ture with fuels that do meet existin~ standards, which are 33 generally low in sulfur and/or low in ~Con Carbon" and 3~ asphaltene content. This situation has resulted in an overall increased demand for fuel oils which meet emission 36 standards despite their diminishing supply and attendant 37 increase in cost.
38 What is desired is a process for increasing the s~
~8~;
utility of these high ~mission yielding residual uel oils for industrial heating purposes in a manner that resulta in acceptable particulate emissions, despite a high sul~ur content, a high Con Carbon residue and/or high asphalten~
content.
In the area of related proble~s, it is known in the art that the use of specific additives in certain hydrocarbon fuels, can reduce smoke or soot upon combus-tion, in certain instances. It is also known to use specific additives in fuels to inhibit corrosion, inhibit slag formation in boilers and to reduce the deleterious efect of vanadium present in such fuels.
However, it has not been shown to use selected additives to reduce particulate emission during combustion of residual fuel oil, and particularly No. 6 fuel oil.
;Summary of Invention ;~t has unexpectedly been~found that by adding a selected oil soluble zirconium salt of an alcohol/phenol or sulfonate to a residual fuel oil, and particularly ~o.
.20 6 fuel oil the amount o~ particulate matt~r formed during combustion can be significantly reduced in ~mounts of 10 to 25 p~rcent or greater.
In accordance with this in~ention, there is provided a process for reducin~ the amount of particulate matter ormed during the combustion o a residual fuel oil which comprises combusting a residual ~uel oil which con-tains an effective amount of an additive selected from the group consisting o~:
n oil soluble zirconium salt of an alcohol or phenol havin~ the ~ormula:
ROH
where R is a hydrocarbyl group of 2 to 24 carbon atoms: i or (ii) an oil soluble zirconium salt of a sulfonic acid having the formula:
.~
_ 3 ~8~
where R is an alkyl, cycloalkyl, aryl, alk~ry1, or ar~lk~l group and said salt has a molecular ~"ei~ht of about 100 to about 2500;
said amount bein~ effective in reducing the amount of particulate matter formed during combustion In another aspect the invention provides a com-position comprising a residual fuel oil and an effective trace amount of the additive previously described.
DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
- .. ... ~ .
10The novelty of the present invention resides in the discovery that zirconium salts of certain alcohols/
phenols or sulfonic acids exert a beneficial efect on ; residual fuel oil, particularly No. 6 fuel oil/ in reducing the amount of particulate matter formed during combustion. The term nresidual fuel oil" as used herein, is well-known and as described hereinabove, and includes Grades No. 4, No. 5 and No. 6 residual fuel oils, mee~ing tha specifications o ASTM D-396. Particularly preferred is No. 6 fuel oil.
20The reason these particular zirconium additives exhibit this surprising effect is not clearly understood.
It may be that the subject compounds promote and acti-vate the complete oxidation of hydrocarbon and sulfur-containing constituents in the fuel ~o volatile or gaseous compounds during combustion, in a highly specific mannerO
The subject zirconium salts or compounds~ also termed "additives~ herein, opera~ive in the instant in-vention, comprise oil soluble zirconium sal~s of an alcohol/phenol or sulfonate~ The zirconium salt of 30selected alcohols or phenols will be a 2irconium salt of an alcohol or phenol having the formula:
ROH
where R is a hydrocarbyl group o 2 to 2~ carbon atoms.
More particularly R is a branched or unbranched, hydro-carbyl group preferably having 2 to 13 carbon atoms.
Preferred compounds are those where R is a sa~urated or Z3~5 1 unsaturated aliphatic group having 2 to 8 and more pce~er-2 ably 3 to 4 carbons. Most preferred are those coMpounds 3 where R is a saturated aliphatic group, and particularl~
6 2. Brief Description of the Prior Art 7 Residual fuel oils, including Grades Nos. 4, 5 8 and 6 (ASTM D-396), are widely used in a variety of g industrial heating and steam boiler applications. A
particularly desired fuel oil is No. 6, which is exten-11 sively used by utility and power companies.
12 State and federal EP~ emission standards are 13 currently limiting the use of residual fuels which produce 14 excessive amounts of particulate emission during combus-tion and thus are not in compliance with standards.
16 However, the situation is relati~ely complicated, 17 since state-to-state emission standards tend to be differ-18 ent and compliance by a residual fuel oil in one state may 1~ not necessarily be achieved in another, and further, since standards are continuously subject to change, a fuel oil 21 currently in compliance may not be in compliance in the 22 near future in the same location and under the same 23 end-use conditions.
24 Fuels which tend to produce excessive amounts of ~5 particulate emission generally have one or more character-26 istics associated with them: a sulfur content above about 27 1 percent; a Conradson Carbon Residue (ASTM D-189, also ~8 termed NCon CarbonN in the art) above about 7 percent; or 29 a high asphaltene content. Fuels yielding particulate emissions that surpass the existing standards can't be 31 directly used, but in some cases can be blended in admix-32 ture with fuels that do meet existin~ standards, which are 33 generally low in sulfur and/or low in ~Con Carbon" and 3~ asphaltene content. This situation has resulted in an overall increased demand for fuel oils which meet emission 36 standards despite their diminishing supply and attendant 37 increase in cost.
38 What is desired is a process for increasing the s~
~8~;
utility of these high ~mission yielding residual uel oils for industrial heating purposes in a manner that resulta in acceptable particulate emissions, despite a high sul~ur content, a high Con Carbon residue and/or high asphalten~
content.
In the area of related proble~s, it is known in the art that the use of specific additives in certain hydrocarbon fuels, can reduce smoke or soot upon combus-tion, in certain instances. It is also known to use specific additives in fuels to inhibit corrosion, inhibit slag formation in boilers and to reduce the deleterious efect of vanadium present in such fuels.
However, it has not been shown to use selected additives to reduce particulate emission during combustion of residual fuel oil, and particularly No. 6 fuel oil.
;Summary of Invention ;~t has unexpectedly been~found that by adding a selected oil soluble zirconium salt of an alcohol/phenol or sulfonate to a residual fuel oil, and particularly ~o.
.20 6 fuel oil the amount o~ particulate matt~r formed during combustion can be significantly reduced in ~mounts of 10 to 25 p~rcent or greater.
In accordance with this in~ention, there is provided a process for reducin~ the amount of particulate matter ormed during the combustion o a residual fuel oil which comprises combusting a residual ~uel oil which con-tains an effective amount of an additive selected from the group consisting o~:
n oil soluble zirconium salt of an alcohol or phenol havin~ the ~ormula:
ROH
where R is a hydrocarbyl group of 2 to 24 carbon atoms: i or (ii) an oil soluble zirconium salt of a sulfonic acid having the formula:
.~
_ 3 ~8~
where R is an alkyl, cycloalkyl, aryl, alk~ry1, or ar~lk~l group and said salt has a molecular ~"ei~ht of about 100 to about 2500;
said amount bein~ effective in reducing the amount of particulate matter formed during combustion In another aspect the invention provides a com-position comprising a residual fuel oil and an effective trace amount of the additive previously described.
DESCRIPTION OF THE INVENTION AND PREFERRED EMBODIMENTS
- .. ... ~ .
10The novelty of the present invention resides in the discovery that zirconium salts of certain alcohols/
phenols or sulfonic acids exert a beneficial efect on ; residual fuel oil, particularly No. 6 fuel oil/ in reducing the amount of particulate matter formed during combustion. The term nresidual fuel oil" as used herein, is well-known and as described hereinabove, and includes Grades No. 4, No. 5 and No. 6 residual fuel oils, mee~ing tha specifications o ASTM D-396. Particularly preferred is No. 6 fuel oil.
20The reason these particular zirconium additives exhibit this surprising effect is not clearly understood.
It may be that the subject compounds promote and acti-vate the complete oxidation of hydrocarbon and sulfur-containing constituents in the fuel ~o volatile or gaseous compounds during combustion, in a highly specific mannerO
The subject zirconium salts or compounds~ also termed "additives~ herein, opera~ive in the instant in-vention, comprise oil soluble zirconium sal~s of an alcohol/phenol or sulfonate~ The zirconium salt of 30selected alcohols or phenols will be a 2irconium salt of an alcohol or phenol having the formula:
ROH
where R is a hydrocarbyl group o 2 to 2~ carbon atoms.
More particularly R is a branched or unbranched, hydro-carbyl group preferably having 2 to 13 carbon atoms.
Preferred compounds are those where R is a sa~urated or Z3~5 1 unsaturated aliphatic group having 2 to 8 and more pce~er-2 ably 3 to 4 carbons. Most preferred are those coMpounds 3 where R is a saturated aliphatic group, and particularl~
4 those having 3 to 4 carbons. Compounds of this t<Jpe include R groups which may be alkyl, aryl, alkar~l, 6 aralkyl and alkenyl. Illustrative alcohol or phenol 7 compounds oE this type include ethanol, propanol, butanol, 8 hexanol, decanol, octadecanol, eicosanol, phenol, benzyl 9 alcohol, xylenol, naphtholv ethyl phenol, crotyl alcohol etc. Further information and description of the useful 11 alcohols of this type may be found in Kirk-Othmer, 12 "Encyclopedia of Chemical Technology" ~econd Edition, 13 1963, Vol 1, pp 531-&38.
14 The zirconium salt of sulfonic acids useful in this invention are the zirconium salts of sulfonic acids 16 having the formula:
18 where R is a hydrocarbyl group having 2 to 200 and prefer-19 ably 10 to 60 car~on atoms. More particularly, the R
group in said sulfonic acids will be an alkyl, cycloalkyl, 21 aryl, alkaryl or aralkyl and said salt ~ill have a molec-22 ular weight of about 100 to about 2500, preferably about 23 200 to about 700.
24 The sulfonic acids are characterized by the presence o~ the sulfo group -SO3H (or -SO2OH) and can 26 be considered derivatives of sulfuric acid with one oE the ~7 hydroxyl groups replaced by an organic radical. Compounds 28 of this type are 9enerally obtained by the treatment of 29 petroleum fractions (petroleum sulfonates). Because of the varying natures of crude oils and the particular oil 31 fraction used, sulfonates generally constitute a complex 32 mixture and it is best to define them in a general manner 33 giving the molecular weight as defined above. Partic-34 ularly preferred sulfonates are those having an alkaryl group, i.g. alkylated benzene or alkylated naphtalene.
36 Illustrative examples of sulfonic acids useful 372~S
in this invention are: dioctyl benzene sulfonic acicl, 2 dodecyl benzene sulfonic acid, didodecyl ben-zelle sulfonic 3 acid, dinonyl naphthalene sulfonic acid, dilauryl benzsne 4 sulfonic acid~ lauryl cetyl benzene sulfonic acid, pol~-
14 The zirconium salt of sulfonic acids useful in this invention are the zirconium salts of sulfonic acids 16 having the formula:
18 where R is a hydrocarbyl group having 2 to 200 and prefer-19 ably 10 to 60 car~on atoms. More particularly, the R
group in said sulfonic acids will be an alkyl, cycloalkyl, 21 aryl, alkaryl or aralkyl and said salt ~ill have a molec-22 ular weight of about 100 to about 2500, preferably about 23 200 to about 700.
24 The sulfonic acids are characterized by the presence o~ the sulfo group -SO3H (or -SO2OH) and can 26 be considered derivatives of sulfuric acid with one oE the ~7 hydroxyl groups replaced by an organic radical. Compounds 28 of this type are 9enerally obtained by the treatment of 29 petroleum fractions (petroleum sulfonates). Because of the varying natures of crude oils and the particular oil 31 fraction used, sulfonates generally constitute a complex 32 mixture and it is best to define them in a general manner 33 giving the molecular weight as defined above. Partic-34 ularly preferred sulfonates are those having an alkaryl group, i.g. alkylated benzene or alkylated naphtalene.
36 Illustrative examples of sulfonic acids useful 372~S
in this invention are: dioctyl benzene sulfonic acicl, 2 dodecyl benzene sulfonic acid, didodecyl ben-zelle sulfonic 3 acid, dinonyl naphthalene sulfonic acid, dilauryl benzsne 4 sulfonic acid~ lauryl cetyl benzene sulfonic acid, pol~-
5 ole~in alkylated benzene sulfonic acid such as pol~-
6 butylene and polypropylene, etc. Further details regard-
7 ing sulfonic acids may be found in Kirk-Othmer, "Encylo-~ pedia of Chemical Technology", Second Edition, 1969, g Vol. 19, pp 311 to 319 and in NPetroieum Sulphonates'1 by 10 R. Leslie in Manufacturing Chemist, October 1950 (XXl, 10) 11 pp 417 to 422.
12 Methods of preparing the subject zirconium salts 13 described above are well known in the art and generally 1~ said salts are commercially available.
The zirconium additive is incorporated into the 16 residual fuel oil by dissolving therein. This is accom-17 plished by conventional methods as by heating, stirring 18 and the like.
19 The amount of zirconium additive to be used is 20 an "effective trace amount" that will reduce the amount of 21 particulate matter formed during combustion of the resi-22 dual fuel oil as compared to the combustion o said fuel 23 oil in the absence of said additive. By the term "effec-24 tive trace amount" is quantitatively meant an amount of 25 about 1 to 1000 ppm by weight and preferably 10-500 ppm 26 by weight, 2irconium additive, taken as metallic zirconium, 27 in said fuel oil, and particularly preferred about 50 to 28 150 ppm by weight zirconium additive, taken as metallic 29 zirconium, in said uel oil. However, lower and higher 30 amounts than the 1-1000 ppm range can also be present 31 provided an effective trace amount, as defined herein, is 32 present in the residual fuel oil.
33 By the term "reduce the amount of particulate 3~ matter formed during combustion", as used herein, is meant 35 that at least about a Eive percent reduction in formed 36 particulate matter, and preferably from about 10 to 25 37 percent and greater, reduction in formed particulate 38 matter is achieved as compared to the combustion of the ~g ~37~35 1 residual fuel oil in the absence of the subjec~ zirconium 2 additive.
3 In the process, the fuel oil containing said ~ additive is generally mixed with ox~gen, usuall~ in the form of air, to form a fuel/air mixture prior to combus-6 tion. Generally, the amount of air utilized is an excess 7 over the stoichiometric amount to completely combust the
12 Methods of preparing the subject zirconium salts 13 described above are well known in the art and generally 1~ said salts are commercially available.
The zirconium additive is incorporated into the 16 residual fuel oil by dissolving therein. This is accom-17 plished by conventional methods as by heating, stirring 18 and the like.
19 The amount of zirconium additive to be used is 20 an "effective trace amount" that will reduce the amount of 21 particulate matter formed during combustion of the resi-22 dual fuel oil as compared to the combustion o said fuel 23 oil in the absence of said additive. By the term "effec-24 tive trace amount" is quantitatively meant an amount of 25 about 1 to 1000 ppm by weight and preferably 10-500 ppm 26 by weight, 2irconium additive, taken as metallic zirconium, 27 in said fuel oil, and particularly preferred about 50 to 28 150 ppm by weight zirconium additive, taken as metallic 29 zirconium, in said uel oil. However, lower and higher 30 amounts than the 1-1000 ppm range can also be present 31 provided an effective trace amount, as defined herein, is 32 present in the residual fuel oil.
33 By the term "reduce the amount of particulate 3~ matter formed during combustion", as used herein, is meant 35 that at least about a Eive percent reduction in formed 36 particulate matter, and preferably from about 10 to 25 37 percent and greater, reduction in formed particulate 38 matter is achieved as compared to the combustion of the ~g ~37~35 1 residual fuel oil in the absence of the subjec~ zirconium 2 additive.
3 In the process, the fuel oil containing said ~ additive is generally mixed with ox~gen, usuall~ in the form of air, to form a fuel/air mixture prior to combus-6 tion. Generally, the amount of air utilized is an excess 7 over the stoichiometric amount to completely combust the
8 fuel oil to carbon dioxide and water. The reason for g utilizing this excess is that complete mixing does not always occur between the fuel oil and the air, and that 11 also a slight excess of air is desirable since it serves 12 to reduce the tendency of soot and smoke formation during 13 combustion. Generally, the excess of air used is about 2 14 to 35 percent (0.4 to 7 percent basad on oxygen) over the stoichiometric amount depending upon the actual 16 end-use conditions which may vary considerably from one 17 type of industrial boiler to the next. One disadvantage 18 in using a large excess of air is that a greater amount of 19 heat is lost through entrainment that would otherwise be utilized for direct heating purposes. We have found 21 that by use of the subject zirconium additives, less 22 excess air is required to reduce smoke and soot formation 23 and thus the heating efficiency of the residual fuel oil 24 is greater, as well as resulting in a reduction of par-ticulate emission.
26 The above-described step of mixing fuel oil and 27 air is conventional and is usually accomplished for 28 example, by steam or air atomi~ation to produce a fine 29 spray which is then combusted to maintain and support a flame. The combustion is controlled and conducted 31 at a particular "firing rate" which is usually expressed 32 as lbs/minute of fuel oil combusted.
33 The combustion of residual fuel oil is usually 3~ carried out in conventional industrial boilers, utility boilers, refinery furnaces and the like.
36 The amount of particulate matter formed during 37 combustion of residual fuel oil will vary over a broad 38 range and is dependent upon a number of factors such as 37Z~
1 type of boiler, boiler size, nuMber and tt~pe of burners, 2 source of the residual fuel oil used, amount o~ e~cess air 3 or oxy~en, firing rate and the like. Generall~, the 4 amount of particulate matter formed wilL be in the range of about O.01 to l.O weight percent of the fuel oil used 6 and higher. One weight percent corresponds to one gram 7 particulate matter formed from the combustion of 100 grams 8 of fuel oil. The amount of particulate matter formed, g herein termed "total particulate matter ,n is actually the sum of two separate measurements; "tube-deposits,'l the 11 amount of particulate matter deposited inside of the 12 boiler, and two, ~filtered stack particulate," which is 13 the amount of particulate matter formed which escapes the 1~ boiler and is actually emitted out of the stack into the air. EPA measurements are generally only concerned 16 with filtered stack particulate which is directly released 17 into the air environment and contributes to a decrease in 18 air quality. However, "tube deposits" lead to corrosion 19 of the equipment, frequent "clean-outs~ and add to the total opera~ing costs. Furthermore, as tube deposits 21 collect on the inside of the apparatus, a critical crust 22 thickness is reached and ~urther tube deposits are then 23 entrained in stack particulate, which signiicantly 24 increases th~ amount of particulate emission. Thus r in order to fully assess the overall operating advantages of 26 a particular residual fuel oil in a boiler operation, the 27 amount of tube deposits should also be considered, as well 28 as total stack particulate for compliance with emission 29 standards~
The amount o allowed stack particulate will 1 vary from state to state and is also subject to a minimum 32 amount allowed under Federal EPA standards. For example, i 33 in Florida, the currently allowable limit for existing power plants is 0.10 lbs. particulate emission per million BTU, which is equi~alent to about 0.185 weight percent of 36 particulate stack emission per weight of combusted fuel 37 oil. Since the allowable emission standards will vary 38 from jurisdiction to jurisdiction, dif~erin~ amounts of the subject zirconium additive will be necessar~ to 2 produce a residual fuel oil composition in compliance ~/ith 3 those standards.
4 Measurement of the amount of "stack particulate matter" is conducted by EPA Method t~5 Stack Sampling 6 System, "Determination of Particulate Emissions from 7 Stationary Sources" and is described in the Federal 8 Register~
g The particulate stack emissions are generally comprised of particulate carbon, sulfur-containing hydro-11 carbons, inorganic sulfates and the like.
12 The following examples are illustrative of this 13 invention and should not be construed as being limitations 14 on the scope and spirit of such invention.
Example 1 16 Combustion runs were carried out in a 50 horse-17 power ABCO, 2-pass, water jacketed forced draft boiler 18 with an air-atomizing burner and a nominal firing rate of g 1.2 lbs/min. of residual fuel oil. The boiler was modi-fied so that closure on each end could be opened easily 21 for recovery of deposits laid down in the boiler. TS~1Q
22 other modifications included installation o a second fuel 23 system so the boiler could be heated to operating tempera-24 tures on No. 2 oil and then switched over to the test fuel without shutting down or upsetting the boiler operation 26 unduly and installation of a two foot length of firebrick 27 linin~ at the burner end of the iretube and a Cleaver-28 Brooks noz~le assembly in place o the Monarch nozzle~
29 These modifications eliminated oil pooling and rapid carbon deposits on the firetube walls when residual uel 31 was fired. The first pass is a ~9 cm (18.375 in.) diameter 32 x 178 cm ~5 ft. 10 in~) long fire tube; the second pass 33 consists of 52 tubes each ~ cm (2.375 in.) diameter x 188 34 cm (6 ft. 2 in.) lon~.
Atomization of the fuel was accomplished using a 3~ low pressure air-atomizing nozzle. Viscosity of the fuel 37 oil a~ the nozzle was maintained at 30 centistokes by 38 heatin~ the oil to a predetermined temperature (about ~37~8~i;
1 105C). Prior to contacting the burner gun, the a~oM-2 ized fue~ oil was mixed with a meas~lred amount of excess 3 "secondary" air which was forced through a diffuser 4 plate to insure efficient combustion. The secondary air was provided by a centrifugal blower mounted in the boiler 6 head. The amount of secondary air was controlled by means 7 of a damper which was regul3ted to keep the oxygen level 8 in the atomized fuel at about 1.5% in excess (over that
26 The above-described step of mixing fuel oil and 27 air is conventional and is usually accomplished for 28 example, by steam or air atomi~ation to produce a fine 29 spray which is then combusted to maintain and support a flame. The combustion is controlled and conducted 31 at a particular "firing rate" which is usually expressed 32 as lbs/minute of fuel oil combusted.
33 The combustion of residual fuel oil is usually 3~ carried out in conventional industrial boilers, utility boilers, refinery furnaces and the like.
36 The amount of particulate matter formed during 37 combustion of residual fuel oil will vary over a broad 38 range and is dependent upon a number of factors such as 37Z~
1 type of boiler, boiler size, nuMber and tt~pe of burners, 2 source of the residual fuel oil used, amount o~ e~cess air 3 or oxy~en, firing rate and the like. Generall~, the 4 amount of particulate matter formed wilL be in the range of about O.01 to l.O weight percent of the fuel oil used 6 and higher. One weight percent corresponds to one gram 7 particulate matter formed from the combustion of 100 grams 8 of fuel oil. The amount of particulate matter formed, g herein termed "total particulate matter ,n is actually the sum of two separate measurements; "tube-deposits,'l the 11 amount of particulate matter deposited inside of the 12 boiler, and two, ~filtered stack particulate," which is 13 the amount of particulate matter formed which escapes the 1~ boiler and is actually emitted out of the stack into the air. EPA measurements are generally only concerned 16 with filtered stack particulate which is directly released 17 into the air environment and contributes to a decrease in 18 air quality. However, "tube deposits" lead to corrosion 19 of the equipment, frequent "clean-outs~ and add to the total opera~ing costs. Furthermore, as tube deposits 21 collect on the inside of the apparatus, a critical crust 22 thickness is reached and ~urther tube deposits are then 23 entrained in stack particulate, which signiicantly 24 increases th~ amount of particulate emission. Thus r in order to fully assess the overall operating advantages of 26 a particular residual fuel oil in a boiler operation, the 27 amount of tube deposits should also be considered, as well 28 as total stack particulate for compliance with emission 29 standards~
The amount o allowed stack particulate will 1 vary from state to state and is also subject to a minimum 32 amount allowed under Federal EPA standards. For example, i 33 in Florida, the currently allowable limit for existing power plants is 0.10 lbs. particulate emission per million BTU, which is equi~alent to about 0.185 weight percent of 36 particulate stack emission per weight of combusted fuel 37 oil. Since the allowable emission standards will vary 38 from jurisdiction to jurisdiction, dif~erin~ amounts of the subject zirconium additive will be necessar~ to 2 produce a residual fuel oil composition in compliance ~/ith 3 those standards.
4 Measurement of the amount of "stack particulate matter" is conducted by EPA Method t~5 Stack Sampling 6 System, "Determination of Particulate Emissions from 7 Stationary Sources" and is described in the Federal 8 Register~
g The particulate stack emissions are generally comprised of particulate carbon, sulfur-containing hydro-11 carbons, inorganic sulfates and the like.
12 The following examples are illustrative of this 13 invention and should not be construed as being limitations 14 on the scope and spirit of such invention.
Example 1 16 Combustion runs were carried out in a 50 horse-17 power ABCO, 2-pass, water jacketed forced draft boiler 18 with an air-atomizing burner and a nominal firing rate of g 1.2 lbs/min. of residual fuel oil. The boiler was modi-fied so that closure on each end could be opened easily 21 for recovery of deposits laid down in the boiler. TS~1Q
22 other modifications included installation o a second fuel 23 system so the boiler could be heated to operating tempera-24 tures on No. 2 oil and then switched over to the test fuel without shutting down or upsetting the boiler operation 26 unduly and installation of a two foot length of firebrick 27 linin~ at the burner end of the iretube and a Cleaver-28 Brooks noz~le assembly in place o the Monarch nozzle~
29 These modifications eliminated oil pooling and rapid carbon deposits on the firetube walls when residual uel 31 was fired. The first pass is a ~9 cm (18.375 in.) diameter 32 x 178 cm ~5 ft. 10 in~) long fire tube; the second pass 33 consists of 52 tubes each ~ cm (2.375 in.) diameter x 188 34 cm (6 ft. 2 in.) lon~.
Atomization of the fuel was accomplished using a 3~ low pressure air-atomizing nozzle. Viscosity of the fuel 37 oil a~ the nozzle was maintained at 30 centistokes by 38 heatin~ the oil to a predetermined temperature (about ~37~8~i;
1 105C). Prior to contacting the burner gun, the a~oM-2 ized fue~ oil was mixed with a meas~lred amount of excess 3 "secondary" air which was forced through a diffuser 4 plate to insure efficient combustion. The secondary air was provided by a centrifugal blower mounted in the boiler 6 head. The amount of secondary air was controlled by means 7 of a damper which was regul3ted to keep the oxygen level 8 in the atomized fuel at about 1.5% in excess (over that
9 needed stoichiometrically to completely combust the fuel).
A run was started by firing the boiler and 11 heating it to operating temperature or 55 minutes using 12 No. ~ oil. The feed was then switched to test fuel and 13 after allowing suficient time for conditions to stabilize 14 (about 25 minutes) samples of about 10 minutes duration were collected isokinetically from the stack on tared, 16 Gelman, Type A (20.3 x 25.4 cm) fiber glass filters. The 17 test fuel was a No. 6 fuel oil.
18 Total particulate matter formed was determined 19 by adding the amount of Stack particulate measured iso-kinetically (EPA Method 5 Stack Sampling System) to the 21 amount deposited in the tubes of the boiler i.e. "tube 22 deposits".
23 The EPA Method 5 Stack Sampling System was 29 conducted with a commercially available system for this purpose. This unit consisted of an 18-inch glass lined 26 probe, a cyclone, a 125 mm glass fiber filter and four 27 impingers. ~he first two impingers contained water, the 28 third was empty and the last one contained silica gel.
29 With the exception o the impingers, the entire sampling train was ~aintained at about 175C to insure that the 31 stack gases entering the sampling system were above 32 the H2S04 dew point.
33 The deposits laid down in each of the 52 tubes 34 is collected on a separate, tared 20.3 x 25.4 cm fiber-glass filter. Deposits are collected by positioning a 36 specially-designed filter holder against the end o each 37 tube in turn, pulling air through the tube and the filter 38 using a high-volume vacuum pump and manually brushing the ~ ~t372~35 1 tube from end-to-end ten times with a 2.50 inch diameter 2 wire shank brush. The brush is mounted on a 8 ft. long, 3 0.25 in. diam. SS rod driven by an electric drlll. This 4 method gives almost 100% recovery of the deposits laid down in the tubes. All the tubes are sampled because for 6 a given run there are large differences in deposit weight 7 from tube-to-tube in each row of tubes across the boiler 8 and from top row to bottom row and there is no consistent g ratio of the weight of deposit collected from a given tube from run-to-run.
11 The fuel oil used (Test Fuel) in the runs 12 analyzed for the following constituents:
13 Analysis of Test Fuel 14 Sulfur 2.0 wt~
ConCarbona14.8 wt%
16 Ashb .1 wt~
17 ~anadium469 ppm 18 Nickel 70 ppm 19 Iron 2.9 ppm aASTM-D-189 21 bASTM-D-482 22 The zirconium additive used in tbe run was 23 zirconium propoxide an alcohol salt and was present in a 24 concentration of 100 ppm taken as metallic zirconium.
For test fuel alonel the stack particulate was 26 0~34 wt~ on uel, while the tube deposits was 0.20 wt% on 27 fuel for a total test particulate wt% of 0.54. The sample 28 o fuel containing the zirconium propoxide measured a ~9 stack particulate of 0.24 wt~ on uel and tube deposits of 0.16 wt% on fuel for a total particulata wt% of 0.40. The 31 improvement in usin~ the zirconium additives was a reduc-2 tion in total particulates of 25.9%.
Example 2 34 Following the same general procedure and using the ABC0 boiler described in Example 1 r a sample run using 36 100 ppm of a zirconium sulfonate additive, i.e. zirconium 1 salt of dodecyl benzene sulfonic acid, ~"as made with the 2 same No. 6 fuel oil as in said Example 1.
3 The results for the sample containing zirconiurn 4 sulfonate were a stack particulate of 0.29 wt~ on ~uel and tube deposlts of 0.18 wt~ on fuel for a total particulate 6 of 0.47 wt% on fuel. The improvement in using the zir-7 conium additive was a reduction in total particulate of 8 13.0 %.
A run was started by firing the boiler and 11 heating it to operating temperature or 55 minutes using 12 No. ~ oil. The feed was then switched to test fuel and 13 after allowing suficient time for conditions to stabilize 14 (about 25 minutes) samples of about 10 minutes duration were collected isokinetically from the stack on tared, 16 Gelman, Type A (20.3 x 25.4 cm) fiber glass filters. The 17 test fuel was a No. 6 fuel oil.
18 Total particulate matter formed was determined 19 by adding the amount of Stack particulate measured iso-kinetically (EPA Method 5 Stack Sampling System) to the 21 amount deposited in the tubes of the boiler i.e. "tube 22 deposits".
23 The EPA Method 5 Stack Sampling System was 29 conducted with a commercially available system for this purpose. This unit consisted of an 18-inch glass lined 26 probe, a cyclone, a 125 mm glass fiber filter and four 27 impingers. ~he first two impingers contained water, the 28 third was empty and the last one contained silica gel.
29 With the exception o the impingers, the entire sampling train was ~aintained at about 175C to insure that the 31 stack gases entering the sampling system were above 32 the H2S04 dew point.
33 The deposits laid down in each of the 52 tubes 34 is collected on a separate, tared 20.3 x 25.4 cm fiber-glass filter. Deposits are collected by positioning a 36 specially-designed filter holder against the end o each 37 tube in turn, pulling air through the tube and the filter 38 using a high-volume vacuum pump and manually brushing the ~ ~t372~35 1 tube from end-to-end ten times with a 2.50 inch diameter 2 wire shank brush. The brush is mounted on a 8 ft. long, 3 0.25 in. diam. SS rod driven by an electric drlll. This 4 method gives almost 100% recovery of the deposits laid down in the tubes. All the tubes are sampled because for 6 a given run there are large differences in deposit weight 7 from tube-to-tube in each row of tubes across the boiler 8 and from top row to bottom row and there is no consistent g ratio of the weight of deposit collected from a given tube from run-to-run.
11 The fuel oil used (Test Fuel) in the runs 12 analyzed for the following constituents:
13 Analysis of Test Fuel 14 Sulfur 2.0 wt~
ConCarbona14.8 wt%
16 Ashb .1 wt~
17 ~anadium469 ppm 18 Nickel 70 ppm 19 Iron 2.9 ppm aASTM-D-189 21 bASTM-D-482 22 The zirconium additive used in tbe run was 23 zirconium propoxide an alcohol salt and was present in a 24 concentration of 100 ppm taken as metallic zirconium.
For test fuel alonel the stack particulate was 26 0~34 wt~ on uel, while the tube deposits was 0.20 wt% on 27 fuel for a total test particulate wt% of 0.54. The sample 28 o fuel containing the zirconium propoxide measured a ~9 stack particulate of 0.24 wt~ on uel and tube deposits of 0.16 wt% on fuel for a total particulata wt% of 0.40. The 31 improvement in usin~ the zirconium additives was a reduc-2 tion in total particulates of 25.9%.
Example 2 34 Following the same general procedure and using the ABC0 boiler described in Example 1 r a sample run using 36 100 ppm of a zirconium sulfonate additive, i.e. zirconium 1 salt of dodecyl benzene sulfonic acid, ~"as made with the 2 same No. 6 fuel oil as in said Example 1.
3 The results for the sample containing zirconiurn 4 sulfonate were a stack particulate of 0.29 wt~ on ~uel and tube deposlts of 0.18 wt~ on fuel for a total particulate 6 of 0.47 wt% on fuel. The improvement in using the zir-7 conium additive was a reduction in total particulate of 8 13.0 %.
Claims (11)
EXCLUSIVE PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS
FOLLOWS:
1. A process for reducing the amount of particulate matter formed during the combustion of a residual fuel oil which comprises combusting a residual fuel oil which contains an effective amount of an additive selected from the group consisting of:
(i) an oil soluble zirconium salt of an alcohol or phenol having the formula:
ROH
where R is a hydrocarbyl group of 2 to 24 carbon atoms: or (ii) an oil soluble zirconium salt of a sulfonic acid having the formula:
where R is an alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group and said salt has a molecular weight of about 100 to about 2500;
said amount being effective in reducing the amount of particulate matter formed during combustion.
(i) an oil soluble zirconium salt of an alcohol or phenol having the formula:
ROH
where R is a hydrocarbyl group of 2 to 24 carbon atoms: or (ii) an oil soluble zirconium salt of a sulfonic acid having the formula:
where R is an alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group and said salt has a molecular weight of about 100 to about 2500;
said amount being effective in reducing the amount of particulate matter formed during combustion.
2. The process of claim 1 wherein said additive is present in said fuel oil is an amount of about 1 to about 1000 ppm by weight, taken as metallic zirconium.
3. The process of claim 2 wherein said fuel oil is No. 6 fuel oil.
4. The process of claim 3 wherein said fuel oil contains above about 1 weight percent sulfur.
5. The process Of claim 1 wherein the R group in said alcohol salt is a saturated or unsaturated ali-phatic group having 2 to 8 carbons.
6. The process of claim 5 wherein said additive is present in said fuel oil in an amount of about 1 to about 1000 ppm by weight, taken as metallic zirconium.
7. The process of claim 6 wherein said fuel oil is No. 6 fuel oil.
8. The process of claim 1 wherein the R group in said sulfonic acid is an alkaryl group and the salt has a molecular weight of about 200 to about 700.
9. The process of claim 8 wherein said additive is present in said fuel oil in an amount of about 1 to about 1000 ppm by weight, taken as metallic zirconium.
10. The process of claim 9 wherein said fuel oil is No. 6 fuel oil.
11. A composition comprising a residual fuel oil and an effective trace amount of an additive selected from the group consisting of:
(i) an oil soluble zirconium salt of an alcohol or phenol having the formula:
ROH
where R is a hydrocarbyl group of 2 to 24 carbon atoms: or (ii) an oil soluble zirconium salt of a sulfonic acid having the formula:
where R is an alkyl, cycloalkyl, aryl r alkaryl or aralkyl group and said salt has a molecular weight of about 100 to about 2500;
said amount being effective in reducing the amount of particulate matter formed during combustion of said fuel oil.
(i) an oil soluble zirconium salt of an alcohol or phenol having the formula:
ROH
where R is a hydrocarbyl group of 2 to 24 carbon atoms: or (ii) an oil soluble zirconium salt of a sulfonic acid having the formula:
where R is an alkyl, cycloalkyl, aryl r alkaryl or aralkyl group and said salt has a molecular weight of about 100 to about 2500;
said amount being effective in reducing the amount of particulate matter formed during combustion of said fuel oil.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29601681A | 1981-08-25 | 1981-08-25 | |
| US296,016 | 1981-08-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1187285A true CA1187285A (en) | 1985-05-21 |
Family
ID=23140238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000407533A Expired CA1187285A (en) | 1981-08-25 | 1982-07-19 | Zirconium additives for residual fuel oil |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0073615B1 (en) |
| JP (1) | JPS5842692A (en) |
| AU (1) | AU546503B2 (en) |
| CA (1) | CA1187285A (en) |
| DE (1) | DE3271555D1 (en) |
| DK (1) | DK380782A (en) |
| ES (1) | ES8400479A1 (en) |
| NO (1) | NO157788C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4462810A (en) * | 1983-08-17 | 1984-07-31 | Exxon Research & Engineering Co. | Zirconium-cerium additives for residual fuel oil |
| DE3781557T2 (en) * | 1986-10-02 | 1993-03-18 | Lubrizol Corp | TATANIUM AND ZIRCONIUM COMPLEXES AND FUEL COMPOSITIONS. |
| US5360459A (en) | 1991-05-13 | 1994-11-01 | The Lubrizol Corporation | Copper-containing organometallic complexes and concentrates and diesel fuels containing same |
| US5344467A (en) | 1991-05-13 | 1994-09-06 | The Lubrizol Corporation | Organometallic complex-antioxidant combinations, and concentrates and diesel fuels containing same |
| TW230781B (en) | 1991-05-13 | 1994-09-21 | Lubysu Co | |
| IL100669A0 (en) | 1991-05-13 | 1992-09-06 | Lubrizol Corp | Low-sulfur diesel fuel containing organometallic complexes |
| US5376154A (en) | 1991-05-13 | 1994-12-27 | The Lubrizol Corporation | Low-sulfur diesel fuels containing organometallic complexes |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB837407A (en) * | 1958-02-26 | 1960-06-15 | Exxon Research Engineering Co | Improvement to the properties of fuel oils |
| DE2316230A1 (en) * | 1972-04-10 | 1973-10-18 | Drew Chem Corp | HEATING OIL ADDITIVE |
| US4297110A (en) * | 1980-03-31 | 1981-10-27 | Exxon Research & Engineering Co. | Zirconium additives for residual fuel oil |
-
1982
- 1982-07-19 CA CA000407533A patent/CA1187285A/en not_active Expired
- 1982-08-11 NO NO822742A patent/NO157788C/en unknown
- 1982-08-20 EP EP82304401A patent/EP0073615B1/en not_active Expired
- 1982-08-20 DE DE8282304401T patent/DE3271555D1/en not_active Expired
- 1982-08-24 ES ES515204A patent/ES8400479A1/en not_active Expired
- 1982-08-25 DK DK380782A patent/DK380782A/en not_active Application Discontinuation
- 1982-08-25 AU AU87574/82A patent/AU546503B2/en not_active Ceased
- 1982-08-25 JP JP57146325A patent/JPS5842692A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NO157788B (en) | 1988-02-08 |
| ES515204A0 (en) | 1983-10-16 |
| JPS5842692A (en) | 1983-03-12 |
| EP0073615B1 (en) | 1986-06-04 |
| NO157788C (en) | 1988-05-25 |
| EP0073615A3 (en) | 1983-04-20 |
| DK380782A (en) | 1983-02-26 |
| DE3271555D1 (en) | 1986-07-10 |
| EP0073615A2 (en) | 1983-03-09 |
| AU8757482A (en) | 1983-03-03 |
| ES8400479A1 (en) | 1983-10-16 |
| AU546503B2 (en) | 1985-09-05 |
| NO822742L (en) | 1983-02-28 |
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| MKEC | Expiry (correction) | ||
| MKEX | Expiry |