EP0359390A1 - Improved combustion of liquid hydrocarbons - Google Patents
Improved combustion of liquid hydrocarbons Download PDFInfo
- Publication number
- EP0359390A1 EP0359390A1 EP89308075A EP89308075A EP0359390A1 EP 0359390 A1 EP0359390 A1 EP 0359390A1 EP 89308075 A EP89308075 A EP 89308075A EP 89308075 A EP89308075 A EP 89308075A EP 0359390 A1 EP0359390 A1 EP 0359390A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- combustion
- oil
- additive
- oils
- ppm
- 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.)
- Withdrawn
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
- C10L1/30—Organic compounds compounds not mentioned before (complexes)
- C10L1/305—Organic compounds compounds not mentioned before (complexes) organo-metallic compounds (containing a metal to carbon bond)
Definitions
- This invention relates to improvements in the combustion of liquid hydrocarbons and consequent reduction in N0 x emissions
- Liquid hydrocarbons are widely used in open flame and internal combustion devices such as oil fired burners and internal combustion engines.
- One of the common problems associated with such combustion devices is the emission of N0 x .
- Many attempts have been made in the past to reduce N0 x emissions but these normally have resulted in reduction of combustion efficiency.
- Oil fired furnaces and boiler arrangements are used world-wide in producing heat and electricity. Normally, petroleum distillates such as fuel oils are used in such oil fired burners. It is highly unusual to burn directly mined crude oil because of the considerable increase in pollutants in the combustion of the products, particularly soot emissions.
- additives may be included in organic materials which are used in oil fired furnaces and the like.
- a particularly suitable additive is ferrocene which is one of many of dicyclopentadienyl iron compounds. Examples of these additive constituents are disclosed in United States patent 3,535,356.
- United States patent 3,341,211 discloses the use of ferrocene in liquid hydrocarbon fuel oils.
- the purpose of the ferrocene is to improve the ignition and combustion characteristics of the fuel.
- a process for burning liquid hydrocarbons in a furnace while maintaining acceptable levels of N0 x emissions, said liquid hydrocarbons having a Conradson carbon content greater than 1% comprising:
- This invention is applicable in improving combustion of a variety of liquid hydrocarbons, either in open flame or internal combustion.
- open flame include various burner systems such as oil fired burners used in heating devices.
- various types of internal combustion devices which include the variety of gasoline engines as well as jet engines.
- the liquid hydrocarbons as burned in either open flame or internal combustion may be selected from a variety of groups.
- the various types of liquid hydrocarbons may be petroleum distillates designed for combustion or may be waste material of hydrocarbon base.
- the invention is particularly suited to burning hydrocarbons selected from the group consisting of gasolines and other petroleum products including lubricating oils, turbine oils, transformer oils, kerosines, jet fuels, fuel oils, greases and asphalts.
- the crude oil is treated in preparation for injection through an oil fired burner.
- Such treatment may include any necessary dilution of the crude oils with combustible solvents and/or heating of the crude oils to reduce the viscosity.
- a holding tank arrangement provided to store the crude oil.
- the crude oil may or may not be treated in the holding tanks.
- the crude oil is removed from the holding tanks and placed in a temporary storage tank where the smaller quantity can then be treated with suitable solvents if needed and heated if desired.
- the treated crude oil is then delivered to the oil fired burner by use of suitable pumps and piping arrangement.
- the additive composition is introduced to the crude oil before combustion of the crude oil in the oil fired burner.
- the additive composition is introduced normally to the crude oil, either in the temporary storage tank where the crude oil is initially treated or injected into the piping which delivers the crude oil to the oil fired burner.
- an injection nozzle may be included with the oil fired burner where the additive composition in an atomized form is sprayed with the crude oil as the crude oil atomized in preparation for combustion.
- a sufficient amount of the additive composition is included in the crude oil to improve measurably combustion efficiency in burning the oil.
- the additive composition comprises:
- alkyl refers to an alkyl group branched or straight chain of 1 to 10 carbon atoms, such as methyl, ethyl, propyl, n-butyl, hexyl, or heptyl.
- cycloalkyl refers to a lower cycloalkyl group of 3 to 7 atoms, such as cyclopentadyl or cyclohexyl.
- aryl refers to an organic radical derived from an aromatic compound by the removal of one hydrogen atom. Such compounds include phenyl and substituted phenyl such as lower alkyl substituted phenyl.
- heterocyclic refers to pyrrol, pyridyl, furfuryl and the like.
- the aryl or heterocyclic group generally contains up to about 15 carbon atoms.
- Dicyclopentadienyliron is commonly referred to as "ferrocene".
- the compounds of the above formula I are considered to be ferrocene and its derivatives.
- the preferred compounds of Formula I include dicyclopentadienyliron, di(methylcyclo-pentadienyl)iron, di(ethylcyclopentadienyl)iron, methylferrocene, ethylferrocene, n-butylferrocene, dihexylferrocene, phenylferrocene, m-tolyferrocene, didecylferrocene, dicyclohexylferrocene and dicyclopentylferrocene.
- the organic carrier is of a type in which the selected dicyclopentadienyl iron compound is soluble. Furthermore, the carrier liquid has a high flash point and is of a viscosity at operating temperatures to enable injection when required through the injection nozzles. Preferably, the flash point of the carrier liquid is in excess of 74°F and has a boiling point in excess of 95°F.
- the viscosity of the carrier is normally 50 centipoises or less at 20°C and is preferably in the range of 0.3 to 3.0 centipoises at 20°C.
- Suitable organic carrier liquids, i.e. solvents are either of the aromatic or hydrocarbon type.
- Aromatic solvents include xylenes, toluenes and Solvesol 100TM (of Imperial Oil) which is a mixture of benzene and naphthalenes having a flash point in the range of 100°F.
- Suitable hydrocarbons include alcohols, such as hexanol, octanol. Other hydrocarbons includes fuel oils, kerosene, petroleum spirits and the like.
- the solvents of this nature have a functional flash point with low viscosity. the solvents are stable and the selected additive is soluble. Of course, the selected solvent is non-toxic when combusted.
- the additive composition may include a variety of commercial dyes to provide a distinctive color for the composition and distinguish it from others used about the oil-fired furnace operation.
- the containers for the additive composition should be explosion safe and are suitably handled.
- the tank containing the additive composition should also be suitably equipped to minimize the risk of explosion and fire.
- the amount of additive composition used will vary depending upon the type of crude oil being burned. Generally, the amount of additive composition used will range from 0.1 ppm up to 100 ppm of iron in the composition based on the amount of crude oil being delivered to the oil fired burner. The preferred range of additive composition used is 1 ppm to 5 ppm of iron based on the amount of crude oil delivered to the burner. According to this invention, crude oils having high asphaltene contents can now be burned in oil fire burner arrangements which could not be accomplished in the past. Crude oils containing higher concentrations of asphaltene usually range from about 2 percent up to 15 percent by weight of asphaltene. Asphaltenes are a class of material having high molecular weight. As common to crude oils they are a hard solid of melting point well above 150°C.
- Asphaltenes are soluble in petroleum naphtha in the range of 0 to 60 percent and 50 to 60 percent soluble in CS2. Asphaltenes are readily precipitated by N-heptane which enables analysis of crude oils for the concentration of asphaltene. Although the structure of asphaltenes is not fully understood, it is believed to be an aromatic sheet of 16 fused rings with various substituents. Normally, when crude oils having higher contents of asphaltenes are burned, the asphaltenes do not readily combust and hence greatly add to the overall carbon containing soot emissions when the "dirty" crude oils are burned.
- soot emissions in burning the dirty crudes can be significantly reduced particularly in the range of approximately a 50 to 80 percent reduction compared to burning the same crude oil without the additive composition.
- the combustion efficiency is appreciably increased which may be in the range of 0.5 percent increase or better depending upon the type of crude oil and its make up.
- Another significant advantage of this invention is the realization that in using the additive composition, the amount of excess air required in the combustion can be reduced. This provides the unexpected advantage that in using less excess air, a reduction in N0 x emissions can be achieved. This is very important from the stand point of environmental concerns where crude oils now can be effectively burned in standard oil fired burner systems.
- Non-dispersive infrared was used to measure C0 and C02 emissions.
- Paramagnetism was use to measure oxygen concentration.
- Chemiluminescence was used to measure the N0 x emissions.
- Pulsed fluorescence was used to measure the S02 emissions and the method "Five" in the "Standards of Performance for new Stationary Sources", Federal Register 36, No. 247, 24876, December 23, 1971 was used to measure the particulate material as well as to analyze the following characteristics of the particular material in the emissions; namely: particulate loading carbon content ash content particle size distribution.
- the pilot plant scale furnace operated on the average of 500 KBtu per hour with an excess air requirement of 26 percent.
- the furnace gas exit temperature was in the range of 2075 to 2225°F.
- the combustion air was not preheated in these tests.
- Based on prior experience it has been found that there is a fairly close relationship between the pilot plant scale oil fired burner and utility scale oil fired burner in terms of effects of additives on composition efficiency.
- a representative crude oil was obtained for testing.
- the crude oil (identified as Italian Vega) had the following characteristics as set out in Table I.
- the carrier liquid used was xylene.
- the additive composition consisted of 5000 ppm by weight of ferrocene iron distributed in a xylene carrier based on the amount of crude oil delivered for any amount of time. The composition was diluted to provide the necessary appropriate iron concentrations in the crude oil before introduction to the oil fired furnace. Xylene was therefore used with and without ferrocene to provide the following test results summarized in Table II.
- combustion efficiency as measured and identified in the above tables relate to carbon combustion efficiency.
- combustion efficiency may be loosely defined as the extent to which elemental carbon in the fuel is oxidized to C02.
- a difficult to burn out high asphaltene low vanadium heavy crude oil was efficiently combusted to match typical utility conditions.
- the amount of thermal energy extracted from the crude oil was also increased thereby reducing fuel costs. This is significant from the stand point that crude oil costs are approximately half the cost of fuel oil normally used in oil fired burners.
- black smoke problems are virtually eliminated. Electrostatic precipitator performance is improved and excess air requirements as already noted, are minimized.
- the additive is particularly suitable for use in the treatment of other oils such as the heavy oils and medium oils having a Conradson carbon content greater than 1%. It is appreciated, of course, that the above crude oil has a Conradson number considerably greater than 1%.
- the furnace used in testing the oils of Table IV is the same as the furnace used in Example 1.
- the furnace is operated though at levels of 10% excess air and 26% excess air.
- the furnace gas exit temperature was in the range of 2075° and 2275°F. There was no preheating of the combustion air.
- the firing rate was at 500 KBtu/hour.
- the duration of the test for the light oil was 12 hours, whereas the duration of the test for the heavy oil was 6 hours.
- the results of combustion of the heavy oil and the light oil of Table IV are set out in the following Tables V and VI.
- the heavy oil was tested at 0, 0.2, 1 and 5 ppm based on iron in the additive. It was found that 0.2 ppm iron had no effect on the combustion efficiency so that the values reported for 0 ppm and 0.2 ppm of the additive are the same. At levels of 1 ppm of the additive, significant changes are noted with further difference at the high level of 5 ppm of the additive. At 1 to 5 ppm of the additive, there was 90% to 97% reduction in particulate carbon with a corresponding increase in combustion efficiency from 0.05 to 1.6 %. The average particulate size was reduced by 50%, whereas N0 x emissions increased by only 5 to 85 ppm.
- the desired combustion efficiency of greater than 99% can be attained at the reduced excess air levels of 10% where the NO x emissions are very close to the value of NO x in additive-free oil burned in 10% excess air.
- the increase in NO x emissions at 26% excess air can be offset by burning the oil with the additive at 10% excess air without any significant reduction in combustion efficiency.
- the incremental reduction in particulate carbon and the incremental increase in combustion efficiency provided by the additive of this invention were greater at lower levels of Carbonex, that is 1 ppm versus 5 ppm, and at lower levels of excess air, that is 10% versus 26%.
- the observed reduction in particulate size was independent of the additive content above 1 ppm.
- the use of the additive of this invention had no apparent effect on the CO or SO2 emissions, or particulate loadings.
- the use of the additive of this invention has a superior effect on the heavy oils and crude oils. These oils have a Conradson carbon content greater than 1%.
- the additive of this invention does, however, have an effect on the burning of the light oils.
- the additive of this invention at a concentration of less than 1 ppm enhances carbon burnout in an already efficiently burning light oil flame, whereas in the heavy oils, the use of the additive at a concentration in the range of 1 to 5 ppm reduce the carbon in the particulate by 90%, thereby improving combustion efficiency up to 1.6%. This is a significant increase in combustion efficiency which can result in the saving of large sums of money in the operation of an electric or thermal generating plant over the span of a year.
- the use of the additive of this invention in the heavy oils and the like aside from providing a reduction of carbon in the particulates, also provides the advantages in eliminating opacity in the smoke from the furnace, improving performance of electrostatic precipitators and minimizing excess air requirements.
- the reliability and economics of oil fired burner operation is improved as a result of these secondary effects.
- the additive of this invention then minimizes corrosion and fouling and improves overall plant efficiency.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Liquid Carbonaceous Fuels (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US23239088A | 1988-08-15 | 1988-08-15 | |
US232390 | 1988-08-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0359390A1 true EP0359390A1 (en) | 1990-03-21 |
Family
ID=22872906
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89308075A Withdrawn EP0359390A1 (en) | 1988-08-15 | 1989-08-09 | Improved combustion of liquid hydrocarbons |
Country Status (9)
Country | Link |
---|---|
EP (1) | EP0359390A1 (da) |
JP (1) | JPH02132188A (da) |
AU (1) | AU627760B2 (da) |
CA (1) | CA1322453C (da) |
DK (1) | DK399089A (da) |
IL (1) | IL91299A0 (da) |
NO (1) | NO893232L (da) |
NZ (1) | NZ230252A (da) |
ZA (1) | ZA896188B (da) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994021755A2 (de) * | 1993-03-20 | 1994-09-29 | Chemische Betriebe Pluto Gmbh | Verwendung von ferrocen |
EP0667387A2 (en) * | 1994-02-10 | 1995-08-16 | Ethyl Corporation | Reducing exhaust emissions from Otto-cycle engines |
WO1997021790A1 (en) * | 1995-12-11 | 1997-06-19 | Exxon Chemical Patents Inc. | Low smoke composition and firefighter training process |
EP0807677A2 (en) * | 1996-05-14 | 1997-11-19 | Ethyl Corporation | Enhanced combustion of hydrocarbonaceous burner fuels |
SG138513A1 (en) * | 2006-06-30 | 2008-01-28 | Afton Chemical Corp | Fuel composition |
TWI408222B (zh) * | 2008-01-16 | 2013-09-11 | Taihokohzai Co Ltd | 燃料添加劑 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4908045A (en) * | 1988-12-23 | 1990-03-13 | Velino Ventures, Inc. | Engine cleaning additives for diesel fuel |
JPH03244692A (ja) * | 1990-02-23 | 1991-10-31 | Taiho Ind Co Ltd | 燃料添加剤 |
US6985487B1 (en) | 1990-07-27 | 2006-01-10 | Kabushiki Kaisha Toshiba | Broadband switching networks |
JP2909165B2 (ja) * | 1990-07-27 | 1999-06-23 | 株式会社東芝 | 広帯域通信網、エンドユーザ端末、通信網、広帯域通信ノード、通信ノード、インターフェースアダプタ、マルチポイント接続インターフェース、マルチポイント接続制御装置及びアクセスユニット |
US6523503B1 (en) * | 1998-02-20 | 2003-02-25 | John J. Kracklauer | Method for providing and maintaining catalytically active surface internal combustion engine |
JP5001376B2 (ja) * | 2006-11-01 | 2012-08-15 | バーラト ペトローリアム コーポレーション リミテッド | 炭化水素燃料組成物 |
JP2010163529A (ja) * | 2009-01-15 | 2010-07-29 | Taihokohzai:Kk | 燃料添加剤 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1140411A (fr) * | 1954-11-22 | 1957-07-22 | Gulf Research Development Co | Composition organique hydrocarburée contenant un métallo-cyclopentadiényle |
GB835870A (en) * | 1958-01-15 | 1960-05-25 | Exxon Research Engineering Co | Fuel compositions |
US3294685A (en) * | 1952-04-21 | 1966-12-27 | Gulf Research Development Co | Organic compositions containing a metallo cyclopentadienyl |
US3341311A (en) * | 1953-07-27 | 1967-09-12 | Du Pont | Liquid hydrocarbon fuels |
FR2273059A1 (da) * | 1974-01-21 | 1975-12-26 | Syntex Inc | |
US4389220A (en) * | 1980-06-04 | 1983-06-21 | Syntex (U.S.A.) Inc. | Method of conditioning diesel engines |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3535356A (en) * | 1968-06-11 | 1970-10-20 | Gulf Research Development Co | Process for producing dicyclopentadienyliron compounds |
-
1989
- 1989-08-04 CA CA000607602A patent/CA1322453C/en not_active Expired - Fee Related
- 1989-08-08 NZ NZ230252A patent/NZ230252A/xx unknown
- 1989-08-09 EP EP89308075A patent/EP0359390A1/en not_active Withdrawn
- 1989-08-11 NO NO89893232A patent/NO893232L/no unknown
- 1989-08-13 IL IL91299A patent/IL91299A0/xx unknown
- 1989-08-14 AU AU39584/89A patent/AU627760B2/en not_active Ceased
- 1989-08-14 DK DK399089A patent/DK399089A/da not_active Application Discontinuation
- 1989-08-14 ZA ZA896188A patent/ZA896188B/xx unknown
- 1989-08-15 JP JP1209730A patent/JPH02132188A/ja active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3294685A (en) * | 1952-04-21 | 1966-12-27 | Gulf Research Development Co | Organic compositions containing a metallo cyclopentadienyl |
US3341311A (en) * | 1953-07-27 | 1967-09-12 | Du Pont | Liquid hydrocarbon fuels |
FR1140411A (fr) * | 1954-11-22 | 1957-07-22 | Gulf Research Development Co | Composition organique hydrocarburée contenant un métallo-cyclopentadiényle |
GB835870A (en) * | 1958-01-15 | 1960-05-25 | Exxon Research Engineering Co | Fuel compositions |
FR2273059A1 (da) * | 1974-01-21 | 1975-12-26 | Syntex Inc | |
US4389220A (en) * | 1980-06-04 | 1983-06-21 | Syntex (U.S.A.) Inc. | Method of conditioning diesel engines |
Non-Patent Citations (1)
Title |
---|
INDUSTRIAL & ENGINEERING CHEMISTRY, vol. 47, May 1955, page 13A, American Chemical Society, Columbus, Ohio, US; "Smoke fighter" * |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1994021755A3 (de) * | 1993-03-20 | 1994-12-08 | Pluto Chem Betriebe | Verwendung von ferrocen |
CN1052034C (zh) * | 1993-03-20 | 2000-05-03 | 德商布卢脱有限公司 | 减少在低速、高压缩、自燃式内燃机中的碳沉积物的方法 |
WO1994021755A2 (de) * | 1993-03-20 | 1994-09-29 | Chemische Betriebe Pluto Gmbh | Verwendung von ferrocen |
US5713964A (en) * | 1993-10-25 | 1998-02-03 | Exxon Chemical Patents Inc. | Low smoke composition and firefighter training process |
EP0667387A3 (da) * | 1994-02-10 | 1995-09-27 | Ethyl Corp | |
EP0667387A2 (en) * | 1994-02-10 | 1995-08-16 | Ethyl Corporation | Reducing exhaust emissions from Otto-cycle engines |
WO1997021790A1 (en) * | 1995-12-11 | 1997-06-19 | Exxon Chemical Patents Inc. | Low smoke composition and firefighter training process |
AU713931B2 (en) * | 1995-12-11 | 1999-12-16 | Exxon Chemical Patents Inc. | Low smoke composition and firefighter training process |
EP0807677A2 (en) * | 1996-05-14 | 1997-11-19 | Ethyl Corporation | Enhanced combustion of hydrocarbonaceous burner fuels |
EP0807677A3 (en) * | 1996-05-14 | 1998-01-07 | Ethyl Corporation | Enhanced combustion of hydrocarbonaceous burner fuels |
SG138513A1 (en) * | 2006-06-30 | 2008-01-28 | Afton Chemical Corp | Fuel composition |
US8852299B2 (en) | 2006-06-30 | 2014-10-07 | Afton Chemical Corporation | Fuel composition |
TWI408222B (zh) * | 2008-01-16 | 2013-09-11 | Taihokohzai Co Ltd | 燃料添加劑 |
Also Published As
Publication number | Publication date |
---|---|
NZ230252A (en) | 1990-08-28 |
IL91299A0 (en) | 1990-03-19 |
AU3958489A (en) | 1990-02-15 |
AU627760B2 (en) | 1992-09-03 |
JPH02132188A (ja) | 1990-05-21 |
ZA896188B (en) | 1990-05-30 |
CA1322453C (en) | 1993-09-28 |
DK399089A (da) | 1990-02-16 |
NO893232L (no) | 1990-02-16 |
DK399089D0 (da) | 1989-08-14 |
NO893232D0 (no) | 1989-08-11 |
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Legal Events
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