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WO1996038518A1 - Additive system for fuel oil - Google Patents

Additive system for fuel oil Download PDF

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Publication number
WO1996038518A1
WO1996038518A1 PCT/US1996/007879 US9607879W WO9638518A1 WO 1996038518 A1 WO1996038518 A1 WO 1996038518A1 US 9607879 W US9607879 W US 9607879W WO 9638518 A1 WO9638518 A1 WO 9638518A1
Authority
WO
WIPO (PCT)
Prior art keywords
fuel oil
magnesium
based compound
additive system
amount
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.)
Ceased
Application number
PCT/US1996/007879
Other languages
French (fr)
Inventor
William J. Gonzales
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ashland Inc
Original Assignee
Ashland Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Ashland Inc filed Critical Ashland Inc
Priority to AU58818/96A priority Critical patent/AU5881896A/en
Publication of WO1996038518A1 publication Critical patent/WO1996038518A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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

Definitions

  • This invention relates to power generation, and more particularly, to an additive system for fuel oil to improve efficiency of boilers, gas turbines and diesel engines burning heavy fuel oil .
  • Ash deposit modifiers in fuel oil are used to reduce prebumer deposits as well as ash formation on turbine blades and the like.
  • Magnesium-based fuel additives such as Amergy 5800M * , sold by Ashland Chemical Co., have been effective to reduce deposit of vanadium contained in the fuel oil, however, while such additives have improved on-line time cycles with longer time periods between shut down, there is the need to improve on-line cycle time. Additionally, ash build-up on turbine blades in stationary units for electric power generation required excessive cleansing requirements and thus there exist longer turnaround times.
  • An object of the present invention is to provide an additive system for fuel oils of improved efficacy.
  • Another object of the present invention is to provide an additive system for fuel oils permitting facile water washing of turbine blades .
  • Still another object of the present invention is to provide an additive system for fuel oils permitting of longer on line firing times .
  • a still further object of the present invention is to provide an additive system for fuel oils permitting of shorter cleaning cycles.
  • an additive system comprised of magnesium sulfonate and t- alkyl primary amines admixed into the fuel oil wherein the magnesium sulfonate content is from 5 to 15 part per part of the vanadium content in the fuel oil and the t-alkyl primary amines content is 0.1 to 2 parts per part of the magnesium sulfonate.
  • An alkanoic acid in an amount of from 0.1 to 2 part per part of
  • magnesium sulfonate may also be added to the basic additive system of the present invention.
  • the vanadium content of the fuel oil to be treated in accordance with the additive system of the present invention ranges from about 1 to 1000 ppms .
  • the fuel oil additive system of the present invention is comprised of a magnesium-based compound and tertiary primary alkyl amines, and optionally a C 6 - C_ ⁇ alkanoic acid.
  • a magnesium-based compound includes overbased magnesium sulfonate, such as Amergy 5800M * , sold by Ashland Chemical Co., and is present in an amount of from about 5 to 15, preferably about 10 parts per part of the vanadium content of the fuel oil .
  • the tertiary alkyl primary amines for example, include the primary amines sold by Rohm and Haas Company under the trademark Primene 81-R (see U.S.P. 3,652,242) .
  • the tertiary alkyl primary amines are present in an amount of from about 0.5 to 10 part per partof the magnesium- based compound.
  • the C 6 to C l ⁇ alkanoic acids optionally included, preferably octanoic acid, are present in an amount of from about 0.5 to about 2 parts per part of the magnesium-based compound.
  • the fuel oil being treated for combustion in a turbine is continuously analyzed for its vanadium conten .
  • the additive system of the present invention when admixed with fuel oil prior to combustion reduces prebumer deposits with concomitant reduction in compression in the gas turbine.
  • the additive system of the present invention comprised of Amergy 5800M ® (4500 ppm) and the t-alkyl primary amine (500 ppm) sold by Rohm and Haas under the trademark Primene 81-R.
  • the deposits in the gas turbine are readily water washed and pre-burner deposit are reduced as well as easily cleaned. A reduction of 30% less fouling is achieved by the additive system of the present invention.

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)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

There is disclosed an additive system comprised of magnesium-sulfonate and t-alkyl primary amines admixed into the fuel oil wherein the magnesium sulfonate content is from 5 to 15 part per part of the vanadium content in the fuel oil and the t-alkyl primary amines content is 0.1 to 2 parts per part of the magnesium sulfonate. An alkanoic acid in an amount of from 0.1 to 2 part per part of magnesium sulfonate may also be added to the basic additive system of the present invention.

Description

ADDITIVE SYSTEM FOR FUEL OIL
RRPyπROTI D OF THE INVENTION
1. FIELD OF THE INVENTION
This invention relates to power generation, and more particularly, to an additive system for fuel oil to improve efficiency of boilers, gas turbines and diesel engines burning heavy fuel oil .
2. Brief Description of the Prior Art
Ash deposit modifiers in fuel oil are used to reduce prebumer deposits as well as ash formation on turbine blades and the like. Magnesium-based fuel additives (such as Amergy 5800M * , sold by Ashland Chemical Co., have been effective to reduce deposit of vanadium contained in the fuel oil, however, while such additives have improved on-line time cycles with longer time periods between shut down, there is the need to improve on-line cycle time. Additionally, ash build-up on turbine blades in stationary units for electric power generation required excessive cleansing requirements and thus there exist longer turnaround times.
OBJECTS OF THE INVENTION
An object of the present invention is to provide an additive system for fuel oils of improved efficacy.
Another object of the present invention is to provide an additive system for fuel oils permitting facile water washing of turbine blades .
Still another object of the present invention is to provide an additive system for fuel oils permitting of longer on line firing times . A still further object of the present invention is to provide an additive system for fuel oils permitting of shorter cleaning cycles. SUMMARY OF THE INVENTION
These and other objects of the present invention are achieved by an additive system comprised of magnesium sulfonate and t- alkyl primary amines admixed into the fuel oil wherein the magnesium sulfonate content is from 5 to 15 part per part of the vanadium content in the fuel oil and the t-alkyl primary amines content is 0.1 to 2 parts per part of the magnesium sulfonate. An alkanoic acid in an amount of from 0.1 to 2 part per part of
magnesium sulfonate may also be added to the basic additive system of the present invention.
BRIEF DESCRIPTION OF THE INVENTION
Generally, the vanadium content of the fuel oil to be treated in accordance with the additive system of the present invention ranges from about 1 to 1000 ppms .
The fuel oil additive system of the present invention is comprised of a magnesium-based compound and tertiary primary alkyl amines, and optionally a C6 - C_β alkanoic acid. A magnesium-based compound includes overbased magnesium sulfonate, such as Amergy 5800M * , sold by Ashland Chemical Co., and is present in an amount of from about 5 to 15, preferably about 10 parts per part of the vanadium content of the fuel oil . The tertiary alkyl primary amines, for example, include the primary amines sold by Rohm and Haas Company under the trademark Primene 81-R (see U.S.P. 3,652,242) . The tertiary alkyl primary amines are present in an amount of from about 0.5 to 10 part per partof the magnesium- based compound. The C6 to Clβ alkanoic acids optionally included, preferably octanoic acid, are present in an amount of from about 0.5 to about 2 parts per part of the magnesium-based compound.
In use, the fuel oil being treated for combustion in a turbine is continuously analyzed for its vanadium conten . The additive system of the present invention when admixed with fuel oil prior to combustion reduces prebumer deposits with concomitant reduction in compression in the gas turbine.
∑∑MΣ The following example is illustrative of the conditions for the use of the invention and it is to be understood that the scope of the invention is not to be limited thereby. E2ΔME E
To a No. 2 fuel oil containing 450 ppm vanadiium, there is added '5000 ppm of the additive system of the present invention comprised of Amergy 5800M® (4500 ppm) and the t-alkyl primary amine (500 ppm) sold by Rohm and Haas under the trademark Primene 81-R. The deposits in the gas turbine are readily water washed and pre-burner deposit are reduced as well as easily cleaned. A reduction of 30% less fouling is achieved by the additive system of the present invention.
While the invention has been described in connection with an exemplary embodiment thereof, it will be understood that many
modifications will be apparent to those of ordinary skill in the art; and that this application is intended to cover any adaptations or variations thereof. Therefore, it is manifestly intended that this invention be only limited by the claims and the equivalents thereof .

Claims

WHAT IS CLAIMED:
1. An additive system for a fuel oil, which comprises-. a magnesium-based compound in an amount of from about 5 to about 15 parts per part of vanadium in said fuel oil, and a tertiary alkyl primary amine in an amount to provide a ratio thereof of from about 0.1 to 2 to said magnesium based compound.
2. The additive system for a fuel oil as defined in Claim 1 wherein said magnesium-based compound is preferably present in an amount of 5 parts per part of vanadium for said fuel oil.
3. The additive system for a fuel oil as defined in Claim
1 and further including a C. to Cιe alkanoic acid in an amount to provide a ratio thereof of from about 0.1 to 2 to said magnesium- based compound. . The additive system for a fuel oil as defined in Claim
2 and further including a C6 to C_B alkanoic acid in an amount to provide a ratio -thereof of from about 0.1 to 2 to said magnesium- based compound.
5. The additive system for a fuel oil as defined in Claim 1 wherein said magnesium-based compound is an overbased megnesium sulfonate.
6 . The additive system for a fuel oil as defined in Claim 4 wherein said alkanoic acid is octanoic acid.
7. A process for burning fuel oil to produce energy, which comprises: a.) analyzing the vanadium content of said fuel oil; and b.) admixing with said fuel oil an additive system comprised of a magnesium-based compound in an amount of from about 5 to about 15 parts per part of vanadium in said fuel oil and a tertiary alkyl primary amine in an amount to provide a ratio thereof of from about 0.1 to 2 to said magnesium-based compound.
8. The process for burning a fuel oil as defined in Claim 7 wherein said magnesium-based compound is preferably present in an amount of 5 parts per part of vanadium in said fuel oil.
9. The process for burning a fuel oil as defined n Claim 7 and further including a C6 to Clβ alkanoic acid in an amount to provide a ratio thereof of from about 0.1 to 2 to said magnesium- based compound.
10. The process for burning a fuel oil as defined in Claim
8 and further including a C6 to Cιe alkanoic acid in an amount to provide a ratio thereof of from about 0.1 to 2 to said magnesium- based compound. 11. The process for burning a fuel oil as defined in Claim 7 wherein said magnesium based compound is an overbased magnesium sulfonate.
12. The process for burning a fuel oil as defined in Claim
9 wherein said alkanoic acid is octanoic acid.
PCT/US1996/007879 1995-05-30 1996-05-29 Additive system for fuel oil Ceased WO1996038518A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58818/96A AU5881896A (en) 1995-05-30 1996-05-29 Additive system for fuel oil

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US45350395A 1995-05-30 1995-05-30
US08/453,503 1995-05-30

Publications (1)

Publication Number Publication Date
WO1996038518A1 true WO1996038518A1 (en) 1996-12-05

Family

ID=23800813

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1996/007879 Ceased WO1996038518A1 (en) 1995-05-30 1996-05-29 Additive system for fuel oil

Country Status (2)

Country Link
AU (1) AU5881896A (en)
WO (1) WO1996038518A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039599A1 (en) * 1997-03-06 1998-09-11 Siemens Westinghouse Power Corporation Staged supplemental firing of high vanadium content fuel oils
WO1999036489A1 (en) * 1998-01-13 1999-07-22 Baker Hughes Incorporated Composition and method to improve lubricity in fuels
WO1999051707A1 (en) * 1998-04-02 1999-10-14 Witco Corporation Overbased magnesium deposit control additive for residual fuel oils
EP0976911A1 (en) * 1998-07-27 2000-02-02 Champion Technologies, Inc. Scale inhibitors
US7820600B2 (en) 2005-06-03 2010-10-26 Exxonmobil Research And Engineering Company Lubricant and method for improving air release using ashless detergents
US7851418B2 (en) 2005-06-03 2010-12-14 Exxonmobil Research And Engineering Company Ashless detergents and formulated lubricating oil containing same

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2832677A (en) * 1953-10-21 1958-04-29 Exxon Research Engineering Co Residual fuel
US2943924A (en) * 1956-05-21 1960-07-05 Gulf Research Development Co Stable fuel oil compositions
US2945749A (en) * 1956-04-18 1960-07-19 Socony Mobil Oil Co Inc Stabilized fuel oil containing tertiary alkyl primary amines
US2949008A (en) * 1958-01-29 1960-08-16 Gulf Research Development Co Residual fuels
US3522022A (en) * 1966-10-07 1970-07-28 Hoechst Ag Corrosion inhibited fuel oils
US3652242A (en) * 1970-02-02 1972-03-28 Mobil Oil Corp Liquid hydrocarbon fuels containing alkylamine salts
US4131433A (en) * 1977-07-27 1978-12-26 The Perolin Company, Inc. Fuel additives, additive compositions and methods of employing same to prevent corrosion of metal surfaces in contact with hot gaseous combustion products

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2832677A (en) * 1953-10-21 1958-04-29 Exxon Research Engineering Co Residual fuel
US2945749A (en) * 1956-04-18 1960-07-19 Socony Mobil Oil Co Inc Stabilized fuel oil containing tertiary alkyl primary amines
US2943924A (en) * 1956-05-21 1960-07-05 Gulf Research Development Co Stable fuel oil compositions
US2949008A (en) * 1958-01-29 1960-08-16 Gulf Research Development Co Residual fuels
US3522022A (en) * 1966-10-07 1970-07-28 Hoechst Ag Corrosion inhibited fuel oils
US3652242A (en) * 1970-02-02 1972-03-28 Mobil Oil Corp Liquid hydrocarbon fuels containing alkylamine salts
US4131433A (en) * 1977-07-27 1978-12-26 The Perolin Company, Inc. Fuel additives, additive compositions and methods of employing same to prevent corrosion of metal surfaces in contact with hot gaseous combustion products

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998039599A1 (en) * 1997-03-06 1998-09-11 Siemens Westinghouse Power Corporation Staged supplemental firing of high vanadium content fuel oils
WO1999036489A1 (en) * 1998-01-13 1999-07-22 Baker Hughes Incorporated Composition and method to improve lubricity in fuels
US6129772A (en) * 1998-01-13 2000-10-10 Baker Hughes Incorporated Composition and method to improve lubricity in fuels
WO1999051707A1 (en) * 1998-04-02 1999-10-14 Witco Corporation Overbased magnesium deposit control additive for residual fuel oils
US6197075B1 (en) 1998-04-02 2001-03-06 Crompton Corporation Overbased magnesium deposit control additive for residual fuel oils
EP0976911A1 (en) * 1998-07-27 2000-02-02 Champion Technologies, Inc. Scale inhibitors
US7820600B2 (en) 2005-06-03 2010-10-26 Exxonmobil Research And Engineering Company Lubricant and method for improving air release using ashless detergents
US7851418B2 (en) 2005-06-03 2010-12-14 Exxonmobil Research And Engineering Company Ashless detergents and formulated lubricating oil containing same

Also Published As

Publication number Publication date
AU5881896A (en) 1996-12-18

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