US20090277080A1 - Coal with improved combustion properties - Google Patents

Coal with improved combustion properties Download PDF

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Publication number
US20090277080A1
US20090277080A1 US12/310,123 US31012307A US2009277080A1 US 20090277080 A1 US20090277080 A1 US 20090277080A1 US 31012307 A US31012307 A US 31012307A US 2009277080 A1 US2009277080 A1 US 2009277080A1
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United States
Prior art keywords
coal
metal
phthalocyanine
iron
combustion
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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.)
Abandoned
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US12/310,123
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English (en)
Inventor
Paul G. Day
Felix Sirovski
Sergej Daut
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Aquafuel Research Ltd
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Aquafuel Research Ltd
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Assigned to AQUAFUEL RESEARCH LIMITED reassignment AQUAFUEL RESEARCH LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DAUT, SERGEJ, DAY, PAUL, SIROVSKI, FELIX
Publication of US20090277080A1 publication Critical patent/US20090277080A1/en
Abandoned legal-status Critical Current

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    • 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
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/10—Treating solid fuels to improve their combustion by using additives
    • 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)
    • C10L1/301—Organic compounds compounds not mentioned before (complexes) derived from metals

Definitions

  • the present invention relates to a method for improving the combustion properties of a coal, to a coal with improved combustion properties, and to a process for combustion of a coal with reduced emissions.
  • the NOx concentration in effluent gases at air excess ( ⁇ ) of 1.4 is 700-900 mg/m 3 (recalculated to NO 2 ) depending on the boiler power.
  • EP1498470 lists several methods for reducing carbon in ash from coal burning, including increasing the excess of air introduced with the fuel, or adding metals such as calcium and magnesium. These methods have undesirable effects, with increased air causing higher NOx emissions, and use of metals such as calcium and magnesium requiring large amounts, and causing fouling of the system.
  • EP1498470 proposes the addition of 2-500 ppm of a manganese compound, preferably a manganese tricarbonyl compound.
  • a method for improving the combustion properties of a coal comprising treating said coal with a metal porphyrin.
  • a second aspect of the invention provides a coal having a metal porphyrin deposited thereon.
  • the invention can provide improved carbon burnout, resulting in reduced carbon content in the ash.
  • the activation energy for oxidation may also be reduced.
  • NO x formation in combustion is related to the excess of air over the stoichiometric requirement: more excess means higher NO x and lower thermal efficiency. Improved rates of combustion/lower activation energy tends to reduce excess air requirement and lower NO x production.
  • the combustion chamber airflow is typically actively managed and can be altered to optimise combustion conditions to minimise carbon content in ash and minimise NO x .
  • the invention is of particular applicability to low-grade coals such as brown coal or bituminous coal.
  • the metal porphyrin of the present invention preferably contains a metal with two or more possible oxidation states.
  • Examples include transition metals such as iron, cobalt or manganese.
  • the metal porphyrin additive may be put up in an aqueous solution and applied to the solid fuel by methods commonly known in the art, for example by spraying onto the solid fuel. Alternately the metal porphyrin is applied by sublimation and vapour deposition.
  • Porphyrins occur widely in nature, and they play very important roles in various biological processes. Synthetic porphyrins such as phthalocyanines have industrial uses, for example copper phthalocyanine is widely used as a cyan pigment. Porphyrins are fully aromatic systems, are capable of hosting a wide variety of metal atoms and have high thermal stability. Porphyrins can be modified, for example by sulphonation, to change their solubility in various media.
  • FIGS. 1-3 are graphs of, respectively, TG, DTG and DTA results for a coal in accordance with an aspect of the invention and comparative samples;
  • FIGS. 4-6 are graphs showing linearised DTG data for, respectively, untreated brown coal, H 2 SO 4 -treated brown coal and Fe additive treated brown coat;
  • FIGS. 7 and 8 are graphs of DTA results for untreated brown coal and for brow coal treated, respectively with an iron-based additive in accordance with the invention and a cobalt-based additive in accordance with the invention;.
  • FIGS. 9-11 are graphs showing, respectively, TG, %sample weight loss, and DTG results for untreated brown coal and brown coal treated with Fe and Co additives in accordance with the invention.
  • TG thermogravimetry
  • DTA differential thermal analysis
  • DSC differential scanning calorimetry
  • Thermogravimetry is widely used to investigate coal/char reactivity. It is well documented that the reactivity depends on coal rank, maceral composition and/or charring temperature.
  • the coal combustion reactivity was measured by TG, in general, under two conditions (i) isothermal, at a constant temperature, and (ii) non-isothermal, at a constant heating rate.
  • Derivative thermogravimetry (DTG) under non-isothermal conditions, namely burning profile has been applied to obtain reactivity parameters such as the temperature of maximum (peak) combustion rate (PT), burnt out temperature (BT), and activation energy.
  • TTDTA Thermal analysis methods
  • the coal used in this study was brown coal from Novomosvsk coal basin.
  • Iron (II) phthalocyanine (0.1-0.2 g) was dissolved in concentrated sulphuric acid (50-60 ml). A sample of brown coal ( ⁇ 2 g) (2-3 mm grain size) was stirred in this solution for 2 hours at room temperature and left overnight to soak. After stirring, the coal with the deposited phthalocyanine was filtered off. The residual concentration of iron (II) phthalocyanine was determined by UV/visible spectrophotometric analysis. The quantity of the deposited iron-based additive was determined by the difference in concentrations of the starting and residual solutions. The filtered coal was washed with water to neutral pH and air-dried to constant weight over 72-144 hours. Calculations showed that 0.2% of iron (II) phthalocyanine was deposited on the coal. This corresponds to about 200 ppm of iron. After drying, the sample of coal was ground to dust in a mortar for DTA/DTG analysis.
  • the DTA results show much higher exothermal activity in the Fe treated sample compared to untreated brown coal. The effect is particularly pronounced around 100 degrees centigrade, between 350 and 450 degrees centigrade, and between 600 and 800 degrees centigrade. Thermal gravimetric measurement was continued to constant weight, with the treated sample losing 91.2% of its initial weight compared to 86.6% for the untreated coal. Furthermore the treated coal reached constant weight at around 800 degrees centigrade, compared to 850 degrees centigrade for the untreated coal. These results demonstrate the additive of the present invention is surprisingly effective in improving the combustion of solid fuels.
  • ⁇ is the conversion degree
  • ⁇ is time
  • k is the temperature dependent Arrhenius rate constant
  • k Aexp( ⁇ E ⁇ /RT).
  • R is the gas constant
  • the model parameters A and ⁇ E ⁇ are the frequency factor and activation energy.
  • T T 0 + ⁇ .
  • the value of the activation energy could be deduced from the slope of the straight lines obtained.
  • the first peak around 100° C. corresponds to the loss of the residual water
  • the second peak at around 300-400° C. corresponds to the release of the volatile matter.
  • a sharp peak is observed due to the char combustion
  • the obtained activation energy values were as follows.
  • the weight loss was achieved at lower temperature, demonstrating the catalytic action of the additive.
  • Linear regression data for FIGS. 4-6 are set out below in Tables 1-3.
  • Example 1 As for Example 1 but using cobalt phthalocyanine disulphonate as the metal porphyrin and distilled water instead of sulphuric acid as the fluid carrier.
  • Results are shown in FIGS. 7-11 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)
US12/310,123 2006-08-12 2007-08-06 Coal with improved combustion properties Abandoned US20090277080A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GBGB0616094.9A GB0616094D0 (en) 2006-08-12 2006-08-12 Coal combustion improvement additives
GB0616094.9 2006-08-12
PCT/GB2007/002991 WO2008020169A2 (fr) 2006-08-12 2007-08-06 Charbon doté de propriétés de combustion améliorées

Publications (1)

Publication Number Publication Date
US20090277080A1 true US20090277080A1 (en) 2009-11-12

Family

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US12/310,123 Abandoned US20090277080A1 (en) 2006-08-12 2007-08-06 Coal with improved combustion properties

Country Status (13)

Country Link
US (1) US20090277080A1 (fr)
EP (1) EP2057254B1 (fr)
JP (1) JP2010500527A (fr)
KR (1) KR20090045325A (fr)
CN (1) CN101501168A (fr)
AT (1) ATE495232T1 (fr)
AU (1) AU2007285609B2 (fr)
BR (1) BRPI0715918A2 (fr)
DE (1) DE602007011944D1 (fr)
EA (1) EA013898B1 (fr)
GB (1) GB0616094D0 (fr)
WO (1) WO2008020169A2 (fr)
ZA (1) ZA200901924B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9551485B2 (en) 2011-02-25 2017-01-24 Mitsubishi Materials Corporation Method for controlling NOx concentration in exhaust gas in combustion facility using pulverized coal
CN110146545A (zh) * 2019-06-28 2019-08-20 陕西煤业化工新型能源有限公司神木分公司 一种利用煤质燃烧判别指数提高锅炉燃烧性能的方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0902517D0 (en) * 2009-02-16 2009-04-01 Innospec Ltd Improvements in or relating to the combustion of coal
US20110131874A1 (en) * 2009-12-08 2011-06-09 Baker Hughes Incorporated Method for improving the efficiency of heat transfer in a coal fired furnace
CN102539376B (zh) * 2012-01-13 2013-07-03 中国矿业大学 一种煤表面官能团物理吸氧量的测定方法
CN110420638A (zh) * 2019-08-22 2019-11-08 安徽工业大学 一种催化燃烧煤焦同时原位脱硝的催化剂及其使用方法

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2460284A (en) * 1944-08-01 1949-02-01 Nat Agrol Company Inc Tobacco composition and method of making it
US2460285A (en) * 1944-08-01 1949-02-01 Nat Agrol Company Inc Tobacco products and method of making them
US4009120A (en) * 1975-08-18 1977-02-22 Uop Inc. Process for the regeneration of a solid bed metal phthalocyanine catalyst system
US4172022A (en) * 1977-04-05 1979-10-23 Krylov Vyacheslav M Electrochemical sensor of hydrogen and hydrogen-containing reducing agents
US5783065A (en) * 1992-09-03 1998-07-21 University Of Utah Research Foundation Method for coal liquefaction
US6156137A (en) * 1999-11-05 2000-12-05 Atlantic Research Corporation Gas generative compositions
US20050257724A1 (en) * 2004-05-24 2005-11-24 Guinther Gregory H Additive-induced control of NOx emissions in a coal burning utility furnace

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GB518958A (en) * 1938-09-02 1940-03-12 David Baird Macdonald Improvements in or relating to fuels for internal combustion engines
JPS5868874A (ja) * 1981-10-19 1983-04-23 Toshiba Battery Co Ltd 空気電池
JPS5875775A (ja) * 1981-10-30 1983-05-07 Pentel Kk 空気極
JPH0768533B2 (ja) * 1986-02-18 1995-07-26 三菱重工業株式会社 固体燃料の燃焼法
FR2601263B1 (fr) * 1986-07-11 1988-11-25 Total France Nouveau produit composite catalytique pour l'oxydation des mercaptans et son utilisation pour l'adoucissement des coupes petrolieres.
JPS6483265A (en) * 1987-09-24 1989-03-29 Dainippon Ink & Chemicals Deodorant
ZA894283B (en) * 1988-06-08 1990-09-26 Velino Ventures Inc Combustion of carbon containing meterials in a furnace
JPH05105889A (ja) * 1991-10-15 1993-04-27 Matsushita Electric Ind Co Ltd 固形燃料
JPH0718279A (ja) * 1993-06-30 1995-01-20 Mitsui Eng & Shipbuild Co Ltd コールクリーニング方法
JPH10226883A (ja) * 1997-02-18 1998-08-25 Ricoh Co Ltd フタロシアニン結晶質薄膜の作製法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2460284A (en) * 1944-08-01 1949-02-01 Nat Agrol Company Inc Tobacco composition and method of making it
US2460285A (en) * 1944-08-01 1949-02-01 Nat Agrol Company Inc Tobacco products and method of making them
US4009120A (en) * 1975-08-18 1977-02-22 Uop Inc. Process for the regeneration of a solid bed metal phthalocyanine catalyst system
US4172022A (en) * 1977-04-05 1979-10-23 Krylov Vyacheslav M Electrochemical sensor of hydrogen and hydrogen-containing reducing agents
US5783065A (en) * 1992-09-03 1998-07-21 University Of Utah Research Foundation Method for coal liquefaction
US6156137A (en) * 1999-11-05 2000-12-05 Atlantic Research Corporation Gas generative compositions
US20050257724A1 (en) * 2004-05-24 2005-11-24 Guinther Gregory H Additive-induced control of NOx emissions in a coal burning utility furnace

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9551485B2 (en) 2011-02-25 2017-01-24 Mitsubishi Materials Corporation Method for controlling NOx concentration in exhaust gas in combustion facility using pulverized coal
US9714196B2 (en) 2011-02-25 2017-07-25 Mitsubishi Materials Corporation Method for controlling NOx concentration in exhaust gas in combustion facility using pulverized coal
CN110146545A (zh) * 2019-06-28 2019-08-20 陕西煤业化工新型能源有限公司神木分公司 一种利用煤质燃烧判别指数提高锅炉燃烧性能的方法

Also Published As

Publication number Publication date
WO2008020169A3 (fr) 2008-07-17
WO2008020169A2 (fr) 2008-02-21
EP2057254B1 (fr) 2011-01-12
KR20090045325A (ko) 2009-05-07
AU2007285609A1 (en) 2008-02-21
EA200900301A1 (ru) 2009-08-28
JP2010500527A (ja) 2010-01-07
BRPI0715918A2 (pt) 2013-07-30
GB0616094D0 (en) 2006-09-20
ATE495232T1 (de) 2011-01-15
DE602007011944D1 (de) 2011-02-24
ZA200901924B (en) 2010-01-27
AU2007285609B2 (en) 2011-03-31
EA013898B1 (ru) 2010-08-30
CN101501168A (zh) 2009-08-05
EP2057254A2 (fr) 2009-05-13

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Owner name: AQUAFUEL RESEARCH LIMITED, UNITED KINGDOM

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:DAY, PAUL;SIROVSKI, FELIX;DAUT, SERGEJ;REEL/FRAME:022272/0264

Effective date: 20090210

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION