EP2057254A2 - Kohle mit verbesserten verbrennungseigenschaften - Google Patents
Kohle mit verbesserten verbrennungseigenschaftenInfo
- Publication number
- EP2057254A2 EP2057254A2 EP07789127A EP07789127A EP2057254A2 EP 2057254 A2 EP2057254 A2 EP 2057254A2 EP 07789127 A EP07789127 A EP 07789127A EP 07789127 A EP07789127 A EP 07789127A EP 2057254 A2 EP2057254 A2 EP 2057254A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- coal
- metal
- metal porphyrin
- porphyrin
- combustion
- 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.)
- Granted
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
- 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 high content of unbumed carbon in the fly ash results in the significant heat losses: up to 5% or even higher depending on the coal ash content .
- 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 ⁇ formation in combustion is related to the excess of air over the stoichiometric requirement: more excess means higher NOx 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.
- Figures 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;
- Figures 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;
- Figures 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;
- Figures 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.
- the degree of conversion ⁇ is give by the expression ⁇ ⁇ (mi - m ⁇ )/(mi-nri f ), where m* and rri f are the initial and final percent masses and m ⁇ the percent mass at time i as they are recorded during a TG experiment.
- the value of the activation energy could be deduced from the slope of the straight lines obtained.
- the first peak around 100 0 C corresponds to the loss of the residual water
- the second peak at around 300-400 0 C corresponds to the release of the volatile matter.
- a sharp peak is observed due to the char combustion
- the weight loss was achieved at lower temperature, demonstrating the catalytic action of the additive.
- Linear regression data for Figures 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.
Landscapes
- 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)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0616094.9A GB0616094D0 (en) | 2006-08-12 | 2006-08-12 | Coal combustion improvement additives |
PCT/GB2007/002991 WO2008020169A2 (en) | 2006-08-12 | 2007-08-06 | Coal with improved combustion properties |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2057254A2 true EP2057254A2 (de) | 2009-05-13 |
EP2057254B1 EP2057254B1 (de) | 2011-01-12 |
Family
ID=37056294
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07789127A Not-in-force EP2057254B1 (de) | 2006-08-12 | 2007-08-06 | Kohle mit verbesserten verbrennungseigenschaften |
Country Status (13)
Country | Link |
---|---|
US (1) | US20090277080A1 (de) |
EP (1) | EP2057254B1 (de) |
JP (1) | JP2010500527A (de) |
KR (1) | KR20090045325A (de) |
CN (1) | CN101501168A (de) |
AT (1) | ATE495232T1 (de) |
AU (1) | AU2007285609B2 (de) |
BR (1) | BRPI0715918A2 (de) |
DE (1) | DE602007011944D1 (de) |
EA (1) | EA013898B1 (de) |
GB (1) | GB0616094D0 (de) |
WO (1) | WO2008020169A2 (de) |
ZA (1) | ZA200901924B (de) |
Families Citing this family (6)
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 |
JP4985857B1 (ja) | 2011-02-25 | 2012-07-25 | 三菱マテリアル株式会社 | 微粉炭を用いた燃焼設備における排ガス中のNOx濃度の制御方法 |
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 |
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 |
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 |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB518958A (en) * | 1938-09-02 | 1940-03-12 | David Baird Macdonald | Improvements in or relating to fuels for internal combustion engines |
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 |
DE2715285C2 (de) * | 1977-04-05 | 1983-08-25 | Vjačeslav Michajlovič Puškino Moskovskaja oblast' Krylov | Elektrochemische Zelle zum Bestimmen von Wasserstoff und wasserstoffhaltigen Reduktionsmitteln |
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 |
US5783065A (en) * | 1992-09-03 | 1998-07-21 | University Of Utah Research Foundation | Method for coal liquefaction |
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 |
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 |
-
2006
- 2006-08-12 GB GBGB0616094.9A patent/GB0616094D0/en not_active Ceased
-
2007
- 2007-08-06 EP EP07789127A patent/EP2057254B1/de not_active Not-in-force
- 2007-08-06 AT AT07789127T patent/ATE495232T1/de not_active IP Right Cessation
- 2007-08-06 BR BRPI0715918-8A patent/BRPI0715918A2/pt not_active IP Right Cessation
- 2007-08-06 JP JP2009523340A patent/JP2010500527A/ja active Pending
- 2007-08-06 CN CNA200780030088XA patent/CN101501168A/zh active Pending
- 2007-08-06 AU AU2007285609A patent/AU2007285609B2/en not_active Expired - Fee Related
- 2007-08-06 WO PCT/GB2007/002991 patent/WO2008020169A2/en active Application Filing
- 2007-08-06 DE DE602007011944T patent/DE602007011944D1/de active Active
- 2007-08-06 US US12/310,123 patent/US20090277080A1/en not_active Abandoned
- 2007-08-06 KR KR1020097005015A patent/KR20090045325A/ko not_active Application Discontinuation
- 2007-08-06 EA EA200900301A patent/EA013898B1/ru not_active IP Right Cessation
-
2009
- 2009-03-10 ZA ZA200901924A patent/ZA200901924B/xx unknown
Non-Patent Citations (1)
Title |
---|
See references of WO2008020169A2 * |
Also Published As
Publication number | Publication date |
---|---|
WO2008020169A3 (en) | 2008-07-17 |
US20090277080A1 (en) | 2009-11-12 |
GB0616094D0 (en) | 2006-09-20 |
EP2057254B1 (de) | 2011-01-12 |
AU2007285609A1 (en) | 2008-02-21 |
ATE495232T1 (de) | 2011-01-15 |
KR20090045325A (ko) | 2009-05-07 |
EA013898B1 (ru) | 2010-08-30 |
JP2010500527A (ja) | 2010-01-07 |
AU2007285609B2 (en) | 2011-03-31 |
EA200900301A1 (ru) | 2009-08-28 |
CN101501168A (zh) | 2009-08-05 |
BRPI0715918A2 (pt) | 2013-07-30 |
WO2008020169A2 (en) | 2008-02-21 |
ZA200901924B (en) | 2010-01-27 |
DE602007011944D1 (de) | 2011-02-24 |
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