CN101501168A - Coal with improved combustion properties - Google Patents

Coal with improved combustion properties Download PDF

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Publication number
CN101501168A
CN101501168A CNA200780030088XA CN200780030088A CN101501168A CN 101501168 A CN101501168 A CN 101501168A CN A200780030088X A CNA200780030088X A CN A200780030088XA CN 200780030088 A CN200780030088 A CN 200780030088A CN 101501168 A CN101501168 A CN 101501168A
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China
Prior art keywords
coal
metalloporphyrin
aforementioned
phthalocyanine
iron
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CNA200780030088XA
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Chinese (zh)
Inventor
保罗·戴
费利克斯·希罗维斯基
谢尔盖·道特
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Aquafuel Research Ltd
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Aquafuel Research Ltd
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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

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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)

Abstract

A method for improving the combustion properties of a coalcomprises treating said coal with a metal porphyrin. The invention also provides a coal having a metal porphyrin deposited thereon, and a method of producing heat, comprising combusting the coal.

Description

Improved combustible coal
Technical field
The present invention relates to improve the method for burning of coal, also relate to and improved combustible coal, and the coal combustion technology that reduces discharging.
Background technology
Incomplete combustion in the coal-fired forging furnace causes residual carbon in the ashes (ash), has limited the efficient of coal-burning power plant.Carbon in the ashes is facilitated overall ash emission, reduces the efficient of the electrostatic precipitator be used to remove ashes, and makes ashes be difficult to handle, for example as cement component.
What many coal-fired power plants (comprising Russia and Chinese power plant) used now is reactive low grizzle.The main challenge that other coal of this grade that burns is faced is:
Carbon content height in the flyash (fly ash): reach 15-20%;
A large amount of NOx dischargings.
Have the unburned carbon of high-content in the flyash and can cause tangible thermosteresis: reach 5% or more, it depends on the coal content (coal ash content) in the ashes.Excess air ratio (α) is that the NOx concentration in 1.4 the waste gas is 700-900mg/m 3(with NO 2Recomputate), depend on boiler performance.
EP1498470 lists the method for the carbon in the ashes that several reduction coal combustion generate, and comprises the excess air that increase is introduced with fuel, or adds metal such as calcium and magnesium.The effect of these methods is undesirable, and the increase of air capacity causes higher NOx quantity discharged, and the requirement of metal (as calcium and magnesium) is big, and the contamination system.EP1498470 proposes to add the manganic compound of 2-500ppm, is preferably manganese tricarbonyl compound.
Summary of the invention
According to a first aspect of the invention, provide the method for improving burning of coal, described method comprises with metalloporphyrin handles described coal.
Second aspect of the present invention provides the coal that deposits metalloporphyrin on it.
Find that the present invention can improve the carbon after-flame, reduce the carbon content in the ashes.Can also reduce the activation energy of oxidation.In the burning formation of NOx be higher than stoichiometry and require the excess air of (requirement) relevant: excessive more NOx of meaning many more more and thermo-efficiency is low more.Rate of combustion increase/activation energy reduces can reduce the growing amount that excess air required and reduced NOx.The general airflow of initiatively regulating and control the combustion chamber, and can make this adjustment impel the combustion conditions optimization, so that reduce the carbon content in the ashes as far as possible and reduce NOx as far as possible.
The present invention is for grizzle (as brown coal or bituminous coal) particularly suitable..
Metalloporphyrin of the present invention preferably contains the metal with oxidation state possible more than 2 kinds or 2 kinds.Example comprises transition metal such as iron, cobalt or manganese.
The metalloporphyrin additive can be placed in the aqueous solution, and is applied to solid fuel by means commonly known in the art, for example by being ejected on the solid fuel.Alternatively, can use metalloporphyrin by distillation and vapour deposition.
Porphyrin is common in nature, and it plays a very important role to various bioprocesss.Synthetic porphyrin (as phthalocyanine (phthalocyanine)) has industrial use, and for example copper phthalocyanine is widely used as green pigment (cyan pigment).Porphyrin is all aromatic system, and it can hold multiple atoms metal and have high thermal stability.Porphyrin can be modified by for example sulfurization, to change its solvability in various media.
Description of drawings
Below, will be to be illustrated as purpose, invention will be further ex-plained with reference to the appended drawings, wherein:
Fig. 1-3 be respectively according to an aspect of the present invention coal and TG, DTG and the DTA result of the coal of comparative example;
Fig. 4-6 shows untreated brown coal respectively, uses H 2SO 4The linearizing DTG data of brown coal of handling and the brown coal crossed with the Fe additive treating;
Fig. 7 and 8 DTA results for untreated brown coal and the brown coal crossed with iron-based additive of the present invention and cobalt-based additive treating of the present invention respectively;
Fig. 9-11 shows untreated brown coal respectively and TG, example weight loss percentage ratio and the DTG result of the brown coal crossed with Fe additive of the present invention and Co additive treating.
Detailed Description Of The Invention
Heat analysis method is such as thermogravimetry (TG), differential thermal analysis (DTA) and differential scanning calorimetry (DSC) extensive use in the research of relevant coal utilization.
Thermogravimetry (TG) is widely used in the reactivity of Study on Coal/charcoal (char). The true demonstration, reactivity depends on that coal rank is other, maceral forms (maceral composition) and/or carbonization temperature (charring temperature). Coal combustion reactivity is generally measured by TG under two conditions, (i) isothermal, and under constant temperature, and (ii) non-isothermal, under constant firing rate. Adopt the thermoconductive TGA (DTG) under the non-isothermal condition (being combustion curve (burning profile)), can obtain reactivity parameter such as temperature, after-flame temperature (BT) and the activation energy of maximum (peak) combustion rate (PT).
Use thermal analysis system (TGDTA) research combustion adjuvant on the impact of the kinetic parameter of coal combustion.
The coal sample specification
The coal that uses in the present invention is the brown coal from the Novomosvsk coal basin.
Embodiment 1
Iron (II) phthalocyanine (0.1-0.2g) is dissolved in the vitriol oil (50-60ml).(～2g) (2-3mm granularity) 2 hours, standing over night is soaked it to stir the brown coal sample under the room temperature in solution.After the stirring, leach the coal that deposits phthalocyanine.Measure the residual concentration of iron (II) phthalocyanine by the visible spectrophotometric analysis of UV/.Determine the amount of sedimentary iron-based additive by the concentration difference of starting soln and residual solution.Water cleans the coal that leaches, and its pH is reached to neutrality, and air-dry 72-144 hour to constant weight.Calculating 0.2% iron (II) phthalocyanine deposits on the coal.It is equivalent to the iron of about 200ppm.After the drying, in mortar, coal sample is ground to form dust and analyze in order to DTA/DTG.
To untreated (" pure (neat) ") brown coal and comparing property of the brown coal measurement of handling with the same terms (different being to use wherein do not have the vitriol oil of dissolved iron phthalocyanine (' Fe additive ')) of embodiment 1.Result and the result who calculates illustrate at Fig. 1-6, below are described.
DTA result shows that sample exothermic activity that Fe handled is much larger than untreated brown coal.Between about 100 ℃, 350-450 ℃ and the influence between 600-800 ℃ especially obvious.Proceed thermogravimetric and measure, until constant weight, the sample loss of wherein handling is 91.2% of an initial weight, and untreated coal is 86.6%.In addition, the coal of handling obtains constant weight at about 800 ℃, and untreated coal reaches constant weight at 850 ℃.This result proves that additive of the present invention is unusual and improves solid-fuelled incendivity effectively.
Reaction model
In handling the DTG data that obtain, similar to existing document, it is the control of the one-level chemical reaction of 0.5＜n＜1 that the kinetics of supposing oxidation of coal is subjected to the power factor (kinetic exponent), and supposition extending influence under used experiment condition can be out in the cold:
dα/dτ＝k(1-α) n
Wherein α is a transformation efficiency, and τ is the time, and k is the Arrhenius rate constant that depends on temperature, k=Aexp (Δ E ≠/ RT).R is a gas law constant, model parameter A and Δ E ≠Be frequency factor (frequencyfactor) and activation energy.Degree of conversion alpha is represented with following formula: α=(m i-m τ)/(m i-m f), m wherein iAnd m fBe starting weight per-cent and final weight per-cent, m τWeight percent under the time τ that is write down for the TG experimental session.Actual time is related simply by constant rate of heating with temperature, T=T 0+ β τ.Suppose n=1, can be by drawing ln[-ln (1-α) T 2] to the figure of 1/T and obtain straight line.Can infer the value of activation energy from the collinear slope that obtains.
The loss of the corresponding residual water of the first peak of about 100 ℃ of temperature, the release of the corresponding volatile matter in about 300-400 ℃ second peak.Because the burning of charcoal is observed a spike in the phase III.
Following the illustrating of value of the activation energy that obtains.
Do not contain additive and H of no use 2SO 4The brown coal of handling: Δ E ≠=16.8kJ/mol.
Do not contain additive but use H 2SO 4The brown coal of handling: Δ E ≠=16.7kJ/mol.
The brown coal that contain the Fe additive: Δ E ≠=11.3kJ/mol.
Use the Fe additive to cause activation energy decline 5.5kJ/mol, be 33% of initial value 16.8kJ/mol.The test of the additive that brown coal are used has shown the carbon after-flame that improves, and causes bigger total weight loss:
Additive The minimizing of carbon content in the ashes
The Fe additive 29％
Lesser temps is realized weight loss down, has proved the katalysis of additive.
Additive Total weight loss
Do not contain additive 87.6％/850℃
The Fe additive 91.2％/800℃
Linear regression data at Fig. 4-6 shown in the following table 1-3.
The linear regression of pure brown coal (Fig. 4):
Y＝A+B*X
The parameter value error
Figure A200780030088D00081
Table 1
The linear regression (Fig. 5) of the brown coal of crossing with vitriolization:
Y＝A+B*X
The parameter value error
Figure A200780030088D00082
Table 2
Contain the linear regression (Fig. 6) of the brown coal of Fe additive:
Y＝A+B*X
The parameter value error
Table 3
Embodiment 2
As embodiment 1, the different disulfonic acid phthalocyanine cobalts (cobalt phthalocyaninedisulphonate) that are to use replace sulfuric acid as fluid carrier as metalloporphyrin and use distilled water.
The result illustrates at Fig. 7-11.
Although the present invention obtains explanation by specific embodiment, ought to understand in the scope of the present invention that does not depart from the claims definition and can modify and modification the present invention.

Claims (24)

1. improve the method for burning of coal, described method comprises with metalloporphyrin handles described coal.
2. method according to claim 1, wherein said porphyrin is a phthalocyanine.
3. method according to claim 1 and 2, wherein said metal are that oxidation state is greater than a kind of transition metal.
4. according to any described method in the aforementioned claim, wherein said metal is selected from the group of being made up of iron, cobalt, manganese or its whole or any two kinds mixture.
5. according to any described method in the aforementioned claim, wherein said metalloporphyrin is an iron-phthalocyanine.
6. according to any described method in the aforementioned claim, wherein said coal is brown coal.
7. according to any described method in the aforementioned claim, the step of wherein handling coal comprises having dissolved the solution of metalloporphyrin in the coal application of fluid carrier, leaches solid subsequently and is dried or makes its drying.
8. method according to claim 7, wherein said fluid carrier comprises the vitriol oil.
9. method according to claim 7, wherein said fluid carrier is a waterborne liquid.
10. according to any described method among the claim 7-9, it further comprises removes the step that water cleans coal behind the solution.
11. according to any described method among the claim 1-6, the step of wherein handling coal comprises the described metalloporphyrin of vapour deposition.
12. deposit the coal of metalloporphyrin.
13. coal according to claim 12, wherein said metalloporphyrin is a phthalocyanine.
14. according to claim 12 or 13 described coals, wherein said metal is that oxidation state is greater than a kind of transition metal.
15. according to any described coal among the aforementioned claim 12-14, wherein said metal is selected from the group of being made up of iron, cobalt, manganese or its whole or any two kinds mixture.
16. according to any described coal among the aforementioned claim 12-15, wherein said metalloporphyrin is an iron-phthalocyanine.
17. according to any described coal among the aforementioned claim 12-16, wherein said coal is brown coal.
18. according to any described coal among the aforementioned claim 12-17, the concentration of wherein said metalloporphyrin is in the 0.05-0.5wt% scope.
19. according to any described coal among the aforementioned claim 12-17, the concentration of wherein said metalloporphyrin is in the 0.1-0.3wt% scope.
20. according to any described coal among the aforementioned claim 12-17, the concentration of wherein said metalloporphyrin is about 0.2wt%.
21. the generation method of heat, it comprises any described coal among the burning claim 12-20.
22. reduce the method for burning and exhausting, it comprises the coal of handling with formation to coal interpolation metalloporphyrin, and the coal of the described processing of burning in the combustion chamber that excess air reduces.
23. metalloporphyrin improves Application of Additives as burning of coal.
24. iron-phthalocyanine is as the combustion modifications Application of Additives of brown coal.
CNA200780030088XA 2006-08-12 2007-08-06 Coal with improved combustion properties Pending CN101501168A (en)

Applications Claiming Priority (2)

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CN102639681A (en) * 2009-12-08 2012-08-15 贝克休斯公司 A method for improving the efficiency of heat transfer in a coal fired furnace

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CN102539376B (en) * 2012-01-13 2013-07-03 中国矿业大学 Method for determining physical oxygen sorption amount of functional groups on coal surface
CN110146545A (en) * 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 A method of boiler combustion performance is improved using coal quality burning discriminant index
CN110420638A (en) * 2019-08-22 2019-11-08 安徽工业大学 A kind of catalyst and its application method of the denitration in situ simultaneously of catalysis burning coal tar

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US20090277080A1 (en) 2009-11-12
JP2010500527A (en) 2010-01-07
ZA200901924B (en) 2010-01-27
ATE495232T1 (en) 2011-01-15
KR20090045325A (en) 2009-05-07
EP2057254B1 (en) 2011-01-12
GB0616094D0 (en) 2006-09-20
DE602007011944D1 (en) 2011-02-24
EP2057254A2 (en) 2009-05-13
EA013898B1 (en) 2010-08-30
EA200900301A1 (en) 2009-08-28
WO2008020169A2 (en) 2008-02-21

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Application publication date: 20090805