CN103305313B - Combustion catalyst for low-heat value coal - Google Patents

Combustion catalyst for low-heat value coal Download PDF

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Publication number
CN103305313B
CN103305313B CN201310286260.5A CN201310286260A CN103305313B CN 103305313 B CN103305313 B CN 103305313B CN 201310286260 A CN201310286260 A CN 201310286260A CN 103305313 B CN103305313 B CN 103305313B
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coal
low value
combustion
low
catalyzer
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CN103305313A (en
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冯绍杰
章祥林
宋箭
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Hebei Bo Chang Trade Ltd By Share Ltd
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Anhui Jianzhu University
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Abstract

The invention provides a combustion catalyst for low-heat value coal. The catalyst comprises 20-100% of main active ingredients and the balance of binder, wherein the main active ingredients comprise Ca3Co4O9, Fe304, CeO2, and K2O in percentage by weight. The catalyst provided by the invention can be used for effectively reducing the initiation temperature of the low-heat value coal, the initiation temperature of the low-heat value coal can be reduced by 3-15 DEG C when the catalyst which accounts for 1-2% of the low-heat value coal is added, stable initiation of the low-heat value coal is achieved, the continuous and complete combustion of the low-heat value coal is promoted, the combustion efficiency and burning clarity of the low-heat value coal are improved, the utilization ratio of the coal is improved, and resource waste and air pollution are reduced.

Description

A kind of low value combustion of coal catalyzer
Technical field
The present invention relates to a kind of fire coal catalyzer, be specifically related to a kind of low value coal or mixture combustion of coal catalyzer.
Background technology
Coal is the main energy of China, accounts for national energy ratio 70% left and right that weighs.A large amount of low value coals that coal produces in process of production, as middle coal, coal slime and coal gangue etc.There is the problems such as calorific value is low, slagging scorification is serious in these low value coals, is difficult to be fully utilized, and forms slag stockyard, causes resource huge waste and environmental disruption.For making full use of these resources, generally take the mode of these low value coals and high-quality combustion of mixed coal to be used, as power plant boiler fire coal.But because the combustion chemistry property difference of low value coal and high-quality combustion of mixed coal is larger, combustion processes is unstable, in coal burning process, exists the difficult problems such as efficiency of combustion is low, seriously polluted.Therefore, improve the efficiency of combustion of low value mixture coal, particularly improve the mixture burning ratio of low value fire coal, there is real important meaning to improving China's Energy resources utilization ratio.
The principle of coal catalyticcombustion is to realize the fracture of the various chemical bonds in coal molecule by catalyzer, provides oxygen molecule required in partial combustion process by strong oxidizer simultaneously.In coal catalyticing combustion process, reduce gaseous sulfur emissions of oxides object in order to reach simultaneously, add sweetening agent toward contact, as the oxide compound of calcium or oxyhydroxide, make the oxysulfide and the reactive metal oxide that in coal combustion process, produce, generate metal sulfate or other sulfide and be fixed in slag.At present patent or bibliographical information is take fat coal or special coal as object to the research of coal combustion catalyst or promotor substantially.This class coal combustion improver or catalyzer are generally mixed by components such as strong oxidizer, metal oxide, metal carboxylate and appropriate permeate agent, dispersion agents.As mentioned in patent of invention 200710132426.2, a kind of efficient additive for fuel coal is mainly made up of potassium permanganate and Repone K.In the coal catalyst that patent of invention 200710120708.0 is mentioned and the addition means of additive, use in a large number various organic permeate agents.The compound catalysis burning-rate accelerator of economizing on coal that patent of invention 201210243149.3 is mentioned selects calcium carbonate, Calucium Silicate powder and calcium oxide as sulphur-fixing agent.
Low value burning of coal characteristic is different from high-quality coal combustioncharacteristics, and in low value coal, the low and high tax of ash oontent of volatile content deposits that characteristic often causes ignition difficulty, combustion processes is unstable, slag is serious.The strong oxidizer decomposition temperature that existing coal combustion catalyst adopts is lower, even, lower than the combustion initiation temperature of coal dust, mixture burning of coal process is difficult to realize promoter action.Therefore, exploitation is applicable to low value coal and low value mixture burning of coal catalyzer, can make full use of low value coal resources, reduces and pollutes and land seizure, realizes the effect of economy and environment doulbe-sides' victory.
Summary of the invention
The object of the present invention is to provide a kind of fire coal catalyzer, be specially adapted to low value coal or mixture combustion of coal catalyzer, reach and improve low value coal combustion efficiency and the object that reduces sulfur oxides emissions.
The present invention is achieved through the following technical solutions:
A kind of low value combustion of coal catalyzer, the main active ingredient that this catalyzer is 20～100% by weight percent and surplus are that tackiness agent forms, described main active ingredient is made up of by weight percentage following component:
Ca 3Co 4O 9：30%～80%
Fe 3O 4：0%～30%
CeO 2：0%～20%
K 2O：0%～20%。
Further, described tackiness agent is metal humate or metal Xanthohumate.
Further, described metal humate is at least one in Sodium salts humic acids, potassium humate or humic acids iron; Described metal Xanthohumate is at least one in SODLUM FULVATE, potassium fulvate or xanthohumic acid iron.
The particle diameter of described catalyzer is for being not more than 100 orders.Its particle diameter is more carefully better, more can promote low value burning of coal.
Low value combustion of coal catalyzer of the present invention is by proportioning, main activeconstituents and tackiness agent to be mixed by mechanical mill, excessively after 100 mesh sieves, obtains.
Generally speaking, coal is heat absorption temperature-rise period at burning leading portion, and the volatilization of simultaneous small molecules composition and part carbon chain break decompose.In combustion initiation temperature interval, first gasification composition burns, and has consumed the circumnuclear oxygen of coal, causes coal cinder generation coking, makes combustion processes be difficult to continue, and then forms carbon residue.The mechanism of action of coal combustion catalyst is to carry out cracking by the coal small molecular in catalysis combustion initiation temperature interval, continues to provide oxygen species to realize simultaneously burn away in the temperature range in ignition stage and contracting nuclear burning stage.For high-quality is coal-fired, volatile content is more, and combustion initiation temperature is lower, and coal combustion catalyst lays particular emphasis on the carbon-carbon bond fracture of catalysis coal tar and the oxygen molecule of coal char combustion is provided.In general coal combustion catalyst, strong oxidizer has completed the process of decomposing oxygen supply 400 ℃ of left and right.For low value coal, this temperature does not still reach the combustion initiation temperature of low value coal.So adopt general coal combustion catalyst to be difficult to realize in comparatively high temps interval the object to contracting nuclear burning stage oxygen-supplying combustion-supporting.
So the main technical points of this catalyzer is to deposit characteristic for the tax that in low value fire coal, volatile content is low, ash content is high, chemical tampering is carried out in and contracting nuclear burning phase temperature interval interval at mixture coal combustion initiation temperature respectively.By the katalysis of metal humate in tackiness agent or metal Xanthohumate and metal oxide composition, effectively reduce the combustion initiation temperature of mixture coal, realize stable ignition; In subsequent combustion process, complex metal oxides Ca 3co 4o 9can continue to provide the contracting nuclear burning stage required oxygen by decomposing, its breakdown be as follows:
Ca 3Co 4O 9→3CaO+4CoO+O 2
Complex metal oxides Ca 3co 4o 9the cobalt oxide (CoO) of one of degradation production participate in the catalysis fracture of coal cinder surface C-C key, accelerating oxidation reaction; Another kind of degradation production is that calcium oxide (CaO) can react with oxysulfide in combustion processes, and its form with calcium salt is fixed in coal ash, reaches and reduces the order ground that reduces sulfur oxides emissions.
Catalyzer of the present invention is applicable to all fire coals, is specially adapted to use in low value coal or mixture coal, and its addition is 1～2% of low value coal or mixture coal weight.
So the present invention is compared with prior art, tool of the present invention has the following advantages:
(1) the present invention is by tackiness agent and metal oxide Fe 3o 4, CeO 2and K 2the katalysis of O, the low value coal effectively reducing or the combustion initiation temperature of mixture coal, can reduce the combustion initiation temperature 3-15 ℃ of low value coal by the catalyzer that adds low value coal 1%, realize the stable ignition of low value coal, and promote continuing, burning completely of low value coal or mixture coal;
(2) the complex metal oxides Ca in catalyzer of the present invention 3co 4o 9can continue to provide the contracting nuclear burning stage required oxygen by decomposing, make low value coal combustion abundant, improve its efficiency of combustion and combustion cleanliness, improve the rate of utilization of coal, and reduced the waste of resource;
(3) catalyzer of the present invention adds in low value coal and can reduce because of insufficient atmospheric pollution causing of burning; And can be in combustion processes and oxysulfide (SO 2) reaction, its form with calcium salt is fixed in coal ash, reach and reduce the discharge that reduces oxysulfide, reduce topsoil.
(4) catalyzer of the present invention can make full use of low value coal resources for low value coal or mixture coal, reduces its pollution and land seizure.
(5) catalyst preparation process of the present invention is simple, only need to mix by simple mechanical mill, can realize scale operation.
(6) the present invention is applicable to the burning of joining of low value coal or multiple mixture coal, does not need existing boiler to transform, can reach economize on coal, the burnt dirt of desulfurization, reduction is in the object of one, energy efficiency and to subtract dirty consumption reduction effect remarkable.
Accompanying drawing explanation
The weightless burning weight loss figure with adding after 1% catalyzer of the present invention of Fig. 1 low value raw coal combustion.
The weightless burning weight loss figure with adding after 1% catalyzer of the present invention of Fig. 2 low value mixture coal combustion.
Embodiment
The invention will be further described for the following stated specific examples, but the present invention's scope required for protection is not limited to the related scope of example.
Embodiment mono-
In hundred parts of ratios of weight, by Ca 3co 4o 970%, Fe 3o 425%, K 2o5% ground and mixed, crosses 100 mesh sieves, makes main active ingredient, and then gets the main active ingredient 80% and Sodium salts humic acids 20% ground and mixed of aforementioned preparation, crosses 100 mesh sieves and obtains catalyzer.
Get the low value raw coal natural air drying in Huainan Mining Group Sun Tuan colliery, through grinding, cross 100 mesh sieves.Get coal sample 10g, add 0.1g catalyst powder, ground and mixed by coal amount 1%.Get its blend sample and be placed in corundum crucible, in the upper air atmosphere of simultaneous thermal analysis instrument (NETZSCH STA409PC), carry out thermogravimetric analysis, result is relatively shown in Fig. 1.
As seen from Figure 1, above a combustion line that line is low value raw coal, below a line be in raw coal, to add catalyzer afterfire curve of the present invention.After adding catalyzer, the firing point of low value raw coal is declined 14 ℃, weightless increasing more than 15%.Illustrate that former burning of coal has very large promoter action to catalyzer of the present invention to low value, reduced the firing point of low value raw coal, and increased the combustion cleanliness of low value raw coal, reduced the waste of low value raw coal.
Embodiment bis-
In hundred parts of ratios of weight, by Ca 3co 4o 980%, Fe 3o 415%, CeO 25% ground and mixed, crosses 100 mesh sieves, makes main active ingredient, and then gets the main active ingredient 70% and potassium fulvate 30% ground and mixed of aforementioned preparation, crosses 100 mesh sieves and obtains catalyzer.
That gets Huainan Mining Group washing coal works washes middle coal, coal slime and coal gangue natural air drying, through grinding, crosses 100 mesh sieves.By weight, get and wash middle coal, coal slime and coal gangue and be respectively 4:3:3 and mix, adopt coning and quartering division, obtain low value mixture coal sample.Get coal sample 10g, add 0.2g catalyst powder, ground and mixed by coal amount 2%.Get its blend sample and be placed in corundum crucible, in the upper air atmosphere of simultaneous thermal analysis instrument (NETZSCH STA409PC), carry out thermogravimetric analysis, result is relatively shown in Fig. 2.
Fig. 2 result shows, above a combustion line that line is low value raw coal, below a line be in raw coal, to add catalyzer afterfire curve of the present invention.In low value mixture coal sample, add after the combustioncatalysts of 1% weight ratio, the firing point of mixture coal declines 3 ℃, weightless increasing more than 10%, illustrate that burning of coal has very large promoter action to catalyzer of the present invention to low value mixture, reduce the firing point of low value mixture coal, and increased the combustion cleanliness of low value mixture coal, reduce the waste of low value mixture coal.
Embodiment tri-
In hundred parts of ratios of weight, by Ca 3co 4o 960%, CeO 220%, K 2o20%, ground and mixed, crosses 100 mesh sieves, obtains catalyzer.
Get Huainan Mining Group grandson village low value raw coal natural air drying, through grinding, cross 100 mesh sieves.Get coal sample 10g, add 0.15g catalyst powder, ground and mixed by coal amount 1.5%.Get its blend sample and be placed in corundum crucible, in the upper air atmosphere of simultaneous thermal analysis instrument (NETZSCH STA409PC), carry out thermogravimetric analysis, and carry out bomb calorific value measurement according to standard GB/T/T213-2003 method at automatic calorimeter (ZDHW-6).Result shows, adds after catalyzer, and the combustion initiation temperature of low value raw coal declines 12 ℃, and net calorific value improves 3.4%.
Embodiment tetra-
In hundred parts of ratios of weight, by Ca 3co 4o 930%, Fe 3o 430%, CeO 220%, K 2o20% ground and mixed, crosses 100 mesh sieves, makes main active ingredient; And then get the main active ingredient 20% and xanthohumic acid iron 40% and SODLUM FULVATE 40% ground and mixed of aforementioned preparation, and cross 100 mesh sieves, obtain catalyzer.
That gets Huainan Mining Group washing coal works washes middle coal, coal slime and coal gangue natural air drying, through grinding, crosses 100 mesh sieves.By weight, get and wash middle coal, coal slime and coal gangue and be respectively 4:3:3 and mix, adopt coning and quartering division, obtain low value mixture coal sample.Get coal sample 10g, add 0.2g catalyst powder, ground and mixed by coal amount 2%.Get its blend sample and be placed in corundum crucible, in the upper air atmosphere of simultaneous thermal analysis instrument (NETZSCH STA409PC), carry out thermogravimetric analysis, and carry out bomb calorific value measurement according to standard GB/T/T213-2003 method at automatic calorimeter (ZDHW-6).Result shows, adds after catalyzer, and the combustion initiation temperature of low value mixture coal declines 8 ℃, and net calorific value improves 4.9%.

Claims (4)

1. a low value combustion of coal catalyzer, is characterized in that: the main active ingredient that this catalyzer is 20～100% by weight percent and surplus are that tackiness agent forms, and described main active ingredient is made up of by weight percentage following component:
Ca 3Co 4O 9?：30%～80%
Fe 3O 4?：0%～30%
CeO 2：0%～20%
K 2O：0%～20%。
2. low value combustion of coal catalyzer according to claim 1, is characterized in that: described tackiness agent is metal humate or metal Xanthohumate.
3. low value combustion of coal catalyzer according to claim 2, is characterized in that: described metal humate is at least one in Sodium salts humic acids, potassium humate or humic acids iron; Described metal Xanthohumate is at least one in SODLUM FULVATE, potassium fulvate or xanthohumic acid iron.
4. low value combustion of coal catalyzer according to claim 1, is characterized in that: the particle diameter of described catalyzer is for being not more than 100 orders.
CN201310286260.5A 2013-07-09 2013-07-09 Combustion catalyst for low-heat value coal Expired - Fee Related CN103305313B (en)

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PL231237B1 (en) 2015-07-23 2019-02-28 Univ Jagiellonski Ecological additive for solid fuels, restricting formation of soot
CN114011419B (en) * 2021-11-15 2023-05-30 上海纳米技术及应用国家工程研究中心有限公司 Anti-sintering VOC (volatile organic compound) s Preparation method of combustion catalyst, product and application thereof
CN114133973A (en) * 2021-11-16 2022-03-04 福建龙麟集团有限公司 Efficient catalytic combustion-supporting process for special coal for cement kiln

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101016495A (en) * 2007-02-26 2007-08-15 刘利明 Fire coal additive
CN101168128A (en) * 2006-10-25 2008-04-30 刘芬 Composite metal oxide catalyst and its preparing process and use
CN101381647A (en) * 2008-10-21 2009-03-11 梁宴邱 High-efficiency coal-saving burning additive
CN101921645A (en) * 2010-09-15 2010-12-22 重庆大学 New application of calcium peroxide and fire coal combustion-supporting solid sulfide additive
CN103131519A (en) * 2013-02-07 2013-06-05 洛阳大泽节能环保科技有限公司 Boiler fire coal sulfur fixation composition method

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU4898699A (en) * 1999-07-16 2001-02-05 Reatech Phosphor addition in gasification
EP1795260A1 (en) * 2005-12-07 2007-06-13 L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Catalyst comprising a solid support, an oxide and an active metal phase grafted on the oxide; process for its preparation and use
US20110131874A1 (en) * 2009-12-08 2011-06-09 Baker Hughes Incorporated Method for improving the efficiency of heat transfer in a coal fired furnace

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101168128A (en) * 2006-10-25 2008-04-30 刘芬 Composite metal oxide catalyst and its preparing process and use
CN101016495A (en) * 2007-02-26 2007-08-15 刘利明 Fire coal additive
CN101381647A (en) * 2008-10-21 2009-03-11 梁宴邱 High-efficiency coal-saving burning additive
CN101921645A (en) * 2010-09-15 2010-12-22 重庆大学 New application of calcium peroxide and fire coal combustion-supporting solid sulfide additive
CN103131519A (en) * 2013-02-07 2013-06-05 洛阳大泽节能环保科技有限公司 Boiler fire coal sulfur fixation composition method

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