CN103305313A - Combustion catalyst for low-heat value coal - Google Patents

Combustion catalyst for low-heat value coal Download PDF

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Publication number
CN103305313A
CN103305313A CN2013102862605A CN201310286260A CN103305313A CN 103305313 A CN103305313 A CN 103305313A CN 2013102862605 A CN2013102862605 A CN 2013102862605A CN 201310286260 A CN201310286260 A CN 201310286260A CN 103305313 A CN103305313 A CN 103305313A
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coal
low value
combustion
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catalyzer
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CN103305313B (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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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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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 and use catalyzer, be specifically related to a kind of low value coal or the combustion of coal catalyzer that is mixed.
Background technology
Coal is the main energy of China, accounts for national energy ratio and weighs about 70%.A large amount of low value coals that coal produces in process of production are as middle coal, coal slime and coal gangue etc.There are problems such as calorific value is low, slagging scorification is serious in these low value coals, are difficult to be fully utilized, and form the slag stockyard, cause resource huge waste and environmental disruption.For taking full advantage of these resources, the mode of generally taking these low value coals and high-quality coal to be mixed burning is used, as the power plant boiler fire coal.But because that low value coal and high-quality coal are mixed the combustion chemistry property difference of burning is bigger, the combustion processes instability in the coal burning process, exists difficult problems such as efficiency of combustion is low, seriously polluted.Therefore, improve the be mixed efficiency of combustion of coal of low value, particularly improve the burning ratio that is mixed of low value fire coal, to improving the important meaning that China's Energy resources utilization ratio has reality.
The principle of coal catalyticcombustion is to realize the fracture of the various chemical bonds in the coal molecule by catalyzer, provides oxygen molecule required in the partial combustion process by strong oxidizer simultaneously.Reduce gaseous sulfur emissions of oxides purpose in the coal catalyticing combustion process simultaneously in order to reach, add sweetening agent toward contact, oxide compound or oxyhydroxide as calcium, make the oxysulfide and the reactive metal oxide that produce in the coal combustion process, generate metal sulfate or other sulfide and be fixed in the slag.The research to coal combustion catalyst or promotor of patent or bibliographical information at present is to be object with fat coal or special-purpose coal basically.This class coal combustion improver or catalyzer are generally mixed by components such as strong oxidizer, metal oxide, metal carboxylate and an amount of permeate agent, dispersion agents.Mainly formed by potassium permanganate and Repone K as mentioning a kind of efficient additive for fuel coal in the patent of invention 200710132426.2.In the coal catalyst that patent of invention 200710120708.0 is mentioned and the addition means of additive, use various organic permeate agents in a large number.The compound catalysis burning-rate accelerator of economizing on coal that patent of invention 201210243149.3 is mentioned selects for use calcium carbonate, Calucium Silicate powder and calcium oxide as sulphur-fixing agent.
Low value burning of coal characteristic is different with high-quality coal combustioncharacteristics, and the low and high tax of ash oontent of volatile content is deposited characteristic and often caused ignition difficulty, combustion processes instability, slag serious in the low value coal.The strong oxidizer decomposition temperature that existing coal combustion catalyst adopts is lower, even is lower than the combustion initiation temperature of coal dust, and the burning of coal process is difficult to realize promoter action to being mixed.Therefore, exploitation is fit to low value coal and the low value burning of coal catalyzer that is mixed, and can take full advantage of the 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 to use catalyzer, be specially adapted to the low value coal or the combustion of coal catalyzer that is mixed, reach and improve low value coal combustion efficient and the purpose that reduces sulfur oxides emissions.
The present invention is achieved through the following technical solutions:
A kind of low value combustion of coal catalyzer, this catalyzer are that 20～100% main active ingredient and surplus are that tackiness agent is formed by weight percent, and described main active ingredient is made 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 tackiness agent is at least a in sodium salt, sylvite or the molysite of humic acids or xanthohumic acid.
The particle diameter of described catalyzer is for being not more than 100 orders.Its particle diameter is more thin more good, more can promote the 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, crosses behind 100 mesh sieves and gets.
Generally speaking, coal is the heat absorption temperature-rise period at the burning leading portion, and the volatilization of simultaneous small molecules composition and the fracture of part carbochain are decomposed.In the combustion initiation temperature interval, the gasification composition at first burns, and has consumed the oxygen around the coal cinder, causes coal cinder generation coking, makes combustion processes be difficult to continue, and forms carbon residue then.The mechanism of action of coal combustion catalyst is to carry out cracking by small molecules in the coal in the catalysis combustion initiation temperature interval, and the temperature range in ignition stage and contracting nuclear burning stage continues to provide the oxygen species to realize burning away simultaneously.For high-quality was coal-fired, volatile content was 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 tar burning is provided.Strong oxidizer has been finished the process of decomposing oxygen supply in the general coal combustion catalyst about 400 ℃.For the 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 be implemented in the comparatively high temps interval to the combustion-supporting purpose of contracting nuclear burning stage oxygen supply.
So the main technical points of this catalyzer is to deposit characteristic at the tax that volatile content is low in the low value fire coal, ash content is high, carry out chemical tampering in be mixed coal combustion initiation temperature interval and contracting nuclear burning phase temperature interval respectively.By the katalysis of metal humate in the tackiness agent or metal Xanthohumate and metal oxide composition, effectively reduce the combustion initiation temperature of the coal that is mixed, realize stable ignition; In the 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:
Figure 2013102862605100002DEST_PATH_IMAGE001
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, promotes oxidn 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 the 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 the coal that is mixed, and its addition is that low value coal or 1～2% of the coal weight that is mixed get final product.
So the present invention is compared with prior art, the present invention has following advantage:
(1) the present invention is by tackiness agent and metal oxide Fe 3O 4, CeO 2And K 2The katalysis of O, effective low value coal that reduces or the combustion initiation temperature of the coal that is mixed, can reduce 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 the continuing of low value coal or the coal that is mixed, burning completely;
(2) the complex metal oxides Ca in the catalyzer of the present invention 3Co 4O 9Can continue to provide the contracting nuclear burning stage required oxygen by decomposing, make the low value coal combustion abundant, improve its efficiency of combustion and combustion cleanliness, improve the rate of utilization of coal, and reduce the waste of resource;
(3) catalyzer of the present invention adds to and can reduce in the low value coal because of insufficient atmospheric pollution that causes of burning; And can be in combustion processes and oxysulfide (SO 2) reaction, its form with calcium salt is fixed in the coal ash, reach and reduce the discharging that reduces oxysulfide, reduce topsoil.
(4) catalyzer of the present invention can take full advantage of the low value coal resources for low value coal or the coal that is mixed, and reduces its pollution and land seizure.
(5) catalyst preparation process of the present invention is simple, only needs 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 the multiple coal that is mixed, and does not need existing boiler is transformed, can reach economize on coal, desulfurization, the burnt dirt of reduction be in the purpose of one, energy efficiency and to subtract dirty consumption reduction effect remarkable.
 
Description of drawings
Burning weight loss figure behind Fig. 1 low value raw coal combustion weightlessness and interpolation 1% catalyzer of the present invention.
Fig. 2 low value coal combustion that is mixed is weightless and add burning weight loss figure behind 1% catalyzer of the present invention.
 
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 one
In hundred parts of ratios of weight, with Ca 3Co 4O 970%, Fe 3O 425%, K 2O 5% ground and mixed is crossed 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 gets 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, press coal amount 1% and add 0.1g catalyst powder, ground and mixed.Get its blend sample and place corundum crucible, go up in the air atmosphere at simultaneous thermal analysis instrument (NETZSCH STA 409 PC) and carry out thermogravimetric analysis, the result relatively sees Fig. 1.
As seen from Figure 1, above the combustion line that line is the low value raw coal, below line be to add catalyzer afterfire curve of the present invention in the raw coal.After adding catalyzer the firing point of low value raw coal is descended 14 ℃, weightless increase is more than 15%.Illustrate that catalyzer of the present invention has very big promoter action to the burning of low value raw coal, 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 two
In hundred parts of ratios of weight, with Ca 3Co 4O 980%, Fe 3O 415%, CeO 25% ground and mixed is crossed 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 gets 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 the coning and quartering division, obtain the low value coal sample that is mixed.Get coal sample 10 g, press coal amount 2% and add 0.2 g catalyst powder, ground and mixed.Get its blend sample and place corundum crucible, go up in the air atmosphere at simultaneous thermal analysis instrument (NETZSCH STA 409 PC) and carry out thermogravimetric analysis, the result relatively sees Fig. 2.
Fig. 2 result shows, above the combustion line that line is the low value raw coal, below a line be to add catalyzer afterfire curve of the present invention in the raw coal.After in low value is mixed coal sample, adding the combustioncatalysts of 1% weight ratio, the firing point of coal of being mixed descends 3 ℃, weightless increase is more than 10%, illustrate that the burning of coal that is mixed has very big promoter action to catalyzer of the present invention to low value, reduced the be mixed firing point of coal of low value, and increased the be mixed combustion cleanliness of coal of low value, reduced the be mixed waste of coal of low value.
Embodiment three
In hundred parts of ratios of weight, with Ca 3Co 4O 960%, CeO 220%, K 2O 20%, and ground and mixed is crossed 100 mesh sieves, gets catalyzer.
Get Huainan Mining Group grandson village low value raw coal natural air drying, through grinding, cross 100 mesh sieves.Get coal sample 10 g, press coal amount 1.5% and add 0.15 g catalyst powder, ground and mixed.Get its blend sample and place corundum crucible, upward carry out thermogravimetric analysis in the air atmosphere at simultaneous thermal analysis instrument (NETZSCH STA 409 PC), and carry out bomb calorific value according to standard GB/T213-2003 method at automatic calorimeter (ZDHW-6) and measure.The result shows that behind the interpolation catalyzer, the combustion initiation temperature of low value raw coal descends 12 ℃, and net calorific value improves 3.4 %.
Embodiment four
In hundred parts of ratios of weight, with Ca 3Co 4O 930%, Fe 3O 430%, CeO 220%, K 2O 20% ground and mixed is crossed 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, get 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 the coning and quartering division, obtain the low value coal sample that is mixed.Get coal sample 10 g, press coal amount 2% and add 0.2 g catalyst powder, ground and mixed.Get its blend sample and place corundum crucible, upward carry out thermogravimetric analysis in the air atmosphere at simultaneous thermal analysis instrument (NETZSCH STA 409 PC), and carry out bomb calorific value according to standard GB/T213-2003 method at automatic calorimeter (ZDHW-6) and measure.The result shows, add catalyzer after, the be mixed combustion initiation temperature of coal of low value descends 8 ℃, net calorific value improves 4.9%.

Claims (4)

1. low value combustion of coal catalyzer is characterized in that: this catalyzer is that 20～100% main active ingredient and surplus are that tackiness agent is formed by weight percent, and described main active ingredient is made 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, it 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 tackiness agent is at least a in sodium salt, sylvite or the molysite of humic acids or xanthohumic acid.
4. low value combustion of coal catalyzer according to claim 1, it 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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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017013476A1 (en) 2015-07-23 2017-01-26 Uniwersytet Jagielloński Ecological solid fuel additive, reducing soot formation
CN114011419A (en) * 2021-11-15 2022-02-08 上海纳米技术及应用国家工程研究中心有限公司 Anti-sintering VOCsPreparation 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

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WO2001005913A1 (en) * 1999-07-16 2001-01-25 Reatech Phosphor addition in gasification
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CN101168128A (en) * 2006-10-25 2008-04-30 刘芬 Composite metal oxide catalyst and its preparing process and use
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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
US20110131874A1 (en) * 2009-12-08 2011-06-09 Baker Hughes Incorporated Method for improving the efficiency of heat transfer in a coal fired furnace
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

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001005913A1 (en) * 1999-07-16 2001-01-25 Reatech Phosphor addition in gasification
CN101326006A (en) * 2005-12-07 2008-12-17 乔治洛德方法研究和开发液化空气有限公司 Catalyst consisting of a solid support, an oxide and a metal active phase which is grafted on the oxide, a method for the preparation and the use thereof
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
US20110131874A1 (en) * 2009-12-08 2011-06-09 Baker Hughes Incorporated Method for improving the efficiency of heat transfer in a coal fired furnace
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017013476A1 (en) 2015-07-23 2017-01-26 Uniwersytet Jagielloński Ecological solid fuel additive, reducing soot formation
CN114011419A (en) * 2021-11-15 2022-02-08 上海纳米技术及应用国家工程研究中心有限公司 Anti-sintering VOCsPreparation 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

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