CN102585965B - Additive capable of improving coal combustion efficiency and reducing NOx emission simultaneously - Google Patents
Additive capable of improving coal combustion efficiency and reducing NOx emission simultaneously Download PDFInfo
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Abstract
The invention relates to an additive which is an improvement on a coal combustion additive taking MMT (methyl-cyclopentadienyl-manganese-tricarbony) as an effective component. The additive contains the following components: 0.01-0.1wt% of the MMT, 0.005-0.02wt% of tetrabutyl titanate, 0.005-0.02wt% of iron acetylacetone, 0.1-0.5wt% of sulfonate type anionic surfactants, 0.1-1wt% of dimethylbenzene and/or diesel oil and the balance of water. With the additive, a cheap water solution solvent which is uniformly dispersed and is diluted by a large mulriple is prepared, so that a ppm (parts per million)-grade trace effective added component MMT is uniformly dispersed on coal particles in practical application, and the amount of the original single MMT in ppm-grade added into the coal is changed into the amount of the water solution in percentage-grade added into the coal, thereby solving the problem of being difficult to add in actual application, not only greatly facilitating the actual adding and use, but also reducing the requirements on adding equipment for mixing with coal. By only adopting a common stirring device, the additive can be uniformly added and dispersed on the surface of the coal powder. As the tetrabutyl titanate and the iron acetylacetone are added simultaneously, by virtue of the synergistic effect, the catalyzing effect of the MMT during combustion of the coal is further improved. The amount of the combination liquid solvent added into the coal is 1-2 wt%. Therefore, the content of carbon in fly ash can be reduced by 26-67 percent, and the NOx emission can be reduced by 30-40 percent.
Description
Technical field
The present invention is the coal combustion additive improvement to being effective ingredient with the methyl cyclopentyl-dialkyl-tricarbon manganium, relate in particular to big times of water gaging dilution of a kind of cheapness and amplify down, still have the additive that can improve coal burning efficient and reduction NOx quantity discharged simultaneously of fine catalytic activity.
Background technology
Coal is subjected to multiple factor affecting in the burner hearth burning, objectively is difficult to abundant perfect combustion, and coal burning is insufficient, not only can not bring into play its heat energy fully, cause the waste of the energy, coal burning also can produce dust and NOx discharging and cause Air quality deterioration, serious environment pollution simultaneously.People endeavour to study various additive for coal combustion always for a long time, to improve the efficiency of combustion of coal, reduce the discharging of NOx and dust.
Chinese patent CN1576356, CN1576357, CN1597832 have disclosed in coal and to have added the trace manganese compound (typical case has methyl cyclopentyl-dialkyl-tricarbon manganium, commodity letter name MMT), has active effect to improving coal burning efficient and reduction NOx and dust discharge, and show better effects, be a kind of novel coal combustion additive.But its precondition to coal burning katalysis performance is the manganic compound that adds can be dispersed on the coal particle or wherein, could better bring into play combustion catalysis, require " manganic compound must reach monokaryon or little form " for this reason, promptly " manganese atom suitably be separated into single atom or maximum 50 atoms bunch; manganese atom just is enough to provide reliable catalytic effect for combustion reactions ", so just can there be more manganese atom to be dispersed on the coal particle, surround and the burning of catalysis coal particle, it adopts and coal is carried in the additive introducing enters in the airflow of combustion chamber.Yet its addition (accounting for coal) is atomic is ppm level (1-500ppm, preferable addition is 20-100ppm), objectively this trace interpolation not only makes troubles to interpolation, also require high to adding equipment requirements, having limited it applies, objectively this trace adds and also to be difficult to accomplish evenly effectively be dispersed in the huge amount coal particle surface in addition, therefore actually is difficult to guarantee giving full play to of industrial application catalytic effect.The applicant also repeats above-mentioned patented method test, really find denier like this (≤500ppm) interpolation, it is very big not only to add difficulty, and actual effect flies carbon content and reduce still greatly inadequately reducing NOx and ash, causes the practical application catalytic performance far below laboratory results.Though CN1576356 mentions can be by forming manganic compound pre-formation compositions of additives, can amplify addition like this, but manganic compound (methyl cyclopentyl-dialkyl-tricarbon manganium) is a non-polar compound, be not can with other any liquid thorough mixing (for example solubleness extreme difference in water, MMT solubleness in water is 10ppm in the time of 20 ℃); CN1597832 proposes manganic compound is added in water, oil, tensio-active agent, polymeric dispersions, polymers soln, flocculation agent and the resin liquid, and it is prepared into solution, emulsion, mixture.Yet some additive can influence the manganic compound catalytic activity, so objectively be not above-mentioned any liquid agent can both mix with manganic compound the good liquid agent of effect, though can dissolving each other with manganic compound, solvent based liquid agent wherein makes liquid agent, but because solvent based liquid agent price problem, making big doubly amount add affiliation causes cost to increase substantially, and lose actual application value, if only be that little times of amount is mixed and made into liquid agent, same trace adds the dispersing uniformity problem still fails to be resolved, and practical significance is little.And adopt the dilution of big doubly amount to make liquid agent, can combustion catalysis effect that the bonding time spent unknown, and these have not only limited it and have applied, and affect giving full play to of catalytic effect.The all not concrete open liquid agent that how to prepare big amount of dilution of particularly above-mentioned prior art still is single interpolation 1-500ppm manganic compound so embodiment is used, and the report result of use, and the Nox quantity discharged is reduced by 18%, reduces carbon content 54% in the flying dust.
Above-mentioned deficiency still has is worth improved place.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art, provides a kind of under big times of water gaging dilution of cheapness amplified, and still has the additive that can improve coal burning efficient and reduction NOx quantity discharged simultaneously of fine catalytic activity.
The object of the invention realizes, on a large amount of experimental basis, main improvement one is to select cheap water as solvent, make (thousand times of levels) the diluted liquid agent of the big doubly amount of methyl cyclopentyl-dialkyl-tricarbon manganium (MMT), be difficult to be dispersed in problem on the coal dust to solve the trace interpolation, make liquid agent because of add-on big (percentage magnitude) easily and coal dust mix, guarantee its dispersiveness in fire coal; The 2nd, by adding tetrabutyl titanate and ferric acetyl acetonade simultaneously, to the coal catalytic performance, further improve " two fall " effect, thereby overcome the deficiencies in the prior art when acting synergistically further raising MMT burning by both, realize the object of the invention.Specifically, the present invention can improve coal burning efficient simultaneously and reduce the additive of NOx quantity discharged, it is levied to be to form and comprises: the methyl cyclopentyl-dialkyl-tricarbon manganium of 0.01-0.1wt%, the tetrabutyl titanate of 0.005-0.02wt%, the ferric acetyl acetonade of 0.005-0.02wt%, the sulfonate type aniorfic surfactant of 0.1-0.5wt%, the dimethylbenzene of 0.1-1wt% and/or diesel oil and excess water.
Before the detailed description, make a presentation earlier, so that those skilled in the art have one clearly to understand to this patent invention general plotting technical scheme and the basic fundamental effect that reaches by the basic function and the effect that can reach to invention.
Compositions of additives of the present invention, owing to selected specific sulfonate type aniorfic surfactant, and dimethylbenzene and/or diesel oil, not only make cheap water to realize dissolving each other fully with MMT, making micro-MMT to be dispersed in greatly doubly measures in the cheap aqueous solution, both solved the water-fast problem of MMT, make micro-MMT greatly doubly measuring homodisperse in the dilution water again, form stable emulsion, thereby being added, micro-MMT becomes relatively large (percentage magnitude) interpolation, reach with coal dust and mix, thus solved micro-MMT can be in coal dust the abundant uniform problem of dispersing and mixing, and greatly reduced adding equipment requirements.Experiment shows that adding ferric acetyl acetonade can improve the NOx decomposition, add tetrabutyl titanate, can improve manganese to the coal pyrolysis performance, the degradation production of pyrolysis coal product and NOx interacts, its synergy has further improved coal-fired catalytic performance, can reduce the NOx quantity discharged simultaneously, and the flying dust carbon content.
Among the present invention.
The sulfonate type anion surfactant can form emulsion oil-in-water, helps oil phase and is dissolved in a large amount of aqueous phases.They are such as but not limited to sodium alkyl benzene sulfonate, sulfonated, alkylsulfonate, sulphosuccinates, high fatty acid amide sulfonate, sulfonated petro-leum, sulfonated lignin, sulfonated alkyl naphathalene.Because they all have similar polar head-group, can be singly with also mixing use.
Dimethylbenzene and/or diesel oil, a kind of cheap solvent, main effect is that the MMT of trace is dissolved in wherein, then by adding the sulfonate type aniorfic surfactant, it is dispersed in the water, forms stable emulsion, thereby it is dispersed in big times of water gaging solution to improve MMT.
Ferric acetyl acetonade, test and Selection result, experiment shows and helps decompose to improve NOx.
Tetrabutyl titanate, test and Selection result, experiment shows can improve manganese to the coal pyrolysis performance, and pyrolysis coal product and NOx degradation production interact, and can reduce the NOx quantity discharged simultaneously, and the flying dust carbon content.Thereby both synergies have further improved MMT when burning catalytic performance.
In addition, the triethyl phosphate and/or the diethyl silicone oil that can also add 0.05-0.1wt% in the solution of the present invention, by improving the lubricity of liquid agent, add fashionable dispersiveness on coal particle with further raising, and do not find that it has restraining effect to the MMT catalytic activity in the test.
The present invention can improve coal burning efficient simultaneously and reduce the additive of NOx quantity discharged, than prior art, owing to adopt the organic solvent of specific cheapness, and specific aniorfic surfactant, make the MMT of trace to dissolve each other with big times of water gaging (thousand times of magnitudes), thereby make the homodisperse cheapness and greatly doubly measure dilute aqueous solution agent (emulsion), solve the practical application trace and added the dispersing uniformity of (ppm level) effective constituent MMT on coal particle, make and become the percentage magnitude (for example 1%-2wt%) that the aqueous solution adds by original single MMTppm magnitude in the coal add-on, thereby solved practical application and added a difficult problem, not only greatly made things convenient for actual interpolation to use, also reduced simultaneously to mix and added equipment requirements with coal, adopt common whipping appts, just can evenly add and be dispersed in the coal dust surface, and good emulsion stability, long-term storage do not influence use properties (deposit after 6 months result of use constant).Owing to add tetrabutyl titanate and ferric acetyl acetonade simultaneously, its synergy has further improved the catalytic effect of MMT in the coal burning process simultaneously.In actual coal furnace, test, present composition liquid agent and coal add with 1%-2wt% percentage magnitude, can reduce flying dust carbon content 26% ~ 67%, reduce NOx discharge capacity 30%-48%, its effect obviously is better than the background prior art, single ppm magnitude adds carbon content 54% in the reduction flying dust, reduces Nox quantity discharged 18%.In addition, do not contain the harmful element that boiler is had detrimental effect in the selected additive of the present invention, thereby use is safe to boiler.Additive of the present invention is a solvent greatly doubly to measure cheap water, makes MMT and greatly doubly measures dilute aqueous solution, not only is the greatest feature of additive of the present invention, is different from the similar additive of prior art institute difference but also constitute additive of the present invention; Simultaneously owing to be added with tetrabutyl titanate and ferric acetyl acetonade in the composition, can by detecting instrument for example gas chromatography differentiated.
Below in conjunction with several specific embodiments and comparative example; essence of the present invention is further understood in exemplary illustration and help; but the embodiment detail only is for the present invention is described; do not represent the present invention to conceive whole technical schemes down; therefore should not be construed as the total technical scheme of the present invention is limited; some are In the view of the technician; the unsubstantiality that does not depart from the present invention's design increases and/or change; for example simple the change or replacement of technical characterictic to have same or similar technique effect all belongs to protection domain of the present invention.
Embodiment
Embodiment: by implementing tabulation 1 proportioning (component unit is wt%), earlier MMT is dissolved in dimethylbenzene and/or the diesel oil, adds sulfonate type anion surfactant and water then successively, under the lucifuge condition, mix, promptly get liquid composition of the present invention.
Respectively with embodiment and comparative example composition, add Shenmu County's pulverized anthracite (composition sees Table 3) with coal dust amount 1.2wt% and spray alr mode, mix more than 1 hour, send into roasting kiln, coal input quantity is sample size 40kg per hour, at primary air velocity 80Pa, under the condition of secondary wind speed 300Pa, each sample sees Table 2 to the unburned carbon in flue dust of coal burning process and the influence of denitration efficiency.
Annotate: experiment is to carry out on the one dimension stove pilot plant test platform of Thermal Power Engineering institute of Zhejiang University, utilizes ignition system to put the kindling temperature of fighting during on-test, for the burning of coal dust creates conditions.When temperature in the stove reaches the temperature that coal dust can stable burning, close ignition system, open fuel system.According to stove internal combustion situation and temperature conditions, and in conjunction with the analytical results of flue gas and the calibration curve of feeding machine, the feeding machine rotating speed is progressively strengthened from 50r/min, and finally be controlled at about 250r/min-300r/min, at this moment, the delivery rate of feeding machine is about 40kg/h, utilizes the heat kindling temperature of coal dust self.After burner hearth second stage temperature keeps stablizing, promptly satisfy test requirements document.Guarantee to finish all preparation work before this: 1. guarantee that temperature acquisition system can works better; 2. guarantee that the flue gas analysis system can works better; 3. guarantee that the Fly ash sampling system can work normally.
The flue gas analysis system is made of jointly M﹠C flue gas pretreater and Horiba PG250 flue gas analyzing apparatus, and Horiba PG250 can detect NOx, SO2, CO, CO2 and O2 simultaneously.The employing dry method detects, and the flue gas pretreater extracts flue gas from the burner hearth afterbody, and the flying dust that carries in the flue gas is carried out filtration treatment, prevents from follow-up test set is polluted and damages.
Fly ash sampling adopts the CCD-304 dynamic pressure balancing constant speed flue gas sampler of Wuhan analytical instrument factory.
Table 2 presentation of results.
1, be measured value in the table.
2, contrast CK (blank coal sample) unburned carbon in flue dust 9.28%, denitration efficiency 0.
3, effect comprehensively illustrates: by table 2, add MMT and have certain reduction unburned carbon in flue dust, reach denitration efficiency (comparing 1) preferably, but do not add tetrabutyl titanate and ferric acetyl acetonade (comparing 1), and add ferric acetyl acetonade (relatively 2) or tetrabutyl titanate (relatively 3) separately, catalytic effect is limited, and unburned carbon in flue dust reduces less, and denitration efficiency is poor; And add both simultaneously, its synergy shows effect preferably, though example 5 shows that MMT increases, because tetrabutyl titanate and ferric acetyl acetonade addition descend, cause the flying dust carbon content to descend, further show the catalysed promoted effect of tetrabutyl titanate and ferric acetyl acetonade.
4, carbon content reduces (26% ~ 67%): be the difference that deducts the unburned carbon in flue dust gained of coal after adding the catalyst emulsion burning with the unburned carbon in flue dust after the blank coal sample CK burning, divided by the unburned carbon in flue dust calculating gained of blank coal sample CK.
To those skilled in the art; under this patent design and specific embodiment enlightenment; some distortion that can directly derive or associate from this patent disclosure and general knowledge; those of ordinary skills will recognize also can adopt additive method; or the substituting of known technology commonly used in the prior art; and the equivalence of feature changes or modification; mutual various combination between feature; for example the concrete kind of sulfonate type aniorfic surfactant changes; or the like unsubstantiality change, can be employed equally, can both realize this patent representation function and effect; launch for example no longer one by one to describe in detail, all belong to this patent protection domain.
Claims (2)
1. can improve the additive of coal burning efficient and reduction NOx quantity discharged simultaneously, it is characterized in that forming and comprise: the methyl cyclopentyl-dialkyl-tricarbon manganium of 0.01-0.1wt%, the tetrabutyl titanate of 0.007-0.02wt%, the ferric acetyl acetonade of 0.005-0.02wt%, the sulfonate type aniorfic surfactant of 0.1-0.5wt%, the dimethylbenzene of 0.7-1wt% and/or diesel oil and excess water.
2. according to the described additive that can improve coal burning efficient simultaneously and reduce the NOx quantity discharged of claim 1, it levies triethyl phosphate and/or the diethyl silicone oil that is to add 0.05-0.1wt%.
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| CN102989510A (en) * | 2012-12-24 | 2013-03-27 | 江南大学 | Catalyst for sludge incineration process |
| CN104645794A (en) * | 2015-01-13 | 2015-05-27 | 广州特种承压设备检测研究院 | Method for optimizing SNCR (selective non-catalytic reduction) denitrification system of garbage incinerator by adding anionic surfactant |
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| GB865343A (en) * | 1958-07-24 | 1961-04-12 | Ethyl Corp | Antiknock fluid |
| CN1179174A (en) * | 1995-03-14 | 1998-04-15 | 普拉蒂纳姆·普拉斯公司 | Utilization of platinum group in diesel engines |
| CN1204684A (en) * | 1997-02-07 | 1999-01-13 | 英国乙基石油添加剂有限公司 | Fuel compound with reducing discharge and its use |
| CN1576356A (en) * | 2003-07-18 | 2005-02-09 | 乙基石油添加剂有限公司 | Lowering the amount of carbon in fly ash from burning coal by a manganese additive to the coal |
| CN1597832A (en) * | 2003-08-28 | 2005-03-23 | 乙基石油添加剂有限公司 | Method and composition for suppressing coal dust |
| CN1718699A (en) * | 2005-04-06 | 2006-01-11 | 尹小林 | Catalytic combustion adjuvant for coal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090071067A1 (en) * | 2007-09-17 | 2009-03-19 | Ian Macpherson | Environmentally-Friendly Additives And Additive Compositions For Solid Fuels |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB865343A (en) * | 1958-07-24 | 1961-04-12 | Ethyl Corp | Antiknock fluid |
| CN1179174A (en) * | 1995-03-14 | 1998-04-15 | 普拉蒂纳姆·普拉斯公司 | Utilization of platinum group in diesel engines |
| CN1204684A (en) * | 1997-02-07 | 1999-01-13 | 英国乙基石油添加剂有限公司 | Fuel compound with reducing discharge and its use |
| CN1576356A (en) * | 2003-07-18 | 2005-02-09 | 乙基石油添加剂有限公司 | Lowering the amount of carbon in fly ash from burning coal by a manganese additive to the coal |
| CN1597832A (en) * | 2003-08-28 | 2005-03-23 | 乙基石油添加剂有限公司 | Method and composition for suppressing coal dust |
| CN1718699A (en) * | 2005-04-06 | 2006-01-11 | 尹小林 | Catalytic combustion adjuvant for coal |
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