CN102260051A - Method for treating NOx generated by firing coal in novel dry-process cement kiln - Google Patents

Method for treating NOx generated by firing coal in novel dry-process cement kiln Download PDF

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Publication number
CN102260051A
CN102260051A CN2010101948060A CN201010194806A CN102260051A CN 102260051 A CN102260051 A CN 102260051A CN 2010101948060 A CN2010101948060 A CN 2010101948060A CN 201010194806 A CN201010194806 A CN 201010194806A CN 102260051 A CN102260051 A CN 102260051A
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coal dust
coal
cement kiln
combustion
nox
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崔素萍
叶文娟
兰明章
王亚丽
王子明
李琛
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Beijing University of Technology
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Beijing University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B7/00—Hydraulic cements
    • C04B7/36—Manufacture of hydraulic cements in general
    • C04B7/364—Avoiding environmental pollution during cement-manufacturing
    • C04B7/365—Avoiding environmental pollution during cement-manufacturing by extracting part of the material from the process flow and returning it into the process after a separate treatment, e.g. in a separate retention unit under specific conditions

Abstract

The invention discloses a method for treating NOx generated by firing coal in a novel dry-process cement kiln, which comprises the following steps of: uniformly mixing a nitrogen fixation agent and coal powder in a decomposing furnace in a molar ratio of the K element in the nitrogen fixation agent to the N element in the coal powder of 5:1-1:5, and performing the next process on the coal fired in the novel dry-process cement kiln according to the conventional method, wherein the nitrogen fixation agent is KOH, K2CO3 or K2SO4. By the method, the aim of expected nitrogen fixation is fulfilled, so that the aim of reducing the NOx emission of the cement kiln is fulfilled.

Description

A kind of coal-fired NO＜sub that produces of new type nonaqueous cement kiln that handles〉x＜/sub method
Technical field
The present invention relates to NO xTreatment process, refer more particularly to and handle in the new type nonaqueous cement kiln because the coal-fired NO that produces xTechnical field, be specifically related to handle in the new type nonaqueous cement kiln because the coal-fired NO that produces xA kind of novel method, NO x(oxynitride) comprises nitrogen protoxide NO, nitrogen peroxide NO 2With nitrous oxide N 2O etc.
Background technology
The main component of cement is a silicate minerals, and its principal element is formed oxygen, calcium, silicon, aluminium etc. and had with global environment and the affine attribute that melts altogether of atmospheric sphere, itself is a kind of product of coordinating with ecotope.But China's Cement industry all occurs with images such as " natural resource and energy-output ratio are big, utilising efficiency is low, and dust and obnoxious flavour disposal of pollutants are serious " all the time.Comparatively speaking, the research of reduction of discharging aspect and application work show hysteresis slightly, concern to tail gas mainly concentrates on dust pollution thing discharging aspect, to the control of gas phase noxious pollutant in the tail gas (for example gas of Cization thing, Sization thing, Nization thing and so on) with reduce discharging research and do not give enough attention.
Just to burn till part be the very important link of manufacture of cement for clinker burning part in the manufacture of cement, and this part mainly is made up of preheater, decomposing furnace, rotary kiln, cooling machine four parts.Raw material decompose to decomposing furnace through the preheater preheating, and after the gas solid separation, decomposed raw material are gone into kiln, and expect that the rate of decomposition of powder generally is controlled at about 90% this moment.Gas from bottom to top, raw material decompose required heat part in decomposing furnace provided by the coal dust of going into decomposing furnace, a required combustion air part is from tertiary air, temperature is at 700 ℃-870 ℃; Another part is from the gas of kiln tail smoke-box.The raw material of predecomposition are gone into rotary kiln, because the kiln body tilts to place and constantly rotation, the raw material of predecomposition constantly to the kiln hood motion, are burnt till grog by the gas heating of high temperature countercurrent flow in kiln, after kiln hood cover lower end falls into the cooling machine, go into clinker warehouse after the cooling.The combustion air of grog rotary kiln is provided by wind and secondary air, and the heat that the violent burning of coal dust provides can make the calcining temperature of clinkering zone reach about 1500 ℃.
In the cement production process process, the generation of NOx mainly comes from nitrogen in the high-temperature fuel and the nitrogen compound in the raw material, and the nitrogen in the raw material is mainly with NH + 4Form is present in the organic constituent, by NH in the raw material of natural material preparation + 4Content is about 80-200g/t.The quantity discharged of cement rotary kiln waste gas NOx is about 300-2200mg/m 3(mark condition, butt) is equivalent to grog discharging 0.8-2.5kg/t-grog per ton.
The method of handling the coal-fired NOx that produces of cement kiln has:
(1) control techniques before the burning
Control techniques before the burning mainly is the denitrogenation of fuel, and the not fine as yet so far exploitation of fuel denitride technology awaits continuing from now on research.
(2) aflame control techniques
Aflame control techniques mainly comprises fractional combustion, low oxygen combustion, and flue gas recirculation.
The ultimate principle of grading combustion technology---fractional combustion is process of coal combustion to be divided into two stages (primary combustion zone and burnt zone) carry out. combustion air is sprayed into burner hearth at twice, reduce the air capacity in coal dust firing zone, just having formed a fuel-rich regions when making coal dust enter burner hearth. the fs is supplied with about 80% of the required theoretical air requirement of burning, fuel burns under the rich fuel condition of anoxybiotic earlier, combustionvelocity and temperature are reduced, thereby suppressed the generation of heating power type NOx. simultaneously, CO and NO that burning generates carry out reduction reaction, and fuel N resolves into intermediate product (as NH, CN, HCN and NH 3Deng) interact or make the NO reduction decomposition, suppressed the generation of fuel type NOx; Subordinate phase is imported the remainder of combustion air with secondary air, become oxygen-enriched combusting, though this moment, air capacity was many, some intermediate products are oxidized to NO, and because of flame temperature is low, the NOx growing amount is little, thereby total NOx growing amount reduces.Adopt the air classifying burning generally can make the NOx quantity discharged reduce by 30%～40%.
The low oxygen combustion technology---this is a kind of optimization device burning, reduces NO xThe simple method of growing amount, go into the kiln air capacity by adjusting control, keep every wind powder ratio that burner nozzle is suitable, or with the low flue gas of kiln afterbody directly or with send into burner hearth after secondary air is mixed, coal dust firing is carried out under near the theoretical air requirement condition as far as possible.In general, adopt low excess air operation can reduce NO xDischarging 15%～20%, but when oxygen concn burner hearth in low excessively (as being lower than 3% below), can cause the rapid rising of CO concentration in flue gas and unburned carbon in flue dust, thus increase chemical incomplete combustion and unburned carbon loss, the economy of burning decline.Low oxygen combustion can make interior some zone of burner hearth present reducing atmosphere in addition, causes slagging scorification of furnace wall cooling wall and high temperature corrosion thereby reduce coal ash fusion temperature.Therefore, during kiln, should choose suitable outlet excess air ratio, in servicely should in time adjust the burning air distribution, avoid occurring because of reducing NO according to burning coal in design xDischarging and cause the generation of some other operation problem.
Flue gas recirculating technique---flue gas recirculation is that a part of cold flue gas (accounting for more than 10% of total exhaust gas volumn) in the afterbody smoke evacuation is sent into burner, or with send into the combustion zone after combustion air mixes mutually, make density loss in the combustion air, the furnace flame temperature reduces and reduces the growing amount of fuel type NO, heating power type NO, generally can reduce by 25% one 35%.And the effect of taking off NO of flue gas recirculation method is not only relevant with fuel type, and relevant with the flue gas recycled amount, NO reduces when the flue gas recirculation multiplying power increases, but further increases circulation ratio, the discharging of NO will be tending towards a definite value, and this value increases with the fuel nitrogen content.But if circulation ratio is excessive, furnace temperature reduces too many, can cause combustion loss to increase.Therefore, the flue gas recirculation rate generally is no more than 30%.When using difficulty and catch fire coal, because the restriction that reduced by furnace temperature and combustion stability, the flue gas recirculation method is inapplicable.A large amount of research work have been done in the improvement of combustion system both at home and abroad, developed many low NO xCombustion technology and equipment, and on some cement furnaces, be applied.According to generation and the failure mechanisms of NOX in the combustion processes, combustion control technology control NOX discharging is mainly based on following strategy: the peak temperature that reduces the burning interior flame; Reduce excess air coefficient and the oxygen concn that reduces ignition zone in the burner; Add NO xReductive agent etc.Mainly comprise following several class methods: low excess air coefficient (LEA), air classifying burning (OFA), flue gas recirculation (FGR), fuel staging or reignition technology, low NO xBurner (LNBs) etc.
But because some low NO xCombustion technology and equipment reduce efficiency of combustion sometimes, cause incomplete combustion loss to increase, and equipment scale increases thereupon, NO xReduced rate also limited, so low at present combustion technology and equipment do not reach the stage of comprehensive practicality as yet, China is because the restriction of economic level mainly is by developing low NO xCombustion technology reduces NO xQuantity discharged; Western developed country mainly adopts flue gases purification and low NO xCombustion technology jointly controls NO xQuantity discharged.
(3) control techniques after the burning
Present domestic cement kiln is the most frequently used is control techniques after the burning.Control techniques after the burning mainly is meant the out of stock technology of flue gas.According to the state of reaction system, denitration technology roughly can be divided into wet method and dry method.Wherein wet method comprises: water absorption method, sour absorption process, alkali absorption method, oxidation absorption process, complexed absorption method and biological clarification etc.Dry method then comprises: catalytic decomposition method, absorbing and reducing method, electronic beam method, plasma-activated method, alternating temperature (transformation) absorption method and catalytic reduction method etc.The dry method denitration accounts for dominant position. and its reason is NOx and SO 2Compare the shortage chemically reactive, be difficult to be absorbed by the aqueous solution; NOx becomes nontoxic N after the dry method reduction 2And O 2, the byproduct of denitration is convenient to handle; Wet method is compared with dry method, and main drawback is that device is complicated and huge, and byproduct for treatment is difficult, and power consumption is big.The cement kiln kiln exit gas adopts catalytic reduction method more at present.Catalytic reduction method can be divided into selective non-catalytic reduction method and selective catalytic reduction two big classes.
The selective non-catalytic reduction method---do not having under the catalyst action, in 900～1100 ℃ of burner hearths, spraying into reductive agent, the rapid pyrolysis of reductive agent and with flue gas in NOx reaction generate N2.Have a certain amount of oxygen in the burner hearth and exist, the reductive agent that sprays into selectively with the NOx reaction, substantially not with oxygen reaction.In the selective non-catalytic reduction process, urine base or amino compound (NH 3Absorbing the NO in the flue gas is alternative, is better reductant) as reductive agent NOx is converted into N 2Non-selective catalytic reduction method needs precious metal as catalyzer, and is expensive bigger.
Selective catalytic reduction---under catalyst action, in about 280～420 ℃ flue gas of temperature, spray into ammonia, NOx is reduced into N 2And H 2O.
Produce now and go up the selective catalytic reductions that use more.This method can be reduced to lower level with the NO emission concentration in the waste gas, and it can solve the NOx pollution problem that vehicle exhaust causes, and domestic and international research person has concentrated on attention on the SCR of NOx, and this method is used widely abroad.
Summary of the invention
The object of the invention provides the oxynitride (NO in a kind of novel method processing cement kiln x), thereby reduce cement kiln NO xQuantity discharged, oxynitride (NO x) comprise nitrogen protoxide NO, nitrogen peroxide NO 2With nitrous oxide N 2O etc.
In the predecomposition clinker burning technological process, fuel is in rotary kiln and the burning of decomposing furnace two places.Wherein fuel is high-temp combustion in rotary kiln, and combustion flame temperature produces a large amount of thermal NOs up to more than 1800 ℃ in the burning.And coal dust burns at low temperatures in the decomposing furnace, and the generation of oxynitride is based on fuel type NOx.In decomposing furnace, the decomposition reaction of coal dust firing and carbonate is mainly taking place, coal dust and raw material mix suspending in hot gas flow, coal dust firing heat release, carbonate thermal endothermic decomposition.Because combustionvelocity is fast, heat release ability height has satisfied the needs of carbonate strong endothermic reaction.On the other hand, continuous minute heat of desorption of carbonate makes the temperature of combustion gas remain on scope a little more than the carbonate eqrilibrium decomposition temperature, limited the rising of gas temperature.
At These characteristics, the present invention mainly takes a kind of new method to handle the NOx that coal dust firing produces in the decomposing furnace, promptly add suitable chemical substance, chemical reaction takes place in the NOx that generates with coal dust firing, generate the nitrogenous salt of high temperatures, thereby reach the purpose that reduces cement kiln NOx discharging, such chemical substance is called nitrogen fixation agent.
The technical solution used in the present invention is: in decomposing furnace, according to K element in the nitrogen fixation agent: the mol ratio of N element is that 5: 1～1: 5 ratio mixes nitrogen fixation agent and coal dust in the coal dust, and the new type nonaqueous cement kiln fire coal according to routine after mixing carries out next step operation;
Described nitrogen fixation agent is KOH, K 2CO 3, K 2SO 4
Draw KOH, K according to interpretation 2CO 3, K 2SO 4These three kinds contain the effect that the K salt can better reach fixed nitrogen.By the analysis of XRD, the main component of the products of combustion of KOH is K 3NO 3, K 3NO 4K 2CO 3The main component of products of combustion be KN 3K 2SO 4The main component of products of combustion be K 4O (NO 2) 2, KNO 2And at KOH, K 2CO 3, K 2SO 4Best in three kinds of salts with the nitrogen fixation effect of KOH.Method of the present invention has reached the purpose of expection fixed nitrogen, thereby reaches the purpose that reduces cement kiln NOx discharging.
Figure of description
Fig. 1 is thermal multigraph, XRD, the infrared figure of embodiment 1KOH and coal dust
The infrared figure of 1-800 ℃ of correspondence among the wherein infrared figure, the infrared figure of 2-606 ℃ of correspondence, the infrared figure of 3-200 ℃ of correspondence, the infrared figure of 4-178 ℃ of correspondence, the infrared figure of 5-152 ℃ of correspondence, the infrared figure of 6-50 ℃ of correspondence;
Fig. 2 is embodiment 2K 2CO 3Thermal multigraph, XRD, infrared figure with coal dust
The infrared figure of 1-45 ℃ of correspondence among the wherein infrared figure, the infrared figure of 2-151 ℃ of correspondence, the infrared figure of 3-204 ℃ of correspondence, the infrared figure of 4-690 ℃ of correspondence, the infrared figure of 5-900 ℃ of correspondence;
Fig. 3 is embodiment 3K 2SO 4Thermal multigraph, XRD, infrared figure with coal dust
The infrared figure of 1-81 ℃ of correspondence among the wherein infrared figure, the infrared figure of 2-204 ℃ of correspondence, the infrared figure of 3-271 ℃ of correspondence, the infrared figure of 4-368 ℃ of correspondence, the infrared figure of 5-464 ℃ of correspondence, the infrared figure of 6-590 ℃ of correspondence, the infrared figure of 7-900 ℃ of correspondence;
Fig. 4 is thermal multigraph, the XRD of Comparative Examples coal dust.
Embodiment
The present invention is described in detail below to enumerate embodiment, but realization of the present invention is not limited to following example, and the nitrogen content in the test coal dust is 0.83%.
The scheme that experiment is taked is: KOH, K 2CO 3, K 2SO 4Burn respectively with after coal dust mixes according to a certain percentage, test as a comparison with independent coal dust firing.Resultant after the burning is carried out XRD analysis, whether contain the N salt in the main component of analyte phase, and the incendiary thermodynamic process is analyzed accurately in conjunction with corresponding thermogravimetric and infrared result.
Embodiment 1
The blending ratio of KOH and coal dust is: K element among the KOH: to equal 2: 1 mixed even for the mol ratio of N element in the coal dust, and its thermal multigraph, XRD, infrared figure see Fig. 1.Fig. 4 is an independent coal dust sample as a comparison, and by the independent coal dust XRD figure of Fig. 4 shape as can be seen, the independent incendiary product of coal dust mainly is SiO, CaSO 4, CaO, and KOH and coal dust firing after the generation product mainly be K 3NO 3, K 3NO 4, CaO, the experiment of this group has added an amount of KOH in coal dust, KOH has participated in reaction in the incendiary process, K ionic salt becomes main product, the XRD of Fig. 1 mainly is the main nitrogenous salt after the analytic combustion.By comparative analysis, add the purpose that KOH has reached expection fixed nitrogen in the coal dust.
Embodiment 2
K 2CO 3With the blending ratio of coal dust be: K 2CO 3In the K element: to equal 1: 1 mixed even for the mol ratio of N element in the coal dust, and its thermal multigraph, XRD, infrared figure see Fig. 2.Fig. 4 is an independent coal dust sample as a comparison, and by the independent coal dust XRD figure of Fig. 4 shape as can be seen, the independent incendiary product of coal dust mainly is SiO, CaSO 4, CaO, and K 2CO 3With coal dust firing after the generation product mainly be K 2CO 3, KN 3, this group experiment has added an amount of K in coal dust 2CO 3, the K of part in the incendiary process 2CO 3Participated in reaction, but K 2CO 3Do not react completely, so in products of combustion, also contain a large amount of K 2CO 3K ionic salt becomes main product, and the XRD of Fig. 2 mainly is the main nitrogenous salt after the analytic combustion.
Embodiment 3
K 2SO 4With the blending ratio of coal dust be: K 2SO 4In the K element: to equal 1: 1 mixed even for the mol ratio of N element in the coal dust, and its thermal multigraph, XRD, infrared figure see Fig. 3.Fig. 4 is an independent coal dust sample as a comparison, and by the independent coal dust XRD figure of Fig. 4 shape as can be seen, the independent incendiary product of coal dust mainly is SiO, CaSO 4, CaO, and K 2SO 4With coal dust firing after the generation product mainly be K 2SO 4, KO 2, K 4O (NO 2) 2, KNO 2, this group experiment has added an amount of K in coal dust 2SO 4, the K of part in the incendiary process 2SO 4Participated in reaction, but K 2SO 4Do not react completely, so in products of combustion, also contain a large amount of K 2SO 4K ionic salt becomes main product, and the XRD of Fig. 3 mainly is the main nitrogenous salt after the analytic combustion.
Comparative Examples
Independent coal dust, its thermal multigraph, XRD, infrared figure see Fig. 4.
The sample of the foregoing description and Comparative Examples carries out the infrared experiment of thermogravimetric; the temperature rise rate of experiment is 5 °/min; final temperature is 900 ℃; under initial temperature, be incubated 120s; at final temperature insulation 900s, shielding gas is a high pure nitrogen, keeps the speed of 80ml/min～150ml/min in the experimentation; reactant gases is a pressurized air, keeps the speed of 60ml/min～100ml/min in the experimentation.The temperature of infrared inlet mouth is set to 200 ℃.
The infrared experiment of thermogravimetric can get the heat decomposition curve of powdered sample and the gaseous constituent of corresponding differing temps, products of combustion remaining in the thermogravimetric instrument carries out XRD analysis again, thereby the main component of concrete analysis solid combustion product, and the corresponding gaseous constituent that draws in infrared.
Draw KOH, K according to interpretation 2CO 3, K 2SO 4These three kinds contain the effect that the K salt can better reach fixed nitrogen.By the analysis of XRD, the main component of the products of combustion of KOH is K 3NO 3, K 3NO 4K 2CO 3The main component of products of combustion be KN 3K 2SO 4The main component of products of combustion be K 4O (NO 2) 2, KNO 2And at KOH, K 2CO 3, K 2SO 4Best in three kinds of salts with the nitrogen fixation effect of KOH.

Claims (4)

1. method of handling the coal-fired NOX that produces of new type nonaqueous cement kiln, it is characterized in that, may further comprise the steps: in decomposing furnace, according to K element in the nitrogen fixation agent: the mol ratio of N element is that 5: 1～1: 5 ratio mixes nitrogen fixation agent and coal dust in the coal dust, and the new type nonaqueous cement kiln fire coal according to routine after mixing carries out next step operation; Described nitrogen fixation agent is KOH, K 2CO 3, K 2SO 4
2. a kind of method of handling the coal-fired NOX that produces of new type nonaqueous cement kiln of claim 1 is characterized in that K element among the KOH: the mol ratio of N element equals 2: 1 in the coal dust.
3. a kind of method of handling the coal-fired NOX that produces of new type nonaqueous cement kiln of claim 1 is characterized in that K 2CO 3With the blending ratio of coal dust be: K 2CO 3Middle K element: the mol ratio of N element equals 1: 1 in the coal dust.
4. a kind of method of handling the coal-fired NOX that produces of new type nonaqueous cement kiln of claim 1 is characterized in that K 2SO 4With the blending ratio of coal dust be: K 2SO 4Middle K element: the mol ratio of N element equals 1: 1 in the coal dust.
CN2010101948060A 2010-05-28 2010-05-28 Method for treating NOx generated by firing coal in novel dry-process cement kiln Pending CN102260051A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103710064A (en) * 2013-12-18 2014-04-09 华中科技大学 Sludge-lignite molded fuel and preparation method thereof
CN104350022A (en) * 2013-04-11 2015-02-11 Khd洪保德韦达克有限公司 Method for operating a plant for producing cement
CN109603505A (en) * 2019-01-25 2019-04-12 广东万引科技发展有限公司 A kind of method of denitration of the dry-process cement rotary kiln flue gas with biomass bamboo charcoal
CN109628196A (en) * 2018-12-27 2019-04-16 湖北工业大学 A kind of preparation method of fixed nitrogen type cement rotary furnace coal-saving agent

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104350022A (en) * 2013-04-11 2015-02-11 Khd洪保德韦达克有限公司 Method for operating a plant for producing cement
US10479727B2 (en) 2013-04-11 2019-11-19 KHD Humbolt Wedag GmbH Method for operating a plant for producing cement
CN103710064A (en) * 2013-12-18 2014-04-09 华中科技大学 Sludge-lignite molded fuel and preparation method thereof
CN103710064B (en) * 2013-12-18 2015-05-20 华中科技大学 Sludge-lignite molded fuel and preparation method thereof
CN109628196A (en) * 2018-12-27 2019-04-16 湖北工业大学 A kind of preparation method of fixed nitrogen type cement rotary furnace coal-saving agent
CN109628196B (en) * 2018-12-27 2021-01-26 湖北工业大学 Preparation method of nitrogen fixation type coal saving agent for cement short kiln
CN109603505A (en) * 2019-01-25 2019-04-12 广东万引科技发展有限公司 A kind of method of denitration of the dry-process cement rotary kiln flue gas with biomass bamboo charcoal

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Application publication date: 20111130