CN209917627U - Novel dry process is living beings deNOx systems for cement kiln - Google Patents
Novel dry process is living beings deNOx systems for cement kiln Download PDFInfo
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- CN209917627U CN209917627U CN201920186626.4U CN201920186626U CN209917627U CN 209917627 U CN209917627 U CN 209917627U CN 201920186626 U CN201920186626 U CN 201920186626U CN 209917627 U CN209917627 U CN 209917627U
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Abstract
The application relates to a novel dry process is living beings deNOx systems for cement kiln, it spouts with the device including the powder that is used for spouting with living beings denitration powder and is used for spouting with the water agent of living beings denitration water agent and spouts with the device, the water agent spouts with the device including the water agent spray gun that is located rotary kiln tail end to the position (1) department between the cubic tuber pipe tail end that is located the cement kiln, spouts with the powder with the device including the powder spray gun that is located position (2) department between the rear segment of decomposing furnace to the bottom one-level cyclone section of thick bamboo entry. The flue gas denitration device has the advantages that the flue gas denitration device is economical, efficient and environment-friendly by utilizing atmosphere characteristics of the decomposing furnace and through synergistic collocation of two biomass denitration agents (water agent and powder) and three spraying and adding positions, the device has the characteristics of low equipment investment, simplicity and convenience in use, green and renewable denitration agents and the like, the emission reduction of NOx in the cement industry and the environmental protection are powerfully promoted, and the device has important environmental, social and economic meanings.
Description
Technical Field
The application belongs to cement industry flue gas denitration field, especially relates to a novel dry process is living beings deNOx systems for cement kiln.
Background
With the expansion of the production scale of cement in China, the discharge amount of nitrogen oxides (NOx) in the cement industry becomes the third largest pollution source second to thermal power generation and automobile exhaust, and the increasingly fragile ecological environment is seriously influenced. In addition, in recent years, smoke denitration in the cement industry is urgent in large and medium-sized cities across the country due to natural disasters such as haze and acid rain. The United release of environmental protection department of 12 months in 2013 and the State quality supervision, inspection and quarantine Bureau jointly release 'emission Standard of atmospheric pollutants for Cement industry' GB4915-2013 to replace the original standard GB4915-2004, and stipulate the NOx (according to NO) of the existing and newly-built cement plants2Meter) emission concentration not exceeding 400mg/m3The critical area implementation special emission limit is 150mg/m3。
Currently, the most widely used flue gas denitration technology in the cement industry is the selective non-catalytic reduction NOx technology (SNCR). The SNCR method may use ammonia, ammonia gas, or urea as a reducing agent. The denitration efficiency of the technology is low (generally<60%), which results in higher flue gas denitration costs for cement enterprises and also fails to meet increasingly stringent NOx emission standards (NOx emission concentration cannot be reduced to 150mg/m 3). Titanium-based vanadium-based catalyst (V) is commonly used in Selective Catalytic Reduction (SCR) technology2O5-WO3/TiO2). The SCR method may also use ammonia, ammonia gas, or urea as a reducing agent. The SCR method has a high active temperature window (320-420 ℃), and an SCR device needs to be arranged in front of a kiln tail dust collector. However, there is dust and SO in the flue gas2The concentration is high, which easily causes catalyst poisoning and reduces the service life of the catalyst. SCR and SIn the NCR denitration technology, the using efficiency of ammonia water is 60-80%, when the temperature is too high, the ammonia reacts with oxygen to generate NOx, and when the temperature is too low, the reduction rate of the NOx is too low, and the ammonia in flue gas escapes seriously. In addition, ammonia water is also a high-energy-consumption and high-pollution product, and the ammonia water denitration is only used for transferring pollution from the cement industry to the fertilizer industry, so that the technology does not have any significance for emission reduction at the national level. Therefore, the development of a low-cost and high-efficiency flue gas denitration technology suitable for the cement industry is urgently needed.
In addition, the prior technical specification GB 51045-. Based on the particularity of the denitration reaction principle of the denitration technology, the source of target pollutants, the denitration reaction conditions (such as the denitration reaction temperature), the reaction environment, the selection of the denitration agent and the like, the skilled person in the field generally considers that the denitration technology is obviously different from other environmental protection technologies such as the desulfurization technology and the like, and then the technology in other fields cannot be directly used for solving the problems in the denitration technology.
Generally, the denitration process in the prior art has low efficiency and poor denitration effect, and the denitration agent has the problems of high cost and serious pollution; moreover, the technical field is easy to limit when a person skilled in the art develops the denitration technology, so that a satisfactory economical, environment-friendly and efficient denitration technology for the dry-process cement kiln still does not appear at present.
On the other hand, biomass resources on earth are very large in quantity and can be continuously regenerated, and the main constituent elements of the biomass resources are C, H and O, which are three elements which are most frequently converted or used in modern chemical industry. Biomass resources play a more important role in the human resource structure, if they can be efficiently converted into starting materials that can be utilized by the chemical industry. Therefore, the preparation of various chemicals from biomass has become an important means for the efficient utilization of biomass resources, and the development of biomass chemical technology is taken as an important strategic deployment and a great deal of manpower and material resources are invested in research and development in all countries in the world. From the redox point of view of reaction, C and H elements contained in the biomass have reducibility, and how to apply the C and H elements in the biomass as a nitrogen oxide reducing agent in the cement industry to replace the currently used high-energy reducing agent ammonia water is an important research target with wide prospect and great economic and social benefits.
The applicant finds that by using the denitration system, the efficiency of the denitration process can be obviously improved, the denitration effect is improved, and the denitration cost is reduced.
SUMMERY OF THE UTILITY MODEL
In order to reduce the emission of NOx in the flue gas of a cement kiln (particularly a novel dry-process cement kiln), the applicant provides a biomass denitration system for the cement kiln according to the characteristics of the cement production process (particularly the characteristics of a decomposing furnace structure and atmosphere), so that economic, efficient and environment-friendly flue gas denitration is realized.
The novel dry cement production method is a modern cement production method taking suspension preheating and kiln outside decomposition technologies as the core, and is a cement production method generally adopted in China. The apparatus used in the new dry cement production process typically includes at least rotary kiln, decomposing furnace and cyclone.
In one aspect, the present application provides a novel biomass denitration system for a dry cement kiln, which comprises a powder spraying device for spraying biomass denitration powder and an aqueous agent spraying device for spraying a biomass denitration aqueous agent, wherein the aqueous agent spraying device comprises an aqueous agent spray gun located at a first position (also referred to as position 1, position (1)) between a tail end of a rotary kiln of the cement kiln and a tail end of a tertiary air duct (preferably a kiln tail smoke chamber), and the powder spraying device comprises a powder spray gun located at a second position (also referred to as position 2, position (2)) between an inlet of a rear section to a lowermost stage cyclone in a decomposing furnace (preferably an upstream part of a connecting air duct from an outlet of the decomposing furnace to the lowermost stage cyclone). Optionally, the aqueous agent spraying device further comprises an aqueous agent spraying gun at a third position (also referred to as position 3, position (3)) between the outlet of the decomposing furnace and the inlet of the lowest stage cyclone (preferably, the outlet of the decomposing furnace to the descending part of the connecting air pipe of the lowest stage cyclone).
The biomass denitration water sprayed by the water agent spraying device at the position 1The biomass in the agent reacts with water to generate CO and CH4、H2And hydrocarbon compounds such as HCN. The mixture can rapidly and efficiently reduce most of NOx into N2. And at the position 2, the powder spraying device sprays the biomass denitration powder to further reduce NOx. At an optional position 3, the other part of the biomass denitration aqueous agent sprayed by the aqueous agent spraying device can reduce the residual NOx in the flue gas into N2And finally, ultra-low NOx emission is realized.
The spraying in this application refers independently at each occurrence thereof to the addition of the denitrifier to the desired location by pressure in the presence or absence of a carrier (e.g., water or a carrier gas such as air). Other means known to those skilled in the art may also be used to add the denitrifier to the desired location, as long as the other means can add the denitrifier to the desired location. In the present application, "add on", "drop on", "inject on" and "add on" may be used interchangeably. In the embodiment of the application, the spraying refers to the spraying realized by the system disclosed by the application.
This application is through using as above spout the combination that adds the position, especially the spray gun with spout the combination that adds the position, can show the efficiency that improves denitration technology, improve the denitration effect to reduce the denitration cost. The applicant found that by using the system in which the aqueous biomass denitration agent is supplied at the position 1 and the powdered biomass denitration agent is supplied at the position 2, an excellent denitration effect can be obtained, and the denitration efficiency achieved is significantly higher than that in the prior art. Moreover, the system in which the aqueous biomass denitration agent is further supplied at the position 3 can achieve higher denitration efficiency than the system in which the aqueous biomass denitration agent is supplied at the position 1 and the aqueous biomass denitration powder is supplied at the position 2.
Besides the water aqua spray gun, the water aqua spraying device preferably further comprises a water aqua storage tank, a circulating pump, a jet pump, a flow meter, a valve, a water aqua pipeline and a compressed air pipeline. The water agent storage tank is preferably provided with a special large-flow circulating pump, the circulating pump can be used as an unloading pump, and the circulating pump can solve the problems of high viscosity and easy layering of the biomass denitration water agent, so that the denitration water agent is uniformly dispersed. The double-fluid spray gun is made of heat-resistant steel materials, the internal structure is very smooth, the denitration water agent can be prevented from being blocked due to wall hanging scaling in a pipeline, and meanwhile, the spray gun can have the service life of more than half a year. The number of the double-fluid spray guns is preferably even, and the double-fluid spray guns are symmetrically arranged in pairs, so that the denitration water agent can be uniformly dispersed in the reaction zone.
Besides the powder spray gun, the powder spraying device preferably further comprises a powder storage bin, a metering feeder, a pneumatic conveying pump, a Roots blower, a powder pipeline, a compressed air pipeline and a valve. The pneumatic conveying pump can preferably adopt a Roots blower or compressed air as an air source. The jet pump needs to overcome the viscosity of the biomass denitration aqueous solution, and preferably can adopt a plunger pump, a gear pump or a multistage centrifugal pump.
The reactions that may be involved in the denitration process are as follows:
(1) the biomass denitration water agent is decomposed or reacts with carbon to release hydrocarbon:
2C+O2→2CO
C+H2O→CO+H2
CxHyOz→(x-z)C+z CO+y/2H2
(2) hydrocarbons reduce NOx to nitrogen:
2NOx+(x+1)H2→2NH+x H2O
NH+NH→N2+H2
2H2+2NO→N2+2H2O
2NOx+x C→N2+x CO2
2NOx+2x C→N2+2x CO
2NOx+2x CO→N2+2x CO2
the reaction principle of the denitration process is complex, various reaction processes are staggered, and the reaction generated under different conditions and environments can change at any time, so that it is not easy to obtain the denitration agent which can obtain excellent denitration effect under various working conditions.
Through theoretical and practical research for many years, this application has creatively provided biomass denitration system's technical scheme. The biomass denitration system comprises a powder spraying device for spraying biomass denitration powder and an aqueous agent spraying device for spraying a biomass denitration aqueous agent.
(1) The method comprises the following steps of (1) biomass denitration powder:
the biomass denitration powder comprises: 50-90 wt% of coal gangue powder; 10-40 wt% of graphite ore powder; and 5-30 wt% of biomass carbon powder. In one embodiment, the gangue powder comprises 50, 55, 60, 65, 70, 75, 80, 85, 90% by weight of the biomass denitration powder. In one embodiment, the graphite ore powder comprises 10, 15, 20, 25, 30, 35, 40% by weight of the biomass denitration dust. In one embodiment, the biomass charcoal powder comprises 5, 8, 10, 12, 15, 18, 20, 25, 28, 30 wt% of the biomass denitration dust. In a preferred technical scheme, the biomass denitration powder consists of 50-90 wt% of coal gangue powder, 10-40 wt% of graphite mineral powder and 5-30 wt% of biomass carbon powder, and the sum of the components is 100%. The biomass denitration powder is prepared by drying, processing, uniformly mixing and the like by using various raw materials according to the expected amount.
In the biomass denitration powder, the coal gangue refers to solid waste discharged in a coal mining process and a coal washing process, and is a black and gray rock which has lower carbon content and is harder than coal and is associated with a coal bed in a coal forming process. The gangue powder in this application may be one sold in the market or obtained in other known ways. In one embodiment, the coal gangue powder used in the present application is produced in Wuping county, Fujian province, and ground to a fineness of 200 mesh with a carbon content of about 25%. The coal gangue powder in the scheme only needs to be coal gangue powder with common mass, and has no over-high requirement on indexes such as carbon content and the like.
The graphite ore powder used in the biomass denitration powder is commercially available graphite ore powder or graphite ore powder obtained by other known methods, and is obtained by crushing and grinding graphite ore. In one embodiment, the graphite ore powder used in the present application is produced in Chenzhou city, Hunan province, and ground to a fineness of 200 mesh with a carbon content of about 70%. It will be clear to those skilled in the art that other suitable fineness or particle size, as well as other carbon content graphite ore fines, are also suitable for use in the denitration dust of the present application.
The biomass carbon powder used in the biomass denitration powder is ground powder of biomass carbon. The biomass charcoal is a charcoal-containing solid substance obtained by carbonizing a biomass material under an anoxic and heating condition (preferably 400-800 ℃). The biomass material comprises any non-petrochemical plant material, animal material or microbial material (preferably plant material), wherein the biomass material used for preparing the biomass denitration powder and the biomass material used for preparing the biomass denitration aqueous solution are optionally the same or different. The biomass material comprises agriculture and forestry byproducts and/or industrial processing organic waste; preferably, wherein the agroforestry byproduct comprises: branches, leaves, bark, wood, grass, corncobs, straw, rice hulls, fruit shells, shrubs, and vines, wherein the industrial organic processing waste comprises: bagasse, wood waste (such as wood chips, wood processing waste, and woodlands), and straw waste. Specifically, the biomass carbon powder used in the test of the application is a carbon-containing solid product obtained by heating and carbonizing straw and rice hull under an anoxic condition, and is ground to 200 meshes of fineness. It is clear to those skilled in the art that other suitable biomass materials such as agriculture and forestry byproducts (including straw, rice hull, corn cob, bean hull, tree branch, wood, etc.), industrial processing organic waste materials (such as sugar cane waste residue in sugar industry, wood chip in wood processing, leftover materials, etc.) can obtain the biomass carbon powder in the present case under similar conditions, and other suitable fineness is also suitable for the denitration powder of the present application.
The pulverized particle size of the biomass denitration powder is not particularly limited as long as it can be injected into the system through an air injection gun at a predetermined rate.
(2) The biomass denitration aqueous solution comprises:
the biomass denitration water agent comprises 40-80 wt% of water; 20-60 wt% of a liquid biomass cracking solution; and 10-40 wt% of C1-C10 monohydric alcohol or polyhydric alcohol. In one embodiment, the water comprises 40, 45, 50, 55, 60, 65, 70, 75, 80 wt% of the aqueous biomass denitration agent. In one embodiment, the liquid biomass cracking solution accounts for 20, 25, 30, 35, 40, 45, 50, 55, and 60 wt% of the aqueous biomass denitration solution. In one embodiment, the C1-C10 monohydric or polyhydric alcohol comprises 10, 15, 20, 25, 30, 35, 40 wt% of the aqueous biomass denitration agent. In a preferred embodiment, the aqueous biomass denitration agent consists of 40-80 wt% of water; 20-60 wt% of a liquid biomass cracking solution; and 10-40 wt% of C1-C10 monohydric alcohol or polyhydric alcohol, wherein the sum of all the components is 100%. The components are uniformly mixed according to a proportion to prepare the biomass denitration aqueous solution. The biomass denitration water agent is a mixture of water, C1-C10 monobasic or polyalcohol solvent and liquid biomass cracking liquid.
The liquid biomass cracking solution in the biomass denitration aqueous solution is a liquid substance containing C4-C17 or C4-C17 hydrocarbon oxygen substances or a mixture thereof, which is obtained in the process of cracking biomass materials under the conditions of oxygen deficiency and heating (preferably 400-800 ℃), and can contain a certain amount of water. The biomass material comprises any non-petrochemical plant material, animal material or microbial material (preferably plant material), wherein the biomass material used for preparing the biomass denitration powder and the biomass material used for preparing the biomass denitration aqueous solution are optionally the same or different. The plant material comprises an agroforestry byproduct and/or an industrial process organic waste, wherein the agroforestry byproduct comprises: branches, leaves, bark, wood, grass, corncobs, straw, rice hulls, fruit shells, shrubs, and vines, wherein the industrial organic processing waste comprises: bagasse, wood waste (such as wood chips, wood processing waste, and woodlands), and straw waste. The pyrolysis (also called pyrolysis or cracking) of biomass generally refers to a process in which biomass is heated to raise temperature under an oxygen-free or low-oxygen environment to cause molecular decomposition, thereby producing coke, condensable liquid and gaseous products, and is an important utilization form of biomass energy. Methods of biomass pyrolysis are known in the art. In one embodiment, used herein are liquid hydrocarbons of C4-C17, or mixtures of C4-C17 hydrocarbon oxygenates, obtained from the thermal cracking of branches and wood chips under anoxic conditions. As previously mentioned, it is clear to those skilled in the art that other suitable biomass materials such as byproducts of agriculture and forestry (including straw, rice hull, corn cob, bean hull, tree branch, wood, etc.), industrial processing organic waste (such as waste sugar cane dregs in sugar industry, wood chips in wood processing, leftover materials, etc.) can also obtain the liquid biomass cracking liquid described in the present case under similar conditions.
Illustrative C1-C10 mono-or polyols include, but are not limited to: methanol, ethanol, propanol, isopropanol, glycerol, n-butanol, isobutanol, tert-butanol, and the like.
Regarding the positions of the aqueous agent spray gun and the dust spray gun (i.e., the injection/addition positions of the biomass denitration agent):
the production line of the novel dry-method cement kiln is quite large in size, nitrogen-containing pollutants are generated in a plurality of devices or production links, and therefore the positions for adding the denitration agent are particularly selected and combined in a plurality of ways. However, the research of the present application finds that the addition position of the denitrifier has a significant influence on the final effect, and when the denitrifier is added at the addition position known in the prior art or in a device other than the present application, the denitration effect cannot achieve the expected technical effect. The applicant has studied and creatively proposed the following combinations of addition positions:
in the present application, the biomass denitration agent (as shown in the attached figure 1 of the specification) can be used in the following way:
spraying a biomass denitration aqueous agent at a position 1 between the tail end of the rotary kiln and the tail end of the tertiary air duct (preferably at a kiln tail smoke chamber) through an aqueous agent spray gun;
and spraying biomass denitration powder through a powder spray gun at a position 2 from the rear section of the decomposing furnace to the inlet of the lowest stage cyclone (preferably from the outlet of the decomposing furnace to the upstream part of the lowest stage cyclone connected with an air pipe, and most preferably from the outlet of the decomposing furnace). The rear section of the decomposing furnace is a section between one third of the height of the decomposing furnace and the outlet of the decomposing furnace, and the direction between one third of the height of the decomposing furnace and the outlet of the decomposing furnace is from bottom to top. The lowest stage of cyclone is the lowest stage of cyclone from bottom to top in the first stage or the multi-stage cyclones. For example, the lowest stage cyclone of the five-stage cyclone is a C5 cyclone, the lowest stage cyclone of the six-stage cyclone is a C6 cyclone, and so on. And the outlet of the decomposing furnace is connected with the lowest stage cyclone cylinder through a connecting air pipe. The connecting air pipe can be in any shape determined according to actual conditions. Typically, the connecting duct comprises an ascending portion and a descending portion. And the ascending part of the connecting air pipe is connected with the outlet of the decomposing furnace and used for leading out gas. The downstream part of the connecting air pipe is connected with the upstream part and the inlet of the lowest stage of cyclone and is used for guiding gas into the cyclone. The ascending portion and the descending portion are intended to indicate that gas flows first through the ascending portion and then through the descending portion, and are not intended to define the gas flow direction in other meanings.
In one embodiment, the connecting duct is curved, having a shape with a middle portion higher than one or both of the ends, such as an inverted U-shape or an n-shape (also known as a gooseneck). In this case, the upward flow portion also means a portion where the gas travels upward, and the downward flow portion also means a portion where the gas travels downward. The furnace outlet is also referred to herein as the burnout zone. In one embodiment, the descending portion of the connecting duct is also referred to as the decomposing furnace tail end.
And optionally spraying another part of biomass denitration water agent through a water agent spray gun at a position 3 between the outlet of the decomposing furnace and the inlet of the lowest stage of cyclone (preferably, the descending part of the connecting air pipe between the outlet of the decomposing furnace and the lowest stage of cyclone, and more preferably, the inlet part of the air pipe of the lowest stage of cyclone).
Said location 3 is after said location 2 with respect to the gas flow direction.
The three spraying positions are reasonably matched and comprise any two or three combinations, and good effects can be achieved.
In one embodiment of the present application, the biomass denitration dust is added from position 2 and the denitration water agent is added from position 1.
In another embodiment of the present application, the biomass denitration dust is added from position 2 and the denitration water agent is added simultaneously from positions 1 and 3.
In one embodiment of the present application, the biomass denitration powder is injected from position 2 by compressed air, and the denitration water agent is atomized into droplets of less than 10 μm by a two-fluid spray gun and injected from position 1.
In another embodiment of the present application, the biomass denitration powder is injected from the position 2 by using compressed air, and the denitration water agent is atomized into droplets of less than 10 μm by using a two-fluid spray gun and injected from the positions 1 and 3.
In one embodiment, the present application may use multiple/multi-layer lances at each of position 1, position 2 and position 3. This application forms full coverage, evenly spouts and adds through multilayer spray gun overall arrangement (preferably stagger certain angle between with each layer spray gun), improves biomass flue gas denitration agent's utilization efficiency.
The amount of the biomass denitration powder is 0.01 to 1.0 wt% (e.g., 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95 wt%) of the feeding amount of the cement raw material, and the amount of the biomass denitration agent is 0.01 to 1.0 wt% (e.g., 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.65, 0.95, 0.5, 0.95, 0.75, 0.0.95, 0.0.0.0.0.95 wt%) of the feeding amount of the cement raw material. The flue gas denitration efficiency realized by the method can reach more than 90%, such as 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% and 99.5%.
In the present application, the denitration efficiency is (pre-denitration background concentration-post-denitration emission concentration)/pre-denitration background concentration 100%.
In addition, the metering feeder, the flow control device and the like are used in the biomass denitration system, so that the biomass denitration water agent and powder spraying amount can be adjusted in real time according to the content of NOx in the flue gas, and continuous and accurate control over emission indexes is achieved. If dust and water agents are added at other locations, such as the front end of the rotary kiln, accurate control of emissions in real time is often not possible.
In conclusion, the spraying positions of the biomass denitration aqueous solution and the biomass denitration powder are extremely exquisite (the optimal spraying position is determined based on thousands of hours of industrial online tests), two biomass denitration agents (aqueous solution and powder) and two or three spraying positions are combined and matched for the first time, the spraying amounts of the biomass denitration aqueous solution and the biomass denitration powder can be automatically controlled and adjusted according to the NOx content of flue gas, and economic, environment-friendly and efficient flue gas denitration is realized. The system can introduce more hydrocarbon compounds through the biomass water aqua and the powder, and can obviously improve the removal rate and efficiency of NOx by mixing with the material to be treated in multiple ways under the environment with proper temperature and atmosphere. More importantly, the comprehensive treatment concept of waste utilization is introduced into the environment-friendly cement industry by innovatively using a powder spraying device for spraying biomass denitration powder and an aqueous agent spraying device for spraying a biomass denitration aqueous agent. The main components of the used denitrifier, namely the biomass denitration aqueous agent and the denitration powder, are prepared by biomass carbonization and thermal cracking with wide sources, the raw materials are easily available, green, environment-friendly and renewable, meanwhile, the equipment investment is small, the process is simple and reliable, the clinker quality is not influenced, the denitration efficiency is high, the cost is low, compared with SCR and SNCR, the denitration agent has incomparable technical, economic and environment-friendly advantages, and has huge application prospect and potential in the field of flue gas denitration in the cement industry.
The application focuses on the spraying position and/or a spray gun capable of providing the material (denitrifier) at the spraying position. Having knowledge of this information, one skilled in the art can readily prepare the denitrification system based on general knowledge in the art.
Unless otherwise specified, percentages, ratios, contents or parts described herein are by weight. Concentrations described herein are weight concentrations.
The temperature units "degrees" referred to herein are degrees celsius.
The application the denitrifier is a denitrifier for removing flue gas. Therefore, the term "biomass denitration agent" in the present application may also be referred to as "biomass flue gas denitration agent", and the two may be used interchangeably. Similarly, the term "biomass denitration dust" in the present application may also be referred to as "biomass flue gas denitration dust", and the two may be used interchangeably as well. The term "aqueous biomass denitration agent" in the application may also be referred to as "aqueous biomass flue gas denitration agent", and the two may be used interchangeably as well. Herein, the denitration agent refers to a denitration water agent and/or denitration powder.
Drawings
FIG. 1: one embodiment of position 1, position 2 and position 3 is shown, where the relative positions of air, clinker, cooler and fuel are also shown.
FIG. 2: one embodiment of spraying the denitrifier from the positions 1 and 2.
FIG. 3: one embodiment of spraying the denitrifier from positions 2 and 3.
FIG. 4: one embodiment of spraying the denitrifier from the position 1, the position 2 and the position 3.
FIG. 5: an exemplary aqueous/powder spray gun arrangement.
FIG. 6: an exemplary aqueous dispensing device.
FIG. 7: an exemplary powder application device.
Description of the reference numerals
1. Position 1
2. Position 2
3. Position 3
4. Rotary kiln
5. Kiln tail smoke chamber
6. Front section of decomposing furnace
7. Middle section of decomposing furnace
8. Rear section of decomposing furnace
9. Connecting the up-going part of the wind pipe
10. Connecting the downstream part of the wind pipe
C5 cyclone
12. Cyclone connecting air pipe
C4 cyclone
C3 cyclone
C2 cyclone
16.C1 cyclone
17. Tertiary air pipe
21. Living beings denitration powder storage bin
22. Metering feeder
23. Powder conveying pipeline
24. Air compressor
25. Gas flowmeter
26. Gas valve
27. Gas delivery pipeline
31. Biomass denitration water agent storage tank
32. Water agent output pump
33. Liquid flowmeter
34. Liquid valve
35. Liquid return valve
36. Liquid conveying pipeline
37. Liquid flowmeter
38. Liquid valve
39. Liquid return valve
40. Air compressor
41. Gas flowmeter
42. Gas valve
43. Gas delivery pipeline
101. Biomass denitration water agent storage equipment
102. Aqueous agent unloading and circulating system
103. Aqueous agent unloading and circulating system
104. Liquid level measuring device
105. Pump delivery device
106. Flow metering device
107. Pressure detection device
108. Atomizing spray gun equipment
109. Compressed air device
301. Pump delivery device
302. Flow metering device
303. Pressure detection device
304. Atomizing spray gun equipment
305. Compressed air device
201. Biomass denitration powder storage equipment
202. Valve device
203. Metering device
204. Metering device
205. Pump delivery device
206. Compressed air device
207. Atomizing spray gun equipment
Detailed Description
For a better understanding of the present application, the contents of the present application will be further described below with reference to examples, but the contents of the present application are not limited to only the following examples. The experimental operations described in the following examples are all routine operations unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified. The cyclones used in the examples and comparative examples are five-stage cyclones, and thus the C5 cyclone is the lowermost stage cyclone.
Example 1: position 1+ position 2+ position 3
The biomass denitration powder comprises the following components in percentage by mass: 70% of coal gangue powder, 20% of graphite mineral powder and 10% of biomass carbon powder. The biomass denitration water agent comprises the following components in percentage by mass: the water content is 45%, the biomass lysate is 35%, and the methanol is 20%.
The embodiment is used on a 5000t/d novel dry method cement production line positioned in Guangdong, and the actual concentration monitoring of NOx in flue gas is 900mg/m3. Adopt this application the system, placed a living beings denitration water agent storage tank and a living beings denitration powder storage storehouse on ground. Spraying a biomass denitration aqueous agent at a kiln tail smoke chamber (position 1) through a multistage centrifugal pump and an aqueous agent spray gun; spraying biomass denitration powder at the outlet part (position 2) of the decomposing furnace through a pneumatic pump and a powder spray gun; and spraying the other part of the biomass denitration aqua through a multistage centrifugal pump and an aqua spray gun at the inlet part (position 3) of the C5 cyclone air pipe. The biomass denitration water agent is sprayed and added at the position 1 through 4 spray guns which are arranged on the same plane at intervals of 90 degrees,spraying 6 spray guns arranged at the position 3 of the biomass denitration water agent at intervals of 60 degrees on the same plane, and atomizing the denitration water agent into the denitration water agent by using high-pressure air<Droplets of 10 μm or less. The biomass denitration powder is sprayed by 1 spray gun at the position 2. The spraying amount of the biomass denitration powder is 1t/h (about 0.3 percent of the feeding amount of the cement raw material), the spraying amount of the biomass denitration water agent is 1000L/h (about 0.3 percent of the feeding amount of the cement raw material), the spraying ratio of the position 1 to the position 3 is 8:2, wherein the spraying amount of the position 1 is about 800L/h, the spraying amount of the position 3 is about 200L/h, and the concentration of NOx in the flue gas can be stabilized at 50mg/m after 10 minutes3The minimum value can be 41mg/m3And the cement kiln flue gas denitration efficiency reaches more than 95%.
Example 2: position 1+ position 2
The biomass denitration powder comprises the following components in percentage by mass: 80% of coal gangue powder, 10% of graphite mineral powder and 10% of biomass carbon powder. The biomass denitration water agent comprises the following components in percentage by mass: 50% of water content, 25% of biomass lysate and 25% of methanol.
The embodiment is used on a 5000t/d novel dry method cement production line in Guangdong, and the actual concentration of NOx in flue gas is monitored to be 850mg/m3. Adopt this application the system, placed a living beings denitration water agent storage tank and a living beings denitration powder storage storehouse on ground. And a biomass denitration aqueous agent is sprayed and added at the position (position 1) of the kiln tail smoke chamber through a multistage centrifugal pump and an aqueous agent spray gun, and biomass denitration powder is sprayed and added at the outlet part (position 2) of the decomposing furnace through a pneumatic pump and a powder spray gun. The biomass denitration water agent is sprayed by 4 spray guns which are arranged on the same plane at intervals of 90 degrees, and the high-pressure air is utilized to atomize the denitration water agent into<Droplets of 10 μm or less. The biomass denitration powder is sprayed by 1 spray gun at the position 2. The spraying amount of the biomass denitration powder is 1.5t/h (about 0.4 percent of the feeding amount of the cement raw material), the spraying amount of the biomass denitration water agent is 1000L/h (about 0.3 percent of the feeding amount of the cement raw material), and the concentration of NOx in the flue gas can be stabilized at 60mg/m after 10 minutes3The minimum value can be 53mg/m3And the cement kiln flue gas denitration efficiency reaches 93 percent.
Example 3: position 2+ position 3
The biomass denitration powder comprises the following components in percentage by mass: 75% of coal gangue powder, 20% of graphite mineral powder and 5% of biomass carbon powder. The biomass denitration water agent comprises the following components in percentage by mass: the water content is 60%, the biomass lysate is 20%, and the methanol is 20%.
The embodiment is used on a 5000t/d novel dry method cement production line in Guangdong, and the actual concentration monitoring of NOx in flue gas is 880mg/m3. Adopt this application the system, placed a living beings denitration water agent storage tank and a living beings denitration powder storage storehouse on ground. And biomass denitration powder is sprayed and added on the outlet part (position 2) of the decomposing furnace through a pneumatic pump and a powder spray gun, and a biomass denitration aqueous solution is sprayed and added on the inlet part (position 3) of the C5 cyclone air pipe through a multistage centrifugal pump and an aqueous solution spray gun. The biomass denitration powder is sprayed by 1 spray gun at the position 2. Spraying 6 spray guns arranged at the position 3 of the biomass denitration water agent at intervals of 60 degrees on the same plane, and atomizing the denitration water agent into the denitration water agent by using high-pressure air<Droplets of 10 μm or less. The spraying amount of the biomass denitration powder is 2t/h (about 0.6 percent of the feeding amount of the cement raw material), the spraying amount of the biomass denitration water agent is 600L/h (about 0.2 percent of the feeding amount of the cement raw material), and the concentration of NOx in the flue gas can be stabilized at 80mg/m after 10 minutes3The minimum value can be 73mg/m3And the cement kiln flue gas denitration efficiency reaches more than 91%.
Example 4: position 1+ position 3
The biomass denitration water agent comprises the following components in percentage by mass: 50% of water content, 20% of biomass lysate and 30% of methanol.
The embodiment is used on a 5000t/d novel dry-process cement production line in Anhui, and the actual concentration of NOx in flue gas is monitored to be 860mg/m3. Adopt this application the system, only placed a living beings denitration aqueous solution storage tank on ground, spout living beings denitration aqueous solution through multistage centrifugal pump and aqueous solution spray gun in kiln tail smoke chamber department (position 1), spout the living beings denitration aqueous solution that adds another part through multistage centrifugal pump and aqueous solution spray gun at C5 whirlwind section of thick bamboo tuber pipe entry part (position 3), living beings denitration aqueous solution is spouted through 4 spray guns that the coplanar interval 90 arranged in position 1, living beings denitration aqueous solution is spouted through two-layer plane interval 9 in position 3Spraying 8 spray guns arranged at 0 degree, and atomizing the denitration water agent into denitration water agent by using high-pressure air<Droplets of 10 μm or less. The spraying amount of the biomass denitration water agent is 1500L/h (about 0.4% of the feeding amount of cement raw materials), the spraying ratio of the position 1 to the position 3 is 3:2, wherein the spraying amount of the position 1 is about 900L/h, the spraying amount of the position 3 is about 600L/h, and the concentration of NOx in the flue gas can be stabilized at 70mg/m after 10 minutes3The lowest possible level is 62mg/m3And the denitration efficiency of the flue gas of the cement kiln reaches more than 92 percent.
Example 5: preparation of Biomass denitration powder
About 10 tons of corn straws are collected, isolated from air in a carbonization furnace, heated to about 600 ℃, carbonized to prepare about 3 tons of carbon-containing solid products (namely biomass carbon), ground to 200 meshes of fineness, and uniformly mixed with 6 tons of graphite ore powder and 21 tons of coal gangue powder to prepare 30 tons of biomass denitration powder used in example 1. The biomass denitration powders used in example 3 and comparative example 5 were prepared using different amounts of the aforementioned biomass carbon powder, gangue powder, and graphite ore powder.
Example 6: preparation of Biomass denitration powder
Collecting about 5 tons of dried shells, isolating air in a carbonization furnace, heating to about 700 ℃, carbonizing to obtain about 2 tons of biomass charcoal, grinding to 200 meshes, and uniformly mixing with 2 tons of graphite ore powder and 16 tons of coal gangue powder to obtain 20 tons of biomass denitration powder used in example 2.
Example 7: preparation of aqueous biomass denitration agent
Collecting about 10 tons of branches, heating the branches in a gasification furnace without air to 500 ℃ to obtain about 7 tons of biomass cracking liquid, and detecting the biomass cracking liquid to contain C4-C17 hydrocarbon and hydrocarbon oxide. The lysate is relatively viscous. After 9 tons of water and 4 tons of methanol were added, the mixture was stirred for about 15 minutes by using a high-speed shearing and stirring device with a speed of 20000 rpm, and 20 tons of substantially uniform aqueous biomass denitration agent was prepared and used in example 1. The aqueous biomass denitration agents used in examples 3 and 4 were prepared using different amounts of the aforementioned biomass lysate, water, and methanol.
Example 8: preparation of aqueous biomass denitration agent
About 8 tons of bagasse are collected, heated in a gasifier without air to 450 ℃ to obtain about 5 tons of biomass lysate, which is detected to contain C4-C17 hydrocarbons and oxygen compounds. The lysate is relatively viscous. After addition of 10 tons of water and 5 tons of methanol, 40 tons of substantially uniform aqueous biomass denitration agent was prepared for example 2 by stirring for about 15 minutes using a high-speed shear stirring apparatus with a speed of 20000 rpm. The aqueous biomass denitration agents used in comparative examples 3, 4, and 6 were prepared using different amounts of the aforementioned biomass lysate, water, and methanol.
Comparative example 1: position 2
The comparative example is used on a 5000t/d novel dry method cement production line in Guangdong, and the actual concentration monitoring of NOx in flue gas is 800mg/m3. By using the prior art (SNCR selective non-catalytic reduction) spraying system, 900L/h (about 0.25 percent of raw material feeding amount) of ammonia water with the concentration of 20 percent is sprayed at the outlet (position 2) of the decomposing furnace through a water agent spray gun, 8 spray guns are arranged at an interval of 45 degrees on the same plane, and the denitration water agent is atomized into denitration water agent by utilizing high-pressure air<Droplets of 10 μm or less. After 10 minutes, the concentration of NOx in the smoke can be stabilized at 350mg/m3About, flue gas denitration efficiency is only 56%.
Comparative example 2: position 1
The comparative example is used on a 5000t/d novel dry method cement production line in Guangdong, and the actual concentration monitoring of NOx in flue gas is 850mg/m3Left and right. Spraying 1000L/h (about 0.25% of raw material feeding amount) of water at the position of a kiln tail smoke chamber (position 1) through water spray guns by using a spraying system in the prior art, spraying through 4 spray guns which are arranged on the same plane at intervals of 90 degrees, and atomizing the denitration water into denitration water by using high-pressure air<Droplets of 10 μm or less. After 10 minutes, the concentration of NOx in the flue gas is still stable at 830-850 mg/m3On the other hand, the denitration effect hardly occurred.
Comparative example 3: other positions
The biomass denitration water agent comprises the following components in percentage by mass: 50% of water content, 25% of biomass lysate and 25% of methanol.
The comparative example was carried out on a new dry 5000t/d scale located in HenanWhen the NOx concentration in the flue gas is actually monitored to be 1000mg/m when the NOx concentration is used on a method cement production line3Left and right. By using the spraying system in the prior art, 8 spray guns are arranged between C2-C3 cyclones for spraying 1500L/h (about 0.4 percent of raw material feeding amount) of biomass denitration water agent, and high-pressure air is utilized to atomize the denitration water agent into the denitration water agent<Droplets of 10 μm or less. After 10 minutes, the concentration of NOx in the flue gas can be stabilized at 800-900 mg/m3About, flue gas denitration efficiency 10-20%, denitration effect is not showing significantly.
Comparative example 4: position 1
The biomass denitration water agent comprises the following components in percentage by mass: the water content is 70%, the biomass lysate is 15%, and the methanol is 15%.
The comparative example is used on a 5000t/d novel dry method cement production line in Guangdong, and the actual concentration monitoring of NOx in flue gas is 850mg/m3. Spraying biomass denitration water agent at the position (position 1) of a kiln tail smoke chamber by using a spraying system in the prior art, spraying by 4 spray guns arranged at intervals of 90 degrees on the same plane, and atomizing the denitration water agent into the denitration water agent by using high-pressure air<Droplets of 10 μm or less. The spraying amount of the biomass denitration water agent is 1000L/h (about 0.3% of the feeding amount of the cement raw material, and the concentration of NOx in the flue gas can be stabilized at 130mg/m after 10 minutes3About, cement kiln flue gas denitration efficiency is 85%.
Comparative example 5: position 2
The biomass denitration powder comprises the following components in percentage by mass: 60% of coal gangue powder, 20% of graphite ore powder and 20% of biomass carbon powder.
The comparative example is used on a 5000t/d novel dry method cement production line in Guangdong, and the actual monitoring of the concentration of NOx in flue gas is 880mg/m3. The spraying system in the prior art is used for spraying the biomass denitration powder at the outlet part (position 2) of the decomposing furnace through a pneumatic pump and a powder spray gun. The spraying amount of the biomass denitration powder is 2t/h (about 0.5 percent of the feeding amount of the cement raw material), and the concentration of NOx in the flue gas can be stabilized at 340mg/m after 10 minutes3About, cement kiln flue gas denitration efficiency is 61%.
Comparative example 6: position 3
The biomass denitration water agent comprises the following components in percentage by mass: the water content is 65%, the biomass lysate is 15%, and the methanol is 20%.
The comparative example is used on a 5000t/d novel dry method cement production line in Guangdong, and the actual concentration monitoring of NOx in flue gas is 950mg/m3. By using the spraying system in the prior art, the biomass denitration water agent is completely sprayed at the inlet part (position 3) of the C5 cyclone air pipe, and is sprayed by 6 spray guns which are arranged on the same plane at an interval of 60 degrees, and the denitration water agent is atomized into the denitration water agent by utilizing high-pressure air<Droplets of 10 μm or less. The spraying amount of the biomass denitration water agent is 1200L/h (about 0.35 percent of the feeding amount of the cement raw material), and the concentration of NOx in the flue gas can be stabilized at 600mg/m after 10 minutes3The cement kiln flue gas denitration efficiency is 37%.
Table 1: denitration efficiency summary table
According to the embodiment and the comparative example, firstly, compared with the traditional pulverized coal and ammonia water denitration agent, the denitration agent provided by the spray gun of the system has higher denitration efficiency; in addition, the spray gun position selected by the application has more excellent denitration effect relative to other positions. If the two are combined, an economic, environment-friendly and efficient denitration technical scheme can be further obtained, and the technical effect of the scheme cannot be achieved by all the prior art at present.
Although the present application has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application, and all changes, substitutions and alterations that fall within the spirit and scope of the application are to be understood as being included within the following description of the preferred embodiment.
Claims (20)
1. The utility model provides a novel dry process is living beings deNOx systems for cement kiln, its is including the powder that is used for spouting with living beings denitration powder spout with the device and be used for spouting with the aqueous agent of living beings denitration aqueous agent and spout with the device, the aqueous agent spouts with the device including the aqueous agent spray gun that is located the rotary kiln tail end of cement kiln to the first position department between the cubic tuber pipe tail end, and the powder spouts with the device including the powder spray gun that is located the second position department between rear section to the bottom one-level cyclone entry in the dore.
2. The biomass denitration system for the cement kiln as recited in claim 1, wherein said powder spraying means further comprises a powder storage bin, a dust collector, a metering feeder, a pneumatic conveying pump, a roots blower, a powder pipeline, a compressed air pipeline, and a valve.
3. The biomass denitration system for the cement kiln according to claim 1 or 2, wherein the aqueous agent spraying system further comprises an aqueous agent storage tank, a circulating pump, a jet pump, a flow meter, a valve, a check valve, an aqueous agent pipeline, and a compressed air pipeline.
4. The biomass denitration system for the cement kiln according to claim 1 or 2, wherein the water agent spray gun is a two-fluid spray gun.
5. The biomass denitration system for the cement kiln according to claim 1 or 2, characterized in that the number of the aqueous agent spray guns is one or more.
6. The biomass denitration system for the cement kiln according to claim 1 or 2, wherein the number of the powder spray guns is one or more.
7. The biomass denitration system for the cement kiln according to claim 3, characterized in that the water agent storage tank is equipped with a large-flow circulation pump.
8. The biomass denitration system for cement kilns as recited in claim 4, wherein said two-fluid spray gun has a smooth interior surface.
9. The biomass denitration system for the cement kiln as claimed in claim 2, wherein the pneumatic conveying pump adopts a roots blower or compressed air as a gas source.
10. The biomass denitration system for the cement kiln according to claim 3, wherein the jet pump is a plunger pump, a gear pump or a multistage centrifugal pump.
11. The biomass denitration system for cement kiln according to claim 1 or 2, wherein the first position is located at a kiln tail smoke chamber.
12. The biomass denitration system for cement kiln according to claim 1 or 2, wherein the second position is located at an upstream portion of a connecting air duct from the outlet of the decomposing furnace to the lowermost cyclone.
13. The biomass denitration system for cement kilns according to claim 1 or 2, wherein the second position is located at an outlet portion of the decomposing furnace.
14. The biomass denitration system for cement kiln according to claim 4, wherein the two-fluid spray gun is a two-fluid spray gun capable of spraying droplets of <10 μm.
15. The biomass denitration system for the cement kiln according to claim 5, wherein the water agent spray gun is a plurality of spray guns which are symmetrically distributed.
16. The biomass denitration system for a cement kiln according to claim 6, wherein the powder spray gun is a plurality of spray guns which are symmetrically distributed.
17. The biomass denitration system for cement kilns as claimed in claim 8, wherein the two-fluid spray gun is a high temperature resistant two-fluid spray gun with smooth interior surfaces.
18. The biomass denitration system for cement kilns according to claim 1 or 2, wherein the water agent spraying device further comprises a water agent spraying gun at a third position between the outlet of the decomposing furnace and the inlet of the lowest stage cyclone.
19. The biomass denitration system for cement kilns according to claim 18, wherein the third position is located at a downstream portion of a connecting air pipe from the outlet of the decomposing furnace to the lowest stage cyclone.
20. The biomass denitration system for cement kilns according to claim 19, wherein the third position is located at an inlet portion of the lowermost cyclone.
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