CN111514726B - Novel composite biomass denitration agent for dry-method cement kiln, application method of novel composite biomass denitration agent and denitration system - Google Patents

Novel composite biomass denitration agent for dry-method cement kiln, application method of novel composite biomass denitration agent and denitration system Download PDF

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CN111514726B
CN111514726B CN201910107954.5A CN201910107954A CN111514726B CN 111514726 B CN111514726 B CN 111514726B CN 201910107954 A CN201910107954 A CN 201910107954A CN 111514726 B CN111514726 B CN 111514726B
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biomass
denitration
powder
agent
water
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CN111514726A (en
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尹标林
王家炜
崔素萍
黄光浩
张同生
陈新智
刘宁
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Guangdong Wanyin Science And Technology Development Co ltd
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Guangdong Wanyin Science And Technology Development Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • B01D53/565—Nitrogen oxides by treating the gases with solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Abstract

The invention relates to a composite biomass denitration agent for a cement kiln, a using method and a denitration system thereof. According to the invention, by utilizing the atmosphere characteristics of the decomposing furnace and through the synergistic collocation of two biomass denitration agents (water agent and powder) and three spraying positions, the economic, efficient and environment-friendly flue gas denitration is realized, and meanwhile, the method has the characteristics of low equipment investment, simplicity and convenience in use, environment-friendly and renewable denitration agents and the like, and the method can effectively promote the emission reduction and environmental protection of cement industry NOx and has important environmental, social and economic significance.

Description

Novel composite biomass denitration agent for dry-method cement kiln, application method of novel composite biomass denitration agent and denitration system
Technical Field
The invention belongs to the field of flue gas denitration in cement industry, and particularly relates to a novel biomass denitration agent for a dry-method cement kiln, a using method of the novel biomass denitration agent and a denitration system.
Background
The emission of nitrogen oxides (NOx) in the cement industry becomes the third largest pollution source after thermal power generation and automobile exhaust. The 12-month environmental protection department in 2013 and the national quality supervision, inspection and quarantine administration jointly issue the emission standard of atmospheric pollutants in the Cement industry GB4915-2013 to replace the original standard GB4915-2004, prescribing the prior art and the new art Construction of cement plant NOx (according to NO) 2 Meter) discharge concentration of not more than 400mg/m 3 The special emission limit value of the key area execution is 150mg/m 3 。
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 or urea as a reducing agent. The denitration efficiency of the technology is low (generally<60 percent) leads to higher flue gas denitration cost of cement enterprises, and cannot meet the increasingly strict NOx emission standard (the NOx emission concentration cannot be reduced to 150 mg/m). The Selective Catalytic Reduction (SCR) technique generally uses a titanium-based vanadium-based catalyst (V 2 O 5 -WO 3 /TiO 2 ). The SCR process may also use ammonia, ammonia or urea as a reducing agent. The SCR method has a higher active temperature window (320-420 ℃), and the SCR device needs to be arranged before the kiln tail dust collector. However, where dust and SO are present in the flue gas 2 The higher the concentration, this is liable to cause catalyst poisoning, reduce catalyst life. In the SCR and SNCR denitration technologies, the use efficiency of ammonia water is 60-80%, when the temperature is too high, ammonia reacts with oxygen to generate NOx, and when the temperature is too low, the NOx reduction rate is too low, and ammonia in flue gas escapes seriously. In addition, ammonia is also a high energy consumption and high pollution product. Therefore, development of low-cost and high-efficiency flue gas denitration technology suitable for cement industry is needed.
In addition, the prior art specification GB 51045-2014 of denitration technology in the cement industry, namely the technical specification of denitration engineering in cement factories, is issued for the denitration technology. Based on the specificity in the denitration reaction principle, the target pollutant source, the denitration reaction condition (such as the denitration reaction temperature), the reaction environment, the selection of the denitration agent and the like of the denitration technology, the skilled artisan generally considers that the denitration technology has obvious differences from other environment-friendly technologies such as a desulfurization technology and the like, and then the technology in other fields can not be directly referred to solve the problems in the denitration technology.
In general, the denitration technology in the prior art has the problems of low efficiency, poor denitration effect, high cost and serious pollution; moreover, the technical field is easy to be limited when the denitration technology is developed by the person skilled in the art, so that a satisfactory economical, environment-friendly and efficient denitration technology for the dry-method cement kiln still does not exist at present.
However, the applicant found that by carefully selecting the kind and the addition position of the denitration agent, the efficiency of the denitration process can be significantly improved, the denitration effect can be improved, and the denitration cost can be reduced.
Disclosure of Invention
In order to reduce the NOx emission of the flue gas of a cement kiln (especially a novel dry-method cement kiln), the applicant provides a biomass denitration agent for the cement kiln, a using method and a denitration system thereof according to the characteristics of cement production technology (especially the characteristics of a decomposing furnace structure and an atmosphere). In particular, the present application achieves economical, efficient, environmentally friendly flue gas denitration by using two biomass denitration agents (aqueous and powder) at two or three locations as detailed below.
The new dry cement production method is a modern cement production method taking suspension preheating and external kiln decomposition technology as cores, and is a cement production method commonly adopted in China. The devices used for the novel dry cement production method generally comprise at least parts such as a rotary kiln, a decomposing furnace, a cyclone cylinder and the like.
In one aspect, the invention adopts the following technical scheme: spraying a biomass denitration water agent at a position 1 (preferably a kiln tail smoke chamber) between the tail end of the rotary kiln and the tail end of the tertiary air pipe; and spraying biomass denitration powder at a position 2 (preferably, the upper part of the air pipe is connected from the outlet of the decomposing furnace to the lowest cyclone) between the inlet of the decomposing furnace from the rear section to the lowest cyclone (the fifth-stage preheater is a C5 cyclone, the sixth-stage preheater is a C6 cyclone, and the like); optionally, spraying another part of biomass denitration water agent at a position 3 between the outlet of the decomposing furnace and the inlet of the cyclone barrel at the lowest stage (preferably, the outlet of the decomposing furnace is connected with the downstream part of the air pipe from the cyclone barrel at the lowest stage).
It is believed that at position 1, the biomass in the biomass denitration agent reacts with water to produce a wastewater containing CO, CH 4 、H 2 Mixtures of hydrocarbons such as HCN. The mixture can rapidly remove most of NOxQuickly and efficiently reduce to N 2 . At position 2, the biomass denitrification powder further reduces NOx. At optional position 3, the further portion of the biomass denitration agent is capable of reducing remaining NOx in the flue gas to N 2 Finally, ultra-low NOx emission is realized.
Spraying as used herein, independently at each occurrence thereof, refers to the means of adding the denitration agent by pressure to a desired location in the presence or absence of a carrier (e.g., water or carrier gas such as air). Other means known to those skilled in the art for adding the denitration agent to a desired position may be employed as long as the other means can add the denitration agent to the desired position. In this application, "spray", "input", "spray" and "add" may be used interchangeably.
The application can remarkably improve the efficiency of the denitration process, improve the denitration effect and reduce the denitration cost by using the combination of the spraying positions, particularly the type of the denitration agent and the combination of the spraying positions. The applicant found that by using a biomass denitration agent at position 1 and a biomass denitration powder at position 2, excellent denitration effects can be obtained, and the denitration efficiency achieved is significantly higher than in the prior art. Moreover, further use of the biomass denitration agent at location 3 may achieve higher denitration efficiency than embodiments using the biomass denitration agent at location 1 and the biomass denitration powder at location 2.
In addition, the invention also relates to a biomass denitration system for the cement kiln, which comprises a biomass denitration water agent, biomass denitration powder, a water agent spraying device and a powder agent spraying device, wherein the biomass denitration water agent and the powder agent are as described herein; the water spray device comprises a water storage tank, a circulating pump and a water spray gun, wherein the water spray gun is arranged at a position 1 between the tail end of the rotary kiln and the tail end of the tertiary air pipe and/or at a position 3 between the outlet of the decomposing furnace and the inlet of the cyclone barrel at the lowest stage; the powder spraying and adding device comprises a powder storage bin, a fan and a powder spray gun, wherein the powder spray gun is arranged at a position 2 between the rear section of the decomposing furnace and the inlet of the lowest cyclone.
In a preferred embodiment, the aqueous spray device further comprises a spray pump, a flow meter, a valve, an aqueous conduit, and a compressed air conduit in addition to the aqueous storage tank, the circulation pump, and the aqueous spray gun.
In a preferred embodiment, the powder injection device comprises, in addition to the powder storage bin, the blower and the powder injection gun, a metering feeder, a pneumatic conveying pump, a Roots blower, a powder pipe, a compressed air pipe, and valves.
The reactions that may be involved in the denitration process are as follows:
(1) The biomass denitration agent is decomposed or reacts with carbon to release hydrocarbon:
2 C + O 2 → 2 CO
C + H 2 O→ CO +H 2
CxHyOz→ (x-z) C + z CO+ y/2 H 2
(2) The hydrocarbon reduces NOx to nitrogen:
2 NOx + (x+1) H 2 → 2 NH +x H 2 O
NH + NH→ N 2 +H 2
2 H 2 + 2 NO→ N 2 + 2 H 2 O
2 NOx + x C→ N 2 + x CO 2
2 NOx + 2x C→ N 2 + 2x CO
2 NOx + 2x CO→ N 2 + 2x CO 2
the reaction principle of the denitration process is complex, various reaction courses are staggered, and the reactions which occur under different conditions and environments also change at any time, so that it is not easy to obtain a denitration agent which can obtain excellent denitration effects under various working conditions.
Through years of theoretical and practical research, the patent creatively proposes a technical scheme of the biomass denitration agent. The biomass denitration agent consists of biomass denitration powder and biomass denitration water.
(1) Biomass denitration powder:
the biomass denitration powder comprises the following components: 50-90 wt% of coal gangue powder; 10-40 wt% of graphite mineral powder; and 5-30 wt% of biomass carbon powder. In one embodiment, the coal gangue powder comprises 50, 55, 60, 65, 70, 75, 80, 85, 90 wt% of the biomass denitrification powder. In one embodiment, the graphite ore fines comprise 10, 15, 20, 25, 30, 35, 40 wt.% of the biomass denitrification powder. In one embodiment, the biomass charcoal comprises 5, 8, 10, 12, 15, 18, 20, 25, 28, 30 wt% of the biomass denitrification powder. 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, wherein the sum of the components is 100%. The biomass denitration powder is prepared by using various raw materials according to the expected amount to carry out operations such as drying, processing, uniform mixing and the like.
In the biomass denitration powder, coal gangue refers to solid waste discharged in the coal mining process and the coal washing process, and is black gray rock which is low in carbon content, hard than coal and accompanies a coal bed in the coal forming process. The gangue powder in this patent may be a gangue powder sold in the market or obtained in other known ways. In one embodiment, the gangue powder used in the present application is produced in the country of Wu Ping county of Fujian province, and is ground to a fineness of 200 meshes, and the carbon content is about 25%. The gangue powder is the gangue powder with general quality, and has no excessively high requirement on indexes such as carbon content and the like.
The graphite mineral powder used in the biomass denitration powder is the graphite mineral powder sold in the market or available in other known ways, and is obtained by crushing and grinding the graphite mineral. In one embodiment, the graphite ore powder used in the present application is produced in the form of powder of about 70% char in the form of powder ground to 200 mesh fineness in the form of powder of the Chenzhou, hunan province. Other suitable fineness or particle sizes, as well as other carbon-containing graphite ore powders, will be apparent to those skilled in the art, as well as suitable for use in the present denitration powders.
The biomass charcoal powder used in the biomass denitration powder is ground powder of biomass charcoal. The biomass charcoal is a charcoal-containing solid substance obtained by carbonizing a biomass material under anoxic and heating conditions (preferably 400-800 ℃). The biomass material comprises any non-fossilized plant material, animal material or microbial material (preferably plant material), wherein the biomass material used to prepare the biomass denitration powder is optionally the same as or different from the biomass material used to prepare the biomass denitration agent. The biomass material comprises agriculture and forestry byproducts and/or industrial processing organic waste materials; preferably, wherein the agriculture and forestry byproducts include: branches, leaves, bark, wood, grass, corncob, straw, rice hulls, husks, shrubs and vines, wherein the industrial process organic waste comprises: bagasse, wood waste (such as wood chips, wood processing waste, and woodland), and grassy waste. Specifically, the biomass carbon powder used in the test of the invention is a carbon-containing solid product obtained by heating and carbonizing straw and rice husk under the anoxic condition, and the carbon-containing solid product is ground to 200 meshes. It will be apparent to those skilled in the art that other suitable biomass materials such as various agricultural and forestry byproducts (including straw, rice hulls, corncobs, bean hulls, branches, wood, etc.), industrial process organic waste materials (e.g., sugar cane waste residues in the sugar industry, wood chips in wood processing, scraps, etc.), can also be used to obtain the biomass charcoal powder described herein under similar conditions, and that other suitable fineness is also suitable for the present denitration powders.
The pulverized particle size of the biomass denitrification powder is not particularly limited as long as it can be injected into the system through an air lance at a predetermined rate.
(2) Biomass denitration agent:
the biomass denitration water agent comprises 40-80 wt% of water; 20-60 wt% of a liquid biomass lysate; and 10 to 40 wt% of a C1-C10 monohydric or polyhydric alcohol. In one embodiment, the water comprises 40, 45, 50, 55, 60, 65, 70, 75, 80 wt% of the biomass denitration agent. In one embodiment, the liquid biomass lysate comprises 20, 25, 30, 35, 40, 45, 50, 55, 60 wt% of the biomass denitration agent. In one embodiment, the C1-C10 monohydric or polyhydric alcohol comprises 10, 15, 20, 25, 30, 35, 40 wt% of the biomass denitration agent. In a preferred mode, the biomass denitration agent consists of 40-80 wt% of water; 20-60 wt% of a liquid biomass lysate; and 10-40 wt% of C1-C10 monohydric alcohol or polyhydric alcohol, wherein the sum of the components is 100%. The components are uniformly mixed according to the proportion to prepare the biomass denitration water agent. The biomass denitration agent is a mixture of water, a C1-C10 monohydric or polyhydric alcohol solvent and liquid biomass pyrolysis liquid.
The liquid biomass pyrolysis liquid in the biomass denitration water agent is a liquid substance containing C4-C17 liquid hydrocarbon or C4-C17 hydrocarbon or a mixture thereof, which is obtained in the pyrolysis process of biomass materials under anoxic and heating conditions (preferably 400-800 ℃), and can contain a certain amount of water. The biomass material comprises any non-fossilized plant material, animal material or microbial material (preferably plant material), wherein the biomass material used to prepare the biomass denitration powder is optionally the same as or different from the biomass material used to prepare the biomass denitration agent. The biomass material comprises agriculture and forestry byproducts and/or industrial process organic waste materials, wherein the agriculture and forestry byproducts comprise: branches, leaves, bark, wood, grass, corncob, straw, rice hulls, husks, shrubs and vines, wherein the industrial process organic waste comprises: bagasse, wood waste (such as wood chips, wood processing waste, and woodland), and grassy waste. The pyrolysis (also known as pyrolysis or cracking) of biomass generally refers to the process of heating biomass in an anaerobic or hypoxic environment to raise the temperature, thereby causing molecular decomposition, thereby producing coke, condensable liquids and gaseous products, which is an important form of utilization of biomass energy. Methods of biomass pyrolysis are known in the art. In one embodiment, used herein is a liquid hydrocarbon of C4-C17, or a mixture of C4-C17 hydrocarbons, obtained by thermal cracking of wood branches and chips under anoxic conditions. As previously mentioned, it will be apparent to those skilled in the art that other suitable biomass materials such as various agricultural and forestry byproducts (including straw, rice hulls, corn cobs, bean hulls, branches, wood, and the like), industrial process organic waste materials (e.g., sugar cane waste residues in the sugar industry, wood chips, scraps in wood processing, and the like) can also be subjected to similar conditions to obtain the liquid biomass lysates described herein.
The C1-C10 monohydric or polyhydric alcohols shown include, but are not limited to: methanol, ethanol, propanol, isopropanol, glycerol, n-butanol, isobutanol, t-butanol and the like.
Regarding the injection position of the biomass denitration agent:
the (dry) cement kiln line is very bulky and nitrogen-containing contaminants are produced in a number of units or production steps, so that there are also a very large number of options and a large number of combinations of locations where the denitration agent is added. However, the inventors have found through studies that the addition position of the denitration agent has a significant influence on the final effect, and the denitration effect cannot achieve the intended technical effect when the denitration agent is added at the addition position known in the prior art or other devices than the present invention. The present inventors have creatively proposed the following combinations of addition positions through studies:
in the present application, the biomass denitration agent (as shown in fig. 1 of the specification) may be used in the following manner, optionally in combination of two or three:
1) Spraying a biomass denitration agent at a position 1 between the tail end of the rotary kiln and the tail end of a tertiary air pipe (preferably at a kiln tail smoke chamber);
2) And spraying biomass denitration powder at a position 2 from the rear section to the inlet of the cyclone cylinder at the lowest stage (preferably from the outlet of the decomposing furnace to the upstream part of the connecting air pipe of the cyclone cylinder at the lowest stage, and most preferably from the outlet part of the decomposing furnace) in the decomposing furnace. The middle and rear sections of the decomposing furnace refer to sections between one third of the height of the decomposing furnace and the outlet of the decomposing furnace, and the direction between the one third of the height of the decomposing furnace and the outlet of the decomposing furnace is from bottom to top. The lowest-level cyclone cylinder refers to the lowest-level cyclone cylinder from bottom to top in one-level or multi-level cyclone cylinders. For example, the lowest level of the five-level cyclone is a C5 cyclone, the lowest level of the six-level cyclone is a C6 cyclone, and so on. The outlet of the decomposing furnace is connected with the cyclone cylinder at the lowest stage through a connecting air pipe. The connecting air pipe can be of any shape determined according to practical conditions. Typically, the connecting duct comprises an upstream portion and a downstream portion. The upward part of the connecting air pipe is connected with the outlet of the decomposing furnace and is used for guiding out gas. The descending part of the connecting air pipe is connected with the ascending part and the inlet of the lowest-stage cyclone cylinder and is used for guiding gas into the cyclone cylinder. The upstream and downstream portions are intended to indicate that gas flows through the upstream portion and then through the downstream portion, and are not intended to limit the direction of gas flow in other sense.
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 portion is also referred to as a portion where the gas travels upward, and the downward portion is also referred to as a portion where the gas travels downward. The decomposing furnace outlet is also referred to herein as the burnout zone.
3) And spraying another part of biomass denitration water agent at a position 3 between the outlet of the decomposing furnace and the inlet of the cyclone cylinder at the lowest stage (preferably, the downstream part of the connecting air pipe of the decomposing furnace outlet and the cyclone cylinder at the lowest stage, and more preferably, the inlet part of the air pipe of the cyclone cylinder at the lowest stage).
The position 3 is behind the position 2 in terms of the direction of gas flow.
The reasonable collocation of the three spraying positions comprises any two or three combinations, and good effects can be obtained.
In one embodiment of the invention, the biomass denitrification powder is added from location 2 and the denitrification water agent is added from location 1.
In another embodiment of the invention, the biomass denitrification powder is added from position 2 and the denitrification water agent is added from both position 1 and position 3.
In one embodiment of the invention, the biomass denitration powder is sprayed from the position 2 by using high-pressure air, the denitration agent is atomized into <10 μm liquid drops by using a double-fluid spray gun, and sprayed from the position 1.
In another embodiment of the invention, the biomass denitration powder is sprayed from the position 2 by using high-pressure air, the denitration agent is atomized into <10 μm liquid drops by using a double-fluid spray gun, and the denitration agent is sprayed from the positions 1 and 3.
In one embodiment, the present application may use multiple/multi-layer lances at each of positions 1, 2 and 3. According to the invention, through the arrangement of the multi-layer spray guns (preferably, the spray guns of all layers are staggered by a certain angle), full-coverage and uniform spraying is formed, and the utilization efficiency of the biomass flue gas denitration agent is improved.
The biomass denitration powder is used in an amount of 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 cement raw material feed, and the biomass denitration agent is used in an amount of 0.01 to 1.0 wt% (e.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, 0.65, 0.7, 0.85, 0.9, 0.95 wt%) of the cement raw material feed. The flue gas denitration efficiency achieved by the method can reach more than 90%, for example 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99% and 99.5%.
In the present invention, the denitration efficiency= (pre-denitration background concentration-post-denitration emission concentration)/pre-denitration background concentration is 100%.
In addition, the invention can realize real-time adjustment of spraying and adding amount of the biomass denitration agent and the powder according to the NOx content of the flue gas by selecting the types and adding positions of the denitration agent, using a metering feeder, a flow control device and the like in a biomass denitration system, thereby achieving continuous and accurate control of the indexes of the emission. If powders and water agents are added at other locations, such as the front end of a rotary kiln, accurate control of emissions indicators in real time is often not achieved.
In summary, the spraying positions of the biomass denitration agent and the powder are extremely studied (the optimal spraying position is determined based on thousands of hours of industrial online tests), two biomass denitration agents (the agent and the powder) and two or three spraying positions are combined and matched for the first time, and the spraying amounts of the biomass denitration agent and the powder can be automatically controlled and adjusted according to the NOx content of the flue gas, so that economical, environment-friendly and efficient flue gas denitration is realized. The invention is a substantial technical innovation based on the existing denitration technology, introduces more hydrocarbon compounds through biomass water aqua and powder, and remarkably improves the removal rate and efficiency of NOx by multiple mixing with materials to be treated under the environment of proper temperature and atmosphere. More importantly, the invention innovatively takes the biomass-derived powder and water as the main components of the denitration agent, and introduces the comprehensive treatment concept of waste utilization in the cement environment-friendly industry. The main components of the used denitration agent, namely the biomass denitration agent and the denitration powder, are prepared by biomass carbonization and thermal cracking with wide sources, the raw materials are easy to obtain, green and 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, and 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 cement industrial flue gas denitration.
The percentages, ratios, levels or parts stated herein are by weight unless specifically stated otherwise. The concentrations described herein are weight concentrations.
The temperature unit "degrees" as used herein refers to degrees celsius.
The denitration agent is used for removing flue gas. Thus, the term "biomass denitration agent" in this application may also be referred to as "biomass flue gas denitration agent" and the two may be used interchangeably. Similarly, the term "biomass denitration powder" in the present application may also be referred to as "biomass flue gas denitration powder", and the two may also be used interchangeably. The term "biomass denitration agent" in the present application may also be referred to as "biomass flue gas denitration agent", and the two agents may also be used interchangeably. Herein, the denitration agent refers to a denitration agent and/or a denitration powder.
Drawings
Fig. 1: one embodiment of positions 1, 2 and 3 is shown, wherein the relative positions of air, clinker, cooler and fuel are also shown.
Fig. 2: one embodiment of the denitration agent is sprayed from the position 1 and the position 2.
Fig. 3: one embodiment of the denitration agent is sprayed from the position 2 and the position 3.
Fig. 4: one embodiment of spraying the denitration agent from the position 1, the position 2 and the position 3.
Fig. 5: an exemplary water/powder spray gun arrangement.
Fig. 6: an exemplary aqueous spray device.
Fig. 7: an exemplary powder spraying 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 upstream part of the air pipe
10. Connecting downstream part of air duct
11. C5 cyclone cylinder
12. Cyclone tube connecting air tube
13. C4 cyclone cylinder
14. C3 cyclone
15. C2 cyclone
16. C1 cyclone
17. Tertiary air duct
21. Biomass 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 delivery 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. Water agent uninstallation and circulation system
103. Water agent uninstallation and circulation 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 invention, the following examples are further illustrated, but are not limited to the following examples. The experimental procedures described in the following examples, unless otherwise specified, were all conventional; the reagents and materials, unless otherwise specified, are commercially available. The cyclone used in the examples and comparative examples was a five-stage cyclone, and thus the C5 cyclone was the lowest-stage cyclone.
Example 1: position 1+position 2+position 3
The biomass denitration powder comprises the following components in percentage by mass: 70% of gangue powder, 20% of graphite powder and 10% of biomass carbon powder. The biomass denitration agent comprises the following components in percentage by mass: 45% of water content, 35% of biomass lysate and 20% of methanol.
This example was used on a 5000t/d new dry cement production line located in Guangdong, where the NOx concentration in the flue gas was actually monitored as 900mg/m3. Adopt this application system place a living beings denitration water aqua storage tank and a living beings denitration water aqua storehouse on ground, spout the living beings denitration water aqua through multistage centrifugal pump and water spray gun in kiln tail smoke chamber department (position 1), spout the living beings denitration powder through pneumatic pump and powder spray gun in decomposing furnace exit portion (position 2), spout the living beings denitration water aqua of another part through multistage centrifugal pump and water spray gun in C5 whirlwind section of pipe entry portion (position 3), 4 spray guns that living beings denitration water aqua was arranged through coplanar interval 90 in position 1 spout the adding through the coplanar interval 60, 6 spray guns that living beings denitration water aqua was arranged through coplanar interval 60 in position 3 spout the adding, utilize high-pressure air to atomize the denitration water aqua to <10 mu m below the liquid droplet. 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 agent is 1000L/h (about 0.3% 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, and the spraying amount of the position 3 is about 200L/h. After 10 minutes, the concentration of NOx in the flue gas can be stabilized below 50mg/m < 3 >, the minimum concentration can reach 41mg/m < 3 >, and the denitration efficiency of the flue gas of the cement kiln can reach more than 95%.
Example 2: position 1+ position 2
The biomass denitration powder comprises the following components in percentage by mass: 80% of gangue powder, 10% of graphite powder and 10% of biomass carbon powder. The biomass denitration agent comprises the following components in percentage by mass: 50% of water content, 25% of biomass lysate and 25% of methanol.
This example was used on a 5000t/d new dry cement production line located in Guangdong with a practical monitoring of the NOx concentration in the flue gas of 850mg/m3. Adopt the system that this application described, placed a living beings denitration agent storage tank and a living beings denitration agent warehouse on ground. The biomass denitration agent is sprayed at a kiln tail smoke chamber (position 1) through a multistage centrifugal pump and an agent spray gun, the biomass denitration powder is sprayed at an outlet part (position 2) of the decomposing furnace through a pneumatic pump and a powder spray gun, the biomass denitration agent is sprayed through 4 spray guns which are arranged on the same plane at an interval of 90 degrees, and the denitration agent is atomized into droplets below 10 mu m through high-pressure air. 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% of the feeding amount of the cement raw material), the spraying amount of the biomass denitration water agent is 1000L/h (about 0.3% of the feeding amount of the cement raw material), the concentration of NOx in the flue gas after 10 minutes can be stabilized below 60mg/m < 3 >, the minimum concentration can reach 53mg/m < 3 >, and the flue gas denitration efficiency of a cement kiln reaches 93%.
Example 3: position 2+ position 3
The biomass denitration powder comprises the following components in percentage by mass: 75% of gangue powder, 20% of graphite powder and 5% of biomass carbon powder. The biomass denitration agent comprises the following components in percentage by mass: 60% of water content, 20% of biomass lysate and 20% of methanol.
This example was used on a 5000t/d new dry cement production line located in Guangdong with the NOx concentration in the flue gas being monitored practically at 880mg/m3. Adopt this application system place a living beings denitration water aqua storage tank and a living beings denitration water aqua storehouse on ground, spout the living beings denitration powder through air pump and powder spray gun in decomposing furnace exit portion (position 2), spout the living beings denitration water aqua through multistage centrifugal pump and water spray gun at C5 whirlwind section of thick bamboo tuber pipe entry portion (position 3), the living beings denitration water aqua is spouted through 6 spray guns that coplanar interval 60 was arranged in position 3, utilize high-pressure air to atomize the denitration water into <10 mu m below liquid droplet. The biomass denitration powder is sprayed by 1 spray gun at the position 2. The spraying amount of the biomass denitration powder is 2t/h (about 0.6% of the feeding amount of the cement raw material), the spraying amount of the biomass denitration agent is 600L/h (about 0.2% of the feeding amount of the cement raw material), the concentration of NOx in the flue gas after 10 minutes can be stabilized below 80mg/m < 3 >, the minimum concentration can reach 73mg/m < 3 >, and the flue gas denitration efficiency of the cement kiln reaches more than 91%.
Example 4: position 1+ position 3
The biomass denitration agent comprises the following components in percentage by mass: 50% of water content, 20% of biomass lysate and 30% of methanol.
This example was used on a 5000t/d new dry cement production line located in Anhui, where the NOx concentration in the flue gas was actually monitored to be 860mg/m3. Adopt this application system a living beings denitration water aqua storage tank has only been placed on ground, spout the living beings denitration water aqua through multistage centrifugal pump and water spray gun in kiln tail smoke chamber department (position 1), spout the living beings denitration water aqua of adding another part through multistage centrifugal pump and water spray gun at C5 whirlwind section of thick bamboo tuber pipe entry (position 3), 4 spray guns that living beings denitration water aqua was arranged through coplanar interval 90 in position 1 spout, 8 spray guns that living beings denitration water aqua was arranged through two-layer plane interval 90 in position 3 spout the addition, utilize high-pressure air to atomize denitration water aqua into <10 mu m below liquid droplet. 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, the spraying amount of the position 1 is about 900L/h, the spraying amount of the position 3 is about 600L/h, the concentration of NOx in flue gas after 10 minutes can be stabilized below 70mg/m < 3 >, the minimum concentration can reach 62mg/m < 3 >, and the flue gas denitration efficiency of a cement kiln can reach above 92%.
Example 5: position 1+ position 2
The biomass denitration powder comprises the following components in percentage by mass: 80% of gangue powder, 10% of graphite powder and 10% of biomass carbon powder. The biomass denitration agent comprises the following components in percentage by mass: 50% of water content, 25% of biomass lysate and 25% of glycerol.
The test conditions and addition locations were the same as in example 2 except that 25wt% glycerol was used instead of 25wt% methanol as the solvent in the denitration agent. The spraying amount of the biomass denitration agent is 1000L/h (about 0.3 percent of the feeding amount of the cement raw material). The initial NOx concentration in the flue gas was actually monitored at 850mg/m3. After denitration for 10 minutes, the concentration of NOx in the flue gas can be stabilized below 60mg/m < 3 >, and the denitration efficiency of the cement kiln flue gas is 93%.
Example 6: position 1+ position 2
The test conditions and addition locations were the same as in example 2. In this example, the biomass charcoal powder in the denitration powder was prepared by carbonizing the shell in a carbonization furnace, and in example 2, the biomass charcoal powder in the denitration powder was prepared by carbonizing the straw. 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). After 10 minutes, the concentration of NOx in the flue gas can be stabilized below 60mg/m < 3 >, and the denitration efficiency of the cement kiln flue gas is 93%.
Example 7: preparation of biomass denitration powder
About 10 tons of corn stalks are collected, air is separated in a carbonization furnace and heated to about 600 ℃, about 3 tons of carbon-containing solid products (namely biomass charcoal) are prepared by carbonization, the solid products are ground to 200 meshes, and the solid products are uniformly mixed with 6 tons of graphite mineral powder and 21 tons of gangue powder to prepare 30 tons of biomass denitration powder, and the 30 tons of the biomass denitration powder are used in the embodiment 1. The biomass denitration powders used in examples 2 to 3 were prepared using different amounts of the aforementioned biomass charcoal powder, coal gangue powder, and graphite ore powder.
Biomass charcoal powder was prepared using rice straw, mixed with a metered amount of gangue powder and graphite ore powder, and biomass denitration powder used in example 5 and comparative example 6 was prepared using the same method as described above.
Example 8: preparation of biomass denitration powder
About 5 tons of dried shells are collected, air is separated in a carbonization furnace and heated to about 700 ℃, about 2 tons of biomass charcoal is prepared by carbonization, the biomass charcoal is ground to 200 meshes of fineness, and the biomass charcoal is uniformly mixed with 2 tons of graphite mineral powder and 16 tons of coal gangue powder to prepare 20 tons of biomass denitration powder, which is used in the embodiment 6.
Example 9: preparation of biomass denitration water agent
About 10 tons of branches are collected, heated to 500 ℃ in a gasifier with air separated, and about 7 tons of biomass lysate is obtained, which contains C4-C17 hydrocarbons and hydrocarbon oxides, as detected. The lysate is more viscous. After adding 9 tons of water and 4 tons of methanol, the mixture was stirred for about 15 minutes using a high-speed shearing stirring device at 20000 rpm to prepare 20 tons of a substantially uniform biomass denitration agent for use in example 1. The biomass denitration agents used in examples 3 and 6 were prepared using different amounts of the aforementioned biomass lysate, water, and methanol.
Example 10: preparation of biomass denitration water agent
About 8 tons of bagasse was collected, heated to 450 ℃ in a gasifier with air separation to obtain about 5 tons of biomass lysate, which was detected to contain C4-C17 hydrocarbons and hydrocarbons oxygenates. The lysate is more viscous. After adding 10 tons of water and 5 tons of methanol, the mixture was stirred for about 15 minutes using a high-speed shearing stirring device at 20000 rpm to prepare 40 tons of a substantially uniform biomass denitration agent for use in example 2. Biomass denitration agents used in example 4, comparative example 5, and comparative example 7 were prepared using different amounts of the aforementioned biomass lysate, water, and methanol. The biomass denitration agents used in example 5 were prepared using different amounts of the aforementioned biomass pyrolysis liquid, water, and glycerol.
Comparative example 1: position 2+ position 3
This comparative example was used on a 5000t/d new dry cement production line located in Guangdong, and the NOx concentration in the flue gas was actually monitored to be 800mg/m3. By using an original technology (SNCR selective non-catalytic reduction) spraying system, 900L/h (about 0.25% of raw material feeding amount) of ammonia water with concentration of 20% is sprayed at an outlet (position 2) of a decomposing furnace and an inlet part (position 3) of a C5 cyclone air pipe through an aqueous spray gun, a layer of each spray gun is arranged at the position 2 and the position 3, 4 spray guns are arranged at the positions which are respectively at the plane interval of 90 degrees, and a denitration aqueous solution is atomized into droplets below 10 mu m by using high-pressure air. After 10 minutes, the concentration of NOx in the flue gas can be stabilized at about 320mg/m < 3 >, and the flue gas denitration efficiency is only 60%.
Comparative example 2: position 1+ position 2
The comparative example was used on a Guangdong 5000t/d novel dry cement production line, and the NOx concentration in the flue gas was actually monitored to be 900mg/m3. 3-5t/h (about 1-1.5% of raw material feeding amount) of coal dust is sprayed by 1 spray gun at a kiln tail smoke chamber (position 1) by using a powder combustion device, 900L/h (0.2-0.3% of raw material feeding amount) of ammonia water with concentration of 20% is sprayed at an outlet (position 2) of a decomposing furnace by using an original technology (SNCR selective non-catalytic reduction) spraying system, the ammonia water is sprayed by 8 spray guns arranged on the same plane at 45 degrees intervals, and a denitration agent is atomized into droplets below 10 mu m by using high-pressure air. After 10 minutes, the concentration of NOx in the flue gas can be stabilized at about 320mg/m < 3 >, and the flue gas denitration efficiency is only 64%.
Comparative example 3: position 1
The comparative example was used on a novel dry cement production line located in Guangdong at 5000t/d, and the NOx concentration in the flue gas was actually monitored to be about 850mg/m 3. Using a prior art (biomass composite denitration) spraying system, 1000L/h (about 0.25% of raw material feeding amount) of water is sprayed at a kiln tail smoke chamber (position 1) through water spray guns, 4 spray guns arranged at 90-degree intervals on the same plane are used for spraying, and a denitration water agent is atomized into droplets below 10 mu m by high-pressure air. After 10 minutes, the concentration of NOx in the flue gas is still stable at about 830-850 mg/m < 3 >, and the denitration effect is almost not achieved.
Comparative example 4: other positions
The biomass denitration agent comprises the following components in percentage by mass: 50% of water content, 25% of biomass lysate and 25% of methanol.
The comparative example is used on a novel 5000t/d dry cement production line positioned in Henan, and the actual concentration of NOx in the flue gas is monitored to be about 1000mg/m < 3 >. By using a spraying system in the prior art (biomass composite denitration), 8 spraying guns (A, B rows of 4 preheaters in each row) are arranged between C2-C3 cyclones to spray 1500L/h (about 0.4% of raw material feeding amount) of biomass denitration agent, and the denitration agent is atomized into droplets below 10 mu m by using high-pressure air. After 10 minutes, the concentration of NOx in the flue gas can be stabilized at about 800-900 mg/m < 3 >, the flue gas denitration efficiency is 10-20%, and the denitration effect is not obvious.
Comparative example 5: position 1
The biomass denitration agent comprises the following components in percentage by mass: 70% of water content, 15% of biomass lysate and 15% of methanol.
This comparative example was used on a 5000t/d new dry cement production line located in Guangdong, and the NOx concentration in the flue gas was actually monitored as 850mg/m3. Spraying a biomass denitration agent at a kiln tail smoke chamber (position 1) by using a spraying system in the prior art (biomass composite denitration), spraying by using 4 spraying guns which are arranged on the same plane at intervals of 90 degrees, and atomizing the denitration agent into droplets below 10 mu m by using high-pressure air. The spraying amount of the biomass denitration water agent is 1000L/h (about 0.3% of the feeding amount of cement raw materials), the concentration of NOx in the flue gas after 10 minutes can be stabilized at about 130mg/m < 3 >, and the denitration efficiency of the flue gas of the cement kiln is 85%.
Comparative example 6: position 2
The biomass denitration powder comprises the following components in percentage by mass: 60% of gangue powder, 20% of graphite powder and 20% of biomass carbon powder.
This comparative example was used on a 5000t/d new dry cement production line located in Guangdong, and the NOx concentration in the flue gas was actually monitored to be 880mg/m3. And spraying the biomass denitration powder on the outlet part (position 2) of the decomposing furnace through a pneumatic pump and a powder spray gun by using a spraying system in the prior art (biomass composite denitration). The spraying amount of the biomass denitration powder is 2t/h (about 0.5 percent of the feeding amount of cement raw materials), the concentration of NOx in the flue gas after 10 minutes can be stabilized at about 340mg/m < 3 >, and the denitration efficiency of the flue gas of a cement kiln is 61 percent.
Comparative example 7: position 3
The biomass denitration agent comprises the following components in percentage by mass: 65% of water content, 15% of biomass lysate and 20% of methanol.
This comparative example was used on a 5000t/d new dry cement production line located in Guangdong, and the NOx concentration in the flue gas was actually monitored as 950mg/m3. The prior art (biomass composite denitration) spraying system is used, all biomass denitration agents are sprayed at the inlet part (position 3) of an air pipe of a C5 cyclone, 6 spraying guns which are arranged on the same plane at an interval of 60 degrees are used for spraying, and the denitration agents are atomized into droplets below 10 mu m by using high-pressure air. The spraying amount of the biomass denitration water agent is 1200L/h (about 0.35% of the feeding amount of cement raw materials), the concentration of NOx in the flue gas after 10 minutes can be stabilized below 600mg/m < 3 >, and the denitration efficiency of the flue gas of a cement kiln is 37%.
Comparative example 8: position 1
The comparative example was used on a novel dry cement production line located in Guangdong at 5000t/d, and the NOx concentration in the flue gas was actually monitored to be about 800mg/m 3. By using a spraying system in the prior art (biomass composite denitration), 1000L/h (about 0.25% of raw material feeding amount) of 20% concentration ammonia water is sprayed at a smoke chamber (position 1) at the kiln tail through water spray guns, 4 spray guns are arranged on the same plane at intervals of 90 degrees, and a denitration water agent is atomized into droplets below 10 mu m through high-pressure air. After 10 minutes, the concentration of NOx in the flue gas is still stable at about 600mg/m < 3 >, and the flue gas denitration efficiency is only 25%.
Comparative example 9: position 2
The comparative example was used on a novel dry cement production line located in Guangdong at 5000t/d, and the NOx concentration in the flue gas was actually monitored to be about 800mg/m 3. Using the prior art (SNCR selective non-catalytic reduction) spraying system, 1000L/h (about 0.25% of raw material feeding amount) of 20% concentration ammonia water is sprayed at the outlet of the decomposing furnace (position 2) through water spray guns, 8 spray guns arranged at 45 degrees intervals on the same plane are used for spraying, and the denitration water is atomized into droplets below 10 mu m through high-pressure air. After 10 minutes, the concentration of NOx in the flue gas is still stable at about 350mg/m < 3 >, and the flue gas denitration efficiency is only 56%.
Comparative example 10: position 3
The comparative example was used on a novel dry cement production line located in Guangdong at 5000t/d, and the NOx concentration in the flue gas was actually monitored to be about 800mg/m3. Using the prior art (SNCR selective non-catalytic reduction) spraying system, 1000L/h (about 0.25% of raw material feeding amount) of 20% concentration ammonia water is sprayed at the inlet part (position 3) of the C5 cyclone tube through a water spray gun, 8 spray guns arranged at 45 degrees on the same plane are used for spraying, and the denitration water is atomized into droplets below 10 mu m through high-pressure air. After 10 minutes, the concentration of NOx in the flue gas is still stable at about 320mg/m < 3 >, and the flue gas denitration efficiency is only 60%.
Comparative example 11: position 1
The comparative example was used on a 5000t/d novel dry cement production line from Anhui, and the NOx concentration in the flue gas was actually monitored as 900mg/m3. 3-5t/h (1-1.5% of raw material feeding amount) of coal dust is sprayed at a kiln tail smoke chamber (position 1) by using an air pump, the concentration of NOx in smoke can be stabilized at about 750mg/m < 3 > after 10 minutes, and the smoke denitration efficiency is only 16.7%.
Comparative example 12: position 2
The comparative example was used on a 5000t/d novel dry cement production line from Anhui, and the NOx concentration in the flue gas was actually monitored as 800mg/m3. 3-5t/h (1-1.5% of raw material feeding amount) of coal dust is sprayed at the outlet (position 2) of the decomposing furnace by using an air pump, the concentration of NOx in the flue gas can be stabilized to be about 750-800mg/m < 3 >, the flue gas denitration efficiency is less than 10%, and the denitration effect is hardly generated after 10 minutes.
Comparative example 13: position 3
The comparative example is used on a novel 5000t/d dry cement production line of Anhui, and the actual monitoring of the concentration of NOx in the flue gas is 900mg/m 3 Left and right. Pulverized coal of 3-5t/h (1-1.5% of raw material feeding amount) is sprayed at the inlet part (position 3) of the air pipe of the C5 cyclone, and the concentration of NOx in the flue gas can be stabilized at 850-900 mg/m after 10 minutes 3 About, the flue gas denitration efficiency is below 10%, and the denitration effect is almost absent.
Examples Position 1 Position 2 Position 3 Other positions Initial NOx concentration (mg/m) 3 ） NOx concentration after denitration (mg/m) 3 ） Denitration efficiency
Example 1 Biomass denitration agent Biomass denitration powder Biomass denitration agent —— 900 50 95%
Example 2 Biomass denitration agent Biomass denitration powder —— —— 850 60 93%
Example 3 —— Biomass denitration powder Biomass denitration agent —— 880 80 91%
Example 4 Biomass denitration agent —— Biomass denitration agent —— 860 70 92%
Example 5 Biomass denitration agent (glycerol) Biomass denitration powder —— —— 850 60 93%
Example 6 Biomass denitration agent Biomass denitration powder (Shell) 850 60 93%
Comparative example 1 —— Ammonia water Ammonia water —— 800 320 60%
Comparative example 2 Pulverized coal Ammonia water —— —— 900 320 64%
Comparative example 3 Water and its preparation method —— —— —— 850 830-850 0
Comparative example 4 —— —— —— Between/generating C2-C3 whirlwind cylinder Substance denitration agent 1000 800-900 10-20%
Comparative example 5 Biomass denitration agent —— —— —— 850 130 85%
Comparative example 6 —— Biomass denitration powder —— —— 880 340 61%
Comparative example 7 —— —— Biomass denitration agent —— 950 600 37%
Comparative example 8 Ammonia water —— 800 600 25%
Comparative example 9 Ammonia water —— 800 350 56%
Comparative example 10 Ammonia water —— 800 320 60%
Comparative example 11 Pulverized coal —— 900 750 16.7%
Comparative example 12 Pulverized coal —— 800 750-800 <10%
Comparative example 13 Pulverized coal —— 800 750-800 <10%
As can be seen from the above examples and comparative examples, firstly, the biomass denitration agent used in the present patent has higher denitration efficiency than the conventional coal dust and ammonia water denitration agent; in addition, the denitration position selected by the patent 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 in all the prior art at present.
While the invention has been described with reference to the preferred embodiments, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the scope of the invention, and it is intended to cover the invention as defined by the appended claims.

Claims (19)

1. The application method of the novel biomass denitration agent for the dry-method cement kiln is characterized in that the biomass denitration agent consists of biomass denitration powder and biomass denitration agent,
the biomass denitration powder comprises the following components: 50-90 wt% of coal gangue powder; 10-40 wt% of graphite mineral powder; and 5-30 wt% of biomass carbon powder;
the biomass charcoal powder in the biomass denitration powder is ground powder of biomass charcoal, and the biomass charcoal is a charcoal-containing solid substance obtained by carbonizing a biomass material under anoxic and heating conditions;
the biomass denitration water agent comprises the following components: 40-80 wt% of water; 20-60 wt% of a liquid biomass lysate; and 10 to 40 wt% of a C1-C10 monohydric or polyhydric alcohol;
the liquid biomass pyrolysis liquid in the biomass denitration water agent is a liquid substance containing C4-C17 liquid hydrocarbon or C4-C17 hydrocarbon or a mixture thereof, which is obtained in the pyrolysis process of biomass materials under anoxic and heating conditions;
and optionally using the biomass denitration agent in combination of two or three in the following manner:
spraying a biomass denitration agent at a position 1 between the tail end of the rotary kiln and the tail end of the tertiary air pipe;
Spraying biomass denitration powder at a position 2 between the rear section of the decomposing furnace and the inlet of the cyclone barrel at the lowest stage; and
and spraying another part of biomass denitration water agent at a position 3 between the outlet of the decomposing furnace and the inlet of the cyclone barrel at the lowest stage.
2. The method of claim 1, wherein the biomass material comprises any non-fossilized plant material, animal material, or microbial material, wherein the biomass material used to produce the biomass denitrification powder is optionally the same or different from the biomass material used to produce the biomass denitrification aqua.
3. The method of claim 1 or 2, wherein the biomass material comprises agriculture and forestry byproducts and/or industrial process organic waste; the agriculture and forestry byproducts include: branches, leaves, bark, wood, grass, corncob, straw, rice hulls, husks, shrubs and vines, or the industrial process organic waste comprises: bagasse, wood waste, and grass waste.
4. The method of claim 1 or 2, wherein the heating conditions comprise conditions heated to 400-800 ℃, wherein the heating conditions for preparing the biomass denitration powder are optionally the same as or different from the heating conditions for preparing the biomass denitration aqueous agent.
5. The method of claim 1 or 2, wherein the C1-C10 monohydric or polyhydric alcohol comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, t-butanol, benzyl alcohol, ethylene glycol, glycerol, or a mixture of two or more thereof.
6. The method of claim 1 or 2, characterized in that a biomass denitration agent is sprayed at position 1; spraying biomass denitration powder at the position 2; and spraying another part of biomass denitration water agent at the position 3.
7. A method according to claim 1 or 2, characterized in that position 1 is selected at the kiln tail smoke chamber.
8. A method according to claim 1 or 2, wherein the location 2 is selected such that the outlet of the decomposing furnace is connected to the upper part of the wind pipe to the lowest cyclone.
9. A method according to claim 1 or 2, characterized in that position 2 selects the decomposing furnace outlet section.
10. A method according to claim 1 or 2, wherein the location 3 is selected such that the outlet of the decomposing furnace is connected to the downstream part of the cyclone of the lowest stage.
11. A method according to claim 1 or 2, characterised in that position 3 selects the outlet of the decomposing furnace to the inlet section of the cyclone tube of the lowest stage.
12. Novel biomass denitration system for dry-method cement kiln, which comprises biomass denitration water agent, biomass denitration powder, water agent spraying device and powder spraying device, wherein
The biomass denitration powder comprises the following components: 50-90 wt% of coal gangue powder; 10-40 wt% of graphite mineral powder; and 5-30 wt% of biomass carbon powder;
the biomass charcoal powder in the biomass denitration powder is ground powder of biomass charcoal, and the biomass charcoal is a charcoal-containing solid substance obtained by carbonizing a biomass material under anoxic and heating conditions;
the biomass denitration water agent comprises the following components: 40-80 wt% of water; 20-60 wt% of a liquid biomass lysate; and 10 to 40 wt% of a C1-C10 monohydric or polyhydric alcohol;
the liquid biomass pyrolysis liquid in the biomass denitration water agent is a liquid substance containing C4-C17 liquid hydrocarbon or C4-C17 hydrocarbon or a mixture thereof, which is obtained in the pyrolysis process of biomass materials under anoxic and heating conditions; the water spray device comprises a water storage tank, a circulating pump and a water spray gun, wherein the water spray gun is arranged at a position 1 between the tail end of the rotary kiln and the tail end of the tertiary air pipe and/or a position 3 between the outlet of the decomposing furnace and the inlet of the cyclone barrel at the lowest stage; the powder spraying and adding device comprises a powder storage bin, a fan and a powder spray gun, wherein the powder spray gun is arranged at a position 2 between the rear section of the decomposing furnace and the inlet of the lowest cyclone barrel.
13. The novel biomass denitrification system for a dry-process cement kiln according to claim 12, wherein the water agent spraying device further comprises a jet pump, a flowmeter, a valve, a water agent pipeline and a compressed air pipeline.
14. The novel biomass denitrification system for a dry-process cement kiln according to claim 12, wherein the powder spraying device further comprises a metering feeder, a pneumatic conveying pump, a Roots blower, a powder pipeline, a compressed air pipeline and a valve.
15. The system of any one of claims 12-14, wherein position 1 is selected at a kiln tail smoke chamber.
16. A system according to any one of claims 12 to 14, wherein position 2 selects the upstream portion of the decomposing furnace outlet to the connecting ductwork of the lowest stage cyclone.
17. The system of any of claims 12-14, wherein position 2 selects the decomposing furnace exit section.
18. A system according to any one of claims 12 to 14, wherein position 3 selects the downstream portion of the decomposing furnace outlet to the connecting ductwork of the lowest stage cyclone.
19. A system according to any one of claims 12 to 14, wherein position 3 selects the inlet portion of the lowest stage cyclone.
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