CN111167276B - Denitration method in alkali recovery furnace - Google Patents
Denitration method in alkali recovery furnace Download PDFInfo
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- CN111167276B CN111167276B CN202010060565.4A CN202010060565A CN111167276B CN 111167276 B CN111167276 B CN 111167276B CN 202010060565 A CN202010060565 A CN 202010060565A CN 111167276 B CN111167276 B CN 111167276B
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Abstract
The invention relates to the technical field of denitration methods, and provides a denitration method in an alkali recovery furnace, which comprises the following steps: and hydrolyzing the solid urea particles through a denitration agent storage and supply system, and carrying out denitration on the hydrolyzed urea product through a denitration reaction system. By adopting the technical scheme, after the solid urea particles are denitrated by the denitration agent storage and supply system and the denitration reaction system respectively, on one hand, the flue gas of the alkali recovery furnace does not contain alkali ash; on the other hand, the method is not influenced by the size of the boiler, the denitration efficiency is higher, the ammonia escape rate is low, the leakage amount is smaller, secondary pollution is avoided, and the reaction temperature and the retention time can be ensured; in addition, NOx in the flue gas at the outlet of the alkali recovery furnace is effectively reduced.
Description
Technical Field
The invention relates to the technical field of denitration methods, and particularly relates to a denitration method in an alkali recovery furnace.
Background
The alkali recovery furnace is the core equipment of a pulping plant, and waste liquid generated in the process of combustion treatment pulping is a chemical reactor for producing sodium carbonate and sodium sulfate and is also a steam generator; the electricity generated by the high-temperature and high-pressure steam generated by the device can meet most of electricity utilization requirements of a pulp mill. The alkali recovery furnace is a key link of a modern pulp mill and is also a main source for the emission of acidic gas pollutants such as nitrogen oxides and the like in the pulp mill. Thus, acid gas pollutant emissions from the soda recovery furnace face significant challenges.
NOx in the flue gas of the soda recovery furnace is generated by combustion reaction of organic nitrogen compounds in the solid matters in the waste liquid and oxygen fed into the air of the soda furnace. The denitration method in the alkali recovery furnace in the prior art mainly comprises selective catalytic reduction, selective non-catalytic reduction and low NOx combustion technologies.
The principle of selective catalytic reduction is to use NH3And a catalyst (metal such as iron, vanadium, chromium, cobalt, molybdenum and the like) for reducing NOx into N in a proper temperature interval2Substantially not with O2And (4) reacting. Although the selective catalytic reduction process is mature, the denitration efficiency is high (70-90%), the ammonia escape is low, and the commercial application is wide. But the method cannot be used industrially in the alkali recovery furnace, and the main reasons are as follows: first, the soda ash component of the soda recovery furnace is mainly Na2SO4、Na2CO3NaCl, KCl, etc., which are very easily synthesizedThe catalyst is easy to lose efficacy due to alkali metal and sulfate which cause catalyst poisoning, and the aim of denitration cannot be achieved. Secondly, the flue gas of the alkali recovery furnace contains alkali ash with strong adhesion, which is easy to cause catalyst blockage.
The principle of selective non-catalytic reduction is to spray a reducing agent containing NHx groups into a narrow temperature range zone, where the reducing agent rapidly decomposes to NH in the absence of a catalyst3And reacts with NOx in the flue gas to reduce the NOx into N2And water, substantially free of O2And (4) reacting. The selective non-catalytic reduction has low industrial manufacturing cost and operation cost, short construction period and no need of catalyst, and is suitable for old plant reconstruction. However, the technology is greatly influenced by the size of the boiler, the denitration efficiency is low, the ammonia escape rate is high, the leakage amount is large, secondary pollution is easily caused, and the reaction temperature and the retention time are difficult to guarantee.
The low NOx combustion technology can realize low-oxygen combustion of fuel at the initial stage of combustion, and achieve the purpose of reducing NOx emission. However, because most of NOx in the flue gas of the soda recovery furnace is generated by N in black liquor of fuel, the O in the air is reduced in the low-nitrogen combustion technology2The concentration of NOx in the flue gas at the outlet of the alkali furnace cannot be effectively reduced.
How to effectively solve the technical problems is a problem to be solved by the technical personnel in the field at present.
Disclosure of Invention
In order to solve the above technical problems or at least partially solve the above technical problems, the present invention provides a method for denitration in a soda recovery furnace.
The denitration method in the alkali recovery furnace comprises the following steps:
hydrolyzing solid urea particles through a denitration agent storage and supply system, and carrying out denitration on a hydrolyzed urea product through a denitration reaction system;
the denitration agent storage and supply system comprises a urea particle storage unit, a dissolving unit, a urea solution storage unit, a urea solution conveying unit and a urea hydrolysis unit;
the hydrolyzing the solid urea particles through the denitration agent storage and supply system comprises the following steps:
feeding the solid urea particles to the urea particle storage unit and then from the urea particle storage unit to the dissolution unit;
stirring and dissolving the solid urea particles in the dissolving unit into a urea solution by using desalted water, and conveying the urea solution to the urea solution storage unit through a dissolving pump;
passing the urea solution through the urea solution delivery unit to the urea hydrolysis unit, where the urea solution is hydrolyzed to produce NH3 and CO 2;
in the process of carrying out denitration on the hydrolyzed urea product through a denitration reaction system, the denitration reaction system comprises: the device comprises a reducing air unit, a metering control unit, a static mixing unit and a hearth reaction unit;
the static mixing unit is used for fully mixing NH3 from the urea hydrolysis unit and air from the reducing air unit in a mixer and a pipeline;
the hearth reaction unit is positioned at the upper part of the reducing air unit, and the height of the hearth reaction unit is positioned at the central height of a hearth of the alkali recovery furnace;
and mixed air enters the furnace through the reducing air unit, and the mixed air, the reducing agent and the coupling agent participate in denitration reaction in the alkali recovery furnace.
Optionally, the urea solution undergoes a hydrolysis reaction at a temperature of 150 ℃ to 160 ℃, and the generated gas contains carbon dioxide, water vapor and ammonia gas, and the chemical reaction formula is as follows:
NH2-CO-NH2+H2O→2NH3↑+CO2↑。
optionally, the upper space in the urea hydrolysis unit is in a gaseous state;
the urea hydrolysis unit is controlled by pressure, and the pressure is 0.4MPa-0.6 MPa;
the concentration of the urea solution in the urea hydrolysis unit is 40-50%.
Optionally, the outlet of the reducing wind unit is provided with a fault interlocking closing device and a fault signal device respectively, and the reducing wind unit is arranged on the front wall and the rear wall of the alkali recovery furnace in a staggered manner;
the reduction wind unit is also provided with a wind pressure interlock and a motor trip interlock.
Optionally, the metering control unit calculates the amount of reducing agent required for denitration for the initial NOx and O2 at the outlet of the soda recovery furnace;
and the metering control unit compares the NOx value detected by the SMES with a preset value, corrects the amount of the reducing agent, and then adjusts a flow regulating valve of an ammonia gas injection mixing system by using the corrected reducing agent so as to control the amount of the reducing agent required by denitration.
Optionally, the reducing agent includes any one of liquid ammonia, ammonia water, urea, nitrogen-containing amino substances and ammonia salts;
the amino substance containing nitrogen comprises any one of ammonium bicarbonate, cyanuric acid, monoethylamine, trimethylamine and dimethylaminobenzaldehyde;
the ammonia salt comprises any one of ammonium acetate, ammonium bicarbonate, ammonium chloride, ammonium oxalate and ammonium citrate;
the coupling agent comprises any one of carbon, carbon monoxide, natural gas, hydrogen peroxide and bio-oil.
In the invention, after the solid urea particles are denitrated by the denitration agent storage and supply system and the denitration reaction system respectively, on one hand, the flue gas of the alkali recovery furnace does not contain alkali ash; on the other hand, the method is not influenced by the size of the boiler, the denitration efficiency is higher, the ammonia escape rate is low, the leakage amount is smaller, secondary pollution is avoided, and the reaction temperature and the retention time can be ensured; in addition, NOx in the flue gas at the outlet of the alkali recovery furnace is effectively reduced.
Drawings
FIG. 1 is a schematic structural diagram of a denitration agent storage and supply system provided by the invention;
fig. 2 is a schematic structural diagram of a denitration reaction system provided by the present invention.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described in detail with reference to the accompanying drawings and examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. The following examples are intended to illustrate the invention, but not to limit it. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention, are within the scope of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. The terms "connected" and "coupled" are used broadly and may include, for example, a fixed connection, a removable connection, or an integral part; can be mechanically or electrically connected; may be directly connected or indirectly connected through an intermediate. The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
An embodiment of the present invention, with reference to fig. 1 and fig. 2, provides a method for denitration in a soda recovery furnace, including the following steps:
and (3) hydrolyzing the solid urea particles through a denitration agent storage and supply system.
And (4) carrying out denitration on the hydrolyzed urea product through a denitration reaction system.
In the implementation, after the solid urea particles are denitrated by the denitration agent storage and supply system and the denitration reaction system respectively, on one hand, the flue gas of the alkali recovery furnace does not contain alkali ash; on the other hand, the method is not influenced by the size of the boiler, the denitration efficiency is higher, the ammonia escape rate is low, the leakage amount is smaller, secondary pollution is avoided, and the reaction temperature and the retention time can be ensured; in addition, NOx in the flue gas at the outlet of the alkali recovery furnace is effectively reduced.
In another embodiment of the present invention, as shown in fig. 1, the denitration agent storage and supply system includes a urea particle storage unit, a dissolving unit, a urea solution storage unit, a urea solution delivery unit, and a urea hydrolysis unit.
Hydrolyzing the solid urea particles through a denitration agent storage and supply system, wherein the denitration agent storage and supply system comprises:
the solid urea particles are fed to a urea particle storage unit from which they are transported to a dissolving unit.
And stirring and dissolving the solid urea particles in the dissolving unit into a urea solution by using desalted water, and conveying the urea solution to a urea solution storage unit by using a dissolving pump.
The urea solution is conveyed to a urea hydrolysis unit through a urea solution conveying unit, and the urea solution is hydrolyzed to generate NH in the urea hydrolysis unit3And CO2。
In this implementation, urea granule storage unit is the storage place of storing the particulate matter, and the unit that dissolves is the dissolving tank, and urea solution storage unit is the holding vessel of storing the solution, and urea solution conveying unit includes delivery pump, thermometer, filter and distributor, and urea hydrolysis unit is for making ammonia reactor, demineralized water is the demineralized water. The conveying pump comprises a centrifugal pump, a screw pump, a gear pump and the like, and the type of the conveying pump is selected correspondingly according to different working requirements.
Further, the solid urea particles in the dissolving unit are stirred and dissolved into a urea solution with the mass concentration of 40-60% by using desalted water.
In another embodiment of the present invention, the urea solution undergoes hydrolysis reaction at a temperature of 150 ℃ to 160 ℃, and the generated gas contains carbon dioxide, water vapor and ammonia, and has a chemical reaction formula:
NH2-CO-NH2+H2O→2NH3↑+CO2↑。
in the present embodiment, the hydrolysis reaction of the urea solution is carried out at a temperature of 150 ℃ to 160 ℃, and the temperature range can accelerate the hydrolysis reaction of the urea solution.
In still another embodiment of the present invention, the headspace in the urea hydrolysis unit is in a gaseous state.
The urea hydrolysis unit is controlled by pressure, and the pressure is 0.4MPa-0.6 MPa.
The concentration of the urea solution in the urea hydrolysis unit is 40-50%.
In the implementation, the pressure is 0.4MPa-0.6MPa, the concentration of the urea solution is 40% -50%, and the hydrolysis reaction of the urea solution can be accelerated within the pressure range and the concentration range of the urea solution. And conveying the ammonia in the ammonia reactor to a denitration reaction system through a pipeline by using the pressure of the reactor.
The ammonia reactor is a pressure vessel, urea intermediate products exist in the hydrolysis reaction process, and the urea intermediate products belong to strong corrosive substances and are in corrosion danger at high temperature, so 316L or dual-phase steel is needed, and equipment and pipelines of other units are made of 316L or dual-phase steel or materials not lower than 304L. The urea intermediate product includes ammonium carbamate, and the like.
Further, the pressure of the gas-liquid two-phase equilibrium system is 0.4MPa-0.6MPa, and the temperature is 150 ℃ to 160 ℃.
In another embodiment of the present invention, as shown in fig. 2, in the process of denitrifying the hydrolyzed urea product through a denitrification system, the denitrification system includes: the device comprises a reducing air unit, a metering control unit, a static mixing unit and a hearth reaction unit.
In the implementation, the reducing air unit comprises a fan device, a reducing air heater, a frequency converter, a pressure gauge, a thermometer and a flowmeter; the metering control unit comprises a pressure gauge, a thermometer and a flow meter (or mass meter) HIC (high-performance communication interface) which is an adjusting valve; the static mixing unit is a static mixer; the hearth reaction unit is a hearth reduction reaction space.
The denitration reaction system can remove NOx in the hydrolyzed urea product and realize denitration.
In another embodiment of the invention, the outlet of the reducing wind unit is respectively provided with a fault interlocking closing device and a fault signal device, and the reducing wind units are arranged on the front wall and the rear wall of the alkali recovery furnace in a staggered manner.
The restoring wind unit is also provided with a wind pressure interlock and a motor trip interlock.
In this embodiment, the fan device includes a recovery fan or an air supply fan, and the air supply process of the air supply fan includes three times of air supply or four times of air supply.
The tertiary air supply can be composed of three air supply fans, and comprises: the primary air supply supplies air to the lower part in the alkali recovery furnace, the secondary air supply supplies air to the middle part in the alkali recovery furnace, and the tertiary air supply supplies air to the upper part in the alkali recovery furnace.
The four air supplies can be composed of four air supply fans, and the four air supplies comprise: the primary air supply supplies air to the lower part in the alkali recovery furnace, the secondary air supply supplies air to the middle-lower part in the alkali recovery furnace, the tertiary air supply supplies air to the middle-upper part in the alkali recovery furnace, and the fourth air supply supplies air to the upper part in the alkali recovery furnace.
When the wind pressure of the wind pressure chain exceeds the normal wind pressure range, the wind pressure chain is automatically broken, so that the influence of the exceeding of the normal wind pressure on the denitration reaction system is reduced.
When the motor is tripped, the motor trip interlock automatically breaks, so that the influence of the motor trip on the denitration reaction system is avoided.
In still another embodiment of the present invention, as shown in fig. 1, the metering control unit calculates the amount of the reducing agent required for denitration based on the amount of the initial NOx discharged from the outlet of the soda recovery furnace, the amount of the flue gas, and the amount of O2.
The metering control unit compares the NOx value detected by the SMES with a preset value, corrects the amount of the reducing agent, and then adjusts a flow regulating valve in the metering control unit by using the corrected amount of the reducing agent so as to control the amount of the reducing agent required by denitration.
In yet another embodiment of the present invention, as shown in FIG. 1, a static mixing unit hydrolyzes NH from a urea hydrolysis unit3And air from the reducing air unit is fully mixed in the mixer and the pipeline.
In another embodiment of the present invention, as shown in fig. 1, the furnace reaction unit is located at the upper part of the reducing air unit, and the height of the furnace reaction unit is located at the central height of the furnace of the alkali recovery furnace.
The mixed air enters the alkali recovery furnace through the reducing air unit, and the mixed air, the reducing agent and the coupling agent participate in denitration reaction in the alkali recovery furnace.
In this embodiment, the height of the furnace reaction unit is located at the central height of the furnace of the soda recovery furnace, which can have sufficient reaction residence time.
In another embodiment of the present invention, as shown in fig. 1, the reducing agent includes any one of liquid ammonia, ammonia water, urea, a nitrogen-containing amino substance, and an ammonia salt.
The nitrogen-containing amino substance includes any one of ammonium bicarbonate, cyanuric acid, monoethylamine, trimethylamine, and dimethylaminobenzaldehyde.
The ammonia salt includes any one of ammonium acetate, ammonium bicarbonate, ammonium chloride, ammonium oxalate and ammonium citrate.
The coupling agent comprises any one of carbon, carbon monoxide, natural gas, hydrogen peroxide and bio-oil.
In the implementation, the reducing agent and the coupling agent are of various types, and the diversity of the reducing agent is enriched. The carbon is secondary fuel carbon. The types of the coupling agents are more, and the temperature field is corrected by adding the coupling agents, so that the temperature field suitable for reaction is obtained in the alkali recovery furnace.
The invention couples selective catalytic reduction, selective non-catalytic reduction and low NOx combustion technologies to form a coupled denitration technology. I.e. a combination of combustion and denitration techniques.
Finally, it should be noted that: the above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments. Those of ordinary skill in the art will understand that: it is to be understood that modifications may be made to the above-described arrangements in the embodiments or equivalents may be substituted for some of the features of the embodiments without departing from the spirit of the present invention.
Claims (4)
1. A denitration method in a soda recovery furnace is characterized in that a device used by the denitration method comprises:
the denitration agent storage and supply system comprises a urea particle storage unit, a dissolving unit, a urea solution storage unit, a urea solution conveying unit and a urea hydrolysis unit;
denitration reaction system, denitration reaction system includes: the device comprises a reducing air unit, a metering control unit, a static mixing unit and a hearth reaction unit; the reducing air unit comprises a fan device, a reducing air heater, a frequency converter, a pressure gauge, a thermometer and a flowmeter;
the fan device comprises four air supply fans for supplying air for four times;
the method comprises the following steps:
hydrolyzing solid urea particles through a denitration agent storage and supply system, and carrying out denitration on a hydrolyzed urea product through a denitration reaction system;
the hydrolysis comprises: feeding the solid urea particles to the urea particle storage unit and then from the urea particle storage unit to the dissolution unit;
stirring and dissolving the solid urea particles in the dissolving unit into a urea solution by using desalted water, and conveying the urea solution to the urea solution storage unit through a dissolving pump;
conveying the urea solution to the urea hydrolysis unit through the urea solution conveying unit, wherein the urea solution is subjected to hydrolysis reaction at the temperature of 150-160 ℃ in the urea hydrolysis unit, and generated gas contains carbon dioxide, water vapor and ammonia gas;
in the process of denitrifying the hydrolyzed urea product through a denitrification reaction system, the static mixing unit fully mixes carbon dioxide, water vapor and ammonia from the urea hydrolysis unit and air from the reducing air unit in a mixer and a pipeline;
the hearth reaction unit is positioned at the upper part of the reduction air unit, and the height position of the hearth reaction unit
The height of the center of a hearth of the alkali recovery furnace;
mixed air enters the alkali recovery furnace through the reducing air unit, and the mixed air, a reducing agent and a coupling agent participate in denitration reaction in the alkali recovery furnace;
the four air supply processes include: the primary air supply supplies air to the lower part in the alkali recovery furnace, the secondary air supply supplies air to the middle lower part in the alkali recovery furnace, the tertiary air supply supplies air to the middle upper part in the alkali recovery furnace, and the fourth air supply supplies air to the upper part in the alkali recovery furnace;
the upper space in the urea hydrolysis unit is in a gas state;
the urea hydrolysis unit is controlled by pressure, and the pressure is 0.4MPa-0.6 MPa;
the concentration of the urea solution in the urea hydrolysis unit is 40% -50%;
the metering control unit is used for controlling the initial NOx amount, the smoke gas amount and the O amount of the outlet of the soda recovery furnace2Calculating the amount of reducing agent required for denitration;
and the metering control unit compares the NOx value detected by the SMES with a preset value, corrects the amount of the reducing agent, and then adjusts a flow regulating valve of an ammonia gas injection mixing system by using the corrected reducing agent so as to control the amount of the reducing agent required by denitration.
2. The method for denitration in a soda recovery furnace according to claim 1, wherein the denitration step comprises the step of, after the denitration step,
the chemical reaction formula of the urea solution for hydrolysis reaction is as follows:
NH2-CO-NH2＋H2O→2NH3↑＋CO2↑。
3. the method for denitration in a soda recovery furnace according to claim 1, wherein the denitration step comprises the step of, after the denitration step,
the outlet of the reducing wind unit is respectively provided with a fault interlocking closing device and a fault signal device, and the reducing wind unit is arranged on the front wall and the rear wall of the alkali recovery furnace in a staggered manner;
the reduction wind unit is also provided with a wind pressure interlock and a motor trip interlock.
4. The method for denitration in a soda recovery furnace according to claim 1, wherein the denitration step comprises the step of, after the denitration step,
the reducing agent comprises any one of liquid ammonia, ammonia water, urea, nitrogenous amino substance and ammonia salt;
the nitrogen-containing amino substances include ammonium bicarbonate, cyanuric acid, monoethylamine, trimethylamine and dimethylamine
Any one of benzaldehydes;
the ammonia salt comprises any one of ammonium acetate, ammonium bicarbonate, ammonium chloride, ammonium oxalate and ammonium citrate;
the coupling agent is any one of carbon, carbon monoxide, natural gas, hydrogen peroxide and bio-oil.
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| DE102004042225B4 (en) * | 2004-09-01 | 2017-08-31 | MAN Truck & Bus Aktiengesellschaft | Apparatus and method for producing ammonia from solid urea pellets |
| JP5269483B2 (en) * | 2008-05-29 | 2013-08-21 | バブコック日立株式会社 | Operation method of water separator |
| CN103301737A (en) * | 2013-06-07 | 2013-09-18 | 大连贝斯特环境工程设备有限公司 | Urea hydrolyzed SNCR (selective non-catalytic reduction) flue gas denitrification device for fluidized bed boiler |
| CN103585867B (en) * | 2013-11-26 | 2016-05-11 | 天津大学 | A kind of flue gas desulfurization and denitration method and device |
| CN103691293B (en) * | 2014-01-13 | 2016-08-17 | 广东清华中邦热能科技有限公司 | A kind of SNCR and SCR mixing denitrating system |
| CN204637957U (en) * | 2015-04-15 | 2015-09-16 | 湖南农业大学 | A kind of equipment for denitrifying flue gas |
| CN205700079U (en) * | 2016-04-11 | 2016-11-23 | 广东理文造纸有限公司 | A kind of coal water slurry boiler denitration in the stove system |
| JP6532433B2 (en) * | 2016-08-02 | 2019-06-19 | 株式会社タクマ | Method of operation of urea hydrolysis apparatus |
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| CN107398176A (en) * | 2017-09-14 | 2017-11-28 | 上海宝钢节能环保技术有限公司 | Urea pyrolysis and spraying system for low-temperature smoke air SCR denitration |
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