CN117282246A - Denitration agent and application thereof - Google Patents
Denitration agent and application thereof Download PDFInfo
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- CN117282246A CN117282246A CN202311428347.1A CN202311428347A CN117282246A CN 117282246 A CN117282246 A CN 117282246A CN 202311428347 A CN202311428347 A CN 202311428347A CN 117282246 A CN117282246 A CN 117282246A
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- denitration
- denitration agent
- agent
- stabilizer
- benzotriazole
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- 239000003795 chemical substances by application Substances 0.000 claims abstract description 85
- -1 alcohol amide compound Chemical class 0.000 claims abstract description 27
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 claims abstract description 24
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003381 stabilizer Substances 0.000 claims abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003546 flue gas Substances 0.000 claims abstract description 13
- 238000005260 corrosion Methods 0.000 claims description 27
- 230000007797 corrosion Effects 0.000 claims description 27
- 239000003112 inhibitor Substances 0.000 claims description 22
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 15
- 239000012964 benzotriazole Substances 0.000 claims description 12
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 229920002367 Polyisobutene Polymers 0.000 claims description 6
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 150000004867 thiadiazoles Chemical class 0.000 claims description 6
- LPMBTLLQQJBUOO-KTKRTIGZSA-N (z)-n,n-bis(2-hydroxyethyl)octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)N(CCO)CCO LPMBTLLQQJBUOO-KTKRTIGZSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- AAJBNRZDTJPMTJ-UHFFFAOYSA-L magnesium;dinitrite Chemical compound [Mg+2].[O-]N=O.[O-]N=O AAJBNRZDTJPMTJ-UHFFFAOYSA-L 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- XGZOMURMPLSSKQ-UHFFFAOYSA-N n,n-bis(2-hydroxyethyl)octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)N(CCO)CCO XGZOMURMPLSSKQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000002826 nitrites Chemical class 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- RAFRTSDUWORDLA-UHFFFAOYSA-N phenyl 3-chloropropanoate Chemical compound ClCCC(=O)OC1=CC=CC=C1 RAFRTSDUWORDLA-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- WBTCPVUCKKBWBS-UHFFFAOYSA-N azetidine-2,4-dione Chemical compound O=C1CC(=O)N1 WBTCPVUCKKBWBS-UHFFFAOYSA-N 0.000 claims 1
- MEVHTHLQPUQANE-UHFFFAOYSA-N aziridine-2,3-dione Chemical compound O=C1NC1=O MEVHTHLQPUQANE-UHFFFAOYSA-N 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 61
- 229910021529 ammonia Inorganic materials 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 21
- 238000003860 storage Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 231100000331 toxic Toxicity 0.000 abstract description 3
- 230000002588 toxic effect Effects 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 28
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- 239000004202 carbamide Substances 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 11
- 238000000197 pyrolysis Methods 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229940049964 oleate Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- MWIRQVRILGQXFA-UHFFFAOYSA-N 2-methylpropan-1-imine Chemical compound CC(C)C=N MWIRQVRILGQXFA-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- UPCXAARSWVHVLY-UHFFFAOYSA-N tris(2-hydroxyethyl)azanium;acetate Chemical compound CC(O)=O.OCCN(CCO)CCO UPCXAARSWVHVLY-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention belongs to the field of waste gas pollution treatment, and particularly relates to a denitration agent and application thereof. The denitration agent provided by the embodiment of the invention comprises ammonium carbamate and a stabilizer, wherein the stabilizer comprises an alcohol amide compound. The denitration agent has the characteristics of high unit ammonia content, high ammonia production efficiency, low ammonia production energy consumption, easiness in storage, high solubility, low corrosiveness, no toxic and harmful components on a denitration system, low thermal decomposition temperature and the like, and is suitable for application in the fields of flue gas denitration and the like.
Description
Technical Field
The invention belongs to the field of waste gas pollution treatment, and particularly relates to a denitration agent and application thereof.
Background
At present, the main technologies of flue gas denitration of pulverized coal boilers of thermal power plants are reduction methods represented by Selective Catalytic Reduction (SCR) and selective non-catalytic reduction (SNCR). The principle of SNCR and SCR for flue gas denitration is basically the same, and the SNCR and SCR are used for selectively reacting with nitrogen oxides (mainly NO and NO 2 ) Carrying out the reaction to finally generate harmless N 2 And H is 2 O。
Under the requirements of double carbon and energy conservation and emission reduction, the development of the flue gas denitration technology also meets a new opportunity, and the development of the efficient novel denitration agent and the ammonia preparation technology thereof has extremely important significance in terms of environmental protection and economic benefit, improves the ammonia preparation efficiency, improves the economical efficiency of denitration, and reduces the energy consumption and the comprehensive cost.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems:
the common denitration reducing agents mainly comprise the following three types: urea, liquid ammonia and ammonia water, and ammonia gas required by the denitration reaction is obtained through different technological processes.
(1) Preparing ammonia by liquid ammonia: liquid ammonia is taken as a denitration reducing agent, and is mainly sent into a liquid ammonia evaporator to be heated and evaporated into ammonia gas, and then the ammonia gas is sent into a denitration system. Therefore, the liquid ammonia system is simpler, has low energy consumption, convenient use and lower operation cost, and is the reducing agent with the best flue gas denitration economy in the thermal power plant. However, liquid ammonia is not only toxic, but also explosive, and has great safety risks in transportation and storage.
(2) Ammonia production method by ammonia water: typically, about 25% aqueous ammonia solution is placed in a storage tank and then vaporized by a heating device to form ammonia gas and water vapor. However, the ammonia water purchase concentration is only about 25%, so that the power plant denitration system is large in use amount and high in transportation cost, and the flue gas denitration is ammonia gas, so that the heating vaporization energy consumption is large, and the operation cost is high. Ammonia water also belongs to dangerous medicines, and has a large safety risk.
(3) Urea: compared with liquid ammonia and ammonia water, urea is widely used as a reducing agent in the denitration ammonia production link. Although the technology for preparing ammonia by using urea for power plant denitration is relatively mature, the technology still has the problems of high cost, high energy consumption, easy blockage of the system and the like.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a denitration agent which has the characteristics of high unit ammonia content, high ammonia production efficiency, low ammonia production energy consumption, easiness in storage, high solubility, low corrosiveness, no toxic or harmful components on a denitration system, low thermal decomposition temperature and the like, and is suitable for application in the fields of flue gas denitration and the like.
The denitration agent comprises ammonium carbamate and a stabilizer, wherein the stabilizer comprises an alcohol amide compound.
The denitration agent provided by the embodiment of the invention has the advantages and technical effects that 1, in the embodiment of the invention, the ammonium carbamate is adopted as the main raw material, so that the ammonia production efficiency is higher, the ammonia production temperature is lower than that of urea by more than 110 ℃, and the operation cost can be obviously reduced; 2. in the embodiment of the invention, the alcohol amide compound is added into the denitration agent as the stabilizer, and the alcohol amide compound has both lipophilicity and hydrophilicity, so that micron-sized micelles can be formed in water, and the amphoteric interface can form a high-strength film to inhibit the decomposition of ammonium carbamate, so that the denitration agent has better stability, and the requirement of the denitration agent for solution storage is met.
In some embodiments, the alcohol amide compound is prepared from ethanolamine and an organic acid; preferably, the ethanolamine comprises at least one of monoethanolamine, diethanolamine and triethanolamine; the organic acid includes at least one of polyisobutylene maleic acid, oleic acid, and stearic acid.
In some embodiments, the alcohol amide compound includes at least one of polyisobutylene maleic diethanolamide, oleic diethanolamide, stearic diethanolamide.
In some embodiments, the stabilizer is present in an amount of 1 to 3wt% of the ammonium carbamate.
In some embodiments, the denitration agent further comprises a corrosion inhibitor.
In some embodiments, the corrosion inhibitor includes at least one of a thiadiazole derivative, a nitrite salt, and a benzotriazole derivative.
In some embodiments, the thiadiazole derivative comprises at least one of a saidiazole, a saidiazole acetyl imine, a saidiazole propionyl imine, the nitrite comprises at least one of sodium nitrite, calcium nitrite, magnesium nitrite, and the benzotriazole derivative comprises at least one of a benzotriazole, a benzotriazole iso Ding Yaan, a benzotriazole propionyl imine.
In some corrosion inhibitors, the content of the corrosion inhibitor is 0.1 to 0.5 weight percent of the amino compound.
The embodiment of the invention also provides application of the denitration agent in flue gas denitration.
In some embodiments, the use of the denitration agent in flue gas denitration comprises preparing the denitration agent into a solution with a concentration of 45-55%.
Drawings
FIG. 1 is a graph showing the stability of the corresponding solution of the denitration agent produced in comparative example 1;
FIG. 2 is a graph showing the stability of the corresponding solution of the denitration agent obtained in comparative example 2;
FIG. 3 is a schematic diagram of a pyrolysis apparatus;
FIG. 4 is a schematic diagram of an apparatus for pyrolysis of a corresponding solution of a denitration agent obtained in comparative example 1;
FIG. 5 is a schematic diagram of an apparatus for pyrolysis of a solution of the denitration agent obtained in example 1.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The denitration agent comprises ammonium carbamate and a stabilizer, wherein the stabilizer comprises an alcohol amide compound.
The denitration agent provided by the embodiment of the invention has the advantages and technical effects that ammonium carbamate is adopted as a main raw material, so that the ammonia production efficiency is higher, the ammonia production temperature is lower than that of urea by more than 110 ℃, and the operation cost can be obviously reduced; the alcohol amide compound is added into the denitration agent as a stabilizer, and has both lipophilicity and hydrophilicity, so that micron-sized micelles can be formed in water, and a high-strength film can be formed at an amphoteric interface to inhibit the decomposition of ammonium carbamate, so that the denitration agent has good stability, and the requirement of the denitration agent for solution storage is met.
In some embodiments, preferably, the alcohol amide compound is prepared from ethanolamine and an organic acid; preferably, the ethanolamine comprises at least one of monoethanolamine, diethanolamine and triethanolamine; the organic acid includes at least one of polyisobutylene maleic acid, oleic acid, and stearic acid.
In some embodiments, preferably, the alcohol amide-based compound includes at least one of polyisobutylene maleic diethanolamide, oleic diethanolamide, stearic diethanolamide.
In some embodiments, preferably, the stabilizer is present in an amount of 1 to 3wt% of the ammonium carbamate.
In the embodiment of the invention, the usage amount of the stabilizer is optimized, so that the denitration agent has better stability, and the production cost can be controlled within a reasonable range: if the dosage of the stabilizer is too low, the stability of the denitration agent is not improved, and if the dosage of the stabilizer is too high, the production cost is increased.
In some embodiments, preferably, the denitration agent further comprises a corrosion inhibitor. Further preferably, the corrosion inhibitor comprises at least one of a thiadiazole derivative, a nitrite salt and a benzotriazole derivative; preferably, the thiadiazole derivative comprises at least one of saidiazole, saidiazole acetyl imine and saidiazole propionyl imine, the nitrite comprises at least one of sodium nitrite, calcium nitrite and magnesium nitrite, and the benzotriazole derivative comprises at least one of benzotriazole, benzotriazole iso Ding Yaan and benzotriazole propionyl imine. Still preferably, the corrosion inhibitor is present in an amount of 0.1 to 0.5wt% of the ammonium carbamate.
In the embodiment of the invention, the corrosion inhibitor is further added into the denitration agent, and the types of the corrosion inhibitor are optimized, so that the corrosion inhibitor can obviously inhibit the corrosiveness of ammonium carbamate on equipment, reduce the maintenance cost of the equipment and ensure the long-time stable operation of the preparation process; the usage amount of the corrosion inhibitor is further optimized, so that the corrosion of the denitration agent to equipment can be reduced, and the production cost of the denitration agent is reduced.
The embodiment of the invention also provides application of the denitration agent in flue gas denitration.
In some embodiments, preferably, the use of the denitration agent in flue gas denitration includes preparing the denitration agent into a solution with a concentration of 45-55%.
The technical scheme of the present invention is described in detail below with reference to specific embodiments and drawings.
Example 1
Adding ammonium carbamate, a diethanolamide oleate stabilizer and benzotriazole i Ding Yaan into a reaction kettle with the pressure of 7.5MPa and the temperature of 155 ℃ for stirring and mixing for 30 minutes, cooling at the speed of 5 ℃/30 minutes after uniform mixing, simultaneously stirring slowly to prevent the denitration agent from condensing into a large block, and opening the reaction kettle to obtain the denitration agent, wherein the addition amount of the diethanolamide oleate is 1wt% of the ammonium carbamate, and the addition amount of the benzotriazole i-butylimine is 0.3wt%.
Example 2
The preparation method of the denitration agent of this example is the same as that of example 1, except that: the addition amount of the oleic acid diethanolamide is 2wt% of the ammonium carbamate.
Example 3
The preparation method of the denitration agent of this example is the same as that of example 1, except that: the addition amount of the oleic acid diethanolamide is 3wt% of the ammonium carbamate.
Example 4
The preparation method of the denitration agent in this comparative example is the same as that in example 1, except that: the adopted corrosion inhibitor is thiadiazole propionyl imine.
Example 5
The preparation method of the denitration agent in this comparative example is the same as that in example 1, except that: the corrosion inhibitor is sodium nitrite.
Example 6
The preparation method of the denitration agent of this example is the same as that of example 1, except that: the addition amounts of benzotriazole isobutyl imine were adjusted to 0.1wt%, 0.2wt%, 0.4wt% and 0.5wt%, respectively.
Example 7
The preparation method of the denitration agent of this example is the same as that of example 4, except that: the addition amounts of thiadiazole propionyl imine were adjusted to 0.1wt%, 0.2wt%, 0.4wt% and 0.5wt%, respectively.
Example 8
The preparation method of the denitration agent of this example is the same as that of example 5, except that: the addition amounts of sodium nitrite were adjusted to 0.1wt%, 0.2wt%, 0.4wt% and 0.5wt%, respectively.
Comparative example 1
In this comparative example, urea alone was used as the denitration agent.
Comparative example 2
In this comparative example, only ammonium carbamate was used as the denitration agent.
Comparative example 3
The preparation method of the denitration agent of the comparative example is the same as that of example 1, except that: the stabilizer used was triethanolamine acetate.
Performance testing
1. Stability of
The denitration agents obtained in examples 1 to 3 and comparative examples 1 to 3 were prepared as 50% strength solutions, and stability of the denitration agents obtained in examples 1 to 3 and comparative examples 1 to 3 was tested at 50 ℃. The stability of the solution corresponding to the denitration agent prepared in comparative example 1 is shown in fig. 1, the stability of the solution corresponding to the denitration agent prepared in comparative example 2 is shown in fig. 2, and the stability of the solution corresponding to the denitration agent prepared in examples 1 to 3 and comparative example 3 is shown in table 1.
As can be seen from fig. 1, the urea solution loss rate remained substantially stable with a slight increase in storage time, with a loss rate of 6.4% at 168 h.
As can be seen from fig. 2, the loss rate of the ammonium carbamate solution rapidly increases with the storage time, and at 168h, the loss rate reaches 25%, which cannot meet the application requirements of storage.
TABLE 1 variation of loss (%) with time
| 24h | 48h | 72h | 96h | 120h | 144h | 168h | |
| Example 1 | 5.2％ | 6.9％ | 8.6％ | 11.3％ | 14.1％ | 15.6％ | 21.4％ |
| Example 2 | 3.6％ | 4.3％ | 7.9％ | 8.7％ | 11.9％ | 12.5％ | 15.2％ |
| Example 3 | 0.5％ | 1.1％ | 1.7％ | 3.2％ | 6.1％ | 6.8％ | 10.0％ |
| Comparative example 3 | 6.5％ | 9.5％ | 12.5％ | 15.5％ | 18.0％ | 20.5％ | 25％ |
As can be seen from table 1, after the addition of the alcohol amide stabilizer to the ammonium carbamate, the decomposition of the ammonium carbamate was suppressed, and the effect of suppressing the decomposition of the ammonium carbamate was better as the addition amount of the alcohol amide stabilizer was increased, and when the addition amount of the alcohol amide stabilizer was 3%, the loss rate of the denitration agent solution was 10% at 168 hours. Namely, the denitration agents prepared in examples 1 to 3 have better stability after being prepared into a solution.
2. Efficiency of ammonia production
The ammonia production efficiency of the denitration agent prepared in example 1 and the denitration agent prepared in comparative example 1 was tested at different temperatures by preparing the denitration agent prepared in comparative example 1 into a solution with a concentration of 50%, wherein ammonia production efficiency=actual measurement NH 3 Concentration/theoretical complete decomposition of NH 3 The concentrations and results are shown in Table 2.
TABLE 2
| Temperature (. Degree. C.) | Urea (%) | Denitration agent (%) |
| 287.5 | 13.59％ | 55.74％ |
| 336.1 | 36.58％ | 98.10％ |
| 375.6 | 40.66％ | 98.60％ |
| 450.2 | 90.93％ | 98.20％ |
| 489.4 | 93.02％ | 98.16％ |
| 582.8 | 96.45％ | 98.84％ |
As can be seen from the data in Table 2, the ammonia production efficiency of urea and the denitration agent is improved along with the temperature rise, wherein the ammonia production efficiency of the denitration agent can reach 98.10% at 336.1 ℃, and the ammonia production efficiency of urea at the temperature is only 36.58%, and the ammonia production efficiency of urea at 450.2 ℃ is 90.93%, so that the ammonia production temperature of the denitration agent in the embodiment of the invention can be more than 110 ℃ lower than that of urea.
3. In order to examine the influence of the denitration agent on equipment under the long-time pyrolysis condition, after the denitration agent prepared in the comparative example 1 and the denitration agent prepared in the example 1 are prepared into a solution with the concentration of 50%, continuous pyrolysis is carried out for 24 hours, the result is shown in figures 3-5, urea in the comparative example 1 is subjected to long-time pyrolysis, black sediment is formed at an outlet during pyrolysis, obvious undecomposed urea crystals are formed at the outlet after pyrolysis, black sediment and crystals do not appear in a device after pyrolysis of the denitration agent in the example 1, and therefore, the denitration agent prepared in the example of the invention can effectively avoid the problem of pyrolysis furnace crystallization under the same pyrolysis condition.
4. Corrosiveness of
(1) The denitration agents prepared in examples 1, 4 to 5 and comparative examples 1 to 2 were prepared as solutions having a concentration of 50%, 10g of the 304 material samples were immersed in the respective solutions, respectively, at 60℃for 6 months, and the weight change amounts of the samples before and after immersion were calculated to evaluate the corrosiveness of the denitration agents prepared in examples 1, 4 to 5 and comparative examples 1 to 2, and the results are shown in Table 3.
TABLE 3 Table 3
| Example 1 | -0.0002 |
| Example 4 | -0.0004 |
| Example 5 | -0.0574 |
| Comparative example 1 | -0.0009 |
| Comparative example 2 | -0.0869 |
As can be seen from the data in Table 3, the denitration agent prepared in comparative example 2 does not contain a corrosion inhibitor, and the amine carbamate is more corrosive to metals than urea. The denitration agents prepared in the embodiment 1 and the embodiments 4 to 5 contain corrosion inhibitors, so that the denitration agents have better corrosion inhibition effect, wherein when the corrosion inhibitors are benzotriazole i Ding Yaan and thiadiazole propionyl imine, the denitration agents have better corrosion inhibition effect.
(2) The series of denitration agents prepared in examples 6 to 8 were prepared as 50% strength solutions, 10g of the sample of 304 material was then immersed in the solutions corresponding to examples 6 to 8, respectively, at 60℃for 6 months, and the weight change amounts of the sample before and after immersion were calculated to evaluate the influence of the amount of the corrosion inhibitor on the corrosiveness thereof, and the results are shown in Table 4.
TABLE 4 Table 4
| Corrosion inhibitor | 0.1wt％ | 0.2wt％ | 0.3wt％ | 0.4wt％ | 0.5wt％ |
| Example 6 | -0.0096 | -0.0045 | -0.0002 | -0.0001 | -0.0004 |
| Example 7 | -0.0081 | -0.0049 | -0.0004 | -0.0003 | -0.0004 |
| Example 8 | -0.0569 | -0.0459 | -0.0574 | -0.0511 | -0.0434 |
5. The patterns of 304 materials were immersed in the solutions corresponding to example 1 and comparative example 1 for 6 months, and the temperature of the solutions was changed to investigate the influence of different temperatures on corrosiveness, and the results are shown in table 5.
TABLE 5
| Temperature (temperature) | 40℃ | 60℃ | 80℃ | 100℃ |
| Example 1 | -0.0004 | -0.0002 | -0.0004 | -0.0003 |
| Comparative example 1 | -0.0003 | -0.0004 | -0.0004 | -0.0003 |
As can be seen from the data in Table 5, the corrosion of the denitration agent to metal does not change obviously with the change of temperature, and the corrosion inhibition effect of the corrosion inhibitor has certain stability.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While the above embodiments have been shown and described, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations of the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the invention.
Claims (10)
1. A denitration agent, which is characterized by comprising ammonium carbamate and a stabilizer, wherein the stabilizer comprises an alcohol amide compound.
2. The denitration agent according to claim 1, wherein the alcohol amide compound is prepared from ethanolamine and an organic acid; preferably, the ethanolamine comprises at least one of monoethanolamine, diethanolamine and triethanolamine; the organic acid includes at least one of polyisobutylene maleic acid, oleic acid, and stearic acid.
3. The de-pinning agent of claim 1 or 2, wherein the alcohol amide compound comprises at least one of polyisobutylene maleic diethanolamide, oleic diethanolamide, stearic diethanolamide.
4. A denitration agent according to claim 1, characterized in that the content of the stabilizer is 1 to 3wt% of the ammonium carbamate.
5. The de-marketing agent of claim 1, wherein the de-marketing agent further comprises a corrosion inhibitor.
6. The de-marketing agent of claim 5, wherein the corrosion inhibitor comprises at least one of a thiadiazole derivative, a nitrite salt, and a benzotriazole derivative.
7. The denitration agent according to claim 6, wherein the thiadiazole derivative comprises at least one of saidiazole, saidiazole acetimide, saidiazole propionimide, the nitrite comprises at least one of sodium nitrite, calcium nitrite, magnesium nitrite, and the benzotriazole derivative comprises at least one of benzotriazole, benzotriazole i Ding Yaan, and benzotriazole propionimide.
8. The de-marketing agent of claim 6 or 7, wherein the corrosion inhibitor is present in an amount of 0.1 to 0.5% by weight of the ammonium carbamate.
9. Use of a denitration agent according to any one of claims 1 to 8 in flue gas denitration.
10. The use of a denitration agent according to claim 9 in flue gas denitration, comprising preparing the denitration agent into a solution with a concentration of 45-55%.
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