CN112717668A - Efficient and stable complexing denitration agent and preparation method thereof - Google Patents
Efficient and stable complexing denitration agent and preparation method thereof Download PDFInfo
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- 230000000536 complexating Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 98
- BAUYGSIQEAFULO-UHFFFAOYSA-L Iron(II) sulfate Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 37
- KCXVZYZYPLLWCC-UHFFFAOYSA-N edta Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 33
- GEHJYWRUCIMESM-UHFFFAOYSA-L Sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 30
- 239000002270 dispersing agent Substances 0.000 claims abstract description 27
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 27
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 24
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims abstract description 22
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 20
- XUJNEKJLAYXESH-REOHCLBHSA-N L-cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 17
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N benzohydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 13
- XEVRDFDBXJMZFG-UHFFFAOYSA-N Carbohydrazide Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims abstract description 12
- 235000018417 cysteine Nutrition 0.000 claims abstract description 12
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000001187 sodium carbonate Substances 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 12
- -1 linnoroline Chemical compound 0.000 claims abstract description 11
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- CFAKWWQIUFSQFU-UHFFFAOYSA-N 2-hydroxy-3-methylcyclopent-2-en-1-one Chemical compound CC1=C(O)C(=O)CC1 CFAKWWQIUFSQFU-UHFFFAOYSA-N 0.000 claims abstract description 10
- SZVJSHCCFOBDDC-UHFFFAOYSA-N Iron(II,III) oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Vitamin C Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 10
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 10
- 235000019799 monosodium phosphate Nutrition 0.000 claims abstract description 10
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims abstract description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 10
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims abstract description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 8
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N 1,2-ethanediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 7
- XOBOCRSRGDBOGH-UHFFFAOYSA-N 5-phenylnonan-5-ol Chemical compound CCCCC(O)(CCCC)C1=CC=CC=C1 XOBOCRSRGDBOGH-UHFFFAOYSA-N 0.000 claims abstract description 7
- GRVFOGOEDUUMBP-UHFFFAOYSA-N Sodium sulfide Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims abstract description 7
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Tris Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 13
- 239000011790 ferrous sulphate Substances 0.000 claims description 9
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 9
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 230000001681 protective Effects 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- FQENQNTWSFEDLI-UHFFFAOYSA-J Tetrasodium pyrophosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 6
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 6
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 6
- 150000002505 iron Chemical class 0.000 claims description 4
- FPKOPBFLPLFWAD-UHFFFAOYSA-N Trinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1[N+]([O-])=O FPKOPBFLPLFWAD-UHFFFAOYSA-N 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K Trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 238000009472 formulation Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- 239000011778 trisodium citrate Substances 0.000 claims description 3
- 230000002035 prolonged Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitrogen oxide Substances O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 26
- 229910052813 nitrogen oxide Inorganic materials 0.000 description 25
- 239000007788 liquid Substances 0.000 description 24
- 239000012153 distilled water Substances 0.000 description 21
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 15
- 239000003546 flue gas Substances 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000006011 modification reaction Methods 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- ZGTMUACCHSMWAC-UHFFFAOYSA-L disodium;2-[2-[carboxylatomethyl(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetate Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000003009 desulfurizing Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CIWBSHSKHKDKBQ-DUZGATOHSA-N (+)-Ascorbic acid Natural products OC[C@@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-DUZGATOHSA-N 0.000 description 2
- 239000002211 L-ascorbic acid Substances 0.000 description 2
- 235000000069 L-ascorbic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 238000005039 chemical industry Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001374 Invar Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N Iron(III) oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003064 anti-oxidating Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 230000003197 catalytic Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000460 iron oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000036962 time dependent Effects 0.000 description 1
Images
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
- B01D53/74—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
- B01D2251/00—Reactants
- B01D2251/90—Chelants
- B01D2251/902—EDTA
Abstract
The invention provides a high-efficiency stable complexing denitration agent, which comprises disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent; the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene; the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide; the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide. The initial denitration rate of the complex denitration agent is 96%, and the failure time of the complex denitration agent is prolonged from the existing 60min to 270 min. The invention also provides a preparation method of the efficient and stable complexing denitration agent.
Description
Technical Field
The invention belongs to the technical field of flue gas denitration, and particularly relates to an efficient and stable complexing denitration agent and a preparation method thereof.
Background
Nitrogen Oxides (NO) as one of the main atmospheric pollutantsX) The discharge of (a) poses a great hazard to humans and the environment. NOXMainly the emission sources of the fuel combustion process and various industrial processes, mainlyIncluding coal-fired power plant flue gas, industrial boiler (kiln) and automobile exhaust, wherein NO is produced by coal-firedXThe emission amount of the solid source accounts for about 70 percent of the total emission amount of the solid source in China.
The fields of steel, cement, metallurgy, coking, coal chemical industry, industrial boilers, industrial kilns and the like are the fields with the largest coal consumption except for the electric industry. Under the condition that the atmospheric pollution control in the thermal power industry reaches a certain degree, the non-electric industries such as steel, metallurgy, building materials and the like also rapidly open the sequence curtain of upgrading and reconstruction. In 2019, in 4 months, the ministry of ecological environment of China issued 'opinion on promoting implementation of ultralow emission in the steel industry', and definitely pointed out that NO in the head flue gas of a sintering machine and the pellet roasting flue gas is generated under the condition that the reference oxygen content is 16%XAverage hourly discharge concentration of less than 50mg/m3. The suggestion points out that the national newly-built (including relocation) steel project is to achieve ultra-low emission in principle, and before the end of 2020, the ultra-low emission modification of steel enterprises in key areas is obviously progressed, and the modification is finished in the strive for about 60% of capacity; by the end of 2025, the ultralow emission modification of iron and steel enterprises in key areas is basically completed, and the national strive for more than 80% of capacity to complete the modification.
Because of the inherent characteristics of low temperature, high humidity, high dust and the like of the sintering flue gas, the selective catalytic reduction denitration technology (SCR) and the selective non-catalytic reduction denitration technology (SNCR) which are applied more in the power industry at present are not suitable for denitration treatment of the sintering flue gas. Fe (II) EDTA complex denitration is used as a low-temperature wet denitration technology, can be well grafted with wet desulphurization equipment, and finally realizes sintering flue gas SO2、NOXThe discharge reaches the standard. But O in flue gas during denitration2Will convert Fe in solution2+Is oxidized into Fe3+And the addition of EDTA chelating agent can accelerate the oxidation reaction, and Fe (III) EDTA formed after the Fe (II) EDTA is oxidized has NO affinity to NO, so that the complex denitration agent is easy to oxidize, has quick failure and generates precipitate, and the industrial application of the technology is severely restricted.
The male invar has developed the experimental research of Fe (II) EDTA removal of NO, and the preparation of the complexing solution is only Fe2+Mutual solubility with EDTA, and Fe2+The molar ratio of EDTA was 3:2, no further additionThe quality and other treatment are carried out, and the complexing liquid has the problems of low absorption capacity, quick failure and the like (industrial safety and environmental protection, vol 43 and No 10 in 2017).
The Chenshuo et al adopts a self-made spray tower to perform a wet-process simultaneous desulfurization and denitrification experiment, and develops the composite absorption liquid on the basis of Ethylene Diamine Tetraacetic Acid (EDTA) complex ferrous iron absorption liquid and cysteine complex ferrous iron absorption liquid. The experimental results show that: for a single complex absorption liquid, the EDTA complex ferrous iron absorption liquid has good denitration effect, can keep more than 60% of NO removal rate within 70min, and the cysteine complex ferrous iron absorption liquid can keep good desulfurization effect for a long time, and can keep more than 90% of SO within 180min2The removal rate; compared with a single complex absorption liquid, the desulfurization and denitrification performance of the composite absorption liquid is obviously improved, the concentration of the complex is 0.05mol/L, the pH of the absorption liquid is 8, the molar ratio of EDTA to cysteine is 1: 2, and Fe2+Under the optimized condition of the concentration of 0.075mol/L, the NO removal rate within 90min is basically kept above 70 percent, and SO2The removal rate basically reaches 100 percent. Through improvement, the denitration performance of the composite absorption liquid is improved, but the problems of low absorption capacity, quick failure and the like of the denitration liquid are not thoroughly solved (chemical industry and environmental protection, No. 37, No. 3 of 2017).
In summary, the research on the optimization and improvement of the solution itself is less in the prior Fe (II) EDTA complexation denitration, and the problems of low absorption capacity, slow mass transfer, easy oxidation, fast failure and the like of the Fe (II) EDTA solution are not fundamentally solved.
Disclosure of Invention
The invention aims to provide an efficient and stable complexing denitration agent and a preparation method thereof.
The invention provides a high-efficiency stable complexing denitration agent, which comprises disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent;
the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene;
the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide;
the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide.
Preferably, the ferrous salt is ferrous sulfate; the concentration of the ferrous salt is 25-50 mmol/L.
Preferably, the concentration of the disodium ethylene diamine tetraacetate is 120-150% of the concentration of the ferrous salt.
Preferably, the concentration of the preparation agent is 30-50% of the concentration of the ferrous salt.
Preferably, the concentration of the auxiliary agent is 50-70% of that of the ferrous salt;
the concentration of the nano reagent is 0.1-0.2% of the concentration of the ferrous salt.
Preferably, the dispersing agent is one or more of sodium citrate, sodium pyrophosphate, trihexyl hexyl phosphoric acid, sodium dodecyl benzene sulfonate, polyacrylamide and triton;
the concentration of the dispersing agent is 1-5% of that of the ferrous salt.
Preferably, the pH value of the complex denitration agent is 6.5-7.5.
The invention provides a preparation method of an efficient and stable complexing denitration agent, which comprises the following steps:
A) mixing disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent and a dispersing agent in a solvent under the condition of introducing protective gas to obtain a mixed solution;
B) and carrying out ultrasonic oscillation on the mixed solution to obtain the complex denitration agent.
Preferably, the frequency of the ultrasonic oscillation is 20-25 KHz, the ultrasonic oscillation is stopped for 15-20 min after every 25-30 min of oscillation, then the ultrasonic oscillation is carried out again, and the process is repeated for 4-6 times.
Preferably, the sonication is performed using an ultrasonic cell disruptor.
The invention provides a high-efficiency stable complexing denitration agent, which comprises disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent; the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene; the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide; the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide. According to the invention, the compounding agent, the auxiliary agent, the nano reagent and the dispersing agent are added into the complexing agent mainly containing Fe (II) (EDTA), so that the oxidation resistance of the denitration agent is improved while the NO complexing capability of the denitration agent is improved, and further, the absorption capacity and the use stability of the denitration agent are improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a graph showing the change of the denitration rate of the complex denitration agent in comparative example 1 of the present invention with time;
FIG. 2 is a graph showing the change of the denitration rate of the complex denitration agent in comparative example 2 of the present invention with time;
FIG. 3 is a graph showing the denitration rate of the complex denitration agent in comparative example 3 according to the present invention with time;
FIG. 4 is a graph showing the denitration rate of the complex denitration agent according to comparative example 4 of the present invention with time;
FIG. 5 is a graph showing the denitration rate of the complex denitration agent according to example 1 of the present invention with time;
FIG. 6 is a graph showing the time-dependent change of the denitration rate of the complex denitration agent in example 2 of the present invention.
Detailed Description
The invention provides a high-efficiency stable complexing denitration agent, which comprises disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent;
the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene;
the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide;
the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide.
In the invention, the ferrous salt is preferably ferrous sulfate, and the concentration of the ferrous salt is preferably 25 to 50mmol/L, more preferably 30 to 45mmol/L, and most preferably 35 to 40mmol/L, and specifically, in the embodiment of the invention, it may be 25mmol/L or 40 mmol/L.
In the present invention, the concentration of the disodium ethylenediaminetetraacetate (EDTA-2Na) is preferably 120 to 150%, more preferably 130 to 140% of the concentration of the divalent iron salt, that is, the concentration of the disodium ethylenediaminetetraacetate is preferably 30 to 75mmol/L, more preferably 30 to 60mmol/L, and specifically, in an embodiment of the present invention, may be 30mmol/L or 52 mmol/L.
In the invention, the preparation agent is mainly used for improving the capability of the denitration liquid for complexing NO and accelerating the reaction, and comprises one or more of cysteine, linnorphine, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene.
The concentration of the preparation is preferably 30 to 50%, more preferably 35 to 45% of the concentration of the divalent iron salt, that is, the concentration of the preparation is preferably 7.5 to 25mmol/L, more preferably 10 to 20mmol/L, most preferably 12 to 15mmol/L, and specifically, in the embodiment of the present invention, 12.5mmol/L or 12mmol/L may be used. More specifically, in one embodiment of the invention, the formulation is 10mmol/L cysteine +2mmol/L piperazine, and in another embodiment of the invention, the formulation is 5mmol/L cysteine +5mmol/L methylcyclopentenolone +2.5mmol/L dibutylhydroxytoluene.
In the invention, the auxiliary agent is mainly used for improving the oxidation resistance of the denitration liquid, and comprises one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide, specifically, in the embodiment of the invention, sodium carbonate + disodium hydrogen phosphate + sodium sulfite + carbohydrazide, or sodium dihydrogen phosphate + sodium sulfite + ascorbic acid.
The concentration of the auxiliary agent is preferably 50-70%, more preferably 55-65% of the concentration of the ferrous salt, that is, the concentration of the auxiliary agent is preferably 12.5-35 mol/L, more preferably 12.5-30 mol/L, specifically, in an embodiment of the present invention, 12.5mol/L or 28mol/L, more specifically, in an embodiment of the present invention, the auxiliary agent is 4mmol/L sodium carbonate +4mmol/L disodium hydrogen phosphate +2.5mmol/L sodium sulfite +2mmol/L carbohydrazide, and in another embodiment of the present invention, the auxiliary agent is 10mmol/L sodium dihydrogen phosphate +10mmol/L sodium sulfite +8mmol/L ascorbic acid.
In the invention, the nano-reagent is mainly used for the antioxidation of the catalytic assistant, and comprises one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano ferric oxide, nano iron powder and nano silicon dioxide, and specifically, in the embodiment of the invention, the nano-reagent can be nickel oxide and ferroferric oxide, or nano titanium dioxide and nano silicon dioxide.
In the invention, the concentration of the nano reagent is preferably 0.1-0.2% of the concentration of the ferrous salt, that is, the concentration of the nano reagent is preferably 0.025-0.1 mmol/L, more preferably 0.03-0.08 mmol/L, most preferably 0.04-0.05 mmol/L, specifically, in an embodiment of the invention, 0.04mmol/L or 0.05mmol/L, more specifically, in an embodiment of the invention, the nano reagent is 0.02mmol/L nickel oxide +0.02mmol/L nano ferroferric oxide, and in another embodiment of the invention, the nano reagent is 0.025mmol/L nano titanium dioxide +0.025mmol/L nano silicon dioxide.
In the invention, the dispersant mainly enables the nano reagent to be well dispersed in the denitration liquid, and the dispersant comprises one or more of sodium citrate, sodium pyrophosphate, trihexyl hexyl phosphoric acid, sodium dodecyl benzene sulfonate, polyacrylamide and triton, and specifically, in the embodiment of the invention, the dispersant can be sodium pyrophosphate + polyacrylamide or sodium dodecyl benzene sulfonate.
The concentration of the dispersant is preferably 1-5%, more preferably 2-4%, and most preferably 3-4% of the concentration of the ferrous salt, that is, the concentration of the dispersant is preferably 0.25-2.5 mmol/L, more preferably 0.5-2 mmol/L, and most preferably 1-1.5 mmol/L, specifically, in an embodiment of the present invention, 1mmol/L, more specifically, in an embodiment of the present invention, 1mmol/L sodium dodecylbenzenesulfonate, and in another embodiment of the present invention, 0.5mmol/L sodium pyrophosphate +0.5mmol/L polyacrylamide
In the present invention, the solvent is preferably water, and may be distilled water or deionized water.
Based on the formula of the complex denitration agent, a person skilled in the art can add other functional additives according to the conventional knowledge in the field on the premise of not influencing the absorption capacity and stability of the complex denitration agent in the scheme so as to meet the use requirements of various working conditions.
The invention provides a preparation method of an efficient and stable complexing denitration agent, which comprises the following steps:
A) mixing disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent and a dispersing agent in a solvent under the condition of introducing protective gas to obtain a mixed solution;
B) and carrying out ultrasonic oscillation on the mixed solution to obtain the complex denitration agent.
In the present invention, the types and amounts of the disodium edta, the ferrous salt, the compounding agent, the auxiliary agent, the nano reagent, the dispersing agent and the solvent are the same as those of the disodium edta, the ferrous salt, the compounding agent, the auxiliary agent, the nano reagent, the dispersing agent and the solvent, and thus, the description thereof is omitted.
The solvent is preferably first freed from oxygen by methods commonly used by those skilled in the art, such as boiling distilled water, introducing protective gas under sealed conditions to remove dissolved oxygen and isolate oxidation of air, and mixing with disodium edetate.
In the invention, the protective gas is preferably nitrogen, helium or argon, and the flow rate of the protective gas is preferably 0.5-3L/min, and more preferably 1-2L/min.
Adding raw materials such as disodium ethylene diamine tetraacetate, continuously introducing protective gas for 60min, and mixing uniformly to obtain a mixed solution.
The invention preferably seals the mixed solution liquid and then puts the mixed solution liquid into an ultrasonic cell disruption instrument for ultrasonic oscillation to obtain the complex denitration agent.
The method utilizes the cavitation effect generated by the ultrasonic cell disruptor in the liquid to treat the solution, can obviously improve the stability and the dispersibility of the solution, and has the ultrasonic oscillation frequency of 20-25 KHz, stops for 15-20 min after oscillation for 25-30 min, then carries out ultrasonic oscillation again, and repeats for 4-6 times.
After ultrasonic oscillation, the pH value of the complexing denitration agent is adjusted to 6.5-7.5 by using acid or alkali, such as sulfuric acid, sodium hydroxide and the like.
The complex denitration agent is used for low-temperature flue gas wet denitration, has large absorption capacity, is more stable and is not easy to lose efficacy.
The invention provides a high-efficiency stable complexing denitration agent, which comprises disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent; the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene; the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide; the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide. According to the invention, the compounding agent, the auxiliary agent, the nano reagent and the dispersing agent are added into the complexing agent mainly containing Fe (II) (EDTA), so that the oxidation resistance of the denitration agent is improved while the NO complexing capability of the denitration agent is improved, and further, the absorption capacity and the use stability of the denitration agent are improved.
In order to further illustrate the present invention, the following examples are provided to describe the efficient and stable complex denitrifier and the preparation method thereof in detail, but the invention should not be construed as limiting the scope of the present invention.
Comparative example 1
Weighing 500ml of distilled water, heating to boil, introducing 1L/min of nitrogen into the distilled water under a sealed condition, removing dissolved oxygen in the water and isolating oxidation of air, and adding 25mmol/L of ferrous sulfate and 25mmol/L of disodium ethylene diamine tetraacetate into the distilled water under the condition of introducing the nitrogen. And continuously introducing nitrogen for 60min, uniformly mixing, and adjusting the pH value to 7 by using sodium hydroxide.
Weighing 250ml of each, placing into a two-stage absorption bottle, and introducing 2L/min of mixed gas for absorption (N)2：85％，O2：15％，NO：300mg/m3) The concentration of NO in the flue gas before and after absorption was measured every 10min, and the denitration rate was calculated, and the results are shown in FIG. 1.
As can be seen from FIG. 1, the highest denitration efficiency of the conventionally prepared complex denitration liquid is only 85% at the beginning, and the denitration liquid is ineffective after 60min absorption reaction.
Comparative example 2
500ml of distilled water is measured, heated and boiled, 1L/min of nitrogen is introduced into the distilled water under the sealed condition, dissolved oxygen in the water is removed, and the oxidation of air is avoided, 25mmol/L of ferrous sulfate, 30mmol/L of disodium ethylene diamine tetraacetate and 12.5mmol/L of preparation (5mmol/L of cysteine, 5mmol/L of methylcyclopentenolone and 2.5mmol/L of dibutylhydroxytoluene) are sequentially added into the distilled water under the condition of introducing the nitrogen. And continuously introducing nitrogen for 60min, uniformly mixing, and adjusting the pH value to 7 by using sodium hydroxide.
Weighing 250ml of each, placing into a two-stage absorption bottle, and introducing 2L/min of mixed gas for absorption (N)2：85％，O2：15％，NO：300mg/m3) The concentration of NO in the flue gas before and after absorption was measured every 10min, and the denitration rate was calculated, and the results are shown in FIG. 2.
Fig. 2 shows that after the compounding agent is added, the absorption rate of the complex denitration liquid to NO is remarkably improved, the highest denitration rate at the beginning is improved from 85% to 95%, but the denitration liquid still loses efficacy after 65min of absorption.
Comparative example 3
500ml of distilled water is weighed out, heated and boiled, 1L/min of nitrogen is introduced into the distilled water under the sealed condition, dissolved oxygen in the water is removed, and oxidation of air is avoided, 25mmol/L of ferrous sulfate, 30mmol/L of disodium ethylene diamine tetraacetate, 12.5mmol/L of preparation (5mmol/L of cysteine +5mmol/L of methylcyclopentenolone +2.5mmol/L of dibutylhydroxytoluene) and 12.5mmol/L of auxiliary agent (4mmol/L of sodium carbonate +4mmol/L of disodium hydrogen phosphate +2.5mmol/L of sodium sulfite +2mmol/L of carbohydrazide) are sequentially added into the distilled water under the condition of introducing the nitrogen. And continuously introducing nitrogen for 60min, uniformly mixing, and adjusting the pH value to 7 by using sodium hydroxide.
Weighing 250ml of each, placing into a two-stage absorption bottle, and introducing 2L/min of mixed gas for absorption (N)2：85％，O2：15％，NO：300mg/m3) The concentration of NO in the flue gas before and after absorption was measured every 10min, and the denitration rate was calculated, and the result is shown in fig. 3.
As can be seen from FIG. 3, after the compounding agent and the auxiliary agent are added, the initial denitration rate is increased from 85% to 97%, and the failure time is prolonged from 60min to 130 min.
Comparative example 4
Weighing 500ml of distilled water, heating to boil, introducing 1L/min of nitrogen into the distilled water under a sealed condition, removing dissolved oxygen in the water and isolating oxidation of air, under the condition of introducing nitrogen, 25mmol/L ferrous sulfate, 30mmol/L disodium ethylene diamine tetraacetate, 12.5mmol/L preparation (5mmol/L cysteine +5mmol/L methylcyclopentadienolone +2.5mmol/L dibutylhydroxytoluene), 12.5mmol/L auxiliary agent (4mmol/L sodium carbonate +4mmol/L disodium hydrogen phosphate +2.5mmol/L sodium sulfite +2mmol/L carbohydrazide), 0.05mmol/L nano reagent (0.025mmol/L nano titanium dioxide +0.025mmol/L nano silicon dioxide) and 1mmol/L dispersing agent (1mmol/L sodium dodecyl benzene sulfonate) are added into distilled water successively. And continuously introducing nitrogen for 60min, uniformly mixing, and adjusting the pH value to 7 by using sodium hydroxide.
Weighing 250ml of each, placing into a two-stage absorption bottle, and introducing 2L/min of mixed gas for absorption (N)2：85％，O2：15％，NO：300mg/m3) The concentration of NO in the flue gas before and after absorption was measured every 10min, and the denitration rate was calculated, and the result is shown in fig. 4.
As can be seen from FIG. 4, after the compounding agent, the auxiliary agent, the nano-reagent and the dispersing agent are added, the initial denitration rate is increased from 85% to 96%, and the failure time is prolonged from 60min to 170 min.
Example 1
Weighing 500ml of distilled water, heating to boil, introducing 1L/min of nitrogen into the distilled water under a sealed condition, removing dissolved oxygen in the water and isolating oxidation of air, under the condition of introducing nitrogen, 25mmol/L ferrous sulfate, 30mmol/L disodium ethylene diamine tetraacetate, 12.5mmol/L preparation (5mmol/L cysteine +5mmol/L methylcyclopentadienolone +2.5mmol/L dibutylhydroxytoluene), 12.5mmol/L auxiliary agent (4mmol/L sodium carbonate +4mmol/L disodium hydrogen phosphate +2.5mmol/L sodium sulfite +2mmol/L carbohydrazide), 0.05mmol/L nano reagent (0.025mmol/L nano titanium dioxide +0.025mmol/L nano silicon dioxide) and 1mmol/L dispersing agent (1mmol/L sodium dodecyl benzene sulfonate) are added into distilled water successively. And continuously introducing nitrogen for 60min, uniformly mixing, sealing the solution, placing the sealed solution into an ultrasonic cell disruption instrument for ultrasonic oscillation, wherein the frequency of the ultrasonic oscillation is 20KHz, stopping the ultrasonic oscillation for 20min after 30min, then performing the ultrasonic oscillation again, repeating the steps for 6 times, and adjusting the pH value of the prepared complex denitration liquid to 7.
Weighing 250ml of each, placing into a two-stage absorption bottle, and introducing 2L/min of mixed gas for absorption (N)2：85％，O2：15％，NO：300mg/m3) The concentration of NO in the flue gas before and after absorption was measured every 10min, and the denitration rate was calculated, and the result is shown in fig. 5.
As can be seen from FIG. 5, after the compounding agent, the auxiliary agent, the nano-reagent and the dispersing agent are added and the ultrasonic crushing treatment is carried out, the initial denitration rate is improved from 85% to 96%, and the failure time is prolonged from 60min to 270 min.
Example 2
Weighing 500ml of distilled water, heating and boiling, introducing 1L/min of nitrogen into the distilled water under a sealed condition, removing dissolved oxygen in the water and oxidizing the distilled water without air, and sequentially adding 40mmol/L ferrous sulfate, 52mmol/L disodium ethylene diamine tetraacetate, 12mmol/L agent (10mmol/L cysteine +2mmol/L piperazine), 28mmol/L auxiliary agent (10mmol/L sodium dihydrogen phosphate +10mmol/L sodium sulfite +8mmol/L ascorbic acid), 0.04mmol/L nano reagent (0.02mmol/L nickel oxide +0.02mmol/L nano ferroferric oxide), and 1mmol/L dispersing agent (0.5mmol/L sodium pyrophosphate +0.5mmol/L polyacrylamide) into the distilled water under the condition of introducing the nitrogen. And continuously introducing nitrogen for 60min, and mixing uniformly. And sealing the solution, placing the solution into an ultrasonic cell disruption instrument for ultrasonic oscillation, wherein the frequency of the ultrasonic oscillation is 20KHz, stopping the ultrasonic oscillation for 15min after 25min, then repeating the ultrasonic oscillation for 4 times, and adjusting the pH value of the prepared complex denitration liquid to 6.5.
Weighing 250ml of each, placing into a two-stage absorption bottle, and introducing 2L/min of mixed gas for absorption (N)2：85％，O2：15％，NO：300mg/m3) The concentration of NO in the flue gas before and after absorption was measured every 10min, and the denitration rate was calculated, and the result is shown in fig. 6.
As can be seen from fig. 6, the denitration rate change curves of comparative example 5 and comparative example 4 are substantially the same, and there is no significant change.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An efficient and stable complexing denitration agent comprises disodium ethylene diamine tetraacetate, divalent iron salt, a mixing agent, an auxiliary agent, a nano reagent, a dispersing agent and a solvent;
the compounding agent is one or more of cysteine, linnoroline, methyl cyclopentenolone, ethylenediamine, triethanolamine, piperazine, hydroquinone and dibutyl hydroxy toluene;
the auxiliary agent is one or more of sodium carbonate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium sulfite, sodium sulfide, ascorbic acid and carbohydrazide;
the nano reagent is one or more of nano titanium dioxide, nano nickel oxide, nano ferroferric oxide, nano iron powder and nano silicon dioxide.
2. The complex denitrifier according to claim 1, wherein the ferrous salt is ferrous sulfate; the concentration of the ferrous salt is 25-50 mmol/L.
3. The complex denitration agent according to claim 1, wherein the concentration of disodium ethylenediaminetetraacetate is 120-150% of the concentration of the divalent iron salt.
4. The complex denitrifier according to claim 1, wherein the concentration of the formulation is 30-50% of that of the ferrous salt.
5. The complex denitration agent according to claim 1, wherein the concentration of the auxiliary agent is 50-70% of the concentration of the ferrous salt;
the concentration of the nano reagent is 0.1-0.2% of the concentration of the ferrous salt.
6. The complex denitrifier according to claim 1, wherein the dispersant is one or more of sodium citrate, sodium pyrophosphate, trihexyl hexyl phosphoric acid, sodium dodecyl benzene sulfonate, polyacrylamide and triton;
the concentration of the dispersing agent is 1-5% of that of the ferrous salt.
7. The complex denitrifier according to any one of claims 1 to 6, wherein the complex denitrifier has a pH value of 6.5 to 7.5.
8. A preparation method of an efficient and stable complex denitration agent comprises the following steps:
A) mixing disodium ethylene diamine tetraacetate, ferrous salt, a mixing agent, an auxiliary agent, a nano reagent and a dispersing agent in a solvent under the condition of introducing protective gas to obtain a mixed solution;
B) and carrying out ultrasonic oscillation on the mixed solution to obtain the complex denitration agent.
9. The preparation method according to claim 8, wherein the frequency of the ultrasonic oscillation is 20 to 25KHz, the ultrasonic oscillation is stopped for 15 to 20min after every 25 to 30min of oscillation, and then the ultrasonic oscillation is performed for 4 to 6 times.
10. The method according to claim 8, wherein the ultrasonic vibration is performed using an ultrasonic cell disruptor.
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