CN115888749A - Synergistic denitration and demercuration catalyst and preparation method and application thereof - Google Patents
Synergistic denitration and demercuration catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims abstract description 24
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 18
- 239000011572 manganese Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 6
- 238000005054 agglomeration Methods 0.000 claims abstract description 4
- 230000002776 aggregation Effects 0.000 claims abstract description 4
- 239000002105 nanoparticle Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 23
- 229910017604 nitric acid Inorganic materials 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000003546 flue gas Substances 0.000 abstract description 21
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 229910020632 Co Mn Inorganic materials 0.000 description 6
- 229910020678 Co—Mn Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940100892 mercury compound Drugs 0.000 description 2
- 150000002731 mercury compounds Chemical class 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
Abstract
The invention provides a synergistic denitration and demercuration catalyst and a preparation method and application thereof, and relates to the technical field of flue gas treatment. The synergistic denitration demercuration catalyst comprises a carrier and an active component, and is formed by agglomeration of nano particles; the carrier is titanium dioxide, and the active components are manganese and cobalt. The preparation method of the catalyst comprises the following steps: mixing manganese nitrate, cobalt nitrate, absolute ethyl alcohol and water to form a mixed system, then adding tetrabutyl titanate solution into the mixed system, stirring to form sol, and drying and roasting in sequence to obtain the catalyst. Application of synergistic denitration and demercuration catalyst: the catalyst is loaded into a fixed bed reactor and then NO and Hg are simultaneously introduced 0 The reaction is carried out, and the space velocity of the reaction is controlled at 40000h ‑1 ‑80000h ‑1 . The catalyst provided by the invention has the advantages of high denitration and demercuration efficiency, strong stability, simple preparation method, easily obtained preparation materials, low cost, suitability for flue gas removal treatment, easy realization of application conditions, and capability of carrying out NO and Hg in flue gas 0 And (4) coordinated control.
Description
Technical Field
The invention belongs to the technical field of flue gas treatment, and particularly relates to a synergistic denitration and demercuration catalyst, and a preparation method and application thereof.
Background
There are approximately 2220 tons of mercury artificially emitted annually in the world, with coal combustion still being the major source of mercury emissions worldwide, accounting for approximately 22.4%, and mercury in coal-fired flue gases being predominantly in particulate form (Hg) p ) In the oxidation state (Hg) 2+ ) Elemental (Hg) state 0 ) Three forms exist, of which Hg 0 Because of easy volatilization and water insolubility, the product is difficult to be removed. The most popular is the activated carbon injection technology at present, but the technology faces many problems, such as secondary pollution of fly ash and the like, and the Hg in the flue gas is removed by using the conventional denitration device in a synergistic manner, so that the investment and operation cost can be reduced, the process can be simplified, and the space can be saved. Therefore, the development of an economical and efficient synergistic denitration and demercuration catalyst is urgent.
Conventional commercial denitration catalyst (V) 2 O 5 -WO 3 /TiO 2 ) The demercuration efficiency is low, the operating temperature is 300-400 ℃, the generated mercury compound is decomposed due to high temperature, the mercury is not removed by using mercury, and energy loss is caused due to high temperature. Therefore, an efficient low-temperature synergistic denitration and demercuration catalyst is developed for synergistically removing NO and Hg in smoke 0 Becomes particularly important.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a synergistic denitration and demercuration catalyst, and a preparation method and application thereof, so as to solve the problems.
In order to realize the purpose, the invention adopts the following technical scheme:
the invention provides a synergistic denitration and demercuration catalyst, which is formed by agglomeration of nano particles and comprises a carrier and an active component; the carrier is titanium dioxide, and the active components are manganese and cobalt.
Alternatively, the titanium dioxide is present in the anatase form and the active component is dispersed on the support in an amorphous structure.
Optionally, the atomic ratio of manganese to titanium is 0.1-0.2, and the atomic ratio of cobalt to manganese is 0.25-1.25.
The nano catalyst taking titanium dioxide as a carrier and manganese and cobalt as active components provided by the invention has NO fixed morphology, has a uniform mesoporous structure, wherein the manganese and the cobalt exist in an amorphous structure and are well dispersed on the carrier, and the catalytic performance of the catalyst is improved by utilizing the interaction between the manganese and the cobalt, so that NO and Hg in flue gas are efficiently removed 0 . Wherein, the atomic ratio of manganese to titanium is 0.1-0.2, and the atomic ratio of cobalt to manganese is 0.25-1.25, the catalyst shows better catalytic performance.
The invention also provides a preparation method of the synergistic denitration and demercuration catalyst, which comprises the steps of mixing manganese nitrate, cobalt nitrate, absolute ethyl alcohol and water to form a mixed system, then adding tetrabutyl titanate solution into the mixed system, stirring to form sol, and drying and roasting in sequence to obtain the catalyst.
Optionally, adding nitric acid to the mixed system before adding the tetrabutyl titanate solution;
preferably, the molar ratio of the nitric acid to the water is 0.02 to 0.12.
The nitric acid is added into the system, so that on one hand, the rate of the hydrolysis polycondensation reaction of tetrabutyl titanate in the preparation process can be controlled, and a more uniform catalyst is obtained, and the synergistic removal efficiency of the catalyst is improved; on the other hand, tetrabutyl titanate is used for generating anatase titanium dioxide by adopting a sol method, and at the moment, when nitric acid exists in the system, the method has the beneficial effects of increasing the specific surface area and controlling the mesoporous aperture of the anatase titanium dioxide, the dispersion efficiency of active components is improved, and the removal activity of the catalyst is further improved. Experiments prove that when the molar ratio of the nitric acid to the water is 0.06, the comprehensive effect on the hydrolysis polycondensation reaction of tetrabutyl titanate is better, and the performance of the product obtained by the reaction is better.
Optionally, the molar ratio of the manganese nitrate to the tetrabutyl titanate is 0.1-0.2;
preferably, the molar ratio of the cobalt nitrate to the manganese nitrate is 0.25-1.25.
Optionally, the volume ratio of the absolute ethyl alcohol to the water is 5:1-8:1.
Optionally, the stirring temperature is 20-50 ℃, and the stirring time is 4-8h;
preferably, the drying temperature is 80-150 ℃, and the drying time is 12-36h;
preferably, the heating rate of the roasting is 2-5 ℃/min, the target temperature is 450-550 ℃, and the roasting time is 4-7h.
The invention creatively takes tetrabutyl titanate as a precursor, manganese and cobalt as active components, nitric acid is added for enhancing assistance, the manganese and the cobalt are uniformly dispersed on anatase titanium dioxide in an amorphous structure by one step through a sol-gel method, and the catalytic performance of the catalyst is improved by utilizing the interaction between the manganese and the cobalt.
Experiments prove that in order to obtain a catalyst with better activity and more stable performance, the reaction conditions need to be further optimized, and preferably, the molar ratio of the manganese nitrate to the tetrabutyl titanate is 0.13; the stirring temperature is 25 ℃, and the stirring time is 4 hours; the drying temperature is 80 ℃, and the drying time is 24 hours; the heating rate of the roasting is 2 ℃/min, the target temperature is 500 ℃, and the roasting time is 5h.
The invention also provides application of the synergistic denitration and demercuration catalyst, wherein the catalyst is loaded into a fixed bed reactor, and then NO and Hg are simultaneously introduced 0 The reaction is carried out, and the space velocity of the reaction is controlled at 40000h -1 -80000h -1 。
Optionally, the application temperature of the catalyst is 150-240 ℃.
Preferably, the catalyst is applied at a temperature of 180 ℃.
The invention creatively prepares Co-Mn/TiO by a sol-gel method 2 The catalyst is applied to the field of collaborative denitration and demercuration, and is lower than the use temperature of a conventional collaborative denitration and demercuration catalyst, so that on one hand, the energy consumption is reduced, the energy is saved, the environment is protected, on the other hand, the lower operation temperature can not cause the decomposition of mercury compounds generated in the removal process, and the removal efficiency of mercury is improved.
Experiments prove that at the preferable application temperature, the denitration efficiency of the catalyst is more than or equal to 95 percent, the demercuration efficiency is more than or equal to 95 percent, the catalyst can stably run for 100 hours, and excellent removal activity and stability are shown.
The invention has the beneficial effects that:
the synergistic denitration and demercuration catalyst provided by the invention is composed of nano particle agglomeration, has no fixed morphology, and has a specific surface area of 176.3m 2 The catalyst has a uniform mesoporous structure with the average pore diameter of 6.8nm, and has stronger redox ability and better synergistic denitration and demercuration performance.
According to the preparation method of the synergistic denitration demercuration catalyst, tetrabutyl titanate is used as a precursor, manganese and cobalt are used as active components, the manganese and the cobalt are uniformly dispersed on anatase titanium dioxide in an amorphous structure by one step through a sol-gel method, and the catalytic performance of the catalyst is improved by utilizing the interaction between the manganese and the cobalt, so that NO and Hg in flue gas are efficiently removed 0 The raw materials are cheap, the operation is simple, the process is environment-friendly, and the method is favorable for industrial large-scale popularization and use.
Compared with the application of the existing catalyst, the application temperature of the synergistic denitration and demercuration catalyst provided by the invention is lower, the process is safer, energy-saving and environment-friendly, and NO and Hg in flue gas can be realized 0 The removal efficiency is higher, the NO conversion rate is up to more than 90 percent, and Hg is higher 0 The conversion rate is close to 100%, the stable operation can be carried out for 100h, and the method has good industrial application potential.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The method provided by the invention is used for preparing the synergistic denitration and demercuration catalyst and is applied to denitration and demercuration reaction of flue gas, and the method comprises the following specific steps:
s1: dissolving cobalt nitrate and manganese nitrate into a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 6:1 to obtain a mixed system, wherein the molar ratio of the cobalt nitrate to the manganese nitrate is 0.75;
s2: adding nitric acid into the S1 mixed system, wherein the molar ratio of the nitric acid to the deionized water is 0.06, stirring at 25 ℃, then dropwise adding a tetrabutyl titanate solution, wherein the molar ratio of manganese nitrate to tetrabutyl titanate is 0.13, stirring vigorously, and stopping after 4 hours to form transparent sol;
s3: drying the sol obtained in the step S2 at the temperature of 80 ℃ for 24h, and finally, raising the temperature to 500 ℃ at the heating rate of 2 ℃/min in the air atmosphere for calcining for 5h to obtain the synergistic denitration and demercuration catalyst which can be recorded as Co-Mn/TiO 2 A catalyst.
S4: the catalyst prepared in the step S3 is loaded into a fixed bed reactor, the reaction temperature is controlled at 180 ℃,500ppm NO and 500ppm NH of simulated flue gas under normal pressure are introduced 3 5% of O 2 ，115μg/m 3 Hg 0 Selecting N 2 As an equilibrium gas, the reaction space velocity is controlled to be 60000h -1 。
The conversion of NO at steady state was 98% Hg 0 The conversion was 100%.
Example 2
The method provided by the invention is used for preparing the synergistic denitration and demercuration catalyst and is applied to denitration and demercuration reaction of flue gas, and the method comprises the following specific steps:
s1: dissolving cobalt nitrate and manganese nitrate into a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 6:1 to obtain a mixed system, wherein the molar ratio of the cobalt nitrate to the manganese nitrate is 0.5;
s2: adding nitric acid into the S1 mixed system, wherein the molar ratio of the nitric acid to the deionized water is 0.06, stirring at 25 ℃, then dropwise adding a tetrabutyl titanate solution, wherein the molar ratio of manganese nitrate to tetrabutyl titanate is 0.13, stirring vigorously, and stopping after 4 hours to form transparent sol;
s3: drying the sol obtained in the step S2 at 80 ℃ for 24h, and finally heating to 500 ℃ at a heating rate of 2 ℃/min in an air atmosphere to calcine for 5h, namelyObtaining the synergistic denitration demercuration catalyst which can be recorded as Co-Mn/TiO 2 A catalyst.
S4: the catalyst prepared in the S3 is loaded into a fixed bed reactor, the reaction temperature is controlled at 150 ℃,500ppm NO and 500ppm NH of simulated flue gas under normal pressure are introduced 3 5% of O 2 ，115μg/m 3 Hg 0 Selecting N 2 As the balance gas, the reaction space velocity is controlled to be 60000h -1 。
NO conversion at steady state was 91% Hg 0 The conversion was 100%.
Example 3
The method provided by the invention is used for preparing the synergistic denitration and demercuration catalyst and is applied to denitration and demercuration reaction of flue gas, and the method comprises the following specific steps:
s1: dissolving cobalt nitrate and manganese nitrate into a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 6:1 to obtain a mixed system, wherein the molar ratio of the cobalt nitrate to the manganese nitrate is 1;
s2: adding nitric acid into the S1 mixed system, wherein the molar ratio of the nitric acid to the deionized water is 0.06, stirring at 25 ℃, then dropwise adding a tetrabutyl titanate solution, wherein the molar ratio of manganese nitrate to tetrabutyl titanate is 0.13, stirring vigorously, and stopping after 4 hours to form transparent sol;
s3: drying the sol obtained in the step S2 at 80 ℃ for 24h, and finally heating to 500 ℃ at a heating rate of 2 ℃/min in an air atmosphere to calcine for 5h to obtain the synergistic denitration and demercuration catalyst which can be marked as Co-Mn/TiO 2 A catalyst.
S4: the catalyst prepared in the step S3 is loaded into a fixed bed reactor, the reaction temperature is controlled at 240 ℃,500ppm NO and 500ppm NH of simulated flue gas under normal pressure are introduced 3 5% of O 2 ，115μg/m 3 Hg 0 Selecting N 2 As an equilibrium gas, the reaction space velocity is controlled to be 60000h -1 。
The NO conversion in the steady state was 93%, hg 0 The conversion was 100%.
Example 4
The method provided by the invention is used for preparing the synergistic denitration and demercuration catalyst and is applied to denitration and demercuration reaction of flue gas, and the method comprises the following specific steps:
s1: dissolving cobalt nitrate and manganese nitrate into a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 6:1 to obtain a mixed system, wherein the molar ratio of the cobalt nitrate to the manganese nitrate is 0.75;
s2: adding nitric acid into the S1 mixed system, wherein the molar ratio of the nitric acid to the deionized water is 0.06, stirring at 25 ℃, then dropwise adding a tetrabutyl titanate solution, wherein the molar ratio of manganese nitrate to tetrabutyl titanate is 0.13, stirring vigorously, and stopping after 6 hours to form transparent sol;
s3: drying the sol obtained in the step S2 at the temperature of 80 ℃ for 24h, and finally, raising the temperature to 500 ℃ at the heating rate of 5 ℃/min in the air atmosphere for calcining for 5h to obtain the synergistic denitration and demercuration catalyst which can be recorded as Co-Mn/TiO 2 A catalyst.
S4: the catalyst prepared in the step S3 is loaded into a fixed bed reactor, the reaction temperature is controlled at 180 ℃,500ppm NO and 500ppm NH of simulated flue gas under normal pressure are introduced 3 5% of O 2 ，115μg/m 3 Hg 0 Selecting N 2 As equilibrium gas, the reaction space velocity is controlled to be 80000h -1 。
NO conversion at steady state was 95% Hg 0 The conversion was 100%.
Example 5
The method provided by the invention is used for preparing the synergistic denitration and demercuration catalyst and is applied to denitration and demercuration reaction of flue gas, and the method comprises the following specific steps:
s1: dissolving cobalt nitrate and manganese nitrate into a mixed solution of absolute ethyl alcohol and deionized water in a volume ratio of 6:1 to obtain a mixed system, wherein the molar ratio of the cobalt nitrate to the manganese nitrate is 0.75;
s2: adding nitric acid into the S1 mixed system, wherein the molar ratio of the nitric acid to the deionized water is 0.06, stirring at 25 ℃, then dropwise adding a tetrabutyl titanate solution, wherein the molar ratio of manganese nitrate to tetrabutyl titanate is 0.13, stirring vigorously, and stopping after 4 hours to form transparent sol;
s3: drying the sol obtained in the step S2 at 80 ℃ for 24h, and finally, in an air atmosphereHeating to 500 ℃ at the heating rate of 2 ℃/min and calcining for 5h to obtain the synergistic denitration and demercuration catalyst which can be recorded as Co-Mn/TiO 2 A catalyst.
S4: the catalyst prepared in the step S3 is loaded into a fixed bed reactor, the reaction temperature is controlled at 180 ℃,500ppm NO and 500ppm NH of simulated flue gas under normal pressure are introduced 3 5% of O 2 ，115μg/m 3 Hg 0 Selecting N 2 As an equilibrium gas, the reaction space velocity is controlled to be 60000h -1 。
After 100h of reaction, the NO conversion was 97%, hg 0 The conversion was 96%.
The parameters of the synergistic denitration and demercuration catalyst prepared in examples 1-5 are shown in the following table 1.
TABLE 1 parameter tables for the synergistic denitration and demercuration catalysts provided in examples 1-5
| Item | Specific surface area m 2 /g | Average pore diameter nm |
| Example 1 | 176.3 | 6.8 |
| Example 2 | 121.8 | 7.0 |
| Example 3 | 171.9 | 6.2 |
| Example 4 | 172.1 | 6.7 |
| Example 5 | 176.3 | 6.8 |
Through examples 1-5, the synergistic denitration and demercuration catalyst provided by the invention has high catalytic activity, the NO conversion rate is more than 90% on the whole at the temperature of 150-240 ℃, and Hg is 0 The conversion rate is close to 100%, and the excellent synergistic denitration and demercuration performance is shown in a low-temperature working environment. And shows stronger stability to NO and Hg under the condition of long-time continuous use 0 Still has higher conversion rate.
Comparative example 1
The difference from example 1 is that in the step S2, the mixed system is reacted by directly adding tetrabutyl titanate solution without adding nitric acid.
NO conversion at steady state was 72% Hg 0 The conversion was 86%.
Comparative example 2
Selecting conventional V 2 O 5 -WO 3 /TiO 2 The catalyst comprises the following components in an atomic ratio of vanadium, tungsten and titanium of 1 3 5% of O 2 ，115μg/m 3 Hg 0 Selecting N 2 As an equilibrium gas, the reaction space velocity is controlled to be 60000h -1 . NO conversion at steady state was 68%, hg 0 The conversion was 41%.
As can be seen from comparison between example 1 and comparative example 1, in the preparation of the catalyst, in the case where other reaction conditions are completely the same, whether or not nitric acid is added to the reaction system controls the hydrolysis and polycondensation rates during the reaction, thereby forming the catalystThe formed particles are precipitated without being agglomerated into large particles, thus obtaining a stable and uniform sol, thereby obtaining a uniform nano catalyst. The fact proves that the influence of the nitric acid on the performance of the prepared catalyst is obvious and crucial, and the observation of experimental data shows that when the nitric acid is added into the catalyst prepared in example 1, the conversion rate of NO is as high as 98 percent, hg is as high as that of the catalyst prepared when the catalyst is used for treating simulated flue gas 0 The conversion rate is up to 100%, while the reaction is carried out in the system of the comparative example 1 without adding nitric acid, the prepared catalyst treats the same simulated smoke under the same conditions as the example 1, the conversion rate of NO is only 72%, and Hg is only 0 The conversion was only 86%, significantly lower than in example 1.
Comparing example 3 with comparative example 2, it can be seen that the existing conventional catalyst treated the same simulated flue gas under the same conditions, whether it is NO conversion, or Hg conversion 0 The conversion rate and the data of the conventional catalyst are far lower than those of the synergistic denitration and demercuration catalyst provided by the embodiment of the invention, which shows that the synergistic denitration and demercuration catalyst provided by the invention has better catalytic activity.
It should be noted that the technical features of the above embodiments can be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the above embodiments are not described, however, as long as there is no contradiction between the combinations of the technical features, the scope of the present description should be considered. The above examples only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The catalyst is characterized by being formed by agglomeration of nano particles and comprising a carrier and an active component; the carrier is titanium dioxide, and the active components are manganese and cobalt.
2. The catalyst according to claim 1, characterized in that the titanium dioxide is present in the anatase form and the active component is dispersed on the support in an amorphous structure.
3. The catalyst according to claim 1 or 2, wherein the atomic ratio of manganese to titanium is 0.1 to 0.2 and the atomic ratio of cobalt to manganese is 0.25 to 1.25.
4. The preparation method of the synergistic denitration and demercuration catalyst as claimed in any one of claims 1 to 3, wherein the preparation method comprises the steps of mixing manganese nitrate, cobalt nitrate, anhydrous ethanol and water to form a mixed system, adding tetrabutyl titanate solution into the mixed system, stirring to form sol, and sequentially drying and roasting to obtain the catalyst.
5. The method according to claim 4, characterized by further comprising adding nitric acid to the mixed system before adding the tetrabutyl titanate solution;
preferably, the molar ratio of the nitric acid to the water is 0.02 to 0.12.
6. The method according to claim 4, wherein the molar ratio of the manganese nitrate to the tetrabutyl titanate is 0.1-0.2;
preferably, the molar ratio of the cobalt nitrate to the manganese nitrate is 0.25-1.25.
7. The preparation method of claim 4, wherein the volume ratio of the absolute ethyl alcohol to the water is 5:1-8:1.
8. The method according to any one of claims 4 to 7, wherein the stirring is carried out at a temperature of 20 to 50 ℃ for a time of 4 to 8 hours;
preferably, the drying temperature is 80-150 ℃, and the drying time is 12-36h;
preferably, the heating rate of the roasting is 2-5 ℃/min, the target temperature is 450-550 ℃, and the roasting time is 4-7h.
9. Use of the synergistic denitration and demercuration catalyst as claimed in any one of claims 1 to 3, wherein the catalyst is loaded into a fixed bed reactor, and then NO and Hg are simultaneously introduced 0 The reaction is carried out, the space velocity of the reaction is controlled to be 40000h -1 -80000h -1 。
10. Use according to claim 9, wherein the catalyst is used at a temperature of 150-240 ℃.
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