CN108889298B - Preparation method of coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas - Google Patents

Preparation method of coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas Download PDF

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CN108889298B
CN108889298B CN201810720841.8A CN201810720841A CN108889298B CN 108889298 B CN108889298 B CN 108889298B CN 201810720841 A CN201810720841 A CN 201810720841A CN 108889298 B CN108889298 B CN 108889298B
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CN108889298A (en
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张华伟
赵淑龙
张志兰
张鼎元
武加峰
梁鹏
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Shandong University of Science and Technology
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Abstract

The invention discloses a preparation method of a coal tar-based carbon material catalyst capable of removing nitrogen oxides and mercury in coal-fired flue gas in a combined manner, belonging to the technical field of energy chemical industry. The combined removal of pollutants in the coal flue gas is realized. The method comprises the following steps: firstly, purifying and pretreating coal tar; mixing with polyvinylpyrrolidone (PVP), and soaking in SnCl2And Mn2+Carrying out in-situ loading in an ethanol solution; sequentially carrying out carbonization and oxidation to obtain the coal tar carbon material catalyst. The coal tar carbon material catalyst prepared by the method has rich pore structures and high specific surface area. The method takes the coal tar as the raw material, the raw material is cheap and easy to obtain, the prepared catalyst has high mercury removal and denitration efficiency which can reach more than 95%, the service life is long, the regeneration performance is good, a new technical scheme is provided for novel and efficient utilization of the coal tar, and the method can be popularized and applied.

Description

Preparation method of coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas
Technical Field
The invention belongs to the technical field of energy chemical industry, and particularly relates to a preparation method of a catalyst suitable for denitration and demercuration.
Background
The flue gas discharged in the coal combustion process contains a large amount of gaseous pollutants and heavy metal trace element pollutants. Wherein, nitrogen oxide and mercury cause serious harm to the environment and human health. Wherein the nitrogen oxide comprises multiple compounds, such as NO, N2O、NO2、N2O3、N2O4Etc. serious pollution to atmosphere includes NO and N2O、NO2. The nitrogen oxides bring great harm to human body and environment, mainly including acid rain and ozone layerVoids, photochemical smog, and the like. And the mercury is mainly Hg in the coal combustion process0、HgCl2、HgCl2And the HgO form, Hg in the general atmosphere, present in flue gases2+The mercury element has higher volatility and lower water solubility, and the prior dust removal device and scrubber can not remove Hg in the atmosphere0It can be transported through the atmosphere over long distances and times to create global environmental pollution.
The application of removing nitrogen oxides in flue gas is widely a dry denitration technology, mainly a Selective Catalytic Reduction (SCR), a selective non-catalytic reduction (SCNR) and a (SCR-SCNR) mixed denitration process, and the SCR denitration efficiency is the best. For Hg0The main methods of removal of (2) are direct adsorption removal and indirect oxidation removal. Hg is a mercury vapor0The method for directly removing the Hg by adsorption is that0Adsorbing on the surface of the adsorbent in a physical or chemical adsorption mode or removing in a mode of forming alloy with metal; hg is a mercury vapor0The method for oxidizing and indirectly removing the Hg is to remove the Hg0Oxidized to mercury removal in the oxidized state0The oxidation indirect removal catalyst mainly comprises a molecular sieve catalyst, a metal oxide catalyst and a metal catalyst.
The research reports related to the removal of pollutants from coal-fired flue gas in the prior art mainly include:
200910062370.7 discloses a combined removal method of coal-fired flue gas pollutants and its special purification reactor, which comprises spraying water into the first and second purification reactors, repeatedly washing the removal product attached to the surface of activated carbon fiber, and filling activated carbon fiber in the drying reactor to remove the pollutants in the coal-fired flue gas.
201510745295.X discloses a combined removal of SO from coal-fired flue gas2、NOXThe method for treating Hg pollutants comprises the steps of spraying a strong oxidant into flue gas before a solid-phase catalytic oxidation catalyst, and oxidizing the flue gas by a solid-phase catalytic oxidation catalyst bed; solid catalyst is filled in a solid phase catalytic oxidation catalyst bed layer, and the method is used for treating SO in flue gas2Oxidation of NO and elemental mercuryThe rate reaches over 75-80%.
In the research reports, the former mainly depends on the physical adsorption of the activated carbon fibers to remove pollutants in the coal-fired flue gas, the process is simple and economic, but the former can not play a good role in removing the pollutants in the coal-fired flue gas, particularly in removing nitrogen oxides and Hg, and the latter adopts a chemical conversion method of a catalytic oxidation catalyst and can be used for removing SO in the coal-fired flue gas2And NO and elementary mercury are removed, but the process flow is complex and the removal efficiency is low. That is, there are technical drawbacks to using different catalysts to remove nitrogen oxides and Hg elements. The development of combined removal of pollutants in coal-fired flue gas is a development trend of pollutant control at present, and has high research value.
Disclosure of Invention
The invention aims to provide a preparation method of a coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas, wherein purified coal tar is used as a carrier, Sn/Mn active metal is loaded on the carrier, so that the nitrogen oxides and mercury in the coal-fired flue gas can be jointly removed, and the removal efficiency can reach 95%.
In order to achieve the above purpose, the technical problems to be overcome mainly include: the high-temperature coal tar raw oil contains a large amount of asphalt, N, S, O and other impurities with high content; the coal tar coke material has low load capacity, and the load process is easy to cause ion agglomeration and uneven load; the prior efficiency of jointly removing nitric oxide and Hg in flue gas is low.
In order to solve the technical problem, the invention adopts the following technical scheme:
a preparation method of a coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas takes coal tar as a raw material, wherein the coal tar is generated in the coking process of coal, and the preparation method sequentially comprises the following steps:
a, purifying coal tar;
b, carrying out in-situ loading, namely mixing the coal tar purified in the step a with polyvinylpyrrolidone, wherein the mass ratio of the coal tar to the polyvinylpyrrolidone is 14:1, mixing the obtained mixture, and immersing the obtained mixture in SnCl2And divalent manganese ion ethanol solution, stirring for 10-16h at room temperature, and drying to constant weight at 80 ℃ to finish Sn2+And Mn2+Carrying out in-situ loading to obtain Sn-Mn loaded coal tar;
c, carbonizing, namely carbonizing the Sn-Mn loaded coal tar, and preserving heat for 2-4 hours by taking inert gas as a medium to prepare a coal tar carbon material catalyst;
d, oxidizing, namely placing the coal tar-based carbon material catalyst in the step c in an oxidizing furnace, heating to 200-500 ℃ at the heating rate of 1-5 ℃/min in the air atmosphere, and preserving the heat for 1-3h to finish the oxidation process, thus obtaining the coal tar-based carbon material catalyst.
The above principle is introduced as follows:
firstly, quinoline insoluble substances in coal tar can be removed by purifying the coal tar, and the content of S, O, N is reduced; then the purified coal tar is loaded in situ, and the purpose is to complete Sn2+And Mn2+In-situ loading, the loading mechanism mainly has two aspects of physics and chemistry: the physical aspect is the mechanical force of the adhesiveness of PVP and tar per se, so that Sn is generated2+And Mn2 +Attached to the surface of coal tar; the chemical aspect is that the complex is combined with hydroxyl and carboxyl in the coal tar through complexation; then carbonizing, wherein the purpose of carbonization is to pyrolyze tar into coke materials at high temperature; finally, the oxidation is carried out, the purpose of the oxidation is to oxidize Sn-Mn metal ions into metal oxides, and the action mechanism is Sn + O2＝SnO2；Mn+O2＝MnO2。
More importantly, the coal tar is directly subjected to in-situ loading after being purified, compared with the loading after purification and carbonization, the loading is carried out before carbonization, and in addition to the binding power of the coal tar and PVP, the complexing action of a large number of organic functional groups such as hydroxyl, carboxyl and the like in the coal tar is also realized, so that the metal loading efficiency is favorably improved, and the problem of agglomeration caused by metal in the loading process is also reduced to a certain extent.
In a preferable scheme of the invention, in the step a, the coal tar is purified by adopting a reduced pressure distillation mode, and in the purification process, quinoline insoluble substances in the coal tar are removed and the S, O, N content is reduced.
As another preferred embodiment of the present invention, in step b, the Sn/Mn molar ratio is 0.6.
Further, in the step b, the divalent manganese ion ethanol solution is a manganese acetate ethanol solution, a manganese nitrate ethanol solution or a manganese chloride ethanol solution.
Further, the divalent manganese ion ethanol solution is manganese acetate ethanol solution.
The beneficial technical effects brought by the invention are as follows:
the coal tar has complex aromatic compounds and phenolic compounds, has a complex structure and great development and utilization potential, and the coal tar is used as a raw material and a carrier to prepare the coal tar-based carbon material catalyst, so that the coal tar is reasonably utilized, and the waste is changed into valuable.
The carbon material catalyst prepared by carbonizing the coal tar has rich pore structures, large specific surface area, flat surface and developed structure, is beneficial to simulating that flue gas can enter the catalyst and fully acts with the active site of the catalyst, so that the catalytic effect of the catalyst is more ideal.
The catalyst obtained by the method has long service life and good regeneration performance.
The catalyst obtained by the method disclosed by the invention is used for denitration by low-temperature SCR, and the principle for removing Hg is an oxidation-reduction reaction.
The efficiency of the combined removal of nitrogen oxides and mercury in the coal-fired flue gas prepared by the method can reach more than 95%.
Compared with the prior art, the coal tar carbon material catalyst prepared by the method has the advantages that the raw materials are byproducts in the coal coking process, are cheap and easily available, and are used as the coking byproducts with lower utilization efficiency. And by loading Sn/Mn active metal, nitrogen oxides and mercury in the coal-fired flue gas can be removed in a combined manner, and the removal efficiency can reach 95%.
Drawings
The invention is further described below with reference to the accompanying drawings:
FIG. 1 shows the selection of different Mn in step b of the process of the present invention2+Influence of ethanol solution impregnation on denitration and demercuration performance (Sn/Mn is 0.6).
FIG. 2 shows that in step b of the process of the present invention, when the fixed Mn loading is 10%, and Sn/Mn is 0.2, 0.6, 1.0, the catalyst NO isxAnd Hg removal efficiency (Mn-selected)2+The ethanol solution is manganese acetate).
Detailed Description
Firstly, the main raw materials and main instruments required by the invention are explained in detail:
coal tar, which is high temperature coal tar, is produced during the coal and coking process.
The carbonization furnace and the oxidation furnace required in the carbonization and oxidation processes are both the carbonization furnace and the oxidation furnace in the prior art.
SnCl is selected as dipping solution2And a manganous ion ethanol solution, wherein the manganous ion ethanol solution is a manganous acetate ethanol solution, a manganous nitrate ethanol solution or a manganous chloride ethanol solution, and can be purchased from commercial sources.
Firstly, purifying coal tar, and specifically comprising the following steps of by a reduced pressure distillation mode: the raw material tar is preheated and then enters a pre-dehydration tower, most water and a small amount of light oil are removed from the tower top, and the tar at the tower bottom automatically flows into the dehydration tower. And distilling light oil fraction and water from the top of the dehydration tower, heating anhydrous tar at the bottom of the dehydration tower by a tubular furnace, feeding the heated anhydrous tar into the lower part of a main distillation tower, performing reduced pressure operation on the main distillation tower, distilling phenol oil fraction from the top of the dehydration tower, respectively cutting naphthalene oil, wash oil and anthracene oil fraction from top to bottom along a lateral line, and extracting soft asphalt from the bottom of the dehydration tower. Coal tar fractions with the temperature range of 180-360 ℃ are selected in an in-situ loading manner, the coal tar components purified by the reduced pressure distillation mainly comprise the coal tar fractions rich in aromatic hydrocarbon components such as phenol oil, naphthalene oil, anthracene oil and the like, and most of asphalt components are removed.
The invention relates to a preparation method of a coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas, which comprises the following specific steps.
The experimental method for evaluating the activity of the catalyst of the invention is as follows:
and (4) evaluating the combined removal activity of the nitrogen oxides and the mercury.
The activity of the catalyst is tested in a fixed bed reactor, the prepared catalyst is ground into powder and put in a quartz tube reactor, the gas source is adjusted, and NO is requiredxAfter the concentration is stable, the simulated flue gas is introduced into a quartz tube reactor of the fixed bed, the mercury generator is opened, the water bath temperature of the mercury generator is controlled at 30 ℃, the temperature is raised, and the simulated flue gas are introduced into the quartz tube reactor together. After equilibrium of the reaction, determination of NO after the reactionxAnd Hg concentration. In the whole process, the gas at the outlet of the reactor is used for detecting the concentration of nitrogen oxides by using a KANE-945 type flue gas analyzer, and the concentration of Hg is detected by using an RA-915 dynamometer for analyzing and calculating the removal efficiency.
The NOx evaluation method comprises the following steps: the conversion can be calculated by measuring the concentration of NOx after the reaction. The calculation formula is as follows:
Figure BDA0001718595060000041
evaluation method of Hg: the mercury removal efficiency can be obtained by varying the mercury content before and after the mercury removal. The calculation formula is as follows:
Figure BDA0001718595060000042
example 1:
step one, purifying coal tar: a reduced pressure distillation method is adopted, which aims to remove quinoline insoluble substances in the coal tar and reduce the S, O, N content;
step two, in-situ loading, namely mixing the coal tar treated in the step one and the step two with polyvinylpyrrolidone (PVP) (the mass ratio of the coal tar to the PVP is 1:1), and soaking the mixture in SnCl2And manganese acetate ethanol solutionStirring at room temperature for 10-16h, and drying at 80 deg.C to constant weight;
step three, carbonizing, namely, carrying out Sn-Mn loaded coal tar in a carbonization furnace, taking inert gas as a medium, and keeping the temperature at 700 ℃ for 2-4h to prepare a coal tar carbon material catalyst;
step four, oxidizing, namely placing the coal tar material subjected to the step three in an oxidizing furnace, heating to 200-500 ℃ at the heating rate of 1-5 ℃/min in the air atmosphere, and preserving the heat for 1-3h to finish the oxidation process to obtain SnO2-MnO2A supported coal tar carbon material catalyst;
wherein, Mn in the second step2+The ethanol solution may be manganese acetate, manganese nitrate and manganese chloride ethanol solution.
In the second step, the loading amount of fixed Mn is 10 percent, and the molar ratio of Sn/Mn is 0.6.
The evaluation experiment of the removal activity of nitrogen oxides and Hg was performed on the coal tar-based carbon material catalyst prepared in this example.
Evaluation of denitration and demercuration activity: the experimental conditions are as follows: space velocity of 30000h-1，NH31.1,/NO at 250 ℃. The simulated gas comprises the following components: the oxygen concentration is 5%, the nitric oxide concentration is 0.1% (5%/95% of nitrogen), the ammonia concentration is 0.12% (5%/95% of nitrogen), the sulfur dioxide concentration is 0.08% (5%/95% of nitrogen), water enters through a preheating section (vaporizer) by water vapor, the volume fraction is 2% -10%, the nitrogen (balance gas) concentration is 99.5%, and the ammonia-nitrogen ratio is 1.1. The Hg generator provides Hg in simulated gas. The total flow rate of gas was 1000 ml/min.
The experimental results are as follows: the removal efficiency of nitrogen oxides can reach 95 percent, the removal efficiency of Hg can reach 92 percent, and the activity evaluation experiment efficiency chart is shown in figure 1.
Example 2:
the difference from the embodiment 1 is that:
mn in preparation step II2+Selecting an ethanol solution as a manganese nitrate ethanol solution;
step two, in-situ loading, namely mixing the coal tar treated in the step one and the step two with polyvinylpyrrolidone (PVP)In a mass ratio of 4:1) in SnCl2And manganese nitrate ethanol solution, stirring for 10-16h at room temperature, and drying to constant weight at 80 ℃.
The fixed Mn loading in the second step is 10%, and the Sn/Mn ratio can be 0.6.
The catalyst prepared in this embodiment was subjected to an evaluation experiment for the removal activity of nitrogen oxides and Hg. The experimental result shows that the removal efficiency of the nitrogen oxides can reach 86 percent, and the removal efficiency of the Hg can reach 84 percent.
Example 3:
the difference from the embodiment 1 is that:
mn in preparation step II2+The ethanol solution is selected from manganese chloride ethanol solution;
step two, in-situ loading, namely mixing the coal tar treated in the step one and the step two with polyvinylpyrrolidone (PVP) (the mass ratio of the coal tar to the PVP is 2:1), and soaking the mixture in SnCl2And manganese chloride ethanol solution, stirring for 10-16h at room temperature, and drying to constant weight at 80 ℃.
The fixed Mn loading in the second step is 10%, and the Sn/Mn ratio can be 0.6.
The catalyst prepared in this example was subjected to an evaluation experiment for the removal activity of nitrogen oxides and Hg. The experimental result shows that the removal efficiency of the nitrogen oxides can reach 83 percent, and the removal efficiency of the Hg can reach 80 percent.
Example 4:
the difference from the embodiment 1 is that:
step two, in-situ loading, namely mixing the coal tar treated in the step one and the step two with polyvinylpyrrolidone (PVP) (the mass ratio of the coal tar to the PVP is 1:1), and soaking the mixture in SnCl2And manganese acetate ethanol solution, stirring for 10-16h at room temperature, and drying to constant weight at 80 ℃.
In the second step, the fixed Mn loading is 10%, and the Sn/Mn ratio is 0.8.
The experimental results are as follows: the removal efficiency of nitrogen oxides can reach 89 percent, and the removal efficiency of Hg can reach 86 percent
Example 5:
the difference from the embodiment 1 is that:
and in the second step, Sn/Mn is 0.4.
The catalyst prepared in this embodiment was subjected to an evaluation experiment for the removal activity of nitrogen oxides and Hg. The experimental result shows that the removal efficiency of the nitrogen oxides can reach 85 percent, and the removal efficiency of the Hg can reach 80 percent.
Example 6:
the difference from the embodiment 1 is that:
and in the second step, Sn/Mn is 0.2.
The catalyst prepared in this embodiment was subjected to an evaluation experiment for the removal activity of nitrogen oxides and Hg. The experimental result shows that the removal efficiency of the nitrogen oxides can reach 79 percent, and the removal efficiency of the Hg can reach 74 percent.
Example 7:
the difference from the embodiment 1 is that: Sn/Mn is 1.0.
The catalyst prepared in this embodiment was subjected to an evaluation experiment for the removal activity of nitrogen oxides and Hg. The experimental result shows that the removal efficiency of the nitrogen oxides can reach 74 percent, and the removal efficiency of the Hg can reach 70 percent.
When the fixed Mn loading amount in the step b of the invention is 10 percent and the Sn/Mn is 0.2, 0.6 and 1.0, the catalyst NO isxAnd Hg removal efficiency are shown in figure 2.
Supplementary explanation: in the preparation method of the coal tar-based carbon material catalyst, experiments show that:
firstly, when the loading amount of Mn is 10 percent (namely 0.1) and only Sn/Mn is 0.6 (molar ratio), the prepared coal tar carbon material catalyst has higher efficiency in jointly removing nitrogen oxides and Hg in coal-fired flue gas. The reason is that: when Sn/Mn is low, the load capacity of Sn ions is low, the removal efficiency of nitrogen oxides and Hg in flue gas is low, the removal efficiency of pollutants is increased along with the increase of the amount of Sn, and simultaneously SnO2The presence of which increases the MnO to some extent2The surface oxygen enhances the pollutant removal efficiency, but as the loading increases, excessive metal ions are caused to agglomerate, affecting the catalytic efficiency.
Secondly, the experiment for evaluating the removal activity of the nitrogen oxide and Hg of the prepared catalyst shows that the selection of the divalent manganese ion ethanol solution has great influence on the result, and the manganese acetate ethanol solution has higher removal efficiency on the nitrogen oxide and Hg. The reason is that: the acetate in the manganese acetate solution has a structure similar to that of the coal tar, can be better fused with carboxylate radicals, hydroxyl radicals and the like in the coal tar, and promotes the complexation of the metal in the impregnation liquid and the groups in the coal tar.
The parts which are not described in the invention can be realized by taking the prior art as reference.
It should be noted that: any equivalents, or obvious variations thereof, which may occur to those skilled in the art and which are commensurate with the teachings of this specification, are intended to be within the scope of the present invention.

Claims (4)

1. A preparation method of a coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas is characterized by comprising the following steps: the preparation method takes coal tar as a raw material, wherein the coal tar is generated in the coking process of coal, and the preparation method sequentially comprises the following steps:
a, purifying coal tar;
b, in-situ loading, mixing the coal tar purified in the step a with polyvinylpyrrolidone in a mass ratio of 1-4: 1, and soaking the mixture obtained in the mixing process in SnCl2And divalent manganese ion ethanol solution, stirring for 10-16h at room temperature, and drying to constant weight at 80 ℃ to finish Sn2+And Mn2+Carrying out in-situ loading to obtain Sn-Mn loaded coal tar;
c, carbonizing, namely carbonizing the Sn-Mn loaded coal tar, and preserving heat for 2-4 hours by taking inert gas as a medium to prepare a coal tar carbon material catalyst;
d, oxidizing, namely placing the coal tar-based carbon material catalyst in the step c into an oxidation furnace, heating to 200-500 ℃ at the heating rate of 1-5 ℃/min in the air atmosphere, and preserving the heat for 1-3h to finish the oxidation process, thus obtaining the coal tar-based carbon material catalyst;
in the Sn-Mn loaded coal tar, the loading amount of Mn is 10%, and the molar ratio of Sn/Mn is 0.2-1;
in the step a, coal tar is purified by adopting a reduced pressure distillation mode, and in the purification process, quinoline insoluble substances in the coal tar are removed and the S, O, N content is reduced.
2. The preparation method of the coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas according to claim 1, characterized by comprising the following steps: the Sn/Mn molar ratio is 0.6.
3. The preparation method of the coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas according to claim 1, characterized by comprising the following steps: in the step b, the divalent manganese ion ethanol solution is a manganese acetate ethanol solution, a manganese nitrate ethanol solution or a manganese chloride ethanol solution.
4. The preparation method of the coal tar-based carbon material catalyst capable of jointly removing nitrogen oxides and mercury in coal-fired flue gas according to claim 3, characterized by comprising the following steps: the divalent manganese ion ethanol solution is manganese acetate ethanol solution.
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