CN114324435A - Method and device for evaluating desulfurization and denitrification performance of activated coke - Google Patents
Method and device for evaluating desulfurization and denitrification performance of activated coke Download PDFInfo
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Abstract
An evaluation method and a device for desulfurization and denitrification performance of active coke comprise the following steps: 1) placing a quartz reactor containing active coke samples in a reaction cavity of microwave equipment, wherein the reaction cavity comprises a heating cavity, a microwave cavity and a mixing heater which are nested from outside to insideA hot chamber; the quartz reactor is provided with a gas inlet and a gas outlet, the gas inlet is connected with gas mixing equipment through a pipeline, and the gas outlet is connected with gas analysis equipment; 2) starting the microwave equipment, and mixing N with gas2、SO2Uniformly mixing the/NO, introducing the mixture into a quartz reactor through an air inlet, simultaneously measuring the outlet gas concentration of an air outlet by using gas analysis equipment, and analyzing the desulfurization and denitrification performance of the active coke sample; 3) and (4) detecting the specific surface area, the micropore volume, the pore size distribution and the like of the active coke sample. The invention can accurately reflect the desulfurization and denitrification performances of different measured active coke samples, provide reasonable performance indexes of the active coke for desulfurization and denitrification, and detect and analyze the performance indexes of different active coke samples.
Description
Technical Field
The invention relates to the field of desulfurization and denitrification, energy conservation and emission reduction, and particularly relates to a method and a device for evaluating desulfurization and denitrification performance of activated coke.
Background
The steel industry is a high energy consumption, high pollution, resource type industry, and the control of waste gas pollution is a major task in the control of pollution in the steel industry, and SO in the waste gas pollution is281.29% of the total emission, 53.52% of NOx and 39.81% of the total emission, so that the treatment of the sintering flue gas is an important influencing factor for the long-term health development of enterprises. From 1 month and 1 day 2015, SO of all metallurgical enterprises2And NOx emission concentration limit of 200mg/m, respectively3And 300mg/m3Regional SO with reduced environmental bearing capacity or fragile ecological environment2And NOx of 50mg/m respectively3And 100mg/m3Thus, the national attention on the work of preventing and controlling the air pollution is increasingly deepened. The active coke is cooperated with desulfurization and denitrification to be a flue gas control technology which is internationally recognized at present.
The active coke has a large specific surface area and a rich pore structure, and simultaneously has a pressure-resistant, impact-resistant and wear-resistant adsorbing material. Desulfurization with activated coke is an economical and efficient desulfurization process. However, due to the difference of the raw materials and the production process for producing the activated coke, the pore structure and the surface chemical property of the activated coke are greatly different, and the desulfurization and denitrification performance of the activated coke is affected, so that the pore structure and the surface chemical property of the activated coke are fully considered when the activated coke is selected as the desulfurization and denitrification agent, and the activated coke can be properly modified to improve the desulfurization and denitrification performance. In the aspect of combined desulfurization and denitrification, due to the similarity between the activated coke and the activated carbon, and compared with the activated carbon, the activated coke has lower price and better mechanical property, so that the activated coke has greater advantages in the aspects of desulfurization and denitrification. As an important adsorbent for the desulfurization and denitrification method of the activated coke, the quality, the difference of pore structures, the difference of surface chemical properties and the like of the activated coke all influence the desulfurization and denitrification performance. How to evaluate the desulfurization and denitrification performance of the active coke and select an active coke sample with the optimal performance is very important in the desulfurization and denitrification process.
The performance of the active coke is evaluated by researching the saturated sulfur capacity of the active coke by related research institutions, and the method is mainly used for detecting the performance of the active coke subjected to single desulfurization.
Chinese patent No. 200910113055.2 discloses a method and apparatus for detecting flue gas denitration catalyst active agent. The method is mainly used for evaluating the performance of the activated coke for single denitration. The two methods are not suitable for being applied to the field of active coke synergistic desulfurization and denitrification.
Chinese patent No. 201210001373.1 discloses a device for evaluating flue gas pollutant adsorbent and application thereof. The patent can evaluate the performance of the adsorbent for removing the pollution gas to a certain extent, and can not accurately detect the desulfurization and denitrification performance of the active coke and apply the performance to actual production.
Chinese patent No. 201020139307.7 discloses a simulated gas analysis system. The desulfurization and denitrification performance of the activated carbon can be detected by a test method, but the equipment is complex in structure, difficult to operate, long in test time and high in material consumption and increase cost, so that the equipment is difficult to popularize.
Chinese patent No. CN201310228085.4 discloses a device for simultaneously removing sulfur, nitrogen and mercury. The patent is complex and immature in process, is not high in commercial application degree, and can only be used for simulation experiments in a laboratory.
According to the evaluation methods, the influences of temperature, gas content, sealing property and the like cannot be accurately controlled, so that the evaluation of the desulfurization and denitrification performance of the active coke is influenced, part of microscopic properties and macroscopic properties of the active coke sample cannot be accurately detected, so that the evaluation of the desulfurization and denitrification performance of the active coke and the detection of the optimal parameters of the detected active coke sample are influenced, the test efficiency is low, the accuracy is poor, the repeatability is difficult, part of detection errors are large, and accurate performance indexes are difficult to provide for the active coke flue gas purification technology.
Disclosure of Invention
The invention aims to provide a method and a device for evaluating desulfurization and denitrification performance of active coke, which can accurately reflect the desulfurization and denitrification performance of different active coke samples to be tested, provide reasonable performance indexes of the active coke for desulfurization and denitrification, and detect and analyze the performance indexes of the different active coke samples.
In order to achieve the purpose, the technical scheme of the invention is as follows:
an evaluation method of desulfurization and denitrification performance of activated coke comprises the following steps:
1) placing a quartz reactor filled with an active coke sample in a reaction cavity in microwave equipment, wherein the reaction cavity consists of a heating cavity, a microwave cavity and a mixed heating cavity which are nested from outside to inside; the quartz reactor is provided with a gas inlet and a gas outlet, the gas inlet is connected with gas mixing equipment through a pipeline, and the gas outlet is connected with gas analysis equipment;
2) starting the microwave equipment to convert N2Mixed gas (10-13): 1 into a gas mixing apparatus, wherein N2The flow rate is 200-300 mL/min, the flow rate of the mixed gas is 20-30 mL/min, and the volume ratio of the components of the mixed gas is as follows: SO (SO)20.30-0.50% of NO, 0.10-0.30% of NO and the balance of argon; gas output from the gas mixing equipment is introduced into the quartz reactor through a gas inlet of the quartz reactor, and meanwhile, outlet gas concentration of a gas outlet of the quartz reactor is measured by using gas analysis equipment to analyze the desulfurization and denitrification performance of an active coke sample; the microwave power required by the microwave equipment experiment is 400-1000W, and the reaction temperature is 100-200 ℃;
3) performing the following detection on the active coke sample, including the detection of the specific surface area, the micropore volume and the pore size distribution of the active coke sample; analyzing the phase composition of the active coke sample; the activated coke samples were analyzed for surface functional groups.
Further, the step 3) comprises observing the surface appearance and element distribution of the active coke sample, detecting and screening the active coke sample meeting the detection requirements, determining the wear resistance of the active coke sample, and determining the compressive strength of the active coke sample.
Preferably, in the step 3), a scanning electron microscope device is adopted to observe the surface morphology and element distribution of the active coke sample; analyzing the phase composition of the active focal sample by adopting an X-ray diffractometer; analyzing the active focal surface functional groups by an infrared spectrometer; pretreating an active coke sample by adopting an electrothermal constant-temperature drying box; screening an active coke sample meeting the detection requirement by using a vibrating screen machine; the wear-resisting strength of the active coke sample is measured by a wear-resisting strength tester; and (4) measuring the compressive strength of the active coke sample by using a compressive strength tester.
Preferably, the specific surface area of the activated coke sample is detected in the step 3), and the activated coke sample is detected by a detection device used in the BET method, wherein N is used2And (3) as an adsorbate, adsorbing at the liquid nitrogen temperature of-196 ℃ under the relative pressure of 0.001-1.0 Pa to obtain an adsorption/desorption isotherm, analyzing the adsorption/desorption isotherm, and calculating by using a BET (BET) model and a DFT (discrete Fourier transform) model to explain the pore structure parameters and the pore size distribution of the measured active coke sample. Among them, liquid nitrogen can be used as a deep refrigerant, because of its chemical inertness, it can directly contact with the active coke and immediately freeze without destroying the properties of the active coke, while the relative pressure (equilibrium pressure/saturated vapor pressure) can affect the result of the specific surface area of the active coke, and under different relative pressures, the specific surface area of the active coke sample is different, therefore, it is important to select a proper relative pressure.
Preferably, the active coke sample is dried at the temperature of 105-115 ℃ in a constant-temperature drying box, and the detection accuracy of the active coke sample under the condition is higher.
In the method for evaluating the desulfurization and denitrification performance of the active coke in the microwave field, the method comprises the following steps:
the method comprises the following steps of putting an active coke sample in microwave equipment, starting gas mixing equipment, introducing mixed gas into the microwave equipment through a gas inlet, measuring outlet gas concentration by using gas analysis equipment, calculating the desulfurization and denitrification rate of the active coke, and preliminarily discussing the desulfurization and denitrification performance of the active coke.
And respectively analyzing the pore structure parameters and the pore size distribution of the active coke original sample, the primary adsorption tower, the secondary adsorption tower and the desorption tower active coke sample by using a specific surface area and pore size analyzer.
And respectively analyzing the sections of the active coke samples of the active coke original sample, the first-stage adsorption tower, the second-stage adsorption tower and the desorption tower by using a scanning electron microscope, and observing the surface microstructures of different active coke samples.
And respectively analyzing the phase compositions of the active coke samples of the active coke original sample, the first-order adsorption tower, the second-order adsorption tower and the desorption tower by using an X-ray diffractometer.
And respectively analyzing the surface functional groups of the active coke original sample, the first-stage adsorption tower, the second-stage adsorption tower and the analysis tower active coke sample by using an infrared spectrometer, and exploring the surface functional groups beneficial to desulfurization and denitrification.
And (4) performing baseline correction on the spectrogram by using an infrared spectrum analyzer and specific analysis software.
And analyzing the particle size distribution of the active coke sample of the active coke original sample, the primary adsorption tower, the secondary adsorption tower and the desorption tower by using a vibrating screen, and exploring the particle size distribution of the active coke with the best desulfurization and denitrification performance.
And (3) researching the wear-resisting strength of the active coke which accords with the actual production by using a wear-resisting strength analyzer to analyze the wear-resisting strength of the active coke sample of the active coke original shape, the first-stage adsorption tower, the second-stage adsorption tower and the desorption tower.
And (3) exploring the pressure-resistant strength of the active coke conforming to the actual production by utilizing a pressure-resistant strength analyzer to analyze the pressure-resistant strength of the active coke sample of the active coke original sample, the first-stage adsorption tower, the second-stage adsorption tower and the desorption tower.
And (3) detecting the macro parameters of the activated coke in different procedures (original sample, first-stage adsorption tower, second-stage adsorption tower and desorption tower), such as bulk density, desulfurization value, denitration rate, ignition point and the like, exploring the optimal macro parameters of the activated coke, and providing reasonable performance indexes of the activated coke for actual production.
The device for the method for evaluating the desulfurization and denitrification performance of the activated coke comprises the following steps: a gas distribution device provided with N2And SO2a/NO mixed gas cylinder which is respectively connected with a gas pipe and is provided with a gas which can be adjustedThe gas distribution cabinet is provided with a gas outlet pipeline; a microwave device, comprising: the body is of a box body structure, and two side surfaces of the body are symmetrically provided with mounting through holes; the microwave magnetrons are wrapped with wires and symmetrically arranged on two sides in the body; the microwave magnetron converts electric energy into microwave energy, and the generated microwave is absorbed by the reaction cavity, so that a stable and continuous heating working environment is provided for experiments; the reaction cavity consists of a heating cavity, a microwave cavity and a mixed heating cavity which are nested from outside to inside, and the reaction cavity is arranged in the center of the body; the heating cavity is made of 304 stainless steel, and the outer layer of the heating cavity is wrapped by a resistance wire; the microwave cavity is filled with graphite materials, and the outer layer of the microwave cavity is wrapped by glass wool; the cavity of the mixed heating cavity is filled with graphite materials, and the outer layer of the cavity of the mixed heating cavity is wrapped by resistance wires; the quartz reactor is a transparent quartz glass tube, the middle part of the quartz reactor is arranged in the cavity of the mixing heating cavity of the reaction cavity in the body in a penetrating way, two ends of the quartz reactor penetrate through the mounting through holes on the two side surfaces of the body, and two ends of the quartz reactor are sealed by connecting flanges; a connecting flange at one end of the quartz reactor is provided with a connecting pipeline which is connected to an air outlet pipeline of the air distribution device; the inlet of the gas analysis equipment is connected with the other end of the quartz reactor through a pipeline and is connected with a flange; and the temperature thermocouple is arranged on the quartz reactor.
Further comprises a specific surface area and aperture analyzer BET, a scanning electron microscope SEM, an X-ray diffractometer XRD, an infrared spectrum analyzer FTIR, an electrothermal constant-temperature drying box, a vibrating screen machine, a wear-resistant strength tester or a compressive strength tester.
The device comprises gas distribution equipment, microwave equipment, gas analysis equipment, a specific surface area and pore size analyzer (BET), a Scanning Electron Microscope (SEM), an X-ray diffractometer (XRD), an infrared spectrum analyzer (FTIR), an electrothermal constant-temperature drying box, a vibrating screen machine, a wear-resistant strength tester and a compressive strength tester, wherein the microwave equipment comprises a heating cavity, a microwave cavity and a mixed heating cavity, can provide an excellent environment for desulfurization and denitrification of active coke, can simulate gas flow distribution and air tightness, and has microwave power (400-1000W) and reaction required by experimentsThe temperature (100-200 ℃) is adjustable, the parameter setting is controlled by a computer, the influence of human factors on the experimental conclusion can be effectively avoided, and the accuracy of the experimental conclusion is improved; n is a radical of2And SO2The gas/NO mixed gas can adjust the gas components and flow through gas distribution equipment; placing the quartz reactor filled with the active coke sample in microwave equipment, connecting the microwave equipment with gas analysis equipment, and analyzing the desulfurization and denitrification performance of the active coke; the specific surface area analyzer is used for detecting the specific surface area, micropore volume, pore size distribution and the like of the active coke sample; the scanning electron microscope device is used for observing the surface appearance, element distribution and the like of the active coke sample; the X-ray diffractometer is used for analyzing the phase composition of the active focal sample; the infrared spectrometer is used for analyzing the active focal surface functional groups; the electric heating constant-temperature drying box is used for pretreating the active coke sample; the vibrating screen machine is used for screening the active coke sample meeting the detection requirement; the wear-resistant strength tester is used for testing the wear-resistant strength of the active coke sample; the compressive strength tester is used for measuring the compressive strength of the activated coke sample.
Gas distribution equipment, microwave equipment and gas analysis equipment are introduced in the desulfurization and denitrification process of the active coke, and the desulfurization and denitrification performances of the active coke under different types and different conditions are explored.
And (3) carrying out online detection on key parameters such as the specific surface area, the micropore volume and the pore size distribution of the active coke sample by a BET device.
And detecting and analyzing the change characteristics of the surface topography of different active coke samples by using an SEM device.
And analyzing the composition of the phase structure of different active coke samples by an XRD device.
And detecting and analyzing the surface functional groups of different active coke samples by an FTIR device, and exploring the influence of the active coke surface functional groups on the desulfurization and denitrification performance of the active coke.
And testing and analyzing the performance indexes of the active coke sample by a compressive strength tester and a wear-resistant strength tester.
The evaluation method of the present invention is as follows:
(1) pretreatment of active coke sample
Weighing 40g of active coke sample, uniformly placing the active coke sample in a crucible, placing the crucible containing the active coke sample in the middle of microwave equipment, treating for 10min under the microwave power of 1000W, and pretreating the active coke sample to improve the desulfurization and denitrification performance of the active coke sample.
(2) Activated coke desulfurization and denitrification simulation experiment
And setting parameters according to the conditions required by the experiment, and carrying out the activated coke desulfurization and denitrification simulation experiment.
(3) BET detection
With N2And (3) as an adsorbate, adsorbing at the liquid nitrogen temperature of-196 ℃ and the relative pressure of 0.001-1.0 to obtain an adsorption/desorption isotherm, analyzing the adsorption/desorption isotherm, and calculating by using models such as BET (BET) and DFT (discrete Fourier transform) to explain the pore structure parameters and the pore size distribution of the measured active coke sample. Among them, liquid nitrogen can be used as a deep refrigerant, because of its chemical inertness, it can directly contact with the active coke and immediately freeze without destroying the properties of the active coke, while the relative pressure (equilibrium pressure/saturated vapor pressure) can affect the result of the specific surface area of the active coke, and under different relative pressures, the specific surface area of the active coke sample is different, therefore, it is important to select a proper relative pressure.
(4) SEM detection
And respectively analyzing the sections of the active coke samples of the active coke original sample, the first-stage adsorption tower, the second-stage adsorption tower and the desorption tower by using a scanning electron microscope, and observing the surface microstructures of different active coke samples.
(5) XRD detection
And respectively analyzing the phase compositions of the active coke samples of the active coke original sample, the first-order adsorption tower, the second-order adsorption tower and the desorption tower by using an X-ray diffractometer.
(6) FTIR detection
Selecting an infrared spectrum analyzer, and performing baseline correction processing on the spectrum by adopting software.
(7) Particle size distribution detection
The particle size distribution of the active coke is detected according to the requirements, and the optimal parameters are provided for the actual production.
(8) Abrasion resistance detection
The wear-resisting strength of the active coke is detected as required, and the optimal parameters are provided for actual production.
(9) Compressive strength detection
And the compressive strength of the activated coke is detected as required, so that the optimal parameters are provided for actual production.
(10) Detection of other Properties of activated Coke
And detecting macro parameters such as the bulk density, the desulfurization value, the denitration rate, the ignition point and the like of the active coke in different processes, exploring the optimal macro parameters of the active coke, and providing reasonable active coke performance indexes for actual production.
The reaction system adopted by the invention is a microwave reaction system, compared with the conventional reaction system, the microwave reaction system has obvious advantages, and the basic properties of the microwave are generally three characteristics of penetration, reflection and absorption.
(1) The microwave is used as a clean energy source, can realize the purpose of high-efficiency and uniform heating from inside to outside, and can excite molecular energy when acting on gas molecules.
(2) The microwave has the characteristics of instantaneity and penetrability, and the microwave device has successfully realized industrialization and is easier to be applied in the performance detection of the active coke.
(3) The microwave almost heats the inside and outside of the active coke sample at the same time to form the state of a body heat source, thereby greatly shortening the heat conduction time in the conventional heating, and when the condition is that the dielectric loss factor and the medium temperature are in a negative correlation relationship, the inside and outside of the material are uniformly heated.
(4) Microwave heating is characterized by selective heating. The heat effect produced is different from substance to substance.
(5) The microwave heats the medium material instantaneously, and the heating speed is high. The output power of the microwave can be adjusted at any time, the temperature rise of the medium can be changed without inertia, and the phenomenon of waste heat does not exist, thereby being greatly beneficial to the requirements of automatic control and continuous production.
(6) The low frequency electric waves do not change the internal structure of the active coke sample or destroy the bonds in the active coke sample.
The microwave system adopted by the invention comprises the heating cavity, the microwave cavity and the mixed heating cavity, so that an excellent environment can be provided for desulfurization and denitrification of the active coke, the air flow distribution and the air tightness can be simulated, the microwave power (400-1000W) and the reaction temperature (100-200 ℃) required by the experiment can be adjusted, the parameter setting is controlled by a computer, the influence of human factors on the experimental conclusion can be effectively avoided, and the accuracy of the experimental conclusion is improved.
In order to avoid the influence of single detection on the experimental conclusion and enable the conclusion to be more accurate, the detection system provided by the invention adopts a macroscopic and microscopic integrated system, and the integration is detected according to the structure parameters, the pore size distribution, the surface microscopic morphology, the phase composition, the surface functional groups, the particle size distribution, the compressive strength, the wear resistance, the stacking density, the ignition point, the desulfurization value and the denitration rate of the active coke, so that the performance of active coke samples in different processes can be accurately and visually reflected, and reasonable performance indexes are provided for actual production.
(1) Macroscopic examination and grading (routine examination)
(2) Microscopic examination (Innovation examination)
The experiment selects and analyzes a sample 1 (an active coke original shape, a primary adsorption tower, a secondary adsorption tower and an analytical tower) and a sample 2 (an active coke original shape, a primary adsorption tower, a secondary adsorption tower and an analytical tower), detects and analyzes active coke pore structure parameters (BET), pore size distribution, surface microstructure (SEM), phase composition (XRD) and functional groups (FTIR), and the larger the parameters such as total adsorption volume, specific surface area, micropore area, total pore volume and micropore pore volume are, the better the active coke performance is.
①BET
| Fail to be qualified | Qualified | Is excellent in | |
| Total adsorption volume (cm)3/g) | <6.52 | 6.52～41.18 | >41.18 |
| Specific surface area (cm)2/g) | <170 | 170～407 | >407 |
| Area of micropores (cm2/g) | <133 | 133～390 | >390 |
| Total pore volume (cm)3/g) | <0.1 | 0.1～0.26 | >0.26 |
| Pore volume (cm) of micropores3/g) | <0.05 | 0.05～0.17 | >0.17 |
②SEM、XRD、FTIR
The invention has the beneficial effects that:
1. the method can simulate the air flow distribution and the equipment tightness, so that the experiment is more accurate.
2. Experiment parameters are controllable, and the influence of experiment errors on the desulfurization and denitrification performance of the active coke is avoided.
3. The experimental process is controlled by a computer, so that the artificial error can be effectively avoided, and the desulfurization and denitrification performance of the reactive coke is accurate and efficient.
4. The method can record the gas discharge concentration in real time, so that the experiment is more convincing, and experimental data with higher accuracy are provided for related researches.
5. The detection and analysis of the performance of the active coke are rigorous and accurate, and the influence of detection errors on the desulfurization and denitrification performance of the active coke is avoided.
6. The desulfurization and denitrification performance of the activated coke is evaluated by analyzing and detecting the microscopic parameters and the macroscopic parameters of the activated coke samples before and after desulfurization and denitrification and in different processes, so that reasonable and accurate performance indexes are provided for actual production.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus used in the method for evaluating desulfurization and denitrification performance of activated coke according to the present invention.
Fig. 2 is a cross-sectional view of the microwave device of fig. 1.
FIG. 3 is SEM photograph 1 of an active coke sample in an embodiment of the present invention.
FIG. 4 is SEM electron micrograph 2 of an active coke sample in an example of the present invention.
FIG. 5 is an electron micrograph of an active coke sample (sample 1) in the example of the present invention.
FIG. 6 is an electron micrograph 1(20 μm) of the active coke (sample 1) of the first-stage adsorption column in the example of the present invention.
FIG. 7 is an electron micrograph 2(2 μm) of the active coke (sample 1) of the first-stage adsorption column in the example of the present invention.
FIG. 8 is an electron micrograph 3(2 μm) of the active coke (sample 1) of the first-stage adsorption column in the example of the present invention.
FIG. 9 is an electron micrograph of the active coke (sample 1) of the secondary adsorption tower in the example of the present invention.
FIG. 10 is an electron micrograph 1(20 μm) of an active coke (sample 1) of a resolving tower in an example of the present invention.
FIG. 11 is an electron micrograph 2(2 μm) of an active coke (sample 1) of a resolving tower in an example of the present invention.
FIG. 12 is an electron micrograph 2(2 μm) of an active coke (sample 1) of a resolving tower in an example of the present invention.
FIG. 13 is an electron micrograph 1 of an active coke sample (sample 2) in the example of the present invention.
FIG. 14 is an SEM 2 of a raw active coke (sample 2) in an example of the present invention.
FIG. 15 is an electron micrograph 1 of the active coke (sample 2) of the first-stage adsorption column in the example of the present invention.
FIG. 16 is an electron micrograph 2 of the active coke (sample 2) of the first-stage adsorption column in the example of the present invention.
FIG. 17 is an electron micrograph 1 of an active coke (sample 2) of the second-stage adsorption tower in the example of the present invention.
FIG. 18 is an electron micrograph 2 of the active coke (sample 2) of the second-stage adsorption column in the example of the present invention.
FIG. 19 is an electron micrograph 1 of an active coke (sample 2) of a resolving tower in an example of the present invention.
FIG. 20 is an electron micrograph 2 of an active coke (sample 2) of a resolving tower in an example of the present invention.
Fig. 21 is an XRD spectrum (sample 1) of the active coke as it is (a), the active coke of the first-stage adsorption column (b), the active coke of the second-stage adsorption column (c), and the active coke of the desorption column (d) in the example of the present invention.
FIG. 22 shows XRD patterns of active coke as it is (a) and active coke of a secondary adsorption tower in examples of the present invention (sample 2).
FIG. 23 shows the IR spectra of an active coke sample (sample 1) under different conditions in the examples of the present invention.
FIG. 24 is an infrared spectrum of an activated coke sample (sample 2) under various conditions in the example of the present invention.
Detailed Description
Referring to fig. 1 and fig. 2, the apparatus for the method for evaluating desulfurization and denitrification performance of activated coke according to the present invention comprises:
a gas distribution device 1 provided with N2And SO2NO mixingThe gas cylinders 11 and 12 are respectively connected to a gas distribution cabinet 13 which is provided with a gas distribution pipeline 14 and can adjust gas components and flow and monitor the gas components on line through gas pipelines;
a microwave device 2, comprising:
the body 21 is a box structure, and two side surfaces of the body are symmetrically provided with mounting through holes;
the reaction cavity 22 consists of a heating cavity 221, a microwave cavity 222 and a mixing heating cavity 223 which are nested from outside to inside, and the reaction cavity 22 is arranged in the center of the body 1; the heating cavity 221 is made of 304 stainless steel, and the outer layer of the heating cavity is wrapped by resistance wires; the microwave cavity 222 is filled with graphite materials, and the outer layer of the microwave cavity is wrapped by glass wool; the cavity of the mixing heating cavity 223 is filled with graphite materials, and the outer layer of the mixing heating cavity is wrapped by resistance wires;
the quartz reactor 23 is a transparent quartz glass tube, the middle part of the quartz reactor is arranged in the cavity of the mixing heating cavity 223 of the reaction cavity 22 in the body 1 in a penetrating way, two ends of the quartz reactor 23 penetrate through the mounting through holes on the two side surfaces of the body 1, and two ends of the quartz reactor 23 are sealed by connecting flanges; a connecting flange 231 at one end of the quartz reactor 23 is provided with a connecting pipeline connected to the gas outlet pipeline 14 of the gas distribution device 1;
the microwave magnetron 24 is wrapped with a lead, and the microwave magnetron 24 is symmetrically arranged on two sides in the body 1; the microwave magnetron 24 is connected with a power supply to convert electric energy into microwave energy, and the generated microwave is absorbed by the reaction cavity 22 to provide a stable and continuous heating working environment for experiments;
the inlet of the gas analysis device 3 is connected with the other end of the quartz reactor 23 through a pipeline and is connected with a flange 232;
the temperature thermocouple 4 is arranged on the quartz reactor 23;
and the display screen 5 (controller) is arranged on the body 1, and the microwave magnetron 24 and the temperature thermocouple 4 are electrically connected with the display screen 5.
Further comprises a specific surface area and aperture analyzer BET, a scanning electron microscope SEM, an X-ray diffractometer XRD, an infrared spectrum analyzer FTIR, an electrothermal constant-temperature drying box, a vibrating screen machine, a wear-resistant strength tester or a compressive strength tester.
The method for evaluating the desulfurization and denitrification performance of the active coke comprises the following steps:
1) placing a quartz reactor filled with an active coke sample in a reaction cavity in microwave equipment, wherein the reaction cavity consists of a heating cavity, a microwave cavity and a mixed heating cavity which are nested from outside to inside; the quartz reactor is provided with a gas inlet and a gas outlet, the gas inlet is connected with gas mixing equipment through a pipeline, and the gas outlet is connected with gas analysis equipment;
2) starting the microwave equipment to convert N2Mixed gas (10-13): 1 into a gas mixing apparatus, wherein N2The flow rate is 200-300 mL/min, the flow rate of the mixed gas is 20-30 mL/min, and the volume ratio of the components of the mixed gas is as follows: SO (SO)20.30-0.50% of NO, 0.10-0.30% of NO and the balance of argon; gas output from the gas mixing equipment is introduced into the quartz reactor through a gas inlet of the quartz reactor, and meanwhile, outlet gas concentration of a gas outlet of the quartz reactor is measured by using gas analysis equipment to analyze the desulfurization and denitrification performance of an active coke sample; the microwave power required by the microwave equipment experiment is 400-1000W, and the reaction temperature is 100-200 ℃;
3) performing at least one of the following detection on the active coke sample, including the detection of the specific surface area, the micropore volume and the pore size distribution of the active coke sample; observing the surface appearance and element distribution of the active coke sample; analyzing the phase composition of the active coke sample; for analysis of active coke surface functional groups; screening an active coke sample meeting the detection requirement; measuring the wear resistance of the active coke sample; and (4) measuring the compressive strength of the activated coke sample.
Preferably, in the step 3), a scanning electron microscope device is adopted to observe the surface morphology and element distribution of the active coke sample; analyzing the phase composition of the active focal sample by adopting an X-ray diffractometer; analyzing the active focal surface functional groups by an infrared spectrometer; pretreating an active coke sample by adopting an electrothermal constant-temperature drying box; screening an active coke sample meeting the detection requirement by using a vibrating screen machine; the wear-resisting strength of the active coke sample is measured by a wear-resisting strength tester; and (4) measuring the compressive strength of the active coke sample by using a compressive strength tester.
Preferably, the specific surface area of the activated coke sample is detected in the step 1), and the activated coke sample is detected by a detection device used in the BET method, wherein N is used2And (3) as an adsorbate, adsorbing at the liquid nitrogen temperature of-196 ℃ under the relative pressure of 0.001-1.0 Pa to obtain an adsorption/desorption isotherm, analyzing the adsorption/desorption isotherm, and calculating by using a BET (BET) model and a DFT (discrete Fourier transform) model to explain the pore structure parameters and the pore size distribution of the measured active coke sample.
Preferably, the detection equipment selects a VECTOR22 type Fourier transform infrared spectrum analyzer, and baseline correction processing is carried out on the spectrum by adopting infrared software OPUS 5.5; samples were prepared by the KBr tabletting method, and dried samples and KBr were pressed at a rate of 1: 120, grinding the mixture in an agate mortar, pouring the mixture powder into a tabletting mold, and pressing the mixture powder into a sheet with the thickness of 0.1-1 mm; the test conditions were flux 15000, and the sample was scanned 32 times while comparing 32 background scans of blank KBr to subtract out the effect of the background.
Preferably, the active coke sample is dried at the temperature of 105-115 ℃ in a constant-temperature drying box, and the detection accuracy of the active coke sample under the condition is higher.
Examples
In the experiment of the embodiment, a sample 1 (an active coke original shape, a primary adsorption tower, a secondary adsorption tower and an analytical tower) and a sample 2 (an active coke original shape, a primary adsorption tower, a secondary adsorption tower and an analytical tower) are selected and used for detecting and analyzing active coke pore structure parameters, pore size distribution, surface microstructures, phase compositions and functional groups.
The process is as follows:
1. pretreatment of active coke sample
Weighing 40g of active coke sample, uniformly placing the active coke sample in a crucible, placing the crucible containing the active coke sample in the middle of microwave equipment, treating for 10min under the microwave power of 1000W, and pretreating the active coke sample to improve the desulfurization and denitrification performance of the active coke sample.
2. Activated coke desulfurization and denitrification simulation experiment
And setting parameters according to the conditions required by the experiment, and carrying out the activated coke desulfurization and denitrification simulation experiment.
3. BET detection
Detecting the active coke samples before and after desulfurization and denitrification of the sample 1 and the sample 2 by adopting a BET (BET method and equipment) device, and adding N2And (3) as an adsorbate, adsorbing at the liquid nitrogen temperature of-196 ℃ under the relative pressure of 0.001-1.0 Pa to obtain an adsorption/desorption isotherm, analyzing the adsorption/desorption isotherm, and calculating by using models such as BET (BET) and DFT (discrete Fourier transform) to explain the pore structure parameters and the pore size distribution of the measured active coke sample.
4. SEM detection
And respectively analyzing the sections of the active coke samples of the active coke original sample, the first-stage adsorption tower, the second-stage adsorption tower and the desorption tower by using a scanning electron microscope, and observing the surface microstructures of different active coke samples.
5. XRD detection
And respectively analyzing the phase compositions of the active coke samples of the sample 1 and the sample 2, the primary adsorption tower, the secondary adsorption tower and the desorption tower by using an X-ray diffractometer.
6. FTIR detection
Selecting an infrared spectrum analyzer, and performing baseline correction processing on the spectrum by adopting software.
7. Analysis results
(1)BET
TABLE 1 comparison of total adsorption volume size for sample 1 and sample 2
| | Sample | 1 | |
| Activated coke specimen (cm)3/g) | 6.52 | 77.99 | |
| First-stage adsorption tower (cm)3/g) | 8.79 | 41.18 | |
| Second-stage adsorption tower (cm)3/g) | 13.23 | 78.09 | |
| Analytical tower (cm)3/g) | 14.60 | 78.91 |
TABLE 2 pore size parameters for the activated coke sample (sample 1)
TABLE 3 pore size parameters for the activated coke sample (sample 2)
Referring to fig. 3 to 20, an SEM of an active coke sample in the example of the present invention.
As can be seen from fig. 3 and 4, the original active coke has a well-developed surface pore structure, uneven pore distribution and irregular shape, and the macropores shown in the figure are mainly macropores, and the macropores shown in the figure are deeper, so that the diffusion of gas into the active coke is facilitated, and the retention time of gas molecules in the active coke is prolonged.
As can be seen from fig. 5, the surface of the activated coke sample is rough, pores are developed, and the activated coke sample is beneficial to promoting desulfurization and denitrification reactions.
As can be seen from FIGS. 6 to 8, the surface comparison of the active coke samples of the first-stage adsorption towerLeveling due to adsorbed SO2After, SO2The active coke is activated, the internal pore channel structure of the active coke is promoted to continue to develop, more micropores are generated, and the specific surface area and the pore volume of the active coke are further increased.
As can be seen from FIG. 9, the surface of the active coke sample of the secondary adsorption tower has a rich but uneven cellular pore structure, and the deeper pores are beneficial to improving the desulfurization and denitrification rate.
As can be seen from FIGS. 10 to 12, the surface of the active coke after desorption was smooth due to the adsorbed SO2The activated coke has activated pore structure to increase its microporous structure, but during the analysis, newly generated SO2When the active coke pore channel is corroded, part of the pore channel structure is damaged, so that the increment of micropores is lower than the newly generated macropore and mesopore, and the phenomenon can be proved by the change of the specific surface area, the total pore volume and the micropore volume in the active coke pore diameter parameter.
As can be seen from fig. 13 and 14, the surface of the active coke sample is rough, white crystalline substances appear, and the active coke surface has no traces of burning or etching.
As can be seen from fig. 15 and 16, white crystalline substances appeared in the active coke of the first-stage adsorption tower, and the surface of the active coke was rough and uneven.
As can be seen from fig. 17 and 18, after the reaction, white crystalline substances appear in the activated coke, and the surface of the surrounding activated coke is flat and has no burning or etching traces.
As can be seen from fig. 19 and 20, the surface of the active coke after the analysis is smooth, because the dust, dioxin, and the like adsorbed on the surface of the active coke are eluted during the analysis, and the blocked pore structure is exposed again. The white crystalline material on the surface was substantially disappeared, indicating that SO was adsorbed during the desorption process2Is converted into other substances and then desorbed and separated out.
Referring to fig. 21 and 22, the XRD patterns of the active coke samples in the examples of the present invention. Fig. 21 shows XRD spectra of the active coke as is (a), the active coke of the first-stage adsorption column (b), the active coke of the second-stage adsorption column (c), and the active coke of the desorption column (d) in the example of the present invention (sample 1). FIG. 22 shows XRD patterns of active coke as it is (a) and active coke of a secondary adsorption tower in examples of the present invention (sample 2).
As can be seen from fig. 21, the activated coke as it is mainly exists in the phase structure of C, and the characteristic peak intensity of C gradually decreases as the desulfurization and denitrification reaction of the activated coke proceeds, and the characteristic peak intensity of C becomes the lowest in the activated coke (d) in the analytical tower. Compared with the active coke original shape (a), the phase structures of CaO in the active coke (d) of the first-stage adsorption tower (b), the second-stage adsorption tower (c) and the desorption tower disappear, and CaSO appears4Novel phase structure. In the active coke (d) of the desorption tower, CaSO is contained in the desorbed active coke4The phase structure does not disappear, and the phase structure remains in the pore channels of the active coke and is attached to a part of the adsorption active sites, so that the adsorption effect of the active coke after analysis is influenced.
In FIG. 22, (a) the main characteristic peaks are C, CaO and Fe2O3Presence of C and CaO to SO2And NO plays a role in oxidation absorption. As can be seen from (b), CaSO appeared4、CaCO3、Fe(NO3)3And a new phase structure of CaS.
Referring to fig. 23, fig. 24, active focal sample FTIR in the embodiment of the present invention. FIG. 23 is an infrared spectrum of an active coke sample (sample 1) under different conditions in the example of the present invention. FIG. 24 is an infrared spectrum of an activated coke sample (sample 2) under various conditions in the example of the present invention.
As can be seen from FIG. 23, in the infrared spectra of the active coke sample (sample 1) under 4 conditions, the absorption peak position was 3459cm-1Chemical functional groups such as corresponding alcohol, carboxylic acid, phenols and the like are not beneficial to desulfurization and denitrification; at 1612cm-1The peak corresponding to C ═ C, C ═ O and other stretching vibration peaks, and related to carboxylic acid, the characteristic peak here shows acidity, and SO is adsorbed to active coke2Adverse effects are produced; at 1115cm-1The C-O stretching vibration peak of the corresponding ether is treated to ensure that the surface functional group of the active coke sample is alkaline, and the improvement of the surface alkaline functional group of the active coke is beneficial to the SO treatment2Absorption of (2).
As can be seen from FIG. 24, the active coke sample (sample 2) under 4 conditions is infraredIn the spectrogram, the position of the characteristic peak is mainly concentrated on 672cm wave number-1、1065cm-1、1522cm-1、1639cm-1、3435cm-1And 3737cm-1The functional groups of the active coke surface corresponding to the 6 characteristic peaks are respectively: methylene (-CH)2) Ether-oxygen bonds (C-O), double bonds (C-C, C ═ O), aliphatic amides (CO-N), phenolic or alcoholic hydroxyl groups (-OH), and free O-H bonds (-OH), wherein ether-oxygen bonds (C-O), double bonds (C-C, C ═ O), aliphatic amides (CO-N), free O-H bonds (-OH) are beneficial for desulfurization and denitrification, and phenolic or alcoholic hydroxyl groups (-OH) are not beneficial for desulfurization and denitrification.
The method combines macroscopic detection and microscopic detection, compared with the conventional macroscopic detection, the microscopic detection can analyze the information of the surface pore structure, the component composition, the internal atomic or molecular structure or form, the microstructure, the functional group and the like of the active coke sample, and the active coke sample with excellent performance can be selected more carefully, intuitively and accurately for practical production.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The method for evaluating the desulfurization and denitrification performance of the activated coke is characterized by comprising the following steps of:
1) placing a quartz reactor filled with an active coke sample in a reaction cavity in microwave equipment, wherein the reaction cavity consists of a heating cavity, a microwave cavity and a mixed heating cavity which are nested from outside to inside; the quartz reactor is provided with a gas inlet and a gas outlet, the gas inlet is connected with gas mixing equipment through a pipeline, and the gas outlet is connected with gas analysis equipment;
2) starting the microwave equipment to convert N2Mixed gas (10-13): 1 into a gas mixing apparatus, wherein N2The flow rate is 200-300 mL/min, the flow rate of the mixed gas is 20-30 mL/min, and the volume ratio of the components of the mixed gas is as follows: SO (SO)2 0.30～0.50 percent of NO, 0.10-0.30 percent of NO and the balance of argon; gas output from the gas mixing equipment is introduced into the quartz reactor through a gas inlet of the quartz reactor, and meanwhile, outlet gas concentration of a gas outlet of the quartz reactor is measured by using gas analysis equipment to analyze the desulfurization and denitrification performance of an active coke sample; the microwave power required by the microwave equipment experiment is 400-1000W, and the reaction temperature is 100-200 ℃;
3) performing the following detection on the active coke sample, including the detection of the specific surface area, the micropore volume and the pore size distribution of the active coke sample; analyzing the phase composition of the active coke sample; the activated coke samples were analyzed for surface functional groups.
2. The method for evaluating the desulfurization and denitrification performance of the activated coke according to claim 1, wherein the step 3) further comprises observing the surface morphology and element distribution of the activated coke sample, detecting and screening the activated coke sample meeting the detection requirements, determining the wear resistance of the activated coke sample, and determining the compressive strength of the activated coke sample.
3. The method for evaluating the desulfurization and denitrification performance of the activated coke according to claim 1 or2, wherein in the step 3), a scanning electron microscope device is used for observing the surface morphology and the element distribution of the activated coke sample; analyzing the phase composition of the active focal sample by adopting an X-ray diffractometer; analyzing the surface functional groups of the active coke sample by using an infrared spectrometer; pretreating an active coke sample by adopting an electrothermal constant-temperature drying box; screening an active coke sample meeting the detection requirement by using a vibrating screen machine; the wear-resisting strength of the active coke sample is measured by a wear-resisting strength tester; and (4) measuring the compressive strength of the active coke sample by using a compressive strength tester.
4. The method for evaluating the desulfurization and denitrification performances of the activated coke according to claim 1, wherein the specific surface area of the activated coke sample is measured in the step 3), and the activated coke sample is measured by a BET method using a measuring device, wherein N is used as N2As adsorbate, adsorbing at liquid nitrogen temperature-196 deg.C under relative pressure of 0.001-1.0 Pa to obtain adsorption/desorptionAnd (3) an isotherm, which is used for explaining the pore structure parameters and the pore size distribution of the measured active coke sample by analyzing the adsorption/desorption isotherm and utilizing BET and DFT model calculation.
5. The method for evaluating the desulfurization and denitrification performance of the activated coke as claimed in claim 1, wherein the activated coke sample is the activated coke dried in a constant temperature drying oven at 105-115 ℃.
6. An apparatus for use in the method of evaluating desulfurization and denitrification performance of activated coke according to claim 1, comprising:
a gas distribution device provided with N2And SO2The gas/NO mixed gas cylinder is respectively connected with a gas distribution cabinet which can adjust gas components and flow and carry out on-line monitoring on the gas components through gas pipelines, and the gas distribution cabinet is provided with a gas outlet pipeline;
a microwave device, comprising:
the body is of a box body structure, and two side surfaces of the body are symmetrically provided with mounting through holes;
the microwave magnetrons are wrapped with wires and symmetrically arranged on two sides in the body;
the reaction cavity consists of a heating cavity, a microwave cavity and a mixed heating cavity which are nested from outside to inside, and the reaction cavity is arranged in the center of the body; the heating cavity is made of 304 stainless steel, and the outer layer of the heating cavity is wrapped by a resistance wire; the microwave cavity is filled with graphite materials, and the outer layer of the microwave cavity is wrapped by glass wool; the cavity of the mixed heating cavity is filled with graphite materials, and the outer layer of the cavity of the mixed heating cavity is wrapped by resistance wires;
the quartz reactor is a transparent quartz glass tube, the middle part of the quartz reactor is arranged in the cavity of the mixing heating cavity of the reaction cavity in the body in a penetrating way, two ends of the quartz reactor penetrate through the mounting through holes on the two side surfaces of the body, and two ends of the quartz reactor are sealed by connecting flanges; a connecting flange at one end of the quartz reactor is provided with a connecting pipeline which is connected to an air outlet pipeline of the air distribution device; the inlet of the gas analysis equipment is connected with the other end of the quartz reactor through a pipeline and is connected with a flange;
and the temperature thermocouple is arranged on the quartz reactor.
7. The apparatus of claim 6, further comprising a specific surface area and pore size analyzer BET, scanning electron microscope SEM, X-ray diffractometer XRD, infrared spectrometer FTIR, oven, sieve shaker, abrasion resistance tester, or compressive strength tester.
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