Flue gas adsorption desulfurization evaluation device and method

Abstract

The invention discloses a flue gas adsorption desulfurization evaluation device and method, and relates to the technical field of sulfur-containing waste gas treatment, the flue gas adsorption desulfurization evaluation device comprises a reaction system, a water supply system, a gas supply system and a reaction system, the reaction system comprises an electric heating box, a plurality of groups of electric heaters are arranged in the electric heating box, reactors are arranged among the plurality of groups of electric heaters, and the reactors are arranged in the electric heating box. The water supply system can add water into the reaction system, the gas supply system can add gas into the reaction system and is communicated with the flue gas analyzer, and the tail gas treatment system receives and treats gas output by the flue gas analyzer and the reactor. The invention further provides a flue gas adsorption desulfurization evaluation method, the performance of the adsorbent is rapidly and conveniently evaluated, the adsorption performance of the adsorbent can be evaluated, the regeneration performance of the adsorbent can also be evaluated, and therefore support is provided for research and development of the adsorbent.

Description

Technical Field

[0001] The present invention relates to the technical field of sulfur-containing waste gas treatment, and in particular to a flue gas adsorption desulfurization evaluation device and method. Background Art

[0002] In recent years, as people's environmental awareness has increased, my country's environmental laws and regulations have become increasingly stringent. In 2015, my country issued a new pollutant emission standard, "Petroleum Refining Industry Pollutant Emission Standard (GB31570-2015)", which stipulates that the special emission limit of SO2 from process heating furnace flue gas is 50mg / Nm 3 The emission limit of catalytic cracking catalyst regeneration flue gas is 100mg / Nm 3 The SO2 special emission concentration limit of the flue gas from the sulfur recovery unit is 100 mg / Nm 3 The following; and sulfur tail gas SO2 emissions are also one of the important indicators in the total pollutant verification and accounting of the Ministry of Environmental Protection. It can be seen that my country's requirements for flue gas SO2 emissions are becoming increasingly stringent. Flue gas SO2 emissions have become a major bottleneck in the development of various industries.

[0003] At present, flue gas desulfurization technologies at home and abroad are mainly divided into two categories. The first is wet desulfurization, which uses a certain liquid absorbent to treat the exhaust gas; the second is dry desulfurization, which uses powdered or granular adsorbents or absorbents to remove SO2 from flue gas. At present, flue gas desulfurization in my country basically adopts technologies introduced from abroad, and these technologies are mainly wet methods. The most representative and fastest-growing wet desulfurization technology is alkaline washing desulfurization, such as DuPont TM LABSORB from BELCO TM If the flue gas post-alkali washing wet desulfurization technology is adopted, 50mg / Nm 3 The following is a lower emission, but this type of process produces new secondary pollutants - sodium sulfate-containing wastewater, which cannot be discharged directly and requires huge investment in the reprocessing process. Dry flue gas desulfurization has developed rapidly in recent years due to its simple operation, low equipment investment, and no secondary pollution. It is considered to be the most promising desulfurization process. Therefore, in recent years, the research and development of dry flue gas desulfurization technology has received widespread attention at home and abroad.

[0004] Dry flue gas desulfurization uses special adsorbents to remove SO2 from flue gas, so the core of dry flue gas desulfurization lies in high-performance adsorbents. The two key indicators of adsorbents are adsorption sulfur capacity and regeneration performance. A good adsorbent should have a high sulfur capacity and good regeneration performance. However, there is currently little research on adsorbents at home and abroad, and there is no good adsorbent evaluation device and method, which makes it impossible to quickly and accurately evaluate the performance of adsorbents, thus hindering the development of high-performance adsorbents.

[0005] Patent CN102565287A discloses a device for evaluating flue gas pollutant adsorbents and its application, including a simulated flue gas cylinder carrying pollutants, a mercury-carrying gas cylinder, a mercury vapor generator, a mass flow meter A, a mass flow meter B, a gas mixing tank, a two-way valve, a mercury form conversion device, a mercury analyzer, a computer, an exhaust gas treatment device and a fixed bed. The invention uses a method that can convert SO2, NO2, and NH3 into a fixed bed at a certain temperature. x The relevant pollutants such as SO2 and Hg0 are adsorbed by the adsorbent therein, so as to conveniently and quickly evaluate the adsorption effect of the adsorbent. It can be seen that the invention cannot evaluate the adsorption of SO2 alone, and it is also impossible to evaluate the regeneration performance of the adsorbent.

[0006] Patent CN108279182B discloses a gas adsorbent evaluation device, which is mainly composed of three parts: a gas supply system, a test system, and an exhaust system. The device discloses a gas adsorbent evaluation device. The test device combines the dynamic adsorption analysis method and the static analysis method well, achieving the purpose of multiple uses of one picture; the dynamic adsorption test of the adsorbent is realized through the control of the mass flow meter and the detection of the gas chromatograph, and the static method test is realized by closing the needle valve and the pressure test table and the temperature test table. The adsorption performance of the adsorbent at different temperatures can be tested by a constant temperature water bath, and the desorption test of the adsorbent can be realized by using a vacuum pump, that is, the regeneration of the adsorbent can be detected. The device is complicated to operate and is mainly used for the evaluation of CO2 adsorption. It uses conventional chromatography for detection and cannot realize continuous online analysis of gas components; in addition, the device uses a vacuum pump for regeneration test, which is suitable for physical adsorption, but not for flue gas desulfurization adsorbents with chemical adsorption.

[0007] Therefore, those skilled in the art provide a flue gas adsorption desulfurization evaluation method and device to solve the problems raised in the above background technology. Summary of the invention

[0008] The present invention provides a flue gas adsorption desulfurization evaluation device and method for quickly and conveniently evaluating the performance of an adsorbent, which can evaluate both the adsorption performance and the regeneration performance of the adsorbent, thereby providing support for the research and development of the adsorbent.

[0009] In order to achieve the above object, the present invention provides the following technical solutions:

[0010] The present invention first provides a flue gas adsorption desulfurization evaluation device, comprising:

[0011] A reaction system, the reaction system comprising an electric heating box, a plurality of groups of electric heaters are arranged inside the electric heating box, and a reactor is arranged between the plurality of groups of electric heaters;

[0012] a water supply system capable of adding water to the reaction system;

[0013] A gas supply system, which can add gas to the reaction system and is connected to the flue gas analyzer;

[0014] The tail gas treatment system receives the output gas from the flue gas analyzer and the reactor and performs treatment.

[0015] Furthermore, the water supply system includes a water storage tank, a water outlet end of the water storage tank is connected to one end of the preheater through a pipeline, and the other end of the preheater is connected to the inlet end of the reactor through a pipeline.

[0016] Furthermore, the gas supply system includes multiple groups of gas supply pipelines, and the gas outlet ends of the multiple groups of gas supply pipelines are connected to the gas inlet end of a mixer, and the gas outlet end of the mixer is connected to the gas preheater, the flue gas analyzer and the gas inlet end of the collector.

[0017] Furthermore, the gas outlet end of the gas preheater is connected to the gas inlet end of the flue gas analyzer and the reactor respectively, and the gas inlet end of the flue gas analyzer is also connected to the gas outlet end of the reactor;

[0018] Furthermore, the gas supply line includes a gas source, which is connected to the gas inlet end of the mixer through a gas transmission pipeline. A pressure reducing valve, a filter, a mass flow meter and a one-way valve are installed on the gas transmission pipeline in sequence, and the one-way valve is arranged close to the mixer.

[0019] Furthermore, the tail gas treatment system comprises an alkali solution absorption tank, the air inlet end of the alkali solution absorption tank is connected to the air outlet end of the buffer tank, and the air inlet end of the buffer tank is connected to the air outlet end of the flue gas analyzer;

[0020] Furthermore, the exhaust gas treatment system also includes a collector, the feed end of the collector is connected to the discharge end of the reactor through a pipeline, the discharge end of the collector is connected to the feed end of the gas-liquid separation tank through a pipeline, and the gas outlet end of the gas-liquid separation tank is connected to the gas inlet end of the flue gas analyzer and the buffer tank through a pipeline.

[0021] The present invention also provides a flue gas adsorption desulfurization evaluation method, comprising:

[0022] Step 1: Grind the adsorbent and sieve it. Put the sieved adsorbent into an oven to dry. After drying, move the adsorbent into a drying dish to cool. Take a certain amount of adsorbent and weigh its mass as m1.

[0023] Step 2: Load the weighed adsorbent into the reactor, place the reactor in an electric heating box, and connect the inlet and outlet pipelines and thermocouples;

[0024] Step 3: Connect nitrogen to purge the reactor. After the purge is completed, start the adsorption performance evaluation of the adsorbent according to the evaluation conditions. Turn on the power of the electric heating box to heat the adsorbent. Before the adsorbent is heated to a temperature close to the reaction temperature, turn on the gas preheater and set the gas volume according to the reaction requirements. The mixed gas in the mixer enters the gas preheater for preheating. When the adsorbent and the mixed gas are heated to the reaction temperature, the mixed gas is introduced into the reactor. At the same time, the water inlet of the preheater is turned on to start the adsorption evaluation, and the reaction start time t1 is recorded;

[0025] Step 4: Use a flue gas analyzer to conduct real-time analysis of the exhaust gas composition and determine the adsorbent breakthrough or saturated sulfur capacity based on evaluation needs.

[0026] Furthermore, the adsorbent breakthrough sulfur capacity is measured: when SO2 gas appears in the tail gas at the reactor outlet, the adsorbent is considered to have reached the breakthrough sulfur capacity, and the reaction end time t2 is recorded. The breakthrough sulfur capacity of the adsorbent is:

[0027]

[0028] Where V is the total flow rate of the reaction gas, L / min

[0029] t1, t2 are the start and end time of the reaction, min;

[0030] C0 is the volume concentration of SO2 in the reaction raw gas;

[0031] m1 is the adsorbent loading mass in the reactor, g.

[0032] Further, the saturated sulfur capacity of the adsorbent is determined as follows: when the SO2 concentration at the reactor outlet is consistent with the SO2 concentration in the feed gas, the adsorbent is considered to have reached the saturated sulfur capacity. The saturated sulfur capacity is calculated by either of the following two methods:

[0033] Chemical analysis: After the adsorption evaluation is completed, part of the adsorbent is unloaded and the sulfur content in the adsorbent is determined by chemical analysis method.

[0034] Integral calculation: After the adsorption evaluation is completed, the flue gas analyzer data is exported and plotted with the adsorption time as the horizontal axis and the SO2 content in the outlet gas as the vertical axis. The SO2 content in the feed gas is the parallel line to the X-axis. The area between the curve and the inlet content line is the adsorbent sulfur capacity.

[0035] Right now

[0036] Where V is the total flow rate of the reaction gas, L / min

[0037] t1, t2 are the start and end time of the reaction, min;

[0038] C0 is the volume concentration of SO2 in the reaction raw gas;

[0039] C t is the volume concentration of SO2 in the outlet gas at time t;

[0040] m1 is the adsorbent loading mass in the reactor, g.

[0041] Furthermore, after the adsorbent reaches breakthrough or saturated sulfur capacity, the regeneration performance can be evaluated, and the specific method is as follows:

[0042] Step 1: Shut down the raw gas, set the regeneration gas volume according to the regeneration conditions, start the gas preheater to preheat the regeneration gas, and start the two sets of reactor electric heaters to heat the adsorbent. After heating to the regeneration temperature, the regeneration gas is introduced into the reactor, and the gas intake time t1 is recorded. At the same time, the flue gas analyzer records the SO2 content in the regeneration gas in real time;

[0043] Step 2: When the SO2 content in the regenerated gas is lower than a certain value, the regeneration is considered to be completed, and the end time t2 is recorded. The regeneration desulfurization amount is compared with the adsorbent sulfur absorption amount to obtain the adsorbent regeneration rate Y:

[0044]

[0045] In the formula, S 再 —Desulfurization amount of adsorbent regeneration, g;

[0046] S 吸 —Sulfur content absorbed by the adsorbent, i.e., sulfur content adsorbed at breakthrough or saturation, g;

[0047] The regeneration desulfurization amount is calculated by the integral method, and the specific method is as follows:

[0048] After the regeneration evaluation is completed, the flue gas analyzer data is exported and plotted with the regeneration time as the horizontal axis and the SO2 content in the outlet gas as the vertical axis. The area between the curve and the X-axis is the adsorbent regeneration desulfurization amount, that is,

[0049] Where, V is the total flow rate of reaction gas, L / min;

[0050] t1, t2 are the start and end time of the reaction, min;

[0051] C0 is the volume concentration of SO2 in the reaction raw gas;

[0052] C t is the volume concentration of SO2 in the outlet gas at time t.

[0053] In the above technical solution, the present invention provides a flue gas adsorption desulfurization evaluation device and method, which has the following beneficial effects:

[0054] 1. It can quickly and conveniently evaluate the performance of the adsorbent, which can evaluate both the adsorption performance and the regeneration performance of the adsorbent, thus providing support for the research and development of the adsorbent;

[0055] 2. The integral method is used to quickly analyze the sulfur capacity and regeneration performance of the adsorbent. The flue gas online instrument is used to analyze the exhaust gas composition. The exhaust gas composition can be monitored in real time, which is helpful to accurately evaluate the adsorption and regeneration performance of the adsorbent, and the sulfur capacity and regeneration degree of the adsorbent can be quickly calculated.

[0056] 3. Adding a buffer tank between the flue gas analyzer and the alkali solution absorption tank can effectively prevent the alkali solution from backflow and causing blockage and corrosion of the analyzer.

[0057] 4. A gas preheater can be set up to flexibly preheat the gas as needed, which helps to accurately evaluate the initial adsorption and regeneration performance of the adsorbent.

[0058] 5. Multiple groups of reactor heaters are set up to achieve rapid heating of the adsorbent.

[0059] 6. Provide a simple and reliable calculation method for evaluating the sulfur capacity of adsorbents, which can accurately evaluate the adsorption performance of adsorbents.

[0060] 7. Provide a simple and easy adsorbent regeneration method and regeneration performance evaluation method, which is accurate and reliable. BRIEF DESCRIPTION OF THE DRAWINGS

[0061] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can also be obtained based on these drawings.

[0062] Figure 1 A schematic diagram of the structure of a flue gas adsorption desulfurization evaluation device provided by an embodiment of the present invention;

[0063] Figure 2 The integral of the regeneration desulfurization amount curve in the flue gas adsorption desulfurization evaluation method provided in Example 1 of the present invention;

[0064] Figure 3 A saturated sulfur capacity integral curve in a flue gas adsorption desulfurization evaluation method provided in Example 4 of the present invention;

[0065] In the figure:

[0066] 10. Electric heating box; 11. Electric heater; 12. Reactor;

[0067] 20. Water storage tank; 21. Preheater;

[0068] 30. Mixer;

[0069] 40. Gas preheater;

[0070] 50. Flue gas analyzer;

[0071] 60. Gas source; 61. Pressure reducing valve; 62. Filter; 63. Mass flow meter; 64. Check valve;

[0072] 70. Alkali solution absorption tank; 71. Buffer tank; 72. Collector; 73. Gas-liquid separation tank. DETAILED DESCRIPTION

[0073] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention will be further described in detail below with reference to the accompanying drawings.

[0074] See also Figure 1 As shown;

[0075] A flue gas adsorption desulfurization evaluation device according to an embodiment of the present invention comprises:

[0076] A reaction system, wherein the reaction system comprises a plurality of electric heating boxes 10, wherein a plurality of electric heaters 11 are arranged inside the electric heating boxes 10, and a reactor 12 is arranged between the plurality of electric heaters 11 for evaluating the adsorption and regeneration performance of the adsorbent, and the internal temperature of the electric heaters 11 and the reactor 12 is controlled by a temperature controller (TIC);

[0077] A water supply system, the water supply system comprises a water storage tank 20, the water outlet end of the water storage tank 20 is connected to one end of a preheater 21 through a pipeline, and the other end of the preheater 21 is connected to the inlet end of the reactor 12 through a pipeline; the water supply system can add water to the reactor 12 by pumping or by nitrogen, and the water can enter the reactor 12 in liquid form or in gaseous form after being vaporized in the preheater;

[0078] A gas supply system, wherein the gas supply system comprises a plurality of gas supply pipelines, wherein the gas outlet ends of the plurality of gas supply pipelines are all connected to the gas inlet end of a mixer 30, wherein the gas outlet end of the mixer 30 is connected to the gas preheater 40, the flue gas analyzer 50 and the gas inlet end of the collector 72, wherein the gas outlet end of the gas preheater 40 is respectively connected to the gas inlet end of the flue gas analyzer 50 and the reactor 12, and the gas inlet end of the flue gas analyzer 50 is also connected to the gas outlet end of the reactor 12; the gas preheater 40 is preferably a tubular electric heating furnace, which is mainly used for heating the mixed gas, on the one hand as auxiliary heating of the reaction system, and on the other hand, it can be preheated separately from the adsorbent when evaluating the adsorbent performance, which is helpful for evaluating the initial adsorption and regeneration performance of the adsorbent;

[0079] The tail gas treatment system receives the flue gas analyzer 50 and the output gas of the reactor 12 and processes it. The flue gas analyzer 50 is used for real-time analysis of the inlet raw gas and the post-reaction gas components.

[0080] The present application can use a separate gas preheater 40 and multiple groups of electric heaters 11. The multiple groups of electric heaters are connected in parallel to achieve separate heating of the mixed gas and the adsorbent. On the one hand, it can make up for the lack of heating capacity of the heating system of the reactor 12, and can evaluate the regeneration performance at a higher temperature. On the other hand, it can quickly heat the adsorbent to evaluate the initial adsorption and regeneration performance of the adsorbent. In the adsorbent evaluation equipment of the prior art, only one group of electric heaters is used to heat the reaction system. During the adsorbent evaluation process, especially the adsorbent regeneration evaluation process, during the heating process of the adsorbent, part of the adsorbent is continuously regenerated, so it is impossible to accurately judge the effect of the regeneration temperature on the regeneration performance of the adsorbent. In the present invention, a separate mixed gas heater is set, and multiple groups of electric heaters are set, so that the gas can be preheated in advance, and the adsorbent can be quickly heated, so that the initial adsorbent regeneration performance of the adsorbent can be accurately judged.

[0081] The gas supply pipeline includes a gas source 60, which is connected to the gas inlet end of the mixer 30 through a gas pipeline. A pressure reducing valve 61, a filter 62, a mass flow meter 63 and a one-way valve 64 are installed in sequence on the gas pipeline. An air pressure indicator is installed on the end of the gas pipeline close to the gas source 60. Valves are respectively provided upstream and downstream of the mass flow meter 63. The gas pipeline between the two valves is connected in parallel with another gas pipeline. Another valve is provided on the other gas pipeline. The valve can be a ball valve or a one-way valve. The one-way valve 64 is provided close to the mixer 30.

[0082] The gas source 60 is SO2, O2, N2 or other gases.

[0083] The exhaust gas treatment system includes an alkali liquid absorption tank 70, the air inlet end of the alkali liquid absorption tank 70 is connected to the air outlet end of the buffer tank 71, and the air inlet end of the buffer tank 71 is connected to the air outlet end of the flue gas analyzer 50; the feed end of the collector 72 is connected to the discharge end of the reactor 12 through a pipeline, the discharge end of the collector 72 is connected to the feed end of the gas-liquid separation tank 73 through a pipeline, and the air outlet end of the gas-liquid separation tank 73 is connected to the air inlet ends of the flue gas analyzer 50 and the buffer tank 71 through a pipeline.

[0084] The buffer tank 71 is provided between the flue gas analyzer 50 and the alkali solution absorption tank 70 of the present application, which can effectively prevent the backflow of alkali solution and prevent the clogging and corrosion of the flue gas analyzer 50. The flue gas analyzer 50 has a certain suction force, and the backflow of alkali solution is very likely to occur during use. The buffer tank 71 is provided to effectively prevent the backflow of alkali solution into the flue gas analyzer 50, and the use effect of the flue gas analyzer can be guaranteed.

[0085] During specific operation, each gas enters the filter 62 after being decompressed by the pressure reducing valve 61 to filter out dust and impurities in the gas. A ball valve or a stop valve is connected to the filter 62, and a mass flow meter 63 is connected to the ball valve or the stop valve. The mass flow meter 63 accurately controls the flow of each gas. A check valve is connected to the mass flow meter 63 to prevent gas backflow. Each gas is collected in the mixer 30 after passing through the check valve. The gas coming out of the mixer 30 is divided into three paths. The first path is directly transported to the flue gas analyzer 50 for raw gas composition analysis. The tail gas coming out of the flue gas analyzer 50 is buffered by the buffer tank 71 and then enters the alkali solution absorption tank 70 for alkali washing and then discharged; the second path directly enters the reactor 12 and enters the collector 72 after passing through the reactor 12; the third path enters the gas preheater 40, and enters the reactor 12 after being preheated to a certain temperature, or the gas can also enter the collector 72 directly after being preheated through the reactor 12. The product coming out of the reactor 12 enters the collector 72 and enters the flue gas analyzer 50 after naturally cooling in the collector 72. The water required for the reaction is introduced by a pump or other means. According to the evaluation requirements, the water can be heated and vaporized by the preheater 21 and then enter the reactor 12, or it can directly enter the reactor 12 in the form of liquid water.

[0086] The materials used in this application for pipelines, valves, mixers, etc. are preferably 316L to reduce the adsorption of sulfur compounds in pipelines. The device of this application can be used for the evaluation of various flue gas desulfurization adsorbents, and can be used for product quality control of adsorbent manufacturers, sample performance testing during adsorbent research and development, optimization of adsorbent use conditions, and application tracking analysis of adsorbents in production equipment operation.

[0087] The present invention also provides a flue gas adsorption desulfurization evaluation method, comprising:

[0088] Step 1: Grind the adsorbent and sieve it, preferably through a 10-60 mesh sieve, put the sieved adsorbent into an oven for drying, the drying temperature is preferably 150±5°C, the drying time is preferably 2h, after drying, the adsorbent is moved into a drying dish to cool, and a certain amount of adsorbent is measured with a measuring cylinder, preferably 5-30mL, and its mass is recorded as m1;

[0089] Step 2: Load the weighed adsorbent into the constant temperature section of the reactor 12, place the reactor 12 into the electric heating box 10, and connect the inlet and outlet pipelines and thermocouples;

[0090] Step 3: Connect nitrogen to purge the reactor 12. After the purge is completed, the adsorption performance of the adsorbent is evaluated according to the evaluation conditions. The power of the electric heating box 10 is turned on to heat the adsorbent with a small flow of nitrogen. The heating temperature is preferably 25-425°C, and the reaction space velocity is preferably 300-5000h -1 Before the adsorbent is heated to a temperature close to the reaction temperature, the gas preheater 40 is turned on, and the gas volume is set according to the reaction requirements. The mixed gas in the mixer 30 enters the gas preheater 40 for preheating. When the adsorbent and the mixed gas are heated to the reaction temperature, the mixed gas is introduced into the reactor 12, and the preheater 21 is turned on to feed water, and adsorption evaluation is started. The reaction start time t1 is recorded, and it is decided whether the gas preheater 40 needs to be shut down according to the actual situation;

[0091] Step 4: Use the flue gas analyzer 50 to perform real-time analysis on the exhaust gas composition, and determine the adsorbent breakthrough or saturated sulfur capacity according to evaluation requirements.

[0092] According to the present invention, the adsorbent breakthrough sulfur capacity is determined as follows: when SO2 gas appears in the tail gas at the outlet of the reactor 12, the adsorbent is deemed to have reached the breakthrough sulfur capacity, and the reaction end time t2 is recorded. The breakthrough sulfur capacity of the adsorbent is:

[0093]

[0094] Where V is the total flow rate of the reaction gas, L / min

[0095] t1, t2 are the start and end time of the reaction, min;

[0096] C0 is the volume concentration of SO2 in the reaction raw gas;

[0097] m1 is the adsorbent loading mass in the reactor, g.

[0098] Determination of saturated sulfur capacity of adsorbent: When the SO2 concentration at the reactor outlet is consistent with the SO2 concentration in the feed gas, the adsorbent is considered to have reached saturated sulfur capacity. The calculation of saturated sulfur capacity can be done by either of the following two methods:

[0099] Chemical analysis: After the adsorption evaluation is completed, part of the adsorbent is unloaded and the sulfur content in the adsorbent is determined by chemical analysis method.

[0100] Integral calculation: After the adsorption evaluation is completed, the flue gas analyzer data is exported and a graph is drawn with the adsorption time as the horizontal axis and the SO2 content in the outlet gas as the vertical axis. The SO2 content in the raw gas is drawn as a line parallel to the X-axis. The area between the curve and the inlet content line is the sulfur adsorption capacity of the adsorbent.

[0101] Right now

[0102] Where V is the total flow rate of the reaction gas, L / min

[0103] t1, t2 are the start and end time of the reaction, min;

[0104] C0 is the volume concentration of SO2 in the reaction raw gas;

[0105] C t is the volume concentration of SO2 in the outlet gas at time t;

[0106] m1 is the adsorbent loading mass in the reactor, g.

[0107] In order to facilitate further evaluation of the regeneration performance of the adsorbent, the integral method is preferably used to calculate the saturated sulfur capacity of the adsorbent.

[0108] According to the present invention, after the adsorbent reaches breakthrough or saturated sulfur capacity, the regeneration performance can also be evaluated, and the specific method is:

[0109] Step 1: Shut down the raw gas. Set the regeneration gas volume according to the regeneration conditions, start the gas preheater 40 to preheat the regeneration gas, the preheating temperature is preferably 200-400°C, and simultaneously start the two groups of reactor electric heaters 11 to quickly heat the adsorbent. After heating to the regeneration temperature, the regeneration gas is introduced into the reactor 12, and the gas intake time t1 is recorded. At the same time, the flue gas analyzer records the SO2 content in the regeneration gas in real time;

[0110] Step 6: When the SO2 content in the regenerated gas is lower than 100ppm, the regeneration is considered to be completed, and the end time t2 is recorded. The regeneration desulfurization amount is compared with the adsorbent sulfur absorption amount to obtain the adsorbent regeneration rate Y:

[0111]

[0112] In the formula, S 再 —Desulfurization amount of adsorbent regeneration, g;

[0113] S 吸 —Sulfur content absorbed by the adsorbent, i.e., sulfur content adsorbed at breakthrough or saturation, g;

[0114] The regeneration desulfurization amount is calculated by the integral method, and the specific method is as follows:

[0115] After the regeneration evaluation is completed, the flue gas analyzer data is exported and a graph is plotted with the regeneration time as the horizontal axis and the SO2 content in the outlet gas as the vertical axis. The area between the curve and the X-axis is the amount of desulfurization by adsorbent regeneration.

[0116] Right now

[0117] Where, V is the total flow rate of reaction gas, L / min;

[0118] t1, t2 are the start and end time of the reaction, min;

[0119] C0 is the volume concentration of SO2 in the reaction raw gas;

[0120] C t is the volume concentration of SO2 in the outlet gas at time t.

[0121] The evaluation method of the present invention is further described below in conjunction with specific embodiments.

[0122] Example 1

[0123] The adsorption regeneration performance of the activated carbon adsorbent is evaluated on the flue gas adsorption desulfurization device of the present invention, and the specific method is as follows:

[0124] (1) Grind the adsorbent and sieve it. Place the sieved adsorbent in an oven and dry it at 150±5°C for 2 h. After drying, move the adsorbent into a drying dish and let it cool. Use a measuring cylinder to measure 20 mL of the adsorbent and weigh its mass, recording it as 8.0 g.

[0125] (2) Load the weighed adsorbent into the reactor, place the reactor in an electric heating box, and connect the inlet and outlet pipelines and thermocouples.

[0126] (3) Connect nitrogen and purge the reactor for 20 minutes. After the purge is completed, measure the inlet gas composition, open the valve for the mixed gas to enter the flue gas analyzer, close the valve for the mixed gas to enter the reactor and the gas preheater, and adjust the gas flow rates of each route so that the inlet gas composition is SO2 600ppm, O2 3.5%, and the rest is N2.

[0127] (4) The adsorption performance of the adsorbent was evaluated according to the following evaluation conditions: adsorption temperature 120°C, water vapor content 10%, reaction space velocity 2500h -1 , then the gas flow rate is 834mL / min. The specific evaluation steps are: close the valve for the mixed gas to enter the flue gas analyzer, open the valve for the mixed gas to enter the reactor directly, turn on the power of the electric heating box to heat the adsorbent with a small flow of nitrogen; before the adsorbent is heated to close to the reaction temperature (100°C), turn on the gas preheater, open the valve for the mixed gas to enter the gas preheater, set the gas volume according to the reaction requirements, and preheat the mixed gas. At the same time, turn on the preheater and be ready to add water at any time. When the adsorbent and the mixed gas are heated to 120°C, close the preheater and the valve for the mixed gas to enter the gas preheater, introduce all the reaction gas into the reactor, turn on the water pump, start the adsorption evaluation, and record the reaction start time t1.

[0128] (5) Use a flue gas analyzer to conduct real-time analysis of the exhaust gas composition and determine the sulfur capacity of the adsorbent.

[0129] (6) When SO2 appears in the reactor outlet gas, record the reaction end time t2, stop the reaction, and calculate the breakthrough sulfur capacity of the adsorbent:

[0130]

[0131] Where V is the total flow rate of the reaction gas, L / min

[0132] t1, t2 are the start and end time of the reaction, min;

[0133] C0 is the volume concentration of SO2 in the reaction raw gas, ppm;

[0134] m1 is the adsorbent loading mass in the reactor, g.

[0135] Where V is 834 mL / min, (t2-t1) is 618 min, C0 is 600 ppm, m1 is 8.0 g, and S is calculated. 穿 It is 11.0%.

[0136] (1) Evaluation of the regeneration performance of the adsorbent. After the adsorbent reaches the breakthrough sulfur capacity, the raw gas is shut down. The adsorbent is regenerated at a temperature of 380°C and a purge gas volume of 834 mL / min. The specific steps are: turn on the gas preheater to preheat the regeneration gas at a preheating temperature of 360°C. After preheating, the gas enters the collector through the reactor cross-line; at the same time, turn on two sets of reactor electric heaters to quickly heat the adsorbent. After the adsorbent is heated to 380°C, the gas is introduced into the reactor and the air intake time t1 is recorded. At the same time, the flue gas analyzer records the SO2 content in the regeneration gas in real time.

[0137] (2) When the SO2 content in the regenerated gas is lower than 100ppm, the regeneration is considered to be completed and the end time t2 is recorded. By comparing the regeneration desulfurization amount with the adsorbent sulfur absorption amount, the adsorbent regeneration rate Y can be obtained:

[0138]

[0139] In the formula, S 再 —Desulfurization amount of adsorbent regeneration, g;

[0140] S 吸 —Sulfur content absorbed by the adsorbent, i.e., sulfur content adsorbed at breakthrough or saturation, g; calculated by the regeneration desulfurization amount integral method, the flue gas analyzer data is exported, and the regeneration time is used as the horizontal axis and the SO2 content in the outlet gas is used as the vertical axis to draw a graph. The resulting regeneration curve is as follows:

[0141] By integrating the curve using data processing software, we can get the curve integral area to be 352695.

[0142] like Figure 2 As shown,

[0143] but

[0144] And S 吸 =S 穿 ×m1=11%×8.0=0.88g

[0145] Y=0.84÷0.88=95.5%

[0146] Example 2

[0147] The adsorption performance of the molecular sieve adsorbent was evaluated on the flue gas adsorption desulfurization device of the present invention. The specific method is as follows: (1) the adsorbent was ground and sieved, and the sieved adsorbent was placed in an oven and dried at 150±5°C for 2h; after drying, the adsorbent was moved into a drying dish to cool, and 10mL of the adsorbent was measured with a measuring cylinder, and its mass was recorded as 3.8g.

[0148] (2) Load the weighed adsorbent into the reactor, place the reactor in an electric heating box, and connect the inlet and outlet pipelines and thermocouples.

[0149] (3) Connect nitrogen and purge the reactor for 20 minutes. After the purge is completed, measure the inlet gas composition, open the valve for the mixed gas to enter the flue gas analyzer, close the valve for the mixed gas to enter the reactor and the gas preheater, and adjust the gas flow rates of each route so that the inlet gas composition is SO2 500ppm, O2 5.0%, and the rest is N2.

[0150] (4) The adsorption performance of the adsorbent was evaluated according to the following evaluation conditions: adsorption temperature 200°C, water vapor content 15%, reaction space velocity 2500h -1 , then the gas flow rate is 417mL / min. The specific evaluation steps are: close the valve for the mixed gas to enter the flue gas analyzer, open the valve for the mixed gas to enter the reactor directly, turn on the power of the electric heating box to heat the adsorbent with a small flow of nitrogen; before the adsorbent is heated to close to the reaction temperature (180°C), turn on the gas preheater, open the valve for the mixed gas to enter the gas preheater, set the gas volume according to the reaction requirements, and preheat the mixed gas. At the same time, turn on the water preheater and be ready to add water at any time. When the adsorbent and the mixed gas are heated to 200°C, close the preheater and the valve for the mixed gas to enter the gas preheater, introduce all the reaction gas into the reactor, turn on the water pump, start the adsorption evaluation, and record the reaction start time t1.

[0151] (5) Use a flue gas analyzer to conduct real-time analysis of the exhaust gas composition and determine the sulfur capacity of the adsorbent.

[0152] (6) When SO2 appears in the reactor outlet gas, record the reaction end time t2, stop the reaction, and calculate the breakthrough sulfur capacity of the adsorbent:

[0153]

[0154] Where V is the total flow rate of the reaction gas, L / min

[0155] t1, t2 are the start and end time of the reaction, min;

[0156] C0 is the volume concentration of SO2 in the reaction raw gas, ppm;

[0157] m1 is the adsorbent loading mass in the reactor, g.

[0158] Where V is 417mL / min, (t2-t1) is 521min, C0 is 500ppm, m1 is 3.8g, and S is calculated. 穿 It is 8.2%.

[0159] Example 3

[0160] The adsorption performance of a certain adsorbent is evaluated on the flue gas adsorption desulfurization device of the present invention, and the specific method is as follows:

[0161] (1) Grind the adsorbent and sieve it. Place the sieved adsorbent in an oven and dry it at 150±5°C for 2 h. After drying, move the adsorbent into a drying dish and let it cool. Use a measuring cylinder to measure 20 mL of the adsorbent and weigh its mass, recording it as 7.8 g.

[0162] (2) Load the weighed adsorbent into the reactor, place the reactor in an electric heating box, and connect the inlet and outlet pipelines and thermocouples.

[0163] (3) Connect nitrogen and purge the reactor for 20 minutes. After the purge is completed, measure the inlet gas composition, open the valve for the mixed gas to enter the flue gas analyzer, close the valve for the mixed gas to enter the reactor and the gas preheater, and adjust the gas flow rates of each route so that the inlet gas composition is SO2 500ppm, O2 5.0%, and the rest is N2.

[0164] (4) The adsorption performance of the adsorbent was evaluated according to the following evaluation conditions: adsorption temperature 120°C, water vapor content 10%, reaction space velocity 2500h -1, then the gas flow rate is 417mL / min. The specific evaluation steps are: close the valve for the mixed gas to enter the flue gas analyzer, open the valve for the mixed gas to enter the reactor directly, turn on the power of the electric heating box to heat the adsorbent with a small flow of nitrogen; before the adsorbent is heated to close to the reaction temperature (100°C), turn on the gas preheater, open the valve for the mixed gas to enter the gas preheater, set the gas volume according to the reaction requirements, and preheat the mixed gas. At the same time, turn on the water preheater and be ready to add water at any time. When the adsorbent and the mixed gas are heated to 120°C, close the preheater and the valve for the mixed gas to enter the gas preheater, introduce all the reaction gas into the reactor, turn on the water pump, and start the adsorption evaluation.

[0165] (5) Use a flue gas analyzer to conduct real-time analysis of the exhaust gas composition and determine the sulfur capacity of the adsorbent.

[0166] (6) When SO2 appears in the reactor outlet gas, the reaction is stopped, the adsorbent is removed and the breakthrough sulfur capacity is analyzed by chemical analysis. The breakthrough sulfur capacity of the adsorbent is 12.5%.

[0167] Example 4

[0168] The adsorption performance of a certain adsorbent is evaluated on the flue gas adsorption desulfurization device of the present invention, and the specific method is as follows:

[0169] (1) Grind the adsorbent and sieve it. Place the sieved adsorbent in an oven and dry it at 150±5°C for 2 h. After drying, move the adsorbent into a drying dish and let it cool. Use a measuring cylinder to measure 20 mL of the adsorbent and weigh its mass, recording it as 6.9 g.

[0170] (2) Load the weighed adsorbent into the reactor, place the reactor in an electric heating box, and connect the inlet and outlet pipelines and thermocouples.

[0171] (3) Connect nitrogen and purge the reactor for 20 minutes. After the purge is completed, measure the inlet gas composition, open the valve for the mixed gas to enter the flue gas analyzer, close the valve for the mixed gas to enter the reactor and the gas preheater, and adjust the gas flow rates of each route so that the inlet gas composition is SO2 500ppm, O2 3.5%, and the rest is N2.

[0172] (4) The adsorption performance of the adsorbent was evaluated according to the following evaluation conditions: adsorption temperature 120°C, water vapor content 10%, reaction space velocity 2500h -1, then the gas flow rate is 834mL / min. The specific evaluation steps are: close the valve for the mixed gas to enter the flue gas analyzer, open the valve for the mixed gas to enter the reactor directly, turn on the power of the electric heating box to heat the adsorbent with a small flow of nitrogen; before the adsorbent is heated to close to the reaction temperature (100°C), turn on the gas preheater, open the valve for the mixed gas to enter the gas preheater, set the gas volume according to the reaction requirements, and preheat the mixed gas. At the same time, turn on the water preheater and be ready to add water at any time. When the adsorbent and the mixed gas are heated to 120°C, close the preheater and the valve for the mixed gas to enter the gas preheater, introduce all the reaction gas into the reactor, turn on the water pump, start the adsorption evaluation, and record the reaction start time t1.

[0173] (5) Use a flue gas analyzer to conduct real-time analysis of the exhaust gas composition and determine the saturated sulfur capacity of the adsorbent.

[0174] (6) When the SO2 in the reactor outlet gas is consistent with that in the inlet, record the reaction end time t2, stop the reaction, and calculate the saturated sulfur capacity of the adsorbent:

[0175] Right now

[0176] Where V is the total flow rate of the reaction gas, L / min

[0177] t1, t2 are the start and end time of the reaction, min;

[0178] C0 is the volume concentration of SO2 in the reaction raw gas;

[0179] C t is the volume concentration of SO2 in the outlet gas at time t;

[0180] m1 is the adsorbent loading mass in the reactor, g.

[0181] The SO2 content in the reaction outlet gas is taken as the ordinate, and the adsorption time is taken as the abscissa. Figure 3 As shown, the graphical integration is as follows:

[0182] but

[0183] Example 5

[0184] According to the given conditions in Example 1, the adsorbent was evaluated for repeatability, and the results of five evaluations are shown in Table 1.

[0185] Table 1 Five repeatability evaluations of the adsorbent

[0186] Serial number 1 2 3 4 5 Sulfur penetration capacity 11.0 10.8 11.1 11.2 10.9

[0187] It can be seen from Table 1 that the deviation of the measured breakthrough sulfur capacity is small when evaluated 5 times under the same conditions. It can be seen that the flue gas adsorption desulfurization device developed by the present invention has good repeatability and high data accuracy.

[0188] Example 6

[0189] According to the given conditions in Example 1, the regeneration performance of the same adsorbent was investigated multiple times, that is, after the adsorbent reached the breakthrough sulfur capacity, the adsorbent was regenerated, and a second adsorption was performed after the regeneration. The adsorbent was regenerated five times, and the evaluation results are shown in Table 2.

[0190] Table 2 Evaluation of adsorbent regeneration performance

[0191] Regeneration times 0 1 2 3 4 Sulfur penetration capacity 11.1 10.8 10.7 10.6 10.6

[0192] It can be seen from Table 2 that the device can quickly and accurately evaluate the regeneration performance of the adsorbent and can accurately evaluate the regeneration performance of the adsorbent.

[0193] Comparative Example 1

[0194] According to the conditions listed in Example 1, the adsorption performance of the adsorbent was evaluated in an ordinary sulfur microreactor. Since the sulfides in the sulfur device are all percentages and there is a certain amount of sulfur accumulation in the device, SO2 flows out from the outlet of the initial reactor during the evaluation, making it impossible to correctly evaluate the adsorption and regeneration performance of the adsorbent.

[0195] The above description is only by way of illustration of certain exemplary embodiments of the present invention. It is undoubted that those skilled in the art can modify the described embodiments in various ways without departing from the spirit and scope of the present invention. Therefore, the above drawings and descriptions are illustrative in nature and should not be construed as limiting the scope of protection of the claims of the present invention.

Claims

1. A flue gas adsorption desulfurization evaluation device, characterized in that: include: A reaction system, the reaction system comprising an electric heating box (10), a plurality of groups of electric heaters (11) being arranged inside the electric heating box (10), and a reactor (12) being arranged between the plurality of groups of electric heaters (11); a water supply system capable of adding water to the reaction system; A gas supply system, which is capable of adding gas to the reaction system and is connected to a flue gas analyzer (50); An exhaust gas treatment system receives the output gas from the flue gas analyzer (50) and the reactor (12) and performs treatment.

2. A flue gas adsorption desulfurization evaluation device according to claim 1, characterized in that: The water supply system comprises a water storage tank (20), the water outlet end of the water storage tank (20) is connected to one end of a preheater (21) through a pipeline, and the other end of the preheater (21) is connected to an inlet end of a reactor (12) through a pipeline.

3. A flue gas adsorption desulfurization evaluation device according to claim 1, characterized in that: The gas supply system comprises a plurality of gas supply pipelines, the gas outlet ends of the plurality of gas supply pipelines are connected to the gas inlet end of a mixer (30), and the gas outlet end of the mixer (30) is connected to the gas preheater (40), the flue gas analyzer (50) and the gas inlet end of the collector (72).

4. A flue gas adsorption desulfurization evaluation device according to claim 1, characterized in that: The gas outlet end of the gas preheater (40) is respectively connected to the flue gas analyzer (50) and the gas inlet end of the reactor (12), and the gas inlet end of the flue gas analyzer (50) is also connected to the gas outlet end of the reactor (12).

5. The flue gas adsorption desulfurization evaluation device according to claim 1, characterized in that: The gas supply line comprises a gas source (60), the gas source (60) being connected to the gas inlet end of the mixer (30) via a gas transmission pipeline, the gas transmission pipeline being provided with a pressure reducing valve (61), a filter (62), a mass flow meter (63) and a one-way valve (64) in sequence, the one-way valve (64) being arranged close to the mixer (30).

6. A flue gas adsorption desulfurization evaluation device according to claim 1, characterized in that: The tail gas treatment system comprises an alkali solution absorption tank (70), the air inlet end of the alkali solution absorption tank (70) is connected to the air outlet end of a buffer tank (71), and the air inlet end of the buffer tank (71) is connected to the air outlet end of a flue gas analyzer (50).

7. A flue gas adsorption desulfurization evaluation device according to claim 6, characterized in that: The tail gas treatment system also includes a collector (72), the feed end of the collector (72) is connected to the discharge end of the reactor (12) through a pipeline, the discharge end of the collector (72) is connected to the feed end of the gas-liquid separation tank (73) through a pipeline, and the gas outlet end of the gas-liquid separation tank (73) is connected to the gas inlet end of the flue gas analyzer (50) and the buffer tank (71) through a pipeline.

8. A method for evaluating flue gas adsorption desulfurization using the device according to claim 1, characterized in that: include: Step 1: Grind the adsorbent and sieve it. Put the sieved adsorbent into an oven to dry. After drying, move the adsorbent into a drying dish to cool. Take a certain amount of adsorbent and weigh its mass as m1. Step 2: Load the weighed adsorbent into the reactor, place the reactor in an electric heating box, and connect the inlet and outlet pipelines and thermocouples; Step 3: Connect nitrogen to purge the reactor. After the purge is completed, start the adsorption performance evaluation of the adsorbent according to the evaluation conditions. Turn on the power of the electric heating box to heat the adsorbent. Before the adsorbent is heated to a temperature close to the reaction temperature, turn on the gas preheater and set the gas volume according to the reaction requirements. The mixed gas in the mixer enters the gas preheater for preheating. When the adsorbent and the mixed gas are heated to the reaction temperature, the mixed gas is introduced into the reactor. At the same time, the water inlet of the preheater is turned on to start the adsorption evaluation, and the reaction start time t1 is recorded; Step 4: Use a flue gas analyzer to conduct real-time analysis of the exhaust gas composition and determine the adsorbent breakthrough or saturated sulfur capacity according to evaluation needs; Determination of the sulfur breakthrough capacity of the adsorbent: When SO2 gas appears in the tail gas at the reactor outlet, it is considered that the adsorbent has reached the sulfur breakthrough capacity, and the reaction end time t2 is recorded. The sulfur breakthrough capacity of the adsorbent is: Where V is the total flow rate of the reaction gas, L / min t1, t2 are the start and end time of the reaction, min; C0 is the volume concentration of SO2 in the reaction raw gas; m1 is the mass of adsorbent loaded in the reactor, g; Determination of the saturated sulfur capacity of the adsorbent: When the SO2 concentration at the reactor outlet is consistent with the SO2 concentration in the feed gas, the adsorbent is considered to have reached the saturated sulfur capacity. The saturated sulfur capacity is calculated by either of the following two methods: Chemical analysis: After the adsorption evaluation is completed, part of the adsorbent is unloaded and the sulfur content in the adsorbent is determined by chemical analysis method. Integral calculation: After the adsorption evaluation is completed, the flue gas analyzer data is exported and plotted with the adsorption time as the horizontal axis and the SO2 content in the outlet gas as the vertical axis. The SO2 content in the feed gas is the parallel line to the X-axis. The area between the curve and the inlet content line is the adsorbent sulfur capacity. Right now Where V is the total flow rate of the reaction gas, L / min t1, t2 are the start and end time of the reaction, min; C0 is the volume concentration of SO2 in the reaction raw gas; C t is the volume concentration of SO2 in the outlet gas at time t; m1 is the adsorbent loading mass in the reactor, g.

9. The flue gas adsorption desulfurization evaluation method according to claim 8, characterized in that: After the adsorbent reaches breakthrough or saturated sulfur capacity, the regeneration performance can also be evaluated. The specific method is as follows: Step 1: Shut down the raw gas, set the regeneration gas volume according to the regeneration conditions, start the gas preheater to preheat the regeneration gas, and start the two sets of reactor electric heaters to heat the adsorbent. After heating to the regeneration temperature, the regeneration gas is introduced into the reactor, and the gas intake time t1 is recorded. At the same time, the flue gas analyzer records the SO2 content in the regeneration gas in real time; Step 2: When the SO2 content in the regenerated gas is lower than a certain value, the regeneration is considered to be completed, and the end time t2 is recorded. The regeneration desulfurization amount is compared with the adsorbent sulfur absorption amount to obtain the adsorbent regeneration rate Y: In the formula, S 再 —Desulfurization amount of adsorbent regeneration, g; S 吸 —Sulfur content absorbed by the adsorbent, i.e., sulfur content adsorbed at breakthrough or saturation, g; The regeneration desulfurization amount is calculated by the integral method, and the specific method is as follows: After the regeneration evaluation is completed, the flue gas analyzer data is exported and plotted with the regeneration time as the horizontal axis and the SO2 content in the outlet gas as the vertical axis. The area between the curve and the X-axis is the adsorbent regeneration desulfurization amount, that is, Where, V is the total flow rate of reaction gas, L / min; t1, t2 are the start and end time of the reaction, min; C0 is the volume concentration of SO2 in the reaction raw gas; C t is the volume concentration of SO2 in the outlet gas at time t.

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