Method for removing CO through catalytic oxidation and application thereof
By using precious metal honeycomb catalysts in the catalytic oxidation system to react with the exhaust gas in contact, the problem that the CO catalytic oxidation method in the prior art is difficult to efficiently remove CO in the exhaust gas under various operating conditions, and the CO removal effect with high efficiency, low energy consumption and no secondary pollution is achieved.
Patent Information
- Application Number
- CN202311367058.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-20
- Publication Date
- 2025-04-22
AI Technical Summary
The existing CO catalytic oxidation method is difficult to efficiently remove CO from exhaust gas under various operating conditions, and there are problems such as high energy consumption, poor secondary pollution, and poor stability.
The noble metal honeycomb catalyst is used to react in contact with the exhaust gas to be treated in the catalytic oxidation system, and efficient removal of CO is achieved by controlling the oxygen atmosphere and the amount of hydrogen introduced.
It has achieved efficient removal of CO exhaust under various operating conditions, low energy consumption, no secondary pollution, good stability, and is suitable for CO emissions in various operating conditions.
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Figure CN119857363A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of energy and environmental technology, and in particular to a method for removing CO by catalytic oxidation and application thereof. Background Art
[0002] At present, many processes in industrial production will produce CO-rich gases, such as coal gasification, coke oven gas, blast furnace gas and converter gas in steel production. The CO concentration in these gases is high (>5vol%), and direct discharge will cause huge waste of resources and serious environmental pollution. For this type of gas, methods such as cryogenic separation, solvent recovery and solid adsorption separation are usually used to purify, separate and purify CO. The CO content of the purified gas is very low and can be directly discharged in compliance with the standards.
[0003] However, there are some processes that produce tail gas with a low concentration of CO (<5000ppm), such as the desorption gas from the low-temperature methanol washing unit used to remove acidic gases in coal gasification units. For this type of tail gas, the recovery cost is relatively high. In order to meet emission requirements, adsorption, photocatalysis, low-temperature plasma conversion, combustion and other methods are usually used to remove CO in order to meet emission requirements. The catalytic oxidation method introduces a high-efficiency catalyst on the basis of the combustion method to reduce the temperature of the combustion process. It has the advantages of simple process and high removal efficiency, and therefore has received widespread attention.
[0004] However, the use of methods and devices for removing CO tail gas in the existing CO catalytic oxidation technology still has great limitations.
[0005] CN207478277U discloses a system for removing CO from flue gas, which uses an injection device to inject a strong oxidant into the flue, oxidizes the CO in the flue into non-toxic and harmless CO2 and then discharges it from the flue; at the same time, the control unit controls the size of the regulating valve according to the concentration of CO in the flue, and then controls the input amount of the oxidant to ensure that the injected oxidant can complete the conversion of CO in the flue into CO2 and discharge it from the flue, so that the CO emission of the fluidized bed waste incinerator can meet the requirements of GB18485-2014 "Standard for Pollution Control of Domestic Waste Incineration", and also avoids the waste of oxidant and saves costs. However, this system is only applicable to the removal of CO in flue gas generated in the power system process. And the system has high energy consumption, and the treatment effect is average when the concentration of CO in the flue gas is high.
[0006] CN107973271A discloses a reaction device for removing trace carbon monoxide from hydrogen-rich gas and a method for using the same. The problem of uneven material distribution in the limited space of the reaction device for removing trace carbon monoxide from hydrogen-rich gas is improved by reasonably setting a material mixing tank, a raw material distribution port and a gas distribution pipe, and avoiding hot spots to improve the conversion efficiency of the carbon monoxide removal catalyst. However, the method and device are mainly suitable for removing CO from hydrogen-rich gas (hydrogen content is 50-75 vol%).
[0007] Therefore, how to provide a CO catalytic oxidation technology that can remove CO from exhaust gas generated under various working conditions, with low energy consumption, no secondary pollution, high efficiency and good stability is a core problem that needs to be solved urgently in this field. Summary of the invention
[0008] The purpose of the present invention is to overcome the problem that the methods and devices for removing CO tail gas in the prior art have limitations in use and cannot be applied to tail gas generated under various working conditions while meeting the requirements of no secondary pollution and high removal rate.
[0009] In order to achieve the above object, the first aspect of the present invention provides a method for removing CO by catalytic oxidation, which is carried out in a catalytic oxidation system provided with a reaction unit, comprising:
[0010] Under a first gas environment, the tail gas to be treated is contacted with the noble metal honeycomb catalyst in the reaction unit to react to obtain a treated gas with a CO content of ≤0.005 vol%; the first gas environment contains an oxygen-containing atmosphere and optionally also contains a hydrogen-containing atmosphere;
[0011] The CO content in the tail gas to be treated is 0.05-10 vol%, and the total content of dust particles is not more than 2000 μg / cm 3 ; The average diameter of the dust particles is 20-100 μm;
[0012] The precious metal honeycomb catalyst contains a first active metal component, which is platinum and / or palladium; based on the total weight of the precious metal honeycomb catalyst, the content of the first active metal component in terms of metal element is 0.5-10wt%;
[0013] The amount of the oxygen-containing atmosphere introduced is controlled so that in the contact reaction system at the initial moment of the contact reaction, the volume concentration ratio of O2 to CO is 5-15:1; and based on the total volume of the hydrogen in the hydrogen-containing atmosphere and the tail gas to be treated, the hydrogen content is 0-5 vol%.
[0014] The second aspect of the present invention provides application of the method for removing CO by catalytic oxidation described in the first aspect in the field of energy and environmental technology.
[0015] The present invention adopts a catalytic oxidation system to remove CO tail gas generated in various working conditions, and has low energy consumption, no secondary pollution, high efficiency, good stability, and is conducive to CO emission compliance and promotion of CO removal technology. BRIEF DESCRIPTION OF THE DRAWINGS
[0016] Figure 1 It is a schematic flow chart of a preferred method for removing CO by catalytic oxidation provided by the present invention. DETAILED DESCRIPTION
[0017] The endpoints and any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.
[0018] As mentioned above, the first aspect of the present invention provides a method for removing CO by catalytic oxidation, which is carried out in a catalytic oxidation system provided with a reaction unit, comprising:
[0019] Under a first gas environment, the tail gas to be treated is contacted with the noble metal honeycomb catalyst in the reaction unit to react to obtain a treated gas with a CO content of ≤0.005 vol%; the first gas environment contains an oxygen-containing atmosphere and optionally also contains a hydrogen-containing atmosphere;
[0020] The CO content in the tail gas to be treated is 0.05-10 vol%, and the total content of dust particles is not more than 2000 μg / cm 3 ; The average diameter of the dust particles is 20-100 μm;
[0021] The precious metal honeycomb catalyst contains a first active metal component, which is platinum and / or palladium; based on the total weight of the precious metal honeycomb catalyst, the content of the first active metal component in terms of metal element is 0.5-10wt%;
[0022] The amount of the oxygen-containing atmosphere introduced is controlled so that in the contact reaction system at the initial moment of the contact reaction, the volume concentration ratio of O2 to CO is 5-15:1; and based on the total volume of the hydrogen in the hydrogen-containing atmosphere and the tail gas to be treated, the hydrogen content is 0-5 vol%.
[0023] Preferably, the noble metal honeycomb catalyst further comprises a support and a carrier; the support is a monolithic honeycomb ceramic made of cordierite, and the carrier is selected from at least one of alumina, silicon oxide, and zirconium oxide; and
[0024] Based on the total weight of the precious metal honeycomb catalyst, the content of the support is 44-95wt%, and the content of the carrier is 5-30wt%.
[0025] Preferably, the precious metal honeycomb catalyst further contains a second active metal component; the second first active metal component is selected from at least one of iron, cobalt and nickel; and
[0026] Based on the total weight of the noble metal honeycomb catalyst, the content of the second active metal component in terms of metal element is 1-10wt%.
[0027] It should be noted that the present invention has no special requirements on the source of the precious metal honeycomb catalyst. It can be prepared using conventional technical means in the field or purchased commercially. It only needs to ensure that the content of the support, carrier, first active metal component and second active metal component meets the requirements.
[0028] According to a preferred embodiment, the oxygen-containing atmosphere is air.
[0029] It should be noted that the inventors have found that in the present invention, when the hydrogen content in the contact reaction system is not greater than 1 vol%, the solution of the present invention can still be implemented.
[0030] Preferably, based on the total volume of the hydrogen in the hydrogen-containing atmosphere and the tail gas to be treated, the content of hydrogen is 0-1 vol%.
[0031] Preferably, the methanol content in the tail gas to be treated is 0-0.2 vol%.
[0032] More preferably, the methanol content in the tail gas to be treated is 0.01-0.05 vol%.
[0033] Preferably, the content of sulfide in the tail gas to be treated is 0-0.005 vol%.
[0034] It should be noted that, in the present invention, the sulfide is carbonyl sulfide and hydrogen sulfide.
[0035] According to a preferred embodiment, the content of hydrocarbon substances in the tail gas to be treated is 0-0.2 vol%.
[0036] It should be noted that in the present invention, the hydrocarbon substance is C 1-4 of hydrocarbons.
[0037] Preferably, the volume concentration of CO in the exhaust gas to be treated and the weight of the first active metal component in the precious metal honeycomb catalyst are in a ratio of 1-10:1, and the volume concentration of CO is expressed in mg / m 3 The weight of the first active metal component is in mg. The inventors found that in this preferred case, the removal efficiency of CO is higher.
[0038] Preferably, the catalytic oxidation system is further provided with a pretreatment unit, and the method further comprises: before subjecting the tail gas to be treated to the contact reaction, first subjecting the tail gas to be treated to liquid removal and dust removal in the pretreatment unit in sequence to obtain pretreated gas I, and then subjecting the pretreated gas I to the contact reaction;
[0039] The conditions of liquid removal and dust removal are controlled so that the total content of the dust particles in the pre-treated gas I is 0-20 μg / cm 3 .
[0040] Preferably, the pretreatment unit comprises a tail gas buffer tank and a tail gas filter connected in sequence, and the liquid removal and the dust removal are respectively performed in the tail gas buffer tank and the tail gas filter. The inventors have found that in this preferred case, the removal rate of CO removal by catalytic oxidation is higher.
[0041] According to a preferred embodiment, at least one filter element is provided in the exhaust gas filter.
[0042] According to a preferred embodiment, a liquid level gauge is provided on the side of the exhaust gas buffer tank, a drain valve is provided at the bottom, and a safety valve is provided at the top; wherein, the liquid level gauge is used to observe the liquid level in the exhaust gas buffer tank, and when the liquid level in the buffer tank reaches more than 2 / 3, the liquid is discharged through the drain valve; when the pressure in the buffer tank reaches more than 0.2MPa, at least part of the exhaust gas to be treated is discharged between the outer cylinder and the inner cylinder of the inlet and outlet heat exchangers.
[0043] Preferably, a gas mixing unit is further provided in the catalytic oxidation system, and the method further comprises: before the pretreatment gas I and the oxygen-containing atmosphere are subjected to the contact reaction, the pretreatment gas I and the oxygen-containing atmosphere are first introduced into the gas mixing unit for mixing to obtain a mixed gas I, and then the mixed gas I is subjected to the contact reaction with the precious metal honeycomb catalyst.
[0044] Preferably, an inlet and outlet reaction heat exchanger is provided in the gas mixing unit, and the inlet and outlet reaction heat exchanger includes an inner cylinder and an outer cylinder; and
[0045] The mixing operation includes: introducing the pre-treated gas I and the oxygen-containing atmosphere from an exhaust gas blower and an oxygen-containing atmosphere blower into the inner cylinder of the inlet and outlet reaction heat exchanger for mixing.
[0046] According to a preferred embodiment, the output range of the oxygen-containing atmosphere blower is 0-1000m 3 / h, the oxygen-containing atmosphere blower is provided with a mass controller and a regulating valve, which are used to adjust the output flow rate of the oxygen-containing atmosphere blower according to the CO content in the tail gas to be treated, so that in the contact reaction system at the initial moment of the contact reaction, the ratio of the concentration of O2 to the volume concentration of CO is 5-15:1. The inventors have found that the CO removal effect is the best under this preferred condition, which can ensure that the CO concentration in the treatment obtained after the contact reaction is ≤0.005vol%.
[0047] Preferably, an electric heater and a reaction furnace are provided in the reaction unit, and the method further comprises: before subjecting the mixed gas I to the contact reaction, first heating the mixed gas I in the electric heater, and then introducing it into the reaction furnace to undergo the contact reaction with the precious metal honeycomb catalyst.
[0048] According to a preferred embodiment, a gas distributor is provided on the top of the reaction furnace.
[0049] Preferably, the instantaneous temperature of the contact reaction is measured by respectively arranging thermocouples at the upper, middle and lower parts of one side of the reaction furnace, and the thermocouples are inserted into the precious metal honeycomb catalyst through a sleeve.
[0050] Preferably, the reaction furnace is provided with a temperature interlock, and when the temperature in the reaction furnace exceeds 450° C., the temperature interlock is activated to stop the pretreatment gas I and the oxygen-containing atmosphere from entering the reaction furnace.
[0051] Preferably, the contact reaction conditions at least meet the following conditions: temperature of 150-350° C. and pressure of 0.05-0.2 MPa.
[0052] Preferably, the method further comprises: exchanging heat between the outer cylinder and the inner cylinder of the inlet and outlet reaction heat exchanger for at least a portion of the treated gas and the mixed gas I. The inventors have found that in this preferred case, the heat utilization efficiency of the system can be improved, the energy consumption can be reduced, and the economy of the system can be improved.
[0053] According to a preferred embodiment, the method of the present invention further comprises: using a flue gas analyzer to perform flue gas analysis on the process gas.
[0054] Preferably, when the CO concentration in the treated gas is lower than 0.005 vol%, the treated gas is discharged at a high point.
[0055] Preferably, before the tail gas to be treated is introduced into the tail gas buffer tank, it is first passed through a pressure reducing valve to reduce the pressure to 0.05-0.2 MPa.
[0056] It should be noted that the protection level of the field instrument in the instrument selection used in the present invention is at least IP65, and there is no requirement for the specific selection of various instruments, which can be defined according to the actual type.
[0057] The following combination Figure 1 The preferred specific implementation of the method for removing CO by catalytic oxidation according to the present invention is described, specifically:
[0058] The method is carried out in a catalytic oxidation system provided with a reaction unit;
[0059] (1) removing liquid and removing dust from the tail gas to be treated in a tail gas buffer tank and a tail gas filter in sequence to obtain a pretreated gas I;
[0060] (2) introducing the pre-treated gas I and the oxygen-containing atmosphere from the tail gas blower and the oxygen-containing atmosphere blower into the inner cylinder of the inlet and outlet reaction heat exchanger respectively for mixing to obtain a mixed gas I;
[0061] (3) heating the mixed gas I in an electric heater and then introducing it into a reaction furnace for contact reaction to obtain a treated gas;
[0062] (4) Use a flue gas analyzer to analyze the CO concentration of the treated gas. When the CO concentration in the treated gas is lower than 0.005 vol%, the treated gas and the mixed gas I are heat exchanged between the outer cylinder and the inner cylinder of the reaction heat exchanger, and the treated gas after the heat exchange is discharged at a high point.
[0063] As mentioned above, the second aspect of the present invention provides the application of the method for removing CO by catalytic oxidation as described in the first aspect in the field of energy and environmental technology.
[0064] The present invention will be described in detail below by way of examples, but the present invention is not limited thereby.
[0065] In the following examples, unless otherwise specified, the chemical reagents used are all products of Sinopharm Chemical Reagent Co., Ltd.
[0066] Unless otherwise specified, the following examples use Figure 1 The process flow shown is carried out.
[0067] Instrument selection: The protection level of the field instrument is IP65;
[0068] Thermocouple: armored Pt100 platinum thermal resistor in accordance with IEC751 standard, accuracy not less than Class A, with reinforcing tube spring compression type, thermal resistor adopts 3-wire system, fixed external thread connection; local temperature indicating instrument uses a protective sleeve with external protection Universal shockproof bimetallic thermometer, with an accuracy level of 1.5;
[0069] Pressure instrument: Remote pressure / differential pressure measurement uses intelligent pressure / differential pressure transmitters with digital gauges, pressure transmitters with stainless steel two-valve group, differential pressure transmitters with stainless steel three-valve group, transmitter accuracy ≤±0.075%; local pressure instruments use dials with a diameter of Shockproof stainless steel spring tube pressure gauge, accuracy is 1.5 grade;
[0070] Quality controller: Equip the throttling device with a differential pressure transmitter;
[0071] Liquid level meter: magnetic flap liquid level meter;
[0072] Control valve: The valve body is made of carbon steel, the valve core is made of stainless steel, and the valve pressure level is not lower than the pressure level of the process pipeline;
[0073] Flue gas analyzer: Model: Testo350, purchased from Testo Instrument International Trading (Shanghai) Co., Ltd.
[0074] Example 1
[0075] This example is used to illustrate the method for removing CO by catalytic oxidation provided by the present invention. The method refers to the parameters in Table 2 and is carried out in a catalytic oxidation system provided with a reaction unit. Specifically;
[0076] (1) The tail gas to be treated is passed through a pressure reducing valve to reduce the pressure to 0.1 MPa, and then liquid removal and dust removal are performed in the tail gas buffer tank and the tail gas filter equipped with a filter element, respectively, to obtain a total content of dust particles of 20 μg / cm 3 Pre-treated gas I;
[0077] The composition of the tail gas to be treated is shown in Table 1. By observing the liquid level gauge on the side of the tail gas buffer tank, when the liquid level in the buffer tank reaches 2 / 3, the liquid is discharged through the drain valve at the bottom of the tail gas buffer tank; when the pressure in the buffer tank reaches 0.2MPa, a part of the tail gas to be treated is discharged between the outer cylinder and the inner cylinder of the inlet and outlet heat exchangers;
[0078] (2) introducing the pre-treated gas I and the oxygen-containing atmosphere (air) from the tail gas blower and the oxygen-containing atmosphere blower into the inner cylinder of the inlet and outlet reaction heat exchanger respectively for mixing to obtain a mixed gas I;
[0079] The amount of the oxygen-containing atmosphere introduced is controlled by a mass controller and a regulating valve provided on the oxygen-containing atmosphere blower, so that the volume concentration ratio of O2 to CO in the contact reaction system at the initial moment of the contact reaction is 5:1;
[0080] (3) The mixed gas I is heated in the electric heater of the reaction unit and then introduced into the gas distributor in the reaction furnace, and is contacted with the precious metal honeycomb catalyst in the reaction furnace under the conditions of temperature of 260°C and pressure of 0.1MPa to obtain a treated gas, and the CO concentration of the treated gas is analyzed using a flue gas analyzer. The CO content is 0.002vol%, which meets the enterprise standard of a concentration lower than 0.01vol%. The treated gas and the mixed gas I are heat exchanged between the outer cylinder and the inner cylinder of the inlet and outlet reaction heat exchanger, and the treated gas after heat exchange is discharged at a high point;
[0081] Wherein, the instantaneous temperature of the contact reaction is measured by respectively setting thermocouples at the upper, middle and lower parts of one side of the reactor, and the thermocouples are inserted into the precious metal honeycomb catalyst through a sleeve; when the temperature in the reactor exceeds 450°C, the temperature interlock on the reactor is activated, and the pretreatment gas I and the oxygen-containing atmosphere are stopped from being passed into the reactor;
[0082] The precious metal honeycomb catalyst is a platinum-alumina catalyst, wherein the support is a monolithic honeycomb ceramic with cordierite material, the carrier is alumina, the second active metal component is iron, and the first active metal component is platinum; and based on the total weight of the precious metal honeycomb catalyst, the content of the support is 70wt%, the content of the carrier is 25wt%, the content of the second active metal component in terms of metal element is 2wt%, and the content of the first active metal component is 1wt%;
[0083] The relationship between the volume concentration of CO in the exhaust gas to be treated and the weight of the first active metal component in the precious metal honeycomb catalyst is 1:1.
[0084] The CO content in the final treated gas is 0.002 vol%, which meets the enterprise standard of a concentration lower than 0.01 vol%.
[0085] Example 2
[0086] This embodiment is carried out in a similar manner to that of embodiment 1, except that the composition of the tail gas to be treated is changed, and sulfide is not contained therein, and the noble metal honeycomb catalyst is a palladium-alumina catalyst.
[0087] Among them, the support body is an integral honeycomb ceramic with cordierite material, the carrier is alumina, the second active metal component is iron, and the first active metal component is palladium; and based on the total weight of the precious metal honeycomb catalyst, the content of the support body is 68wt%, the content of the carrier is 25wt%, the content of the second active metal component in terms of metal element is 2wt%, and the content of the first active metal component is 1wt%.
[0088] The contact reaction conditions and parameters are different, see Table 2 for specific parameters; the CO content in the final treated gas is 0.001 vol%, which meets the enterprise standard of a concentration lower than 0.01 vol%.
[0089] Example 3
[0090] This embodiment is carried out in a similar manner to that of Embodiment 1, except that the composition of the exhaust gas to be treated is changed, wherein H2 is not contained, and the precious metal honeycomb catalyst is a platinum-alumina catalyst, wherein the support is a monolithic honeycomb ceramic made of cordierite, the carrier is alumina, the second active metal component is cobalt, and the first active metal component is platinum; and based on the total weight of the precious metal honeycomb catalyst, the content of the support is 65wt%, the content of the carrier is 25wt%, the content of the second active metal component in terms of metal element is 2wt%, and the content of the first active metal component is 5wt%;
[0091] The contact reaction conditions are different, see Table 2 for specific parameters; the CO content in the final treated gas is 0.002 vol%, which meets the enterprise standard of a concentration lower than 0.01 vol%.
[0092] Example 4
[0093] This embodiment is carried out using a method similar to that of Embodiment 1, except that the composition of the tail gas to be treated is changed, wherein hydrocarbon substances are contained, and the condition parameters of the contact reaction are different. For specific parameters, see Table 2; the CO content in the final treated gas is 0.0015 vol%, which meets the enterprise standard of a concentration below 0.01 vol%.
[0094] Example 5
[0095] This embodiment is carried out in a similar manner to that of Embodiment 1, except that the amount by weight of the first active metal component in the precious metal honeycomb catalyst is different and meets the following conditions: the volume concentration of CO in the exhaust gas to be treated and the amount by weight of the first active metal component in the precious metal honeycomb catalyst are in a relationship of 11:1; the CO content in the treated gas obtained at last is 0.009 vol%, which meets the enterprise standard of a concentration lower than 0.01 vol%.
[0096] Comparative Example 1
[0097] This comparative example is carried out in a method similar to that of Example 1, except that the precious metal honeycomb catalyst is a silver-alumina catalyst, wherein the support is a monolithic honeycomb ceramic made of cordierite, the carrier is alumina, the second active metal component is iron, and the first active metal component is silver; and based on the total weight of the precious metal honeycomb catalyst, the content of the support is 70wt%, the content of the carrier is 25wt%, the content of the second active metal component in terms of metal element is 2wt%, and the content of the first active metal component is 1wt%; the CO content in the finally obtained treated gas is 0.02vol%, which does not meet the enterprise standard of a concentration lower than 0.01vol%.
[0098] Comparative Example 2
[0099] This comparative example is carried out in a method similar to that of Example 1, except that the precious metal honeycomb catalyst is a platinum-alumina catalyst, wherein the support is a monolithic honeycomb ceramic made of cordierite, the carrier is alumina, the second active metal component is cobalt, and the first active metal component is platinum; and based on the total weight of the precious metal honeycomb catalyst, the content of the support is 72wt%, the content of the carrier is 25wt%, the content of the second active metal component in terms of metal element is 2wt%, and the content of the first active metal component is 0.2wt%; the CO content in the finally obtained treated gas is 0.03vol%, which does not meet the enterprise standard of a concentration lower than 0.01vol%.
[0100] Comparative Example 3
[0101] This comparative example is carried out using a method similar to that of Example 1, except that in the contact reaction system at the initial moment of the contact reaction, the volume concentration ratio of O2 to CO is 4:1; the CO content in the treated gas finally obtained is 0.02 vol%, which does not meet the enterprise standard of a concentration lower than 0.01 vol%.
[0102] Table 1
[0103] Content of tail gas to be treated Example 1 Example 2 Example 3 Example 4 CO(vol%) 1 8 3 2 <![CDATA[H2(vol%)]]> 0.2 1 0 3 <![CDATA[CH3OH(vol%)]]> 0 0.15 0.08 0.1 Sulfide (vol%) 0.002 0 0.005 0.002 Hydrocarbons (vol%) 0 0 0 0.1 <![CDATA[Dust particulate matter (μg / cm 3 )]]> 1800 1200 800 1500
[0104] Note: The sulfides mentioned are carbonyl sulfide and hydrogen sulfide;
[0105] The hydrocarbon substance is C 1-4 of hydrocarbons;
[0106] The average diameter of dust particles is 20-100μm.
[0107] Table 2
[0108]
[0109] Note: The relationship between the amount of CO and active metal is: CO volume concentration (mg / m 3 ) and the ratio of the weight (mg) of the first active metal component in the precious metal honeycomb catalyst.
[0110] From the above results, it can be seen that the present invention adopts a catalytic oxidation system, which can remove CO tail gas under various working conditions, especially can remove CO from tail gas under non-hydrogen-rich conditions. This method has simple process, convenient operation, low energy consumption, no secondary pollution, and has good application prospects.
[0111] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.
Claims
1. A method for removing CO by catalytic oxidation, characterized in that: The method is carried out in a catalytic oxidation system provided with a reaction unit, comprising: Under a first gas environment, the tail gas to be treated is contacted with the noble metal honeycomb catalyst in the reaction unit to react to obtain a treated gas with a CO content of ≤0.005 vol%; the first gas environment contains an oxygen-containing atmosphere and optionally also contains a hydrogen-containing atmosphere; The CO content in the tail gas to be treated is 0.05-10 vol%, and the total content of dust particles is not more than 2000 μg / cm 3 ; The average diameter of the dust particles is 20-100 μm; The precious metal honeycomb catalyst contains a first active metal component, which is platinum and / or palladium; based on the total weight of the precious metal honeycomb catalyst, the content of the first active metal component in terms of metal element is 0.5-10wt%; The amount of the oxygen-containing atmosphere introduced is controlled so that in the contact reaction system at the initial moment of the contact reaction, the volume concentration ratio of O2 to CO is 5-15:1; and based on the total volume of the hydrogen in the hydrogen-containing atmosphere and the tail gas to be treated, the hydrogen content is 0-5 vol%.
2. The method according to claim 1, wherein: Based on the total volume of the hydrogen in the hydrogen-containing atmosphere and the tail gas to be treated, the content of hydrogen is 0-1 vol%.
3. The method according to claim 1 or 2, wherein: The content of methanol in the tail gas to be treated is 0-0.2 vol%.
4. The method according to any one of claims 1 to 3, wherein: The content of sulfide in the tail gas to be treated is 0-0.005 vol%.
5. The method according to any one of claims 1 to 4, wherein: The volume concentration of CO in the exhaust gas to be treated and the weight of the first active metal component in the precious metal honeycomb catalyst are in a relationship of 1-10:
1. The volume concentration of CO is expressed in mg / m 3 The amount of the first active metal component used is in mg.
6. The method according to any one of claims 1 to 5, wherein: The catalytic oxidation system is also provided with a pretreatment unit, and the method further comprises: before subjecting the tail gas to be treated to the contact reaction, first subjecting the tail gas to be treated to liquid removal and dust removal in the pretreatment unit in sequence to obtain pretreated gas I, and then subjecting the pretreated gas I to the contact reaction; The conditions of liquid removal and dust removal are controlled so that the total content of the dust particles in the pre-treated gas I is 0-20 μg / cm 3 .
7. The method according to claim 6, wherein: The pretreatment unit comprises an exhaust gas buffer tank and an exhaust gas filter which are connected in sequence, and the liquid removal and the dust removal are respectively performed in the exhaust gas buffer tank and the exhaust gas filter.
8. The method according to claim 6 or 7, wherein: The catalytic oxidation system is also provided with a gas mixing unit, and the method further includes: before the pre-treatment gas I and the oxygen-containing atmosphere are subjected to the contact reaction, the pre-treatment gas I and the oxygen-containing atmosphere are first introduced into the gas mixing unit for mixing to obtain a mixed gas I, and then the mixed gas I is subjected to the contact reaction with the precious metal honeycomb catalyst.
9. The method according to claim 8, wherein: An inlet and outlet reaction heat exchanger is arranged in the gas mixing unit, and the inlet and outlet reaction heat exchanger comprises an inner cylinder and an outer cylinder; as well as The mixing operation includes: introducing the pre-treated gas I and the oxygen-containing atmosphere from an exhaust gas blower and an oxygen-containing atmosphere blower into the inner cylinder of the inlet and outlet reaction heat exchanger for mixing.
10. The method according to claim 8 or 9, wherein: The reaction unit is provided with an electric heater and a reaction furnace, and the method further comprises: before subjecting the mixed gas I to the contact reaction, first heating the mixed gas I in the electric heater, and then introducing the mixed gas I into the reaction furnace to undergo the contact reaction with the precious metal honeycomb catalyst.
11. The method according to any one of claims 1 to 10, wherein: The contact reaction conditions at least meet the following requirements: temperature of 150-350° C. and pressure of 0.05-0.2 MPa.
12. The method according to any one of claims 9 to 11, wherein: The method further comprises: performing heat exchange between the outer cylinder and the inner cylinder of the inlet and outlet reaction heat exchanger by at least a portion of the treated gas, the tail gas to be treated and the oxygen-containing atmosphere.
13. Application of the method for removing CO by catalytic oxidation as described in any one of claims 1 to 12 in the field of energy and environmental technology.
Citation Information
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