CN111375304B - Method for treating organic waste gas containing low-carbon hydrocarbon - Google Patents

Method for treating organic waste gas containing low-carbon hydrocarbon Download PDF

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CN111375304B
CN111375304B CN201811651652.6A CN201811651652A CN111375304B CN 111375304 B CN111375304 B CN 111375304B CN 201811651652 A CN201811651652 A CN 201811651652A CN 111375304 B CN111375304 B CN 111375304B
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waste gas
catalytic oxidation
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catalyst
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CN111375304A (en
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赵磊
汪鹏
刘忠生
王新
王筱喃
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
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Abstract

The invention relates to a method for treating organic waste gas containing low-carbon hydrocarbon, which comprises the steps of carrying out low-temperature catalytic oxidation treatment on the waste gas, and then carrying out high-temperature catalytic oxidation treatment on the treated gas, wherein a high-temperature catalytic oxidation catalyst is slurry obtained by mixing a honeycomb ceramic as a carrier, a coated metal oxide/MOFs composite material and ball-milling slurry, the ball-milling slurry is prepared by mixing active alumina, pseudo-boehmite powder and a dilute nitric acid solution and then carrying out ball milling, and the treated waste gas reaches the standard and is discharged. The invention adopts the low-temperature catalytic oxidation treatment-high-temperature catalytic oxidation treatment process, and has the characteristics of good treatment effect, good operation stability, stable catalyst activity and the like.

Description

Method for treating organic waste gas containing low-carbon hydrocarbon
Technical Field
The invention belongs to the technical field of organic waste gas treatment, and particularly relates to a method for treating organic waste gas containing low-carbon hydrocarbons.
Background
Volatile organic pollutants (VOCs) are one of the major pollutants in the atmosphere, and their overproof emissions pose serious threats to human health and ecological environment. The catalytic oxidation technology is an effective method for degrading VOCs, and the core of the technology is a catalytic oxidation catalyst. The currently widely used catalytic oxidation catalyst for VOCs is a noble metal catalyst with Pt and Pd as active components, and has good low-temperature (< 400 ℃) catalytic activity. However, VOCs organic waste gases containing high concentrations of lower hydrocarbons (ethane and propane) are difficult to completely oxidize at low temperatures, and the waste gases can be discharged up to standard by raising the reaction temperature (> 500 ℃). The currently commonly used noble metal catalyst is operated under an overhigh temperature condition (> 600 ℃) for a long time, and is easy to irreversibly inactivate, thereby influencing the treatment effect of waste gas.
CN102441379A discloses a catalytic oxidation catalyst and a preparation method thereof, which takes honeycomb ceramics as a carrier, and SiO is sequentially arranged on the surface of the honeycomb ceramics carrier2Coating and CeO2The coating contains 80 to 95 weight percent of active SiO based on the total weight of the coating 25 to 20 percent of CeO2And Pt, Zr and La metal element active components are loaded on the surface of the coating. The preparation method comprises the carrier pretreatment process, the sol preparation process, the carrier sol coating and the metal active component loading process. The catalyst has high coating firmness and high-temperature activity stability in the catalytic oxidation process of treating organic waste gas, and has good treatment effect on different high-temperature high-airspeed waste gases. However, the catalyst is a noble metal catalyst, and the noble metal catalyst is easy to irreversibly deactivate after being operated under the condition of overhigh temperature for a long time, influences the treatment effect of waste gas and has higher cost.
CN104971729A discloses a propane catalytic oxidation monolithic catalyst, which is prepared by coating an active component, a cocatalyst, pseudoboehmite and gamma-Al on a monolithic carrier2O3The coating slurry prepared by the components is formed by high-temperature roasting, wherein the integral carrier is cordierite honeycomb ceramic, and the active component of the catalyst is Co 3O4The cocatalyst is ZrO2、CeO2、La2O3One or more of them. The catalyst adopts cobaltosic oxide powder catalyst to prepare monolithic catalyst, and reduces inert component CoAl2O4Ensures the reproduction of the activity of the powder catalyst. The catalyst is suitable for operation at temperatures below 400 ℃ and does not allow complete oxidation of propane.
CN107983329A discloses a cerium-based composite oxide VOCs combustion catalyst using a metal organic framework as a template and a preparation method thereof, wherein a cerium-based metal organic framework material and a transition metal salt are soaked and mixed in a solvent, then the mixture is taken out, dried, ground into powder and roasted in the air, and the cerium-based composite oxide VOCs combustion catalyst using the metal organic framework as the template is obtained. Compared with the cerium-based composite oxide prepared by the traditional method, the invention greatly improves the dispersity of the transition metal by introducing the transition metal by using the metal organic framework, obviously improves the catalytic capability of the prepared cerium-based composite oxide on organic waste gas, has stronger catalytic activity, and can still maintain good catalytic performance after circulating multiple catalytic reactions. However, under the condition of long-term high-temperature operation, the active components of the cerium-based metal organic framework material are aggregated to form large-size particles, so that the loss of active sites and the reduction or inactivation of catalytic activity are caused.
Disclosure of Invention
Aiming at the defects of the prior art for treating the organic waste gas containing the low carbon hydrocarbon, the invention provides a method for treating the organic waste gas containing the low carbon hydrocarbon. The invention adopts the low-temperature catalytic oxidation treatment-high-temperature catalytic oxidation treatment process, and has the characteristics of good treatment effect, good operation stability, stable catalyst activity and the like.
The invention provides a method for treating organic waste gas containing low-carbon hydrocarbons, which comprises the following steps:
the method comprises the following steps of carrying out heat exchange and heating on organic waste gas containing low-carbon hydrocarbon, carrying out low-temperature catalytic oxidation treatment on the treated gas, and carrying out high-temperature catalytic oxidation treatment on the treated gas, wherein the high-temperature catalytic oxidation catalyst is slurry obtained by mixing honeycomb ceramics serving as a carrier, a coated metal oxide/MOFs composite material and ball-milling slurry, the ball-milling slurry is prepared by mixing active alumina, pseudo-boehmite powder and a dilute nitric acid solution and then carrying out ball milling, and the treated waste gas reaches the standard and is discharged.
In the invention, the metal oxide/MOFs composite material is obtained by placing a copper-based metal organic framework material in a salt solution of metal Mn or/and Ce, stirring for reaction for a period of time, and then filtering, drying and roasting. The copper-based metal organic framework material is at least one of Cu-BTC, Cu-BDC, Cu-MOF-74 and the like, and Cu-BTC is preferred. The salt solution of Mn and Ce is soluble salt solution of nitrate, chlorate, acetate and the like, preferably nitrate. The mass concentration of the Mn salt solution and the Ce salt solution is 5-30 percent, and preferably 20-25 percent. The stirring reaction time is 0.5-5h, then the solid is separated by filtration, dried at 80-120 ℃ for 6-12 h, and roasted at 200-220 ℃ for 1-2 h.
In the invention, the weight ratio of the activated alumina, the pseudo-boehmite powder and the dilute nitric acid solution is 1-5:1-5:1. The active alumina is gamma-Al2O3The mass concentration of the dilute nitric acid solution is 0.3-0.5 mol/L. And placing the mixed materials in a ball mill for ball milling for 6-10 hours to obtain ball milling slurry.
In the invention, the metal oxide/MOFs composite material is mixed with the ball-milling slurry, and the composite material is controlled to account for 2-5% of the mass of the ball-milling slurry.
In the invention, the honeycomb ceramic carrier is preferably a cordierite honeycomb ceramic carrier. The coating is to dip the honeycomb ceramic carrier into the mixed slurry for 3-5 min; taking out and purging after the impregnation is finished, and then drying and roasting at the drying temperature of 100 ℃ and 120 ℃ for 6-12 hours; the roasting temperature is 500-800 ℃, and the roasting time is 2-4 hours.
In the invention, the specific surface area of the prepared high-temperature catalytic oxidation catalyst is 30-40m2Per g, pore volume of 0.06-0.09cm3(ii) in terms of/g. Calculated by honeycomb ceramic carrier, the content of copper-based metal organic framework material is 5% -10%, the content of manganese oxide is 2% -5%, and the content of aluminum oxide is 5% -15%.
In the invention, the organic waste gas containing low-carbon hydrocarbons is mainly derived from organic waste gas containing low-carbon hydrocarbons produced by production devices, storage and transportation systems, petrochemical sewage treatment systems and the like in the petrochemical industry, such as organic waste gas containing low-carbon hydrocarbons discharged by structures such as production devices, storage and transportation operations, oil separation tanks of sewage treatment plants, flotation tanks and the like in petrochemical enterprises. The concentration of non-methane total hydrocarbons in the waste gas is 3000-100000mg/m 3Wherein the concentration of the low-carbon hydrocarbon is 100-10000mg/m3Lower hydrocarbons are primarily ethane and/or propane. Besides the low carbon hydrocarbon, the waste gas may contain hydrogen sulfide and C4And the concentration of pollutants in the waste gas of the organic matters such as the hydrocarbons and the benzene series can be greatly different according to different emission sources. According to the characteristics of pollutants in the waste gas, the waste gas can be correspondingly pretreated to remove particles, sulfides and the like, the concentration of organic matters in the waste gas is controlled to be lower than 25% of the lower limit value of the explosion limit of the most explosive component or mixed gas (the requirements of the technical Specification for treating industrial organic waste gas by a catalytic combustion method (HJ 2027 and 2013)), and the concentration of the waste gas is prevented from greatly fluctuating.
In the present invention, theThe low-temperature catalytic oxidation mainly comprises a heat exchanger, a heater and a catalytic oxidation reactor, wherein a noble metal catalyst is filled in the reactor, a carrier of the catalyst is a cordierite honeycomb carrier coated with alumina, the density of honeycomb pores is 200-300 meshes, the active metal is Pt/Pd, and the active component accounts for 0.1% -2% of the weight of an alumina coating in terms of elements; and other additives such as cerium and the like can be contained. In the catalytic oxidation reactor, the inlet temperature of the reactor is 150-400 ℃, preferably 200-350 ℃, and the volume space velocity of the waste gas passing through the catalyst bed is 1000- -1。
The high-temperature catalytic oxidation mainly comprises a heater-catalytic oxidation reactor, wherein the high-temperature catalytic oxidation catalyst prepared by the invention is filled in the reactor, the inlet temperature of the reactor is 500-700 ℃, the preferred temperature is 500-650 ℃, and the volume space velocity of waste gas passing through a catalyst bed layer is 1000--1。
Compared with the prior art, the invention has the following outstanding characteristics:
(1) the high-temperature catalytic oxidation catalyst with specific composition and proportion is adopted, metal oxides in the high-temperature catalytic oxidation catalyst are difficult to migrate and agglomerate, active components can keep high-efficiency catalytic activity, the high-temperature stability of the catalyst is improved, the hydrocarbon conversion rate is more than 95% after organic waste gas containing low-carbon hydrocarbon is treated, and the high-efficiency, stable and low-cost treatment of the waste gas can be realized; and active substances are not easy to lose, and the long-period stable operation can be maintained.
(2) In order to oxidize low-carbon hydrocarbons, the noble metal catalyst used in the existing low-temperature catalytic oxidation is operated under an excessively high temperature condition for a long time, and is easy to irreversibly deactivate, thereby influencing the treatment effect of waste gas. The invention adopts a low-temperature catalytic oxidation-high-temperature catalytic oxidation combined treatment mode, the noble metal catalyst only needs to operate at low temperature, the irreversible inactivation of the catalyst can not be caused, the high-efficiency treatment of the organic waste gas containing the low-carbon hydrocarbon is finally realized, and the long-term operation stability is good.
Drawings
FIG. 1 is a process flow diagram of the treatment process of the present invention.
Wherein, 1-pretreatment unit, 2-heat exchanger, 3-heater; 4-a low-temperature catalytic oxidation reactor, 5-a heater and 6-a high-temperature catalytic oxidation reactor; 101-organic waste gas containing low-carbon hydrocarbon, 102-pretreated waste gas and 103-preheated waste gas; 104-waste gas after low-temperature section heating, 105-waste gas after low-temperature catalytic oxidation, 106-waste gas after high-temperature heating, 107-high-temperature purified gas and 108-purified gas after heat exchange.
Detailed Description
The treatment method and effect of the present invention will be further described by examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the invention, the non-methane total hydrocarbon is detected by gas chromatography in HJ/T38 determination of non-methane total hydrocarbon in exhaust gas of fixed pollution source. The low-carbon hydrocarbon is detected by gas chromatography in air and waste gas monitoring and analyzing method (fourth edition) published by the State environmental protection administration.
The invention adopts the flow shown in figure 1 for treatment, organic waste gas 101 containing low-carbon hydrocarbon enters a pretreatment unit 1 which can be washing desulfurization, filtering dust removal, low-temperature diesel oil absorption desulfurization or high-concentration oil gas recovery, and the like, and specifically selects according to the characteristics of the waste gas, controls the concentration of organic matters to be less than 25% of the lower limit of the explosion limit, and the pretreated waste gas 102 enters a heat exchanger 2 for preheating, and the preheated waste gas 103 enters a heater 3 for heating to the initial reaction temperature, and the waste gas 104 enters a low-temperature catalytic oxidation reactor 4 after being heated in a low-temperature section for mainly catalytically oxidizing C4 and above organic matters, and the waste gas 105 after being subjected to low-temperature catalytic oxidation, the waste gas 106 after being heated is further heated by the heater 5 and enters the high-temperature catalytic oxidation reactor 6 to be mainly used for catalytic oxidation treatment of ethane and propane, the high-temperature purified gas 107 enters the heat exchanger 2 to preheat the waste gas, and the purified gas 108 after heat exchange is discharged.
Example 1
A petrochemical enterpriseThe maximum amount of the organic waste gas containing low-carbon hydrocarbon discharged from the sewage treatment field is 5000Nm3H, sulfide concentration of 100-3The concentration of non-methane total hydrocarbons is 3000-20000mg/m3Wherein the concentration of ethane and propane is 100-5000mg/m3The other pollutants are mainly benzene series, C4 and above hydrocarbons. The method is adopted for processing, and the specific process is as follows:
Preparation of high-temperature catalytic oxidation catalyst: placing Cu-BDC material in 25 percent manganese nitrate solution, stirring for 1 hour, filtering, drying for 6 hours at 120 ℃, roasting for 2 hours at 200 ℃ to obtain MnO2a/Cu-BDC composite material. Mixing gamma-Al2O3Mixing the powder, the pseudo-boehmite powder and 0.3mol/L nitric acid solution according to the weight ratio of 1:1:1, and placing the mixture in a ball mill for ball milling for 10 hours to obtain slurry. MnO of2Mixing the/Cu-BDC composite material with the ball-milling slurry, wherein the composite material accounts for 3% of the mass of the ball-milling slurry, and stirring for 1 hour to obtain the mixed slurry. The cordierite honeycomb ceramic carrier was immersed in the mixed slurry for 3 min. And taking out and purging after the impregnation is finished, drying for 6 hours at 120 ℃, and roasting for 2 hours at 600 ℃ to obtain the high-temperature catalytic oxidation catalyst.
The method comprises the steps of firstly pretreating organic waste gas containing low-carbon hydrocarbon to remove sulfide, controlling the concentration of the waste gas to be lower than 25% of the lower limit of the explosion limit of mixed gas, then exchanging heat with high-temperature purified gas, controlling the inlet temperature of a low-temperature catalytic oxidation reactor to be 230-350 ℃, filling a noble metal catalyst in the reactor, wherein the carrier of the catalyst is a cordierite honeycomb carrier coated with alumina, the density of honeycomb pores is 200 meshes, active metals are Pt and Pd, and the Pt content and the Pd content are respectively 0.2% and 0.15% in terms of the weight of elements in the alumina coating. The volume space velocity of the waste gas passing through the catalyst bed layer is not more than 12000h -1The C4 and above hydrocarbon substances in the waste gas are mainly removed, and a small amount of propane and ethane are oxidized. The waste gas after low-temperature catalytic oxidation enters a high-temperature catalytic oxidation reactor, the inlet temperature of the reactor is controlled to be 550-650 ℃, and the volume space velocity is not more than 15000h-1And the high-temperature purified gas is discharged after preheating the waste gas. Since the exhaust gas has a high concentration and the heat is recovered by the heat exchanger, the heater is basically not operated, and the supplementary heat is started only when the heat is insufficient, because of C4 and CThe organic matters are oxidized to release heat, the outlet temperature of the low-temperature catalytic oxidation reactor can basically meet the inlet temperature requirement of the high-temperature catalytic oxidation reactor, and heating is generally not needed.
The process of the invention runs for a long time of 1000h, the low-temperature catalyst does not have the deactivation phenomenon, the effect of the catalyst for oxidizing the low-carbon hydrocarbon is stable, and the loss of active substances is less. After treatment, the concentration of non-methane total hydrocarbon is always less than 13mg/m3And characteristic pollutants such as low-carbon hydrocarbon, benzene series and the like cannot be detected.
Example 2
The maximum amount of the organic waste gas containing low-carbon hydrocarbon discharged from sewage treatment plants and tank areas of certain petrochemical enterprises is 1000Nm3H, sulfide concentration of 500-5000mg/m3The concentration of non-methane total hydrocarbons is 3000-100000mg/m3Wherein the ethane and propane concentrations are 100-10000mg/m 3The other pollutants are mainly benzene series substances, C4 and above hydrocarbons. The method is adopted for processing, and the specific process is as follows:
preparation of high-temperature catalytic oxidation catalyst: placing Cu-BTC material in 25% manganese nitrate solution, stirring for 1 hr, filtering, drying at 120 deg.C for 6 hr, and calcining at 200 deg.C for 2 hr to obtain MnO2a/Cu-BTC composite material. Mixing gamma-Al2O3Mixing the powder, the pseudo-boehmite powder and 0.3mol/L nitric acid solution according to the weight ratio of 1:1:1, and placing the mixture in a ball mill for ball milling for 10 hours to obtain slurry. MnO of2Mixing the/Cu-BTC composite material with ball-milling slurry, wherein the composite material accounts for 3% of the mass of the ball-milling slurry, and stirring for 1 hour to obtain mixed slurry. The cordierite honeycomb ceramic carrier was immersed in the mixed slurry for 3 min. And taking out and purging after the impregnation is finished, drying for 6 hours at 120 ℃, and roasting for 2 hours at 600 ℃ to obtain the high-temperature catalytic oxidation catalyst.
The organic waste gas containing low-carbon hydrocarbon is firstly absorbed by low-temperature diesel oil and is subjected to desulfurization pretreatment, the concentration of the waste gas is controlled to be lower than 25% of the lower limit of the explosion limit of the mixed gas, and the total hydrocarbon concentration of the waste gas is controlled to be 20000mg/m3Then exchanging heat with high-temperature purified gas, controlling the inlet temperature of a low-temperature catalytic oxidation reactor to be 280-360 ℃, filling a noble metal catalyst into the reactor, wherein the carrier of the catalyst is cordierite coated with alumina The carrier is a bluestone honeycomb carrier, the density of honeycomb holes is 200 meshes, active metals are Pt and Pd, and the content of Pt is 0.2 percent and the content of Pd is 0.15 percent based on the weight of elements accounting for the alumina coating. The volume space velocity of the waste gas passing through the catalyst bed layer is not more than 13000h-1The C4 and above hydrocarbon substances in the waste gas are mainly removed, and a small amount of propane and ethane are oxidized. The waste gas after low-temperature catalytic oxidation enters a high-temperature catalytic oxidation reactor, the inlet temperature of the reactor is controlled to be 550-650 ℃, and the volume space velocity is not more than 13000h-1And the high-temperature purified gas is discharged after preheating the waste gas. Because the waste gas concentration is higher, retrieve the heat through the heat exchanger, the heater does not work basically, just start the supplementary heat when the heat is not enough, because C4 and above organic matter oxidation are exothermic, low temperature catalytic oxidation reactor outlet temperature can satisfy high temperature catalytic oxidation reactor inlet temperature requirement basically, does not generally need the heater heating.
The process of the invention is operated for a long time of 600h, the low-temperature catalyst does not have the deactivation phenomenon, the effect of the catalyst for oxidizing the low-carbon hydrocarbon is stable, and the loss of active substances is less. After treatment, the concentration of non-methane total hydrocarbon is always less than 15mg/m3And characteristic pollutants such as low-carbon hydrocarbon, benzene series and the like cannot be detected.
Example 3
The maximum amount of the organic waste gas containing low-carbon hydrocarbon discharged from a sewage treatment plant of a petrochemical enterprise is 3000Nm3H, sulfide concentration of 100-300mg/m3The concentration of non-methane total hydrocarbon is 2000-15000 mg/m3Wherein the ethane and propane concentrations are 100-2000mg/m3The other pollutants are mainly benzene series, C4 and above hydrocarbons. The method is adopted for processing, and the specific process is as follows:
preparation of high-temperature catalytic oxidation catalyst: putting the Cu-MOF-74 material in a 25% manganese nitrate solution, stirring for 1 hour, filtering, drying at 120 ℃ for 6 hours, roasting at 200 ℃ for 2 hours to obtain MnO2A/Cu-MOF-74 composite material. Mixing gamma-Al2O3Mixing the powder, the pseudo-boehmite powder and 0.3mol/L nitric acid solution according to the weight ratio of 1:1:1, and placing the mixture in a ball mill for ball milling for 10 hours to obtain slurry. MnO of2Mixing the/Cu-MOF-74 composite material with the ball-milling slurry, wherein the composite material occupies the ball3% of the slurry by mass, and stirring for 1 hour to obtain a mixed slurry. The cordierite honeycomb ceramic carrier was immersed in the mixed slurry for 3 min. And taking out and purging after the impregnation is finished, drying for 6 hours at 120 ℃, and roasting for 2 hours at 600 ℃ to obtain the high-temperature catalytic oxidation catalyst.
The method comprises the steps of firstly pretreating organic waste gas containing low-carbon hydrocarbon to remove sulfide, controlling the concentration of the waste gas to be lower than 25% of the lower limit of the explosion limit of mixed gas, then exchanging heat with high-temperature purified gas, controlling the inlet temperature of a low-temperature catalytic oxidation reactor to be 230-350 ℃, filling a noble metal catalyst in the reactor, wherein the carrier of the catalyst is a cordierite honeycomb carrier coated with alumina, the density of honeycomb pores is 200 meshes, active metals are Pt and Pd, and the Pt content and the Pd content are respectively 0.2% and 0.15% in terms of the weight of elements in the alumina coating. The volume space velocity of the waste gas passing through the catalyst bed layer is not more than 15000h -1The C4 and above hydrocarbon substances in the waste gas are mainly removed, and a small amount of propane and ethane are oxidized. The waste gas after low-temperature catalytic oxidation enters a high-temperature catalytic oxidation reactor, the inlet temperature of the reactor is controlled to be 550-650 ℃, and the volume space velocity is not more than 20000h-1And the high-temperature purified gas is discharged after preheating the waste gas. Because the waste gas concentration is higher, retrieve the heat through the heat exchanger, the heater does not work basically, just start the supplementary heat when the heat is not enough, because C4 and above organic matter oxidation are exothermic, low temperature catalytic oxidation reactor outlet temperature can satisfy high temperature catalytic oxidation reactor inlet temperature requirement basically, does not generally need the heater heating.
The process of the invention is operated for a long time of 1000h, the low-temperature catalyst does not have the deactivation phenomenon, the effect of the catalyst for oxidizing the low-carbon hydrocarbon is stable, and the loss of active substances is less. After treatment, the concentration of non-methane total hydrocarbon is always less than 10mg/m3And characteristic pollutants such as low-carbon hydrocarbon, benzene series and the like cannot be detected.
Comparative example 1
The same as in examples 1 to 3, except that: the high-temperature catalytic oxidation catalyst is not adopted, and only the low-temperature catalytic oxidation catalyst is adopted. Controlling the inlet temperature of the reactor at 400 ℃ and 300 ℃, wherein the concentration of non-methane total hydrocarbons in the purified gas is about 30-150mg/m 3Mainly ethane and a small amount of propane.
Comparative example 2
The same as in examples 1 to 3, except that: the high-temperature catalytic oxidation catalyst is not adopted, and only the low-temperature catalytic oxidation catalyst is adopted. The inlet temperature of the reactor is controlled to be 400-450 ℃, and the concentration of non-methane total hydrocarbon in the purified gas can be less than 120mg/m3However, the device has small elasticity, the phenomenon of overtemperature shutdown of the catalytic oxidation device often occurs, and the operation is unstable. Moreover, the catalytic oxidation catalyst shows a decrease in activity after 2 months due to exceeding the tolerance temperature of the catalyst, resulting in a decrease in oxidation effect.
Comparative example 3
The same as in examples 1 to 3, except that: the low-temperature catalytic oxidation catalyst is not adopted, only the high-temperature catalytic oxidation catalyst is adopted, the inlet temperature of the reactor is controlled to be 230-3。
Comparative example 4
The same as in examples 1 to 3, except that: the low-temperature catalytic oxidation catalyst is not adopted, only the high-temperature catalytic oxidation catalyst is adopted, the inlet temperature of the reactor is controlled to be 500-.

Claims (18)

1. The method for treating the organic waste gas containing the low-carbon hydrocarbons is characterized by comprising the following steps of: carrying out low-temperature catalytic oxidation treatment on organic waste gas containing low-carbon hydrocarbon, carrying out high-temperature catalytic oxidation treatment on the treated gas, wherein the high-temperature catalytic oxidation catalyst is slurry obtained by mixing a honeycomb ceramic as a carrier, a coated metal oxide/MOFs composite material and ball-milling slurry, the ball-milling slurry is prepared by mixing active alumina, pseudo-boehmite powder and a dilute nitric acid solution and then carrying out ball milling, and the treated waste gas reaches the standard and is discharged; the metal oxide/MOFs composite material is obtained by placing a copper-based metal organic framework material in a salt solution of metal Mn or/and Ce, stirring for reaction for a period of time, and then filtering, drying and roasting; the specific surface area of the high-temperature catalytic oxidation catalyst is 30-40m 2Per g, pore volume of 0.06-0.09cm3(ii)/g; based on the weight of the honeycomb ceramic carrier, the copper-based metal organic framework5-10% of material, 2-5% of metal oxide, 5-15% of alumina, wherein the metal oxide is oxide of Mn or/and Ce.
2. The method of claim 1, wherein: the copper-based metal organic framework material is at least one of Cu-BTC, Cu-BDC and Cu-MOF-74.
3. The method of claim 2, wherein: the copper-based metal organic framework material is Cu-BTC.
4. The method of claim 1, wherein: the salt solution of Mn and Ce is at least one of nitrate, chloride and acetate.
5. The method of claim 4, wherein: the salt solution of Mn and Ce is nitrate.
6. The method of claim 1 or 4 or 5, wherein: the mass concentration of the Mn salt solution and the Ce salt solution is 5-30 percent.
7. The method of claim 6, wherein: the mass concentration of the Mn salt solution and the Ce salt solution is 20-25 percent.
8. The method of claim 1, wherein: the stirring reaction time is 0.5-5h, then the solid is separated by filtration, dried at 80-120 ℃ for 6-12 h, and roasted at 200-220 ℃ for 1-2 h.
9. The method of claim 1, wherein: the weight ratio of the activated alumina to the pseudo-boehmite powder to the dilute nitric acid solution is 1-5:1-5: 1.
10. The method according to claim 1 or 9, characterized in that: the active alumina is gamma-Al2O3The concentration of the dilute nitric acid solution is 0.3-0.5 mol/L.
11. The method according to claim 1 or 2, characterized in that: and controlling the metal oxide/MOFs composite material to account for 2-5% of the mass of the ball-milling slurry.
12. The method of claim 1, wherein: the honeycomb ceramic carrier is a cordierite honeycomb ceramic carrier, and the coating is to dip the honeycomb ceramic carrier in the mixed slurry for 3-5 min.
13. The method of claim 12, wherein: taking out and purging after the impregnation is finished, and then drying and roasting at the drying temperature of 100 ℃ and 120 ℃ for 6-12 hours; the roasting temperature is 500-800 ℃, and the roasting time is 2-4 hours.
14. The method of claim 1, wherein: the organic waste gas containing the low-carbon hydrocarbon is derived from organic waste gas containing the low-carbon hydrocarbon generated by a production device, a storage and transportation system and a petrochemical sewage treatment system in the petrochemical industry, wherein the concentration of the non-methane total hydrocarbon is 3000-100000mg/m 3Wherein the concentration of the low-carbon hydrocarbon is 100-10000mg/m3Lower hydrocarbons refer to ethane and/or propane.
15. The method according to claim 1 or 14, characterized in that: according to the characteristics of pollutants in the waste gas, corresponding pretreatment is carried out to remove particles and sulfides, and the concentration of organic matters in the waste gas is controlled to be lower than 25% of the lower limit value of the explosion limit of the most explosive component or mixed gas.
16. The method of claim 1, wherein: the low-temperature catalytic oxidation comprises a heat exchanger, a heater and a catalytic oxidation reactor, wherein a noble metal catalyst is filled in the reactor, a carrier of the catalyst is a cordierite honeycomb carrier coated with alumina, the density of honeycomb pores is 200-300 meshes, the active metal is Pt/Pd, and the active component accounts for 0.1-2% of the weight of an alumina coating in terms of elements.
17. The method according to claim 1 or 16, characterized in that: in the low-temperature catalytic oxidation reactor, the inlet temperature of the reactor is 150-400 ℃, and the volume space velocity of the waste gas passing through the catalyst bed layer is 1000--1。
18. The method of claim 1, wherein: the high-temperature catalytic oxidation comprises a heater-catalytic oxidation reactor, the inlet temperature of the reactor is 500-700 ℃, the volume space velocity of the waste gas passing through the catalyst bed layer is 1000- -1。
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