CN109261144B - Catalyst for chlorine-containing organic waste gas treatment process - Google Patents
Catalyst for chlorine-containing organic waste gas treatment process Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention provides a catalyst for a chlorine-containing organic waste gas treatment process, which avoids the technical problem that the tail gas emission does not reach the standard due to the fact that a single catalyst is not suitable for multi-component CVOCs catalytic combustion by arranging three catalyst layers in a reaction column, improves the total removal rate of organic waste gas, has stable catalytic activity and long service life of more than 300 hours, and has the removal rate of organic chlorine waste gas of more than 99%.
Description
The present application is a divisional application of the following applications: the application date is 11 and 09 in 2017, the application number is 201711098348.9, and the invention is named as a treatment process for chlorine-containing organic waste gas.
Technical Field
The invention relates to chlorine-containing waste gas treatment, in particular to a catalyst for a chlorine-containing organic waste gas treatment process.
Background
Volatile Organic Compounds (VOCs) are a general name of a class of compounds, and although there are different definitions of VOCs in international organizations, organizations or countries such as WHO, EU, USAEPA, ISO, etc., VOCs generally refer to organic compounds with a boiling point of less than 373.15K at 101KPa, have a low boiling point, are easy to volatilize into the atmosphere to cause pollution, and are a class of organic pollutants which generally exist in the air and have complex components.
chlorine-Containing Volatile Organic Compounds (CVOC) are a class of important branches of VOCs, mainly comprise methyl Chloride (CM), Dichloromethane (DCM), Vinyl Chloride (VC), Chlorobenzene (CB), 1, 2-Dichloroethane (DCE), Trichloroethylene (TCE) and the like, and the substances have strong toxicity, and can cause the increase of the concentration of ozone on the earth surface under certain conditions by photochemical reaction with nitrogen oxides in the atmosphere to form photochemical smog which can also react with some free radicals in the atmosphere to form secondary organic aerosol. Some compounds deplete stratospheric ozone, creating ozone voids, while some generate too much ozone in the troposphere. In addition, some recent studies have shown that VOCs can pose certain health risks to humans. Therefore, based on the important effects of these substances on human health and ecological environment, more and more researchers and organizations are beginning to pay attention to their treatment methods.
In view of the serious harm of the chlorine-containing volatile organic compounds, the treatment method of the chlorine-containing volatile organic compounds also becomes a hot problem in the international environment nowadays. CVOCs processing methods are now mainly divided into two major categories: one non-destructive technique, also known as recovery, is to enrich CVOCs by changing physical conditions, such as temperature, pressure, etc., and then separate them, and includes adsorption, membrane separation, absorption, and condensation. Another is a destructive technique, by chemical or biological means, to convert CVOCs to CO2、H2O, HCl and other non-toxic or toxic small molecular inorganic matters, and the method includes direct combustion, photocatalytic oxidation, catalytic combustion, biodegradation and other steps. The methods have different applicable conditions, for example, the adsorption method has good elimination effect on low-concentration waste gas, but can cause pollution to be transferred from a gas phase to a solid phase, so that the problem of secondary pollution is caused; the condensation method is mainly used for treating waste gas with high concentration and small air volume, but has the defects of large investment, high operation cost, low benefit and the like for the waste gas with low concentration and large air volume; direct combustion processes high concentrations of exhaust gases, but is substantially above 800 ℃ due to the reaction old woman degrees being too high. And dioxin, NO, occurs in combustion productsxAnd toxic by-products; however, the catalytic combustion has the characteristics of low energy consumption, no secondary pollution, high efficiency and the like under the condition of low-concentration waste gas, and is one of the most effective treatment methods for treating industrial waste gas in commerce at present.
The use of CVOCs catalytic combustion has mainly focused on three types of catalysts: noble metal catalysts, solid acid catalysts, transition metal oxide catalysts. The noble metal catalyst has the problems of relatively high price, high chlorination activity (easily generating polychlorinated byproducts with higher toxicity), easy poisoning by generating oxychloro compounds, poisoning in a high-temperature area due to loss of noble metals and the like, so that the application of the noble metal catalyst is limited. The transition metal catalyst for catalytic combustion of chloro-aromatic hydrocarbon is mainly V2O5-TiO2Base catalysts, and the like. However, V2O5-TiO2TiO in base catalyst2Has toxic and toxic effectsIt is easy to cause secondary pollution, and limits its application. Other types of catalysts, such as solid acid catalysts, have some applications and have not been widely popularized due to their low activity or high number of by-products.
The transition metal oxide, which is the main catalyst active component used in the patent literature, is UO2、MnO2、Co3O4、La2O3、LaO2And noble metals such as Pt and Pd, and the carrier is SiO2, Al2O3, TiO2 and ZrO 2. Representative patents are JP2002219364, JP2001286729, JP2001278630, JP2001009284, JP2001286734, JP2001327869, JP10085559a2, US4031149A, US4059677A, US4065543A, US4561969A, US58116628A, US4169862A, US7052663A, and the like.
CVOCs tail gases, however, are often not a single halogenated hydrocarbon, often accompanied by other types of organics. Due to the influence of competitive adsorption and reaction temperature, the catalyst with high activity and selectivity screened by researching single-component CVOCs is not necessarily applicable to multi-component CVOCs.
Disclosure of Invention
In order to solve the technical problem, the invention provides a catalyst for a chlorine-containing organic waste gas treatment process, chlorine-containing organic waste gas and oxygen enter a gas buffer tank through a waste gas conveying pipeline and an oxygen steel cylinder respectively, are mixed and buffered, are simultaneously introduced into a reaction column at a certain flow rate for catalytic combustion, and tail gas treated by catalytic combustion enters a tail gas collecting device and is discharged from an exhaust port after adsorption treatment;
the reaction column is divided into three sections along the flowing direction of the waste gas, and a first catalyst bed layer, a second catalyst bed layer and a third catalyst bed layer are loaded in sequence.
The catalyst loaded on the first catalyst bed layer is as follows: using activated carbon as carrier, LaO2Is an active component, and alkali metal is an auxiliary agent; wherein, LaO26-15% of the catalyst, 0.1-2% of alkali metal and the balance of active carbon; the alkali metal is one or more of Li, Na, K, Ru and Cs.
Rare earth composite oxides, especially LaO2Has good storageThe oxygen release performance and the oxygen mobility are very beneficial to the deep oxidation of the CVOCs, so that the application of the CVOCs in the field of catalytic oxidation is widely concerned. And LaO2Has certain acidity and La4+/La3+Has good oxygen storage and release performance and oxygen mobility. So that the catalyst can stably convert chloralkane such as chlorine-containing volatile organic compounds methylene dichloride and the like into H for a long time in air environment2O、CO2And HCl.
The catalyst is prepared by the following method: an amount of soluble lanthanum salt and an amount of alkali metal salt were dissolved in an amount of water, followed by adding activated carbon support to the solution and maintaining the mixture under stirring for 2 hours, then heating the mixture to 130 ℃ and maintaining the temperature for 24 hours. Filtering, drying at 80 deg.C overnight, calcining at high temperature in air, tabletting, and sieving (40-60 mesh).
The concentration and the impregnation ratio of each solution are controlled in the preparation process, so that the obtained catalyst has the following characteristics: LaO26-15% of the catalyst, 0.1-2% of alkali metal and the balance of active carbon; the high-temperature roasting is roasting at 400-600 ℃ for 2-5 hours.
The catalyst loaded on the second catalyst bed layer is as follows: with TiO2Particles as carrier and CuO-Co3O4Is an active component; wherein CuO accounts for 6-18% of the weight of the catalyst, and Co3O420-45% of the weight of the catalyst, and the balance of TiO2And (3) granules. By using TiO2The particles are used as carriers, the active components and the matrix have strong bonding force, are not easy to fall off and crack, and can still keep higher activity under high airspeed airflow and thermal shock. The conversion rate of the catalyst to chlorinated aromatic hydrocarbons such as o-dichlorobenzene and the like at 300 ℃ reaches more than 95 percent.
The catalyst is prepared by the following method: dissolving a quantity of a soluble copper salt and a quantity of a cobalt salt in a quantity of water, followed by addition of TiO to the solution2Granulate and the mixture is kept under stirring for 2 hours, then the mixture is heated to 130 ℃ and kept at this temperature for 24 hours. For treatingFiltering, drying at 80 deg.C overnight, calcining at high temperature in air, tabletting, and sieving (40-60 mesh).
The concentration and the impregnation ratio of each solution are controlled in the preparation process, so that the obtained catalyst has the following characteristics: CuO accounts for 6-18% of the weight of the catalyst, and Co3O420-45% of the weight of the catalyst, and the balance of TiO2And (3) granules.
The catalyst loaded on the third catalyst bed layer is as follows: the catalyst comprises cerium oxide nanorods and metal palladium, wherein the content of the palladium is 0.5 percent by weight, and the balance is the cerium oxide nanorods. The catalyst is prepared by taking noble metal palladium with high catalytic activity as an active component of the catalyst, and is particularly suitable for catalytic conversion of chlorinated organic matters and catalytic combustion byproducts when the content of chlorinated alkanes in tail gas is low.
The catalyst is prepared by the following method: mixing cerium nitrate and a sodium hydroxide solution, uniformly stirring in a beaker, then putting into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing for a certain time at different temperatures, filtering, washing and drying a precipitate, and calcining for 3 hours at 350 ℃ in an air atmosphere to obtain cerium oxide carriers with different shapes; soaking soluble palladium salt water solution into cerium oxide carrier powder, dispersing uniformly, standing, drying, calcining at 400 ℃ for 4h in air atmosphere, tabletting, and sieving (40-60 meshes).
The adsorbent used in the adsorption treatment is granular activated carbon, and the particle size of the adsorbent is 2-5 mm.
The reaction column is divided into three sections along the gas flow direction, the temperature of the first section is controlled between 100 ℃ and 200 ℃, the temperature of the second section is controlled between 200 ℃ and 300 ℃, and the temperature of the third section is controlled between 300 ℃ and 400 ℃.
Introducing the chlorine-containing organic waste gas and the oxygen into a gas buffer tank for buffering, and introducing into a reaction column at a flow rate of 3.8-6.9L/min; the oxygen accounts for 50-80% (V/V) of the total amount of the mixed gas.
Compared with the prior art, the invention has the technical effects that:
(1) aiming at the situation that the composition of CVOCs tail gas is complex, three reactors are arranged in the reaction columnThe section catalyst layer is used for avoiding the technical problem that the tail gas emission does not reach the standard caused by that a single catalyst is not suitable for multi-component CVOCs catalytic combustion, wherein the first catalyst bed layer adopts LaO2The activated carbon is used as a catalyst, so that the catalyst can stably and pertinently convert chloralkane containing chlorine volatile organic compounds such as dichloromethane and the like into H for a long time in an air environment2O、CO2And HCl. For chlorinated aromatic hydrocarbon component, TiO is adopted as a second catalyst layer arranged in the reaction column2The particles are used as carriers, the active components and the matrix have strong bonding force, are not easy to fall off and crack, and can still keep higher activity under high airspeed airflow and thermal shock. The conversion rate of the catalyst to chlorinated aromatic hydrocarbons such as o-dichlorobenzene and the like at 300 ℃ reaches more than 95 percent. And the third catalyst bed layer adopts a palladium/nano cerium oxide rod as a catalyst active component, and is particularly suitable for catalytic conversion of chlorinated organic matters and catalytic combustion byproducts when the content of chlorinated alkanes in tail gas is low.
(2) The invention has simple process, stable catalytic activity, long service life of more than 300 hours and organic chlorine waste gas removal rate of more than 99 percent.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
[ example 1 ]
Preparation of the catalyst:
(1) an amount of lanthanum nitrate and an amount of potassium chloride were dissolved in an amount of water, followed by adding activated carbon support to the solution and maintaining the mixture under stirring for 2 hours, and then heating the mixture to 130 ℃ and maintaining the temperature for 24 hours. Filtering, drying the solid product at 80 ℃ overnight, finally roasting for 4.5h at 500 ℃ in an air atmosphere, tabletting, and sieving (40-60 meshes) to obtain the catalyst A.
Controlling each solution in the preparation processThe concentration of the solution and the impregnation ratio were such that the catalyst a obtained had the following characteristics: LaO27.2 percent of the weight of the catalyst, 0.8 percent of the weight of the metal potassium and the balance of active carbon.
(2) Dissolving copper nitrate and cobalt chloride in a quantity of water, and then adding TiO to the solution2Granulate and the mixture is kept under stirring for 2 hours, then the mixture is heated to 130 ℃ and kept at this temperature for 24 hours. Filtering, drying the solid product at 80 ℃ overnight, finally roasting at 430 ℃ in an air atmosphere for 3h, tabletting, and sieving (40-60 meshes) to obtain the catalyst B.
The concentration and the impregnation ratio of each solution are controlled in the preparation process, so that the obtained catalyst B has the following characteristics: CuO accounts for 12% of the weight of the catalyst, and Co3O432% of the catalyst, and the balance of TiO2And (3) granules.
(3) Mixing cerium nitrate and a sodium hydroxide solution, uniformly stirring in a beaker, then putting into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing for a certain time at different temperatures, filtering, washing and drying a precipitate, and calcining for 3 hours at 350 ℃ in an air atmosphere to obtain cerium oxide carriers with different shapes; soaking soluble palladium salt water solution into cerium oxide carrier powder, dispersing uniformly, standing, drying, calcining at 400 ℃ for 4h in air atmosphere, tabletting, and sieving (40-60 meshes) to obtain the catalyst C. The concentration and the impregnation ratio of each solution are controlled in the preparation process, so that the obtained catalyst B has the following characteristics: the palladium content was 0.5% by weight.
Treating chlorine-containing organic waste gas:
chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, chlorobenzene 2500ppm, 1, 2-dichloroethane 380 ppm.
The chlorine-containing organic waste gas and the oxygen respectively enter a gas buffer tank through a waste gas conveying pipeline and an oxygen steel cylinder for mixing and buffering, the oxygen accounts for 56% (V/V) of the total amount of the mixed gas, then the mixed gas is introduced into a 55mm reaction column at the flow rate of 5.2L/min, the reaction column is divided into three sections along the flow direction of the waste gas, the first section is loaded with a catalyst A, the second section is loaded with a catalyst B, the third section is loaded with a catalyst C, the temperature of the first section is controlled at 175 ℃, the temperature of the second section is controlled at 300 ℃, and the temperature of the third section is controlled at 370 ℃. Tail gas treated by catalytic combustion enters a tail gas collecting device, is discharged from an exhaust port after adsorption treatment, and the content of chlorine-containing organic matters in discharged airflow is detected: methyl chloride 1.2ppm, dichloromethane 1ppm, vinyl chloride 0ppm, chlorobenzene 1ppm, 1, 2-dichloroethane 0.5 ppm. The removal rate of the main chlorine-containing organic matters is calculated to be more than 99.7 percent.
After the test is carried out for 330 hours, the content of chlorine-containing organic matters in the exhaust gas is: methyl chloride 2.4ppm, dichloromethane 3.1ppm, chloroethylene 0.2ppm, chlorobenzene 2.2ppm, 1, 2-dichloroethane 3.2 ppm. The removal rate of the main chlorine-containing organic matters is calculated to be more than 99.1 percent.
[ example 2 ]
Chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, chlorobenzene 2500ppm, 1, 2-dichloroethane 380 ppm.
The chlorine-containing organic waste gas and the oxygen respectively enter a gas buffer tank through a waste gas conveying pipeline and an oxygen steel cylinder for mixing and buffering, the oxygen accounts for 56% (V/V) of the total amount of the mixed gas, then the mixed gas is introduced into a 55mm reaction column at a flow rate of 4.4L/min, the reaction column is divided into three sections along the flow direction of the waste gas, the first section is loaded with a catalyst A, the second section is loaded with a catalyst B, the third section is loaded with a catalyst C, the temperature of the first section is controlled to be 120 ℃, the temperature of the second section is controlled to be 210 ℃, and the temperature of the third section is controlled to be 350 ℃. Tail gas treated by catalytic combustion enters a tail gas collecting device, is discharged from an exhaust port after adsorption treatment, and the content of chlorine-containing organic matters in discharged airflow is detected: methyl chloride 1.7ppm, methylene chloride 2.1ppm, vinyl chloride 0.5ppm, chlorobenzene 1.0ppm, 1, 2-dichloroethane 0.3 ppm. Through calculation, the removal rate of the main chlorine-containing organic matters is over 99.6 percent.
After the test is carried out for 500 hours of continuous operation, the content of chlorine-containing organic matters in the exhaust gas is: methyl chloride 2.7ppm, methylene chloride 4.5ppm, vinyl chloride 0.3ppm, chlorobenzene 2.7ppm, 1, 2-dichloroethane 3.6 ppm. The removal rate of the main chlorine-containing organic matters is calculated to be more than 99.0 percent.
Comparative example 1
Treating chlorine-containing organic waste gas:
chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, chlorobenzene 2500ppm, 1, 2-dichloroethane 380 ppm.
And respectively feeding the chlorine-containing organic waste gas and oxygen into a gas buffer tank through a waste gas conveying pipeline and an oxygen steel cylinder for mixing and buffering, controlling the oxygen to account for 56% (V/V) of the total amount of the mixed gas, then introducing the oxygen into a 55mm reaction column at a flow rate of 5.2L/min, dividing the reaction column into three sections along the flow direction of the waste gas, loading a catalyst A in the three sections, controlling the temperature of the first section at 175 ℃, the temperature of the second section at 300 ℃, and the temperature of the third section at 370 ℃. Tail gas treated by catalytic combustion enters a tail gas collecting device, is discharged from an exhaust port after adsorption treatment, and the content of chlorine-containing organic matters in discharged airflow is detected: methyl chloride 1.2ppm, methylene chloride 0.2ppm, vinyl chloride 0.9ppm, chlorobenzene 456ppm, 1, 2-dichloroethane 8.4 ppm. The removal rate of chlorobenzene was calculated to be only 81.76%.
Comparative example 2
Treating chlorine-containing organic waste gas:
chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, chlorobenzene 2500ppm, 1, 2-dichloroethane 380 ppm.
And respectively feeding the chlorine-containing organic waste gas and oxygen into a gas buffer tank through a waste gas conveying pipeline and an oxygen steel cylinder for mixing and buffering, controlling the oxygen to account for 56% (V/V) of the total amount of the mixed gas, then introducing the oxygen into a 55mm reaction column at a flow rate of 5.2L/min, dividing the reaction column into three sections along the flow direction of the waste gas, loading a catalyst B in each section, controlling the temperature of the first section at 175 ℃, the temperature of the second section at 300 ℃, and the temperature of the third section at 370 ℃. Tail gas treated by catalytic combustion enters a tail gas collecting device, is discharged from an exhaust port after adsorption treatment, and the content of chlorine-containing organic matters in discharged airflow is detected: methyl chloride 15ppm, methylene chloride 152ppm, vinyl chloride 3.5ppm, chlorobenzene 0.3ppm, 1, 2-dichloroethane 0.7 ppm. The removal of dichloromethane was calculated to be only 87.3%.
Comparative example 3
Treating chlorine-containing organic waste gas:
chlorine-containing organic waste gas discharged from a certain chemical plant: methyl chloride 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, chlorobenzene 2500ppm, 1, 2-dichloroethane 380 ppm.
And respectively feeding the chlorine-containing organic waste gas and oxygen into a gas buffer tank through a waste gas conveying pipeline and an oxygen steel cylinder for mixing and buffering, controlling the oxygen to account for 56% (V/V) of the total amount of the mixed gas, then introducing the oxygen into a 55mm reaction column at a flow rate of 5.2L/min, dividing the reaction column into three sections along the flow direction of the waste gas, loading a catalyst C in each section, controlling the temperature of the first section at 175 ℃, the temperature of the second section at 300 ℃, and the temperature of the third section at 370 ℃. Tail gas treated by catalytic combustion enters a tail gas collecting device, is discharged from an exhaust port after adsorption treatment, and the content of chlorine-containing organic matters in discharged airflow is detected: methyl chloride 0ppm, methylene chloride 0ppm, vinyl chloride 0ppm, chlorobenzene 0ppm, 1, 2-dichloroethane 0.1 ppm. The removal rate of the main chlorine-containing organic matters is close to 100 percent by calculation.
After the test is carried out for 30 hours of continuous operation, the content of chlorine-containing organic matters in the exhaust gas is: 35ppm of methyl chloride, 56ppm of dichloromethane, 18ppm of vinyl chloride, 102ppm of chlorobenzene and 45ppm of 1, 2-dichloroethane. The calculated removal rate of the main chlorine-containing organic matters is only about 88 percent.
Therefore, the method adopts a reaction column sectional arrangement mode, and sequentially loads the catalyst A, the catalyst B and the catalyst C with specific activity, so that the technical problem that the tail gas emission does not reach the standard due to the fact that a single catalyst is not suitable for multi-component CVOCs catalytic combustion is solved, and the removal rate of the chlorine-containing organic waste gas reaches more than 99%; in addition, the service life of the catalyst is prolonged, and satisfactory removal rate can be obtained after continuous operation for more than 300 hours, so that the method has incomparable advantages compared with the traditional chlorine-containing organic waste gas removal process.
The foregoing description has disclosed fully preferred embodiments of the present invention. It should be noted that those skilled in the art can make modifications to the embodiments of the present invention without departing from the scope of the appended claims. Accordingly, the scope of the appended claims is not to be limited to the specific embodiments described above.
Claims (1)
1. A catalyst for a chlorine-containing organic waste gas treatment process, characterized in that: the catalyst comprises a catalyst loaded on a first catalyst bed layer, a catalyst loaded on a second catalyst bed layer and a catalyst loaded on a third catalyst bed layer, wherein the catalyst loaded on the first catalyst bed layer is as follows: using activated carbon as carrier, LaO2Is an active component, and alkali metal is an auxiliary agent; wherein, LaO27.2 percent of the weight of the catalyst, 0.8 percent of alkali metal of the weight of the catalyst and the balance of active carbon; the alkali metal is K; the catalyst loaded on the second catalyst bed layer is as follows: with TiO2Particles as carrier and CuO-Co3O4Is an active component; wherein CuO accounts for 12 percent of the weight of the catalyst, and Co3O432% of the catalyst, and the balance of TiO2Particles; the catalyst loaded on the third catalyst bed layer is as follows: the catalyst comprises cerium oxide nanorods and metal palladium, wherein the content of the palladium is 0.5 percent by weight, and the balance is the cerium oxide nanorods;
wherein:
the preparation method of the catalyst loaded on the first catalyst bed layer comprises the following steps: dissolving a certain amount of lanthanum nitrate and a certain amount of potassium chloride in a certain amount of water, subsequently adding an activated carbon support to the solution and keeping the mixture stirred for 2 hours, and then heating the mixture to 130 ℃ and keeping the temperature for 24 hours; filtering, drying the solid product at 80 ℃ overnight, roasting at 500 ℃ in an air atmosphere for 4.5h, tabletting, and sieving by a 40-60 mesh sieve to obtain the catalyst loaded on the first catalyst bed layer;
the preparation method of the catalyst loaded on the second catalyst bed layer comprises the following steps: dissolving copper nitrate and cobalt chloride in a quantity of water, and then adding TiO to the solution2Granulating and maintaining the mixture under stirring for 2 hours, then heating the mixture to 130 ℃ and maintaining the temperature for 24 hours; filtering, drying the solid product at 80 deg.C overnight, and air atmosphere 430Roasting for 3h at the temperature of 40-60 meshes, tabletting, and sieving to obtain a catalyst loaded on a second catalyst bed layer;
the preparation method of the catalyst loaded on the third catalyst bed layer comprises the following steps: mixing cerium nitrate and a sodium hydroxide solution, uniformly stirring in a beaker, then putting into a crystallization kettle with a polytetrafluoroethylene lining, crystallizing for a certain time at different temperatures, filtering, washing and drying a precipitate, and calcining for 3 hours at 350 ℃ in an air atmosphere to obtain cerium oxide nanorod carriers with different morphologies; and (3) soaking the soluble palladium salt aqueous solution into the cerium oxide nanorod carrier powder, uniformly dispersing, standing, drying, calcining at 400 ℃ for 4 hours in an air atmosphere, tabletting, and sieving by using a 40-60-mesh sieve to obtain the catalyst loaded on the third catalyst bed layer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811275722.2A CN109261144B (en) | 2017-11-09 | 2017-11-09 | Catalyst for chlorine-containing organic waste gas treatment process |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711098348.9A CN107597122B (en) | 2017-11-09 | 2017-11-09 | A kind for the treatment of process for the organic exhaust gas containing chlorine |
| CN201811275722.2A CN109261144B (en) | 2017-11-09 | 2017-11-09 | Catalyst for chlorine-containing organic waste gas treatment process |
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| CN201711098348.9A Division CN107597122B (en) | 2017-11-09 | 2017-11-09 | A kind for the treatment of process for the organic exhaust gas containing chlorine |
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| CN109261144A CN109261144A (en) | 2019-01-25 |
| CN109261144B true CN109261144B (en) | 2021-08-31 |
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| CN102698751A (en) * | 2012-06-26 | 2012-10-03 | 华东理工大学 | Catalyst for eliminating chlorine-containing volatile organic compounds by low-temperature catalytic combustion |
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| CN105013508A (en) * | 2015-06-29 | 2015-11-04 | 浙江大学 | Catalyst for low temperature catalytic combustion of chlorinated volatile organic compounds and preparation method |
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| CN107597122B (en) | 2018-12-04 |
| CN109224761B (en) | 2019-10-25 |
| CN109224761A (en) | 2019-01-18 |
| CN107597122A (en) | 2018-01-19 |
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