CN109261144A - Catalyst for the technique of VOCs treatment containing chlorine - Google Patents

Catalyst for the technique of VOCs treatment containing chlorine Download PDF

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CN109261144A
CN109261144A CN201811275722.2A CN201811275722A CN109261144A CN 109261144 A CN109261144 A CN 109261144A CN 201811275722 A CN201811275722 A CN 201811275722A CN 109261144 A CN109261144 A CN 109261144A
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catalyst
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catalyst bed
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containing chlorine
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CN109261144B (en
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不公告发明人
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YANTAI BAICHUAN HUITONG TECHNOLOGY Co.,Ltd.
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Xinchang Yilin Environmental Protection Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 present invention provides a kind of catalyst for the technique of VOCs treatment containing chlorine, by the way that three sections of catalyst layers are arranged in reaction column, single catalyst is avoided not to be suitable for multi-component CVOCs catalysis burning bring emission technical problem not up to standard, improve the overall removal efficiency of organic exhaust gas, and catalytic activity stablizes the service life up to 300 hours or more, organochlorine exhaust gas removal efficiency is up to 99% or more.

Description

Catalyst for the technique of VOCs treatment containing chlorine
The application is the divisional application of following application: the applying date is on November 09th, 2017, application No. is 201711098348.9 a kind of entitled treatment process for the organic exhaust gas containing chlorine.
Technical field
The present invention relates to chlorine contained exhaust gas processing, in particular to are used for the catalyst of the technique of VOCs treatment containing chlorine.
Background technique
Volatile organic compounds (VOCs) is the general designation of a kind of compound, although WHO, EU, USAEPA, ISO etc. at present International organization, mechanism or the national definition in relation to VOCs are had different versions, but VOCs is often referred to the boiling point in 101KPa and is lower than The organic compound of 373.15K, boiling point is lower, readily volatilized to pollute into atmosphere, be it is generally existing in air and at Divide more complicated a kind of organic pollutant.
Volatile organic matter containing chlorine (CVOC) is a kind of important branch of VOCs, mainly includes chloromethanes (CM), dichloromethane Alkane (DCM), vinyl chloride (VC), chlorobenzene (CB), 1,2- dichloroethanes (DCE) and trichloro ethylene (TCE) etc., these substances have Stronger toxicity occurs photochemical reaction with nitrogen oxides under certain condition in an atmosphere, can cause surface ozone concentration Increase, secondary organic aerosol can also be formed with some radical reactions in atmosphere by forming photochemical fog.Some chemical combination Object then consumes stratospheric ozone, causes the Ozone hole heart, and some then can generate excessive ozone in troposphere.In addition, recently Some bright VOCs of result of study page table can result in certain harm to human health.Therefore strong to human body based on these substances The great influence of health and ecological environment, more and more researchers and mechanism then begin to focus on its administering method.
In view of the serious harm of the volatile organic compounds containing chlorine, making its administering method also becomes the heat of current international environment Point problem.Nowadays it is other to be broadly divided into two major classes for CVOCs processing method: one is non-destructive techniques, also known as absorption method, can By changing physical condition, such as temperature, pressure condition, it is enriched with CVOCs, is then separated again, this method includes absorption Method, UF membrane, absorption process and condensation method etc..Another kind is destructive technology, by the method for chemistry or biology, makes CVOCs It is converted into CO2、H2O and HCl etc. is nontoxic or toxic small molecule inorganic matter, and this method includes direct burning, photochemical catalytic oxidation, urges Change burning, biodegrade etc..The applicable elements of these types of method are different, for example, absorption method has the exhaust gas of low concentration There is good eradicating efficacy, but may cause and pollution is transferred to solid phase from gas phase, causes secondary pollution problem；Condensation method is main High concentration, the exhaust gas of small air quantity are handled, but there is investment greatly for the exhaust gas of low concentration, Wind Volume, operating cost is high, and income is low The disadvantages of；Directly burning processing high-concentration waste gas, but since reaction old woman spends height, substantially higher than 800 DEG C.And in combustion product It will appear dioxin, NOxEqual harmful by-products；But catalysis burning not only has that low energy consumption under conditions of low concentration gas, The features such as without secondary pollution and high-efficient, and be also the most effective processing method of currently commercially processing industrial waste gas it One.
The catalyst of three types: noble metal catalyst, solid acid catalysis is concentrated mainly on for CVOCs catalysis burning Agent, catalyst of transition metal oxide.There are prices that relatively expensive, the active height of chloro (is also easy to produce toxicity more for noble metal catalyst Big more chloro by-products), oxychlorination easily generated closes object and is poisoned, is poisoned etc. and asks because of the loss of noble metal in high-temperature region Topic, so that the application of noble metal catalyst is restricted.Transition-metal catalyst currently used for chlorination aromatic hydrocarbon catalysis burning Mainly V2O5-TiO2Base catalyst etc..But V2O5-TiO2TiO in base catalyst2With toxicity, it be easy to cause secondary dirt Dye, limits its application.Though other kinds of catalyst such as solid acid catalyst has some applications, eventually because activity is low or secondary Product is mostly without widely being promoted.
Main catalyst activity component transition metal oxide to be used is UO in patent document2、MnO2、Co3O4、La2O3、 LaO2Deng and precious metals pt, Pd etc., carrier SiO2, Al2O3, TiO2, ZrO2.Representative patent has JP2002219364、JP2001286729、JP2001278630、JP2001009284、JP2001286734、 JP2001327869、JP10085559A2、US4031149A、US4059677A、US4065543A、US4561969A、 US58116628A, US4169862A, US7052663A etc..
But CVOCs tail gas is frequently not a kind of single halogenated hydrocarbons, is often accompanied with other kinds of organic matter.And due to The influence of competitive Adsorption and reaction temperature, then study one pack system CVOCs and screen the catalyst with high activity and selectivity not Centainly it is suitable for multi-component CVOCs.
Summary of the invention
In order to solve the technical problem, the present invention is provided to the catalyst of the technique of VOCs treatment containing chlorine, and it is organic will to contain chlorine Exhaust gas and oxygen pass through waste gas delivery pipeline road respectively and oxygen bottle enter in gas buffer tank carry out mixing buffering after with certain Flow is passed through in reaction column carries out catalysis burning simultaneously, and the tail gas of catalysis burning processing enters tail gas collecting device, at absorption It is discharged after reason by exhaust outlet；
It is divided into three sections along exhaust gas flow direction in the reaction column, successively loads the first catalyst bed, the second catalyst Bed and third catalyst bed.
The catalyst that first catalyst bed loads are as follows: using active carbon as carrier, LaO2For active component, alkali metal For auxiliary agent；Wherein, LaO2The 6-15% of catalyst weight is accounted for, alkali metal accounts for the 0.1%~2% of catalyst weight, and surplus is to live Property charcoal；The alkali metal is one or more of Li, Na, K, Ru, Cs.
Complex rare-earth oxidate containing valuable metal, especially LaO2With good storage put oxygen performance and oxygen mobility, to the depth of CVOCs Aoxidize it is highly beneficial, therefore CVOCs catalysis oxidation field application have received widespread attention.And LaO2With certain acidity With because of La4+/La3+Reversible transformation and have good storage put oxygen performance and oxygen mobility.Allow catalyst in air ring In border, the chloralkanes such as chlorine volatile organic matter methylene chloride will be contained long-term and stably and be converted into H2O、CO2And HCl.
Above-mentioned catalyst is prepared via a method which: a certain amount of soluble lanthanum salt and a certain amount of alkali metal salt are dissolved In a certain amount of water, then to being added absorbent charcoal carrier in solution, and the mixture is kept stirring 2 hours, it then will mixing Object is heated to 130 DEG C, and keeps the temperature 24 hours.Solid product, is then dried overnight, finally in height by filtering at 80 DEG C It is roasted in the lower air of temperature, tabletting, sieving (40-60 mesh) is afterwards to obtain the final product.
The concentration and impregnation ratio for controlling each solution during the preparation process, make resulting catalyst have following characteristics: LaO2The 6-15% of catalyst weight is accounted for, alkali metal accounts for the 0.1%~2% of catalyst weight, and surplus is active carbon；The high temperature Roasting refers in 400~600 DEG C of 2~5h of roasting.
The catalyst that second catalyst bed loads are as follows: with TiO2Particle is carrier, with CuO-Co3O4For active group Point；Wherein, CuO accounts for 6~18%, Co of catalyst weight3O4Account for the 20%~45% of catalyst weight, surplus TiO2Particle. Using TiO2Particle is carrier, and active component is strong with basal body binding force, not easily to fall off and cracking, in high-speed air-flow and thermal shock Under be still able to maintain greater activity.Catalyst reaches 95% or more to the conversion ratio of the chlorinated aromatic hydrocarbons such as o-dichlorohenzene at 300 DEG C.
Above-mentioned catalyst is prepared via a method which: by a certain amount of soluble copper salt and a certain amount of salt solubility in one In gauge water, then to TiO is added in solution2Particle, and the mixture is kept stirring 2 hours, then mixture is heated To 130 DEG C, and keep the temperature 24 hours.Solid product, is then dried overnight by filtering at 80 DEG C, finally empty at high temperature It is roasted in gas, tabletting, sieving (40-60 mesh) is afterwards to obtain the final product.
The concentration and impregnation ratio for controlling each solution during the preparation process, make resulting catalyst have following characteristics: CuO Account for 6~18%, Co of catalyst weight3O4Account for the 20%~45% of catalyst weight, surplus TiO2Particle.
The catalyst that the third catalyst bed loads are as follows: the catalyst includes cerium oxide nano-rod and Metal Palladium, is pressed Weight calculates, and the content of palladium is 0.5%, remaining is cerium oxide nano-rod.Using the precious metal palladium conduct with high catalytic activity Catalyst activity component, especially suitable for when chloralkane content is low in tail gas, chlorinatedorganic and catalysis combustion by-products Catalyzed conversion.
Above-mentioned catalyst is prepared via a method which: cerous nitrate being mixed with sodium hydroxide solution, is stirred in beaker equal It is fitted into after even in the crystallizing kettle with polytetrafluoroethyllining lining, after a certain period of time, sediment is filtered for crystallization at different temperatures Drying is washed, 350 DEG C of calcining 3h, obtain the cerium oxide carrier of different-shape in air atmosphere；By soluble palladium saline solution It is impregnated into cerium oxide carrier powder, is uniformly dispersed, dried after standing, in air atmosphere 400 DEG C of calcining 4h, tabletting, sieving (40-60 mesh) afterwards to obtain the final product.
The adsorbent that the adsorption treatment uses is granular activated carbon, partial size 2-5mm.
The reaction column is divided into three sections along airflow direction, and first segment temperature controls between 100-200 DEG C, second segment Temperature controls between 200-300 DEG C, and the temperature of third section controls between 300-400 DEG C.
The organic exhaust gas containing chlorine and oxygen is passed through after gas buffer tank is buffered logical with 3.8~6.9L/min flow Enter reaction column；The oxygen accounts for the 50%-80% (V/V) of mixed gas total amount.
What the compare with the existing technology present invention had has the technical effect that
(1) three sections of catalyst layers are arranged in reaction column to avoid single in the case where being directed to the complicated composition of CVOCs tail gas Catalyst is not suitable for multi-component CVOCs catalysis burning bring emission technical problem not up to standard, wherein first urges Agent bed uses LaO2/ active carbon allows catalyst in air environment as catalyst, is directed to long-term and stably Property will contain the chloralkanes such as chlorine volatile organic matter methylene chloride is converted into H2O、CO2And HCl.For chlorinated aromatic hydrocarbons component, instead Second catalyst layer of Ying Zhuzhong setting uses TiO2Particle is carrier, and active component is strong with basal body binding force, it is not easily to fall off and Cracking, is still able to maintain greater activity under high-speed air-flow and thermal shock.Catalyst is at 300 DEG C to chlorinated aromatic hydrocarbons such as o-dichlorohenzenes Conversion ratio reach 95% or more.Third catalyst bed, it is special using palladium/nano-cerium oxide stick as catalyst activity component When chloralkane content is not low suitable for tail gas, chlorinatedorganic and the catalyzed conversion for being catalyzed combustion by-products.
(2) present invention process is simple, and catalytic activity stablizes the service life up to 300 hours or more, and organochlorine exhaust gas removal efficiency can Up to 99% or more.
Specific embodiment
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects It encloses.
[embodiment 1]
The preparation of catalyst:
(1) a certain amount of lanthanum nitrate and a certain amount of potassium chloride are dissolved in a certain amount of water, then to being added in solution Absorbent charcoal carrier, and the mixture is kept stirring 2 hours, 130 DEG C are then heated the mixture to, and keep the temperature 24 small When.Solid product, is then dried overnight by filtering at 80 DEG C, and 4.5h, tabletting, sieving are finally roasted at 500 DEG C of air atmosphere (40-60 mesh) is afterwards up to catalyst A.
The concentration and impregnation ratio for controlling each solution during the preparation process make resulting catalyst A have following characteristics: LaO2The 7.2% of catalyst weight is accounted for, metallic potassium accounts for the 0.8% of catalyst weight, and surplus is active carbon.
(2) copper nitrate and cobalt chloride are dissolved in a certain amount of water, then to TiO is added in solution2Particle, and this is mixed It closes object to be kept stirring 2 hours, then heats the mixture to 130 DEG C, and keep the temperature 24 hours.Filtering, then by solid Product is dried overnight at 80 DEG C, 3h is finally roasted at 430 DEG C of air atmosphere, tabletting, sieving (40-60 mesh) is afterwards up to catalyst B。
The concentration and impregnation ratio for controlling each solution during the preparation process make resulting catalyst B have following characteristics: CuO accounts for 12%, Co of catalyst weight3O4Account for the 32% of catalyst weight, surplus TiO2Particle.
(3) cerous nitrate is mixed with sodium hydroxide solution, is packed into after mixing evenly in beaker in polytetrafluoroethylene (PTFE) In the crystallizing kettle of lining, crystallization is after a certain period of time, dry by sediment filtration washing at different temperatures, and in air atmosphere 350 DEG C calcining 3h, obtain the cerium oxide carrier of different-shape；Soluble palladium saline solution is impregnated into cerium oxide carrier powder, point It dissipates uniformly, is dried after standing, in air atmosphere 400 DEG C of calcining 4h, tabletting, sieving (40-60 mesh) is afterwards up to catalyst C.? The concentration and impregnation ratio that each solution is controlled in preparation process make resulting catalyst B have following characteristics: calculating by weight, The content of palladium is 0.5%.
VOCs treatment containing chlorine:
The organic exhaust gas containing chlorine of certain chemical plant emission: chloromethanes 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, Chlorobenzene 2500ppm, 1,2- dichloroethanes 380ppm.
Above-mentioned organic exhaust gas containing chlorine and oxygen are passed through into waste gas delivery pipeline road respectively and oxygen bottle enters gas buffer tank In carry out mixing buffering, control 56% (V/V) that the oxygen accounts for mixed gas total amount, be then passed through with 5.2L/min flow 55mm reaction column is divided into three sections, first segment loading catalyst A along exhaust gas flow direction in the reaction column, and second segment loading is urged Agent B, third section loading catalyst C, the control of first segment temperature is at 175 DEG C, and the temperature control of second segment is at 300 DEG C, third section Temperature control at 370 DEG C.The tail gas of catalysis burning processing enters tail gas collecting device, is arranged after adsorption treatment by exhaust outlet Out, discharge air-flow detect chlorinated organics content: chloromethanes 1.2ppm, methylene chloride 1ppm, vinyl chloride 0ppm, chlorobenzene 1ppm, 1,2- dichloroethanes 0.5ppm.It is computed, the removal efficiency of main chlorinated organics is 99.7% or more.
Continuous operation is tested after 330 hours, emission chlorinated organics content: chloromethanes 2.4ppm, methylene chloride 3.1ppm, vinyl chloride 0.2ppm, chlorobenzene 2.2ppm, 1,2- dichloroethanes 3.2ppm.It is computed, main chlorinated organics take off Except rate is 99.1% or more.
[embodiment 2]
The organic exhaust gas containing chlorine of certain chemical plant emission: chloromethanes 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, Chlorobenzene 2500ppm, 1,2- dichloroethanes 380ppm.
Above-mentioned organic exhaust gas containing chlorine and oxygen are passed through into waste gas delivery pipeline road respectively and oxygen bottle enters gas buffer tank In carry out mixing buffering, control 56% (V/V) that the oxygen accounts for mixed gas total amount, be then passed through with 4.4L/min flow 55mm reaction column is divided into three sections, first segment loading catalyst A along exhaust gas flow direction in the reaction column, and second segment loading is urged Agent B, third section loading catalyst C, the control of first segment temperature is at 120 DEG C, and the temperature control of second segment is at 210 DEG C, third section Temperature control at 350 DEG C.The tail gas of catalysis burning processing enters tail gas collecting device, is arranged after adsorption treatment by exhaust outlet Out, discharge air-flow detects chlorinated organics content: chloromethanes 1.7ppm, methylene chloride 2.1ppm, vinyl chloride 0.5ppm, chlorobenzene 1.0ppm, 1,2- dichloroethanes 0.3ppm.It is computed, the removing of main chlorinated organics is 99.6% or more.
Continuous operation is tested after 500 hours, emission chlorinated organics content: chloromethanes 2.7ppm, methylene chloride 4.5ppm, vinyl chloride 0.3ppm, chlorobenzene 2.7ppm, 1,2- dichloroethanes 3.6ppm.It is computed, main chlorinated organics take off Except rate is 99.0% or more.
[comparative example 1]
VOCs treatment containing chlorine:
The organic exhaust gas containing chlorine of certain chemical plant emission: chloromethanes 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, Chlorobenzene 2500ppm, 1,2- dichloroethanes 380ppm.
Above-mentioned organic exhaust gas containing chlorine and oxygen are passed through into waste gas delivery pipeline road respectively and oxygen bottle enters gas buffer tank In carry out mixing buffering, control 56% (V/V) that the oxygen accounts for mixed gas total amount, be then passed through with 5.2L/min flow 55mm reaction column is divided into three sections, three sections of equal loading catalyst A along exhaust gas flow direction in the reaction column, first segment temperature control System is at 175 DEG C, and at 300 DEG C, the temperature of third section is controlled at 370 DEG C for the temperature control of second segment.The tail gas of catalysis burning processing It into tail gas collecting device, is discharged after adsorption treatment by exhaust outlet, discharge air-flow detects chlorinated organics content: chloromethanes 1.2ppm, methylene chloride 0.2ppm, vinyl chloride 0.9ppm, chlorobenzene 456ppm, 1,2- dichloroethanes 8.4ppm.It is computed, chlorobenzene Removal efficiency only 81.76%.
[comparative example 2]
VOCs treatment containing chlorine:
The organic exhaust gas containing chlorine of certain chemical plant emission: chloromethanes 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, Chlorobenzene 2500ppm, 1,2- dichloroethanes 380ppm.
Above-mentioned organic exhaust gas containing chlorine and oxygen are passed through into waste gas delivery pipeline road respectively and oxygen bottle enters gas buffer tank In carry out mixing buffering, control 56% (V/V) that the oxygen accounts for mixed gas total amount, be then passed through with 5.2L/min flow 55mm reaction column is divided into three sections, three sections of equal loading catalyst B along exhaust gas flow direction in the reaction column, first segment temperature control System is at 175 DEG C, and at 300 DEG C, the temperature of third section is controlled at 370 DEG C for the temperature control of second segment.The tail gas of catalysis burning processing It into tail gas collecting device, is discharged after adsorption treatment by exhaust outlet, discharge air-flow detects chlorinated organics content: chloromethanes 15ppm, methylene chloride 152ppm, vinyl chloride 3.5ppm, chlorobenzene 0.3ppm, 1,2- dichloroethanes 0.7ppm.It is computed, dichloro The removal efficiency of methane is only 87.3%.
[comparative example 3]
VOCs treatment containing chlorine:
The organic exhaust gas containing chlorine of certain chemical plant emission: chloromethanes 500ppm, methylene chloride 1200ppm, vinyl chloride 90ppm, Chlorobenzene 2500ppm, 1,2- dichloroethanes 380ppm.
Above-mentioned organic exhaust gas containing chlorine and oxygen are passed through into waste gas delivery pipeline road respectively and oxygen bottle enters gas buffer tank In carry out mixing buffering, control 56% (V/V) that the oxygen accounts for mixed gas total amount, be then passed through with 5.2L/min flow 55mm reaction column is divided into three sections, three sections of equal loading catalyst C along exhaust gas flow direction in the reaction column, first segment temperature control System is at 175 DEG C, and at 300 DEG C, the temperature of third section is controlled at 370 DEG C for the temperature control of second segment.The tail gas of catalysis burning processing It into tail gas collecting device, is discharged after adsorption treatment by exhaust outlet, discharge air-flow detects chlorinated organics content: chloromethanes 0ppm, methylene chloride 0ppm, vinyl chloride 0ppm, chlorobenzene 0ppm, 1,2- dichloroethanes 0.1ppm.It is computed, it is mainly organic containing chlorine The removal efficiency of object is close to 100%.
Continuous operation is tested after 30 hours, emission chlorinated organics content: chloromethanes 35ppm, methylene chloride 56ppm, vinyl chloride 18ppm, chlorobenzene 102ppm, 1,2- dichloroethanes 45ppm.It is computed, the removal efficiency of main chlorinated organics Only 88% or so.
It can be seen that the present invention uses reaction column subsection setup mode, it is successively loaded with the catalyst with given activity A, catalyst B and catalyst C solves single catalyst and is not suitable for multi-component CVOCs catalysis burning bring discharge tail The removal efficiency of gas technical problem not up to standard, the organic exhaust gas containing chlorine reaches 99% or more；The service life of catalyst is additionally extended, It remains within continuous operation 300 hours or more obtain satisfied removal efficiency, there is nothing compared to traditional removing process of organic exhaust gas containing chlorine The advantage of method analogy.
Above description sufficiently discloses a specific embodiment of the invention.It should be pointed out that being familiar with the field Range of any change that technical staff does a specific embodiment of the invention all without departing from claims of the present invention. Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.

Claims (1)

1. a kind of catalyst for the technique of VOCs treatment containing chlorine, it is characterised in that: the catalyst is by the first catalyst The catalyst composition of catalyst, the catalyst that the second catalyst bed loads and third catalyst bed loading that bed loads, The catalyst that first catalyst bed loads are as follows: using active carbon as carrier, LaO2For active component, alkali metal is auxiliary agent； Wherein, LaO2The 7.2% of catalyst weight is accounted for, alkali metal accounts for the 0.8% of catalyst weight, and surplus is active carbon；The alkali gold Belonging to is K；The catalyst that second catalyst bed loads are as follows: with TiO2Particle is carrier, with CuO-Co3O4For active component； Wherein, CuO accounts for 12%, Co of catalyst weight3O4Account for the 32% of catalyst weight, surplus TiO2Particle；The third catalysis The catalyst that agent bed loads are as follows: the catalyst includes cerium oxide nano-rod and Metal Palladium, is calculated by weight, the content of palladium is 0.5%, remaining is cerium oxide nano-rod；
Wherein:
The catalyst that first catalyst bed loads the preparation method comprises the following steps: by a certain amount of lanthanum nitrate and a certain amount of chlorination Potassium is dissolved in a certain amount of water, is kept stirring 2 hours then to being added absorbent charcoal carrier in solution, and by the mixture, then 130 DEG C are heated the mixture to, and keeps the temperature 24 hours；Solid product, is then dried overnight, most by filtering at 80 DEG C 4.5h is roasted at 500 DEG C of air atmosphere afterwards, tabletting obtains the first catalyst bed loading after the sieving of 40-60 mesh screen Catalyst；
The catalyst that second catalyst bed loads the preparation method comprises the following steps: copper nitrate and cobalt chloride are dissolved in a certain amount of water In, then to TiO is added in solution2Particle, and the mixture is kept stirring 2 hours, then heat the mixture to 130 DEG C, and keep the temperature 24 hours；Solid product, is then dried overnight, finally at 430 DEG C of air atmosphere by filtering at 80 DEG C 3h is roasted, tabletting obtains the catalyst of the second catalyst bed loading after the sieving of 40-60 mesh screen；
The catalyst that the third catalyst bed loads the preparation method comprises the following steps: cerous nitrate is mixed with sodium hydroxide solution, in Be fitted into after mixing evenly in beaker in the crystallizing kettle with polytetrafluoroethyllining lining, at different temperatures crystallization after a certain period of time, Sediment filtration washing is dry, and 350 DEG C of calcining 3h, obtain the cerium oxide carrier of different-shape in air atmosphere；It will be solvable Property palladium salt aqueous solution be impregnated into cerium oxide carrier powder, be uniformly dispersed, dried after standing, in air atmosphere 400 DEG C calcining 4h, tabletting obtain the catalyst of third catalyst bed loading after the sieving of 40-60 mesh screen.
CN201811275722.2A 2017-11-09 2017-11-09 Catalyst for chlorine-containing organic waste gas treatment process Active CN109261144B (en)

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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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