Dust removal and VOCs (volatile organic compounds) purification integrated multi-layer adsorption catalysis ceramic filter material and flue gas dust removal and purification device

Abstract

The utility model provides a dust removal and VOCs (volatile organic compounds) purification integrated multilayer adsorption catalysis ceramic filter material and a flue gas dust removal and purification device, the filter material comprises a compact conductive metal net rack, a 3D (three-dimensional) foam porous ceramic fiber filter material layer, an adsorption-catalysis-porous carrier composite material layer and a discharge electrode, one side of the 3D foam porous ceramic fiber filter material layer is fixed on one side of the adsorption-catalysis-porous carrier composite material layer through coating, and the discharge electrode is fixed on the other side of the adsorption-catalysis-porous carrier composite material layer; and the other side of the 3D foam porous ceramic fiber filter material layer is fixed on the compact conductive metal net rack. The filter material has the functions of dust removal and VOCs purification at the same time, and the dust removal efficiency and the VOCs mineralization efficiency are high and can reach 98% or above and 95% or above respectively.

Description

Technical Field

[0001] The utility model relates to a multi-layer adsorption catalytic ceramic filter material and a flue gas dust removal and purification device integrating dust removal and VOCs purification, belonging to the technical field of flue gas purification. Background Art

[0002] VOCs (Volatile Organic Compounds) control is a key link and severe challenge in air pollution prevention and control. Coke ovens in the coking industry are coking production facilities and the main source of pollution in the coking industry. At present, this field has put forward increasingly higher environmental protection requirements for the unorganized PM (Particulate Matter) and VOCs emitted from coke ovens. Since the "leakage" phenomenon in the coking process is an important reason for the excessive emission of VOCs. Therefore, starting from source reduction and process control, it is an effective means to achieve the total reduction of VOCs and PM. The use of new large-scale coke ovens and strengthening the sealing of furnace bodies and furnace doors, and the active promotion of LDAR technology (Leak Detection and Repair, leak detection and repair technology) can greatly reduce the unorganized emission of VOCs waste gas from coking furnace bodies, equipment pipelines, and chemical production workshops. However, due to the reasons such as the large number of overall process dew points, the large size of equipment, and the low collection efficiency, the collection technology has become a difficult point in the control technology of unorganized PM and VOCs. At present, the commonly used coking VOCs treatment technologies are mainly concentrated on negative pressure system purification, multi-stage washing adsorption / return to coke oven incineration and other technologies. However, the amount of gas released during the coking process is large, and the impurity components in the tail gas are relatively complex. How to effectively control the process safety issues and stably remove VOCs without affecting the normal production of the coke oven and controlling S and N compounds has become a difficult problem that needs to be solved in the core of the process.

[0003] At present, most filter materials can only meet the functions of single dust removal or integrated denitrification and dust removal. However, porous ceramic filter materials are widely used in environmental management technology due to their low cost, corrosion resistance, wear resistance, chemical stability, and high-precision filtering performance.

[0004] The following briefly introduces several prior art documents related to this application:

[0005] CN112892110A discloses a ceramic fiber catalytic filter tube and dust collector with catalytic oxidation of organic pollutants. The ceramic fiber tube body structure with an opening at the top is constructed, a honeycomb carrier is filled in the top opening of the ceramic fiber tube, a Cu-Pb-Zr-TiO2 composite oxide is prepared by a citric acid method, and a catalyst coating is coated on the inner wall of the ceramic fiber tube and the honeycomb carrier, so as to prepare a ceramic fiber catalytic filter tube and a corresponding dust collector with dust removal and degradation functions of organic pollutants in process tail gas such as soil thermal desorption. The dust collector can remove dust more than 99%, and at the same time, combined with pulse soot blowing and supplementary oxygen, the ceramic fiber catalytic filter tube is prevented from being blocked, while the oxidation efficiency of benzene is 23-31%, and the oxidation efficiency of C10-C40 is 31-64%, which can achieve the effect of dust removal and oxidation of pollutants. However, the process is aimed at high-temperature soil thermal desorption tail gas, and the operating temperature is between 300-550°C, which is the temperature range of medium and high temperature catalyst activity, and is not suitable for the removal of low-temperature unorganized emission pollutants. At the same time, most of the organic pollutants in soil thermal desorption are POPs pollutants (Persistent Organic Pollutants) containing chlorine and polyphenyls, and the removal rate of toluene is low. At the same time, the impurity composition in the tail gas of the coking plant is relatively complex. Therefore, this solution has certain application limitations in the flue gas treatment of the coking industry.

[0006] CN102772971A discloses an ultrafine particle purification device, which establishes a gas discharge-electrocoagulation-electrostatic enhancement bag dust collector integrated device, adds a gas discharge-electrocoagulation device at the front end of the dust collector, increases the charging capacity of fine particles and increases the coagulation effect between particles. At the same time, in the electrostatic enhancement bag dust collector integrated device, due to the effect of electrostatic enhancement, the initial layer of dust on the surface of the filter bag is formed within 1 second, so that the bag dust collector can achieve a high dust removal efficiency of more than 99% in the initial stage. Since gas discharge forms NTP (Non-thermal Plasma, low-temperature plasma), it has a certain degradation effect on pollutants in flue gas. However, in this technology, the dust removal filter material has a single function and can only capture fine particles. Due to the large volume of industrial flue gas, the gas residence time is short, and the activation factor generated by the gas discharge NTP is instantaneous, and it is impossible to achieve efficient removal of batch SO2, NOx and other harmful gases on the surface of the filter material layer. At the same time, the concentration of pollutants in the coking industry's unorganized flue gas emissions is unstable, and the power loss is too large under continuous discharge conditions, which is not conducive to energy conservation and emission reduction in flue gas treatment in the steel coking industry.

[0007] Therefore, researching and developing a multifunctional ceramic filter material that can remove PM and VOCs simultaneously, so that these pollutants can be removed when the unorganized flue gas passes through the ceramic fiber tube, thereby greatly saving equipment and operating costs has become a technical problem that needs to be solved urgently in this field. Utility Model Content

[0008] In order to solve the above-mentioned shortcomings and deficiencies, one object of the utility model is to provide a multi-layer adsorption catalytic ceramic filter material integrating dust removal and VOCs purification.

[0009] Another object of the utility model is to provide a flue gas dust removal and purification device, which includes the above-mentioned dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material.

[0010] In order to achieve the above objectives, on the one hand, the utility model provides a dust removal and VOCs purification integrated multilayer adsorption catalytic ceramic filter material, wherein the dust removal and VOCs purification integrated multilayer adsorption catalytic ceramic filter material comprises a dense conductive metal grid (dense metal grounding grid layer), a 3D foam porous ceramic fiber filter material layer, an adsorption-catalysis-porous carrier composite material layer and a discharge electrode, wherein one side of the 3D foam porous ceramic fiber filter material layer is fixed to one side of the adsorption-catalysis-porous carrier composite material layer by coating, and the discharge electrode is fixed to the other side of the adsorption-catalysis-porous carrier composite material layer;

[0011] The other side of the 3D foam porous ceramic fiber filter material layer is fixed on the dense conductive metal grid.

[0012] As a specific embodiment of the filter material described above in the utility model, the filter material is provided with a plurality of filter material installation through holes, and a plurality of flanges are sealed and fixedly connected with the plurality of filter material installation through holes in a one-to-one correspondence, so as to fix the filter material as a whole on the dense conductive metal grid. The dense conductive metal grid has the function of grounding and fixing the filter material as a whole. In addition, the utility model does not make specific requirements on the number of installation through holes, and can be reasonably adjusted according to the actual on-site operation needs, such as the size of the filter material, as long as the purpose of fixed connection can be achieved.

[0013] As a specific embodiment of the filter material described above in the utility model, the 3D foam ceramic fiber filter material in the 3D foam ceramic fiber filter material layer is foam-shaped and has an asymmetric filtering structure.

[0014] As a specific implementation of the filter material described above in the utility model, the porosity of the 3D foam ceramic fiber filter material is 72-92%.

[0015] As a specific embodiment of the filter material described above in the utility model, the pore size of the internal pores of the 3D foam ceramic fiber filter material is 25-45 μm.

[0016] As a specific implementation of the filter material described above in the utility model, the thickness of the 3D foam porous ceramic fiber filter material layer is 30-55 mm.

[0017] The 3D foam porous ceramic fiber filter material layer in the integrated multi-layer adsorption catalytic ceramic filter material for dust removal and VOCs purification provided by the utility model has the functions of efficient water removal, dust removal, oil removal, etc. When the dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material is used to remove dust and purify flue gas, the flue gas passes vertically through the filter material surface and first reaches the 3D foam porous ceramic fiber filter material layer. The 3D foam porous ceramic fiber filter material layer filters fine particles in the flue gas through mechanisms such as interception, inertial collision, and diffusion effect, and the filtration efficiency can be greater than 98%.

[0018] As a specific embodiment of the filter material described above in the utility model, the adsorption-catalysis-porous carrier composite material layer comprises a porous carrier, a composite catalyst and an adsorbent, and the composite catalyst and the adsorbent are loaded on the surface of the porous carrier;

[0019] The composite catalyst comprises a carrier and a metal active component, and the metal active component is loaded on the carrier.

[0020] In view of the large difference in VOCs gas emission in the coking industry, the complex impurity components in the tail gas, the poor recovery value, and the need for direct terminal treatment, the utility model sets the adsorption-catalysis-porous carrier composite material layer with adsorption-catalysis VOCs function in the dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material, thereby realizing the further purification of flue gas by the cyclic discharge degradation process of first adsorption and then in-situ catalytic degradation. This process has a higher VOCs mineralization efficiency and can fully utilize the NTP discharge efficiency. In addition, by loading catalysts that degrade different VOCs, efficient and energy-saving degradation of different VOCs can be achieved.

[0021] As a specific embodiment of the filter material described above in the utility model, the carrier includes one or a combination of activated carbon, molecular sieve and TiO2, and the metal active component includes at least three of Ce, Mn, Co, Cu, Fe, Sn and Zr. Preferably, the molecular sieve is a molecular sieve with different pore sizes. For example, in some embodiments of the utility model, the molecular sieve includes at least two molecular sieves of ZSM-5 molecular sieve, high silicon USY molecular sieve and 13X molecular sieve.

[0022] As a specific embodiment of the filter material described above in the utility model, the carrier is an acid-modified carrier or an alkali-modified carrier. The modifier used for acid modification includes dilute nitric acid or phosphate, and the modifier used for alkali modification includes urea, ammonia water or strong base. By acid-modifying or alkali-modifying the carrier, the acid or alkali sites of the carrier can be increased, the adsorption performance can be improved, and the deactivation can be reduced.

[0023] As a specific embodiment of the filter material described above in the utility model, the adsorbent includes activated carbon and / or molecular sieve and the like.

[0024] As a specific embodiment of the filter material described above in the utility model, the adsorbent is an acid-modified adsorbent or an alkali-modified adsorbent. The modifier used for acid modification includes dilute nitric acid or phosphate, and the modifier used for alkali modification includes urea, ammonia water or strong base. By acid-modifying or alkali-modifying the adsorbent, the acid or alkali sites of the adsorbent can be increased, the adsorption performance can be improved, and the deactivation can be reduced.

[0025] In the filter material described above in the present invention, the carrier used in the adsorbent and the composite catalyst may be the same or different, and needs to be reasonably determined based on the actual situation on site, such as the composition of the flue gas.

[0026] As a specific embodiment of the filter material described above in the utility model, the porosity of the adsorption-catalysis-porous carrier composite material layer is 70-80%.

[0027] As a specific embodiment of the filter material described above in the utility model, the thickness of the adsorption-catalysis-porous carrier composite material layer is 50-90 mm.

[0028] As a specific embodiment of the filter material described above in the utility model, the discharge electrode (high voltage electrode / high purity discharge electrode) is a high purity (purity not less than 99.9%) conductive metal discharge rod, etc. For example, in some embodiments of the utility model, the high purity conductive metal discharge rod includes a high purity stainless steel discharge rod or a high purity tungsten discharge rod, etc.

[0029] The integrated multi-layer adsorption catalytic ceramic filter material for dust removal and VOCs purification provided by the utility model can be applied to flue gas dust removal and purification. It can be adapted to different flue gas scenes and can achieve deep purification of different dusts and a variety of VOCs.

[0030] The dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material described in the utility model can be prepared by a variety of different processes. In order to further illustrate the dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material of the utility model, the utility model also provides a preparation method of the dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material, comprising the following steps:

[0031] Step (1): firstly, the crushed ceramic material, the first pore-forming agent and the template agent are mixed with a solvent to obtain a foaming slurry, then the foaming slurry is made into a green product, and then the green product is calcined under anaerobic conditions and aerobic conditions in turn to obtain a 3D foam porous ceramic fiber filter material;

[0032] Step (2): mixing a porous carrier, a composite catalyst, an adsorbent, a binder, a second pore-forming agent, a pH adjuster, an extrusion aid and a solvent to obtain a mud material (high plastic mud material), and then aging, kneading, molding, drying and calcining the mud material in sequence to obtain an adsorption-catalysis-porous carrier composite material;

[0033] Step (3): Use melt-blowing to coat the 3D foam porous ceramic fiber filter material on the adsorption-catalysis-porous carrier composite material, then fix the other side of the 3D foam porous ceramic fiber filter material layer on a dense conductive metal grid, and finally fix the discharge electrode on the other side of the adsorption-catalysis-porous carrier composite material layer to obtain the dust removal and VOCs purification integrated multi-layer adsorption catalysis ceramic filter material.

[0034] In step (1) of the preparation method described above, the raw materials used to prepare the 3D foam porous ceramic fiber filter material include ceramic material, a first pore-forming agent, a template agent and a solvent, wherein the mass ratio of the ceramic material, the first pore-forming agent and the template agent is 40-60:5-10:2-5.

[0035] In step (1) of the preparation method described above, the size of the pulverized ceramic material is 200-700 nm, wherein the pulverized ceramic material may be ceramic fiber or the like.

[0036] In step (1) of the preparation method described above, the preparation method of the foaming slurry comprises the following specific steps:

[0037] Firstly, the crushed ceramic material is added into a solvent to prepare a slurry, and then a first pore-forming agent and a template agent are added into the slurry to prepare a foaming slurry.

[0038] The present invention does not make specific requirements for the preparation process of 3D foam porous ceramic fiber filter material, that is, the first pore-forming agent, template agent and solvent used in step (1), and can be reasonably selected according to the actual needs of the on-site operation. For example, in some embodiments of the present invention, the first pore-forming agent includes one or a combination of polyethylene glycol, graphene and fly ash, the template agent includes one or a combination of glycerol, carboxymethyl cellulose, polyvinyl alcohol and polypropylene alcohol, and the solvent includes one or a combination of distilled water, anhydrous ethanol and ethylene glycol, and the present invention does not make specific requirements for the amount of solvent used to prepare the 3D foam porous ceramic fiber filter material, and can be reasonably adjusted according to the actual needs of the operation.

[0039] In step (1) of the above preparation method of the present invention, the calcination temperature is 900-1300°C, the anaerobic conditions include Ar atmosphere or N2 atmosphere, and the aerobic conditions include air atmosphere.

[0040] In step (2) of the preparation method described above, the raw materials used to prepare the adsorption-catalysis-porous carrier composite material include a porous carrier, a composite catalyst, an adsorbent, a binder, a second pore-forming agent, a pH adjuster, an extrusion aid, and a balance of solvent;

[0041] The mass ratio of the porous carrier, the composite catalyst, the adsorbent, the binder, the second pore-forming agent, the pH adjuster and the extrusion aid is 40-50:20-30:5-10:2-5:1-2:1-2:1-2.

[0042] In step (2) of the above-mentioned preparation method of the present invention, the binder used in the preparation process of the adsorption-catalysis-porous carrier composite material includes one or a combination of acrylic acid, acid phosphate and water glass, the second pore-forming agent includes one or a combination of polyethylene glycol, graphene, fly ash, starch, polyethylene oxide and carboxymethyl cellulose, the pH adjuster includes one or a combination of saturated NaHCO3-Na2CO3 solution, formic acid, acetic acid, hydrochloric acid, citric acid, phosphoric acid, nitric acid, ammonia water, sodium carbonate and sodium hydroxide, the extrusion aid includes polyvinyl alcohol and / or silica sol, and the solvent includes one or a combination of distilled water, anhydrous ethanol and ethylene glycol, and the present invention does not make specific requirements on the amount of solvent used in the preparation of the adsorption-catalysis-porous carrier composite material, which can be reasonably adjusted according to actual operation needs.

[0043] In step (2) of the preparation method described above, the preparation method of the composite catalyst comprises:

[0044] The metal active component precursor, the carrier and the mixing auxiliary agent are dissolved in a solvent, and then the obtained mixed liquid is aged and filtered, and then the filtered solid is calcined to obtain a composite catalyst.

[0045] In step (2) of the preparation method described above, the raw materials used to prepare the composite catalyst include a metal active component precursor, a carrier, a mixing aid and a solvent;

[0046] Among them, the mass ratio of the metal active component precursor, the carrier and the mixing auxiliary agent is 2-35:50-65:5-15.

[0047] In step (2) of the preparation method described above in the present invention, the preparation method of the composite catalyst specifically comprises:

[0048] Firstly, the metal active component precursor is dissolved in a solvent, and then a carrier and a mixing aid are added and mixed uniformly. The uniform mixing is achieved by a high-speed mixing process of 30-60r / min.

[0049] In step (2) of the preparation method described above, the composite catalyst is prepared by an impregnation method, and no specific requirements are made for the aging, filtering and calcining operations and the process parameters involved in the preparation of the composite catalyst described above, which can be reasonably adjusted and selected according to the actual needs of the on-site operation. For example, in some embodiments of the present invention, the aging is aging overnight, and the calcination is calcining at 550° C. for 4 hours.

[0050] In step (2) of the above-mentioned preparation method of the present invention, the mixing auxiliary agent used in the preparation process of the composite catalyst includes one or a combination of polyethylene glycol, glycerol, carboxymethyl cellulose, polyvinyl alcohol and polypropylene alcohol, and the solvent includes one or a combination of distilled water, anhydrous ethanol and ethylene glycol, and the present invention does not make specific requirements on the amount of the solvent used in the preparation of the composite catalyst, which can be reasonably adjusted according to actual operation needs.

[0051] In step (2) of the above-mentioned preparation method of the present invention, the preparation method of the porous carrier comprises:

[0052] Firstly, the crushed carrier material, the third pore-forming agent and the binder are mixed with a solvent to obtain a dispersed slurry, and then the dispersed slurry is dried and calcined in sequence to obtain a porous carrier.

[0053] In step (2) of the preparation method described above in the present invention, the preparation method of the porous carrier specifically includes: preparing a highly dispersed slurry with the crushed carrier material, the third pore-forming agent and auxiliary agents such as a binder through a sand milling pulping process; and then drying and calcining the dispersed slurry in sequence to obtain a porous carrier.

[0054] In step (2) of the above preparation method of the present invention, the raw materials used to prepare the porous carrier include a carrier material, a binder, a third pore-forming agent and a solvent;

[0055] Wherein, the mass ratio of the carrier material, the binder and the third pore-forming agent is 60-80:1-5:2-7.

[0056] In the process of preparing the porous carrier in step (2) of the preparation method described above of the utility model, the carrier material includes one or a combination of several of multi-level porous silicon carbide, ceramic fiber, polycrystalline fiber, graphite, cordierite and sepiolite.

[0057] In step (2) of the above-mentioned preparation method of the present invention, the size of the carrier material after crushing is 200-700nm.

[0058] The present invention does not make specific requirements for the third pore-forming agent, binder and solvent used in the preparation of the porous carrier in step (2), and can be reasonably adjusted and selected according to the actual needs of the on-site operation. For example, in some embodiments of the present invention, the third pore-forming agent includes one or a combination of sodium dodecyl sulfate, polyvinyl alcohol and polyvinyl chloride, the binder includes one or a combination of acrylic acid, acid phosphate and water glass, and the solvent includes one or a combination of distilled water, anhydrous ethanol and ethylene glycol, and the present invention does not make specific requirements for the amount of the solvent used to prepare the porous carrier, and can be reasonably adjusted according to the actual needs of the operation.

[0059] In addition, the present invention does not make specific requirements on the drying and calcining operations and the process parameters involved in preparing the porous carrier in step (2), and can be reasonably adjusted and selected according to the actual needs of the on-site operation. For example, in some embodiments of the present invention, the drying temperature is 120°C, and the calcination is 1300°C for 2h.

[0060] As a specific embodiment of the preparation method described above of the utility model, in step (2), during the preparation of the adsorption-catalysis-porous carrier composite material, the mixing adopts a high-speed mixing process, the rotation speed is 30-60r / min, and the mixing time is 2-4h.

[0061] The present invention does not make specific requirements on the aging, slurry preparation, molding, drying and other operations and the process parameters involved in preparing the adsorption-catalysis-porous carrier composite in step (2), and can be reasonably adjusted and selected according to the actual needs of the on-site operation. For example, in some embodiments of the present invention, the aging time is 24 hours, the molding is extrusion molding by pressurized liquid discharge method, and the drying includes primary drying and secondary drying.

[0062] In step (2) of the preparation method described above in the utility model, the calcination in the preparation process of the adsorption-catalysis-porous carrier composite material includes: first heating the temperature to 350-450°C at a heating rate of 3-5°C / min, then keeping the temperature for 30-120min, and then heating the temperature to 400-600°C at a heating rate of 10-15°C / min, and keeping the temperature for 2-4h.

[0063] In step (3) of the above-mentioned preparation method of the present invention, the 3D foam porous ceramic fiber filter material is coated on the adsorption-catalysis-porous carrier composite material by melt-blowing.

[0064] In step (3) of the above-mentioned preparation method of the present invention, the discharge electrode is fixed in parallel to the other side of the adsorption-catalysis-porous carrier composite material layer through a molding process, wherein the molding process can be, for example, an extrusion molding process.

[0065] On the other hand, the utility model also provides a flue gas dust removal and purification device, wherein the flue gas dust removal and purification device comprises two pieces of the above-mentioned dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter materials, the two filter materials are arranged in the form of discharge electrodes facing each other, and a gas channel is formed between the two filter materials;

[0066] The discharge electrodes in the two filter materials are electrically connected to a high voltage power supply, and the dense conductive metal grid is grounded.

[0067] The flue gas dust removal and purification device provided by the utility model can realize the integrated treatment of ultrafine particulate matter and VOCs in the flue gas, thereby achieving industrial energy saving and carbon emission reduction, and providing guidance for the coordinated and integrated treatment of industrial PM and VOCs.

[0068] The flue gas described in the utility model is not limited to the flue gas containing VOCs emitted in the coking industry in an unorganized manner, but can also be any other flue gas containing PCDFs (Polychloro-Dibenzofurans, furans), PCDDs (Polychlorodibenzo-p-Dioxins, dioxins) and PM, etc.

[0069] Compared with the prior art, the beneficial technical effects that can be achieved by the utility model include:

[0070] In the integrated multi-layer adsorption catalytic ceramic filter material for dust removal and VOCs purification provided by the utility model, pore channels of different pore sizes between different material layers are arranged in an alternating manner, ensuring sufficient filtration time, filtration efficiency and filtration accuracy. In addition, due to the large pore size (such as the internal pore size of 3D foam ceramic fiber filter material is 25-45μm, etc.), there is a lower filtration pressure drop, and energy consumption is also reduced.

[0071] Existing ordinary filter materials can usually only realize a single dust removal function, while the dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material provided by the utility model has both dust removal and VOCs purification functions, and the dust removal efficiency and VOCs mineralization efficiency are both relatively high, reaching more than 98% and more than 95% respectively, which can solve the problems existing in the existing purification process of unorganized flue gas emissions in the coking industry. BRIEF DESCRIPTION OF THE DRAWINGS

[0072] In order to more clearly illustrate the embodiments of the utility model or the technical solutions in the prior art, the drawings required for the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are some embodiments of the utility model. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0073] Figure 1 A schematic diagram of the structure of a multi-layer adsorption catalytic ceramic filter material for integrated dust removal and VOCs purification provided in an embodiment of the utility model.

[0074] Figure 2 This is a schematic diagram of the installation method of the integrated multi-layer adsorption catalytic ceramic filter material for dust removal and VOCs purification in the flue gas dust removal and purification process in the application example of the present utility model.

[0075] 1. Dense conductive metal grid;

[0076] 2. 3D foam porous ceramic fiber filter layer;

[0077] 3. Adsorption-catalysis-porous carrier composite material layer;

[0078] 4. Discharge electrode. DETAILED DESCRIPTION

[0079] It should be noted that the term "comprises" and any variations thereof in the specification and claims of the present invention and the above-mentioned drawings are intended to cover non-exclusive inclusions. For example, a process, method / process, system, product or equipment that includes a series of steps or units is not necessarily limited to those steps or units clearly listed, but may include other steps or units that are not clearly listed or inherent to these processes, methods / processes, products or equipment.

[0080] In the present invention, the terms "upper", "lower", "inner", "outer", "middle", "top" and "bottom" indicate positions or positional relationships based on the positions or positional relationships shown in the accompanying drawings. These terms are mainly used to better describe the present invention and its embodiments, and are not used to limit the indicated devices, elements or components to have specific positions, or to be constructed and operated in specific positions.

[0081] In addition, some of the above terms may be used to express other meanings in addition to indicating orientation or positional relationship. For example, the term "on" may also be used to express a certain dependency or connection relationship in some cases. For those skilled in the art, the specific meanings of these terms in this utility model can be understood according to specific circumstances.

[0082] In addition, the terms "disposed" and "connected" should be understood in a broad sense. For example, "connected" can be a fixed connection, a detachable connection, or an integral structure; it can be a mechanical connection, or an electrical connection; it can be a direct connection, or an indirect connection through an intermediate medium, or it can be an internal connection between two devices, elements or components. For those of ordinary skill in the art, the specific meanings of the above terms in this utility model can be understood according to specific circumstances.

[0083] The "range" disclosed in the utility model is given in the form of a lower limit and an upper limit. It can be one or more lower limits, and one or more upper limits respectively. A given range is defined by selecting a lower limit and an upper limit. The selected lower limit and upper limit define the boundaries of a particular range. All ranges defined in this way are combinable, i.e. any lower limit can be combined with any upper limit to form a range. For example, for a specific parameter, a range of 60-120 and 80-110 is listed, and it is understood that a range of 60-110 and 80-120 is also expected. In addition, if the minimum range values ​​listed are 1 and 2, and the maximum range values ​​listed are 3, 4 and 5, then the following ranges can all be expected: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5.

[0084] In the present invention, unless otherwise specified, the numerical range "ab" represents an abbreviation of any real number combination between a and b, where a and b are real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed in the present invention, and "0-5" is just an abbreviation of these numerical combinations.

[0085] In the present invention, unless otherwise specified, all embodiments and preferred embodiments mentioned in the present invention can be combined with each other to form a new technical solution.

[0086] In the present invention, unless otherwise specified, all technical features and preferred features mentioned in the present invention can be combined with each other to form a new technical solution.

[0087] In order to make the purpose, technical scheme and advantages of the utility model clearer, the utility model is further described in detail below in conjunction with the accompanying drawings and examples. The following embodiments are part of the embodiments of the utility model, rather than all of them, and are only used to illustrate the utility model, and should not be regarded as limiting the scope of the utility model. Based on the embodiments in the utility model, all other embodiments obtained by ordinary technicians in the field without creative work are within the scope of protection of the utility model. If the specific conditions are not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used without indicating the manufacturer are all conventional products that can be purchased commercially.

[0088] Example 1

[0089] This embodiment provides a multi-layer adsorption catalytic ceramic filter material for dust removal and VOCs purification. Figure 1 As shown, from Figure 1It can be seen that it includes a dense conductive metal grid 1, a 3D foam porous ceramic fiber filter material layer 2, an adsorption-catalysis-porous carrier composite material layer 3 and a discharge electrode 4, wherein one side of the 3D foam porous ceramic fiber filter material layer 2 is fixed to one side of the adsorption-catalysis-porous carrier composite material layer 3 by coating, and the discharge electrode 4 is fixed to the other side of the adsorption-catalysis-porous carrier composite material layer 3;

[0090] The other side of the 3D foam porous ceramic fiber filter material layer 2 is fixed on the dense conductive metal grid 1;

[0091] The 3D foam ceramic fiber filter material in the 3D foam ceramic fiber filter material layer 2 is foam-shaped and has an asymmetric filtering structure. The porosity of the 3D foam ceramic fiber filter material is 90%, the pore size of the internal pores is 40 μm, and the thickness of the 3D foam porous ceramic fiber filter material layer 2 is 40 mm.

[0092] The adsorption-catalysis-porous carrier composite material layer 3 comprises a porous carrier, a composite catalyst and an adsorbent, and the composite catalyst and the adsorbent are loaded on the surface of the porous carrier;

[0093] Wherein, the composite catalyst comprises a carrier and a metal active component, and the metal active component is loaded on the carrier;

[0094] The adsorption-catalysis-porous carrier composite material layer 3 has a porosity of 80% and a thickness of 90 mm;

[0095] Wherein, the discharge electrode 4 is a high-purity tungsten discharge rod.

[0096] In order to more clearly illustrate the dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material provided in Example 1 of the present utility model, the preparation method thereof is now introduced in detail, including:

[0097] Step (1): The adsorbent and the carrier in the composite catalyst are 13X molecular sieve and ZSM-5 molecular sieve respectively, which are firstly modified by strong alkali (sodium hydroxide aqueous solution) impregnation modification method to increase the basic sites and increase the S and N capacity of the adsorbent surface, thereby obtaining the adsorbent and carrier modified by strong alkali.

[0098] Step (2): using an impregnation method, nitrates of Ce, Mn, Co and Zr, 30 g and 60 g of the carrier modified by the strong base obtained in step (1), and 10 g of polyethylene glycol are dissolved in anhydrous ethanol, aged overnight, filtered, heated to 550°C, and calcined for 4 hours to obtain a composite catalyst.

[0099] Step (3): 70 g of graphite with a particle size range of 200-700 nm, 5 g of acrylic acid, 5 g of sodium dodecyl sulfate and 20 g of anhydrous ethanol are mixed and prepared into a highly dispersed slurry through a sand milling slurry process, followed by drying at 120° C. and calcining at 1300° C. for 2 hours to obtain a porous carrier.

[0100] Step (4): by a high-speed mixing process at 60 r / min, 45 g of the porous carrier prepared in step (3), 25 g of the composite catalyst prepared in step (2), 5 g of the strongly alkaline modified adsorbent prepared in step (1), 2 g of a binder (acrylic acid), 1 g of a second pore-forming agent (polyethylene glycol), 1 g of a pH adjuster (saturated NaHCO3-Na2CO3 solution), 1 g of an extrusion aid (polyvinyl alcohol) and anhydrous ethanol are mixed for 3 hours to prepare a high-plasticity mud material, which is then aged for 24 hours, kneaded, extruded by a pressure drainage method, dried in one stage, dried in two stages, and then heated to 400°C at a heating rate of 5°C / min and kept warm for 60 minutes, and then heated to 550°C at a heating rate of 15°C / min and kept warm for 2 hours to prepare an adsorption-catalysis-porous carrier composite material with a porosity of 80% and a thickness of 90 mm.

[0101] Step (5): The high-voltage electrode layer is a high-purity tungsten discharge rod, which is fixed on one side of the adsorption-catalysis-porous carrier composite material by an extrusion molding process in parallel.

[0102] Step (6): Add 50g of crushed ceramic material, such as ceramic fiber, into anhydrous ethanol to prepare a slurry, then add 5g of a first pore-forming agent (graphene) and 2g of a template (polyvinyl alcohol) into the slurry to prepare a foaming slurry, and then form the foaming slurry into a green product, first calcine the green product at 900°C in an Ar or N2 gas protective atmosphere for 2h, and then heat it to 1200°C in an air atmosphere at a heating rate of 20°C / min and calcine it for 2h to obtain a 3D foam porous ceramic fiber filter material, which is foamy and has an asymmetric filtration structure, a porosity of 90%, and an internal pore size of 40μm.

[0103] Step (7): The 3D foam porous ceramic fiber filter material obtained in step (6) is coated on the other side of the adsorption-catalysis-porous carrier composite material by melt-blowing, and its thickness is ensured to be 40 mm.

[0104] Step (8): fix the outer layer, i.e. the other side of the 3D foam porous ceramic fiber filter material to a dense conductive metal grid made of aluminum and ground it at the same time. The dense conductive metal grid is fixedly connected to the flange above the filter material to obtain the dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material.

[0105] Example 2

[0106] This embodiment provides a multi-layer adsorption catalytic ceramic filter material for dust removal and VOCs purification, which differs from Embodiment 1 only in that:

[0107] The 13X molecular sieve used as an adsorbent and the ZSM-5 molecular sieve used as a carrier in the composite catalyst were not modified with a strong base.

[0108] In order to further illustrate the integrated multilayer adsorption catalytic ceramic filter material for dust removal and VOCs purification provided by Examples 1 and 2 of the utility model, Application Examples 1 and 2 are now provided to respectively introduce in detail the process of dust removal and purification of flue gas using the integrated multilayer adsorption catalytic ceramic filter material for dust removal and VOCs purification provided by Examples 1 and 2.

[0109] Application Example 1

[0110] This application example uses the dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material provided in Example 1 of the utility model to remove dust and purify the flue gas, wherein the flue gas is various types of unorganized emission gases from the coking production workshop, which contains PM, VOCs with relatively complex components (such as substances containing benzene), H2S and NH3. During the dust removal and purification process of the flue gas, the assembly method of two pieces of dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter materials is as follows: Figure 2 As shown;

[0111] During the flue gas dust removal and purification process, the flue gas passes vertically through the filter surface and first reaches the 3D foam porous ceramic fiber filter layer. The 3D foam porous ceramic fiber filter layer filters the fine particles in the flue gas by interception, inertial collision, diffusion effect, etc., and the filtration efficiency can be greater than 98%. At the same time, under the action of the low-temperature plasma generated by the subsequent discharge electrode discharge, the surface of the fine particles is charged, and the initial layer of dust on the surface of the 3D foam porous ceramic fiber filter layer is quickly formed, so that the dust removal efficiency reaches more than 98%. At the same time, the dust residing on the surface of the filter material has the same polarity, and the mutual repulsion has a loosening effect, which reduces the filtration resistance, reduces the number of times the filter bag is cleaned, and extends the service life of the filter bag. This structure of the integrated multi-layer adsorption catalytic ceramic filter material for dust removal and VOCs purification is conducive to reducing the resistance of airflow, making the operating resistance much smaller than that of traditional filter materials.

[0112] Then the dust-free flue gas passes through the adsorption-catalysis-porous carrier composite material layer to first achieve the adsorption of VOCs. When the adsorption is close to saturation, the high-voltage power supply is turned on, and the VOCs on the filter material are degraded in the form of pulse discharge or DBD dielectric barrier discharge NTP (10-30kv, 50-2kHz). After cycling in sequence, the VOCs mineralization efficiency can reach more than 95%, and the H2S and NH3 conversion efficiency is 70-80%. The low-temperature plasma discharge form in the adsorption-in-situ catalytic degradation process can effectively realize the utilization of energy, and can achieve efficient degradation of VOCs of different concentrations and gas volumes, meeting the requirements of zero emission of by-products.

[0113] Finally, the clean flue gas flows out through the channel between the two filter media, and under the action of the induced draft fan, it merges with other clean air flows that have undergone the same action and is discharged. When the filter media reaches or approaches its active life cycle, it does not need to be removed and can be cleaned by backblowing and online cleaning to ensure dust removal and VOCs purification efficiency.

[0114] Application Example 2

[0115] This application example uses the dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter material provided in Example 2 of the utility model to remove dust and purify the flue gas, wherein the flue gas is the unorganized emission of the coke oven, which contains PM and VOCs (mainly including benzene-containing substances). During the dust removal and purification process of the flue gas, the assembly method of two pieces of dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter materials is as follows: Figure 2 As shown;

[0116] During the flue gas dust removal and purification process, the flue gas passes vertically through the filter surface and first reaches the 3D foam porous ceramic fiber filter layer. The 3D foam porous ceramic fiber filter layer filters the fine particles in the flue gas by interception, inertial collision, diffusion effect, etc., and the filtration efficiency can be greater than 98%. At the same time, the fine particles are charged on the surface of the particles under the action of the low-temperature plasma generated by the discharge of the discharge electrode, and the initial layer of dust on the surface of the 3D foam porous ceramic fiber filter layer is quickly formed, so that the dust removal efficiency reaches more than 98%. At the same time, the dust residing on the surface of the filter material has the same polarity, and the mutual repulsion has a loosening effect, which reduces the filtration resistance, reduces the number of times the filter bag is cleaned, and extends the service life of the filter bag. This structure of the integrated multi-layer adsorption catalytic ceramic filter material for dust removal and VOCs purification is conducive to reducing the resistance of airflow, making the operating resistance much smaller than that of traditional filter materials.

[0117] Then, the dust-free flue gas passes through the adsorption-catalysis-porous carrier composite layer to first adsorb VOCs. When the adsorption is close to saturation, the high-voltage power supply is turned on to degrade the VOCs on the filter material in the form of pulse discharge or DBD dielectric barrier discharge NTP (10-30kv, 50-2kHz). The mineralization efficiency of VOCs can reach more than 95% after repeated cycles. The low-temperature plasma discharge form in the adsorption-in-situ catalytic degradation process can effectively realize the utilization of energy, and can achieve efficient degradation of VOCs of different concentrations and gas volumes, meeting the requirement of zero emission of by-products.

[0118] Finally, the clean flue gas flows out through the channel between the two filter media, and under the action of the induced draft fan, it merges with other clean air flows that have undergone the same action and is discharged. When the filter media reaches or approaches its active life cycle, it does not need to be removed and can be cleaned by backblowing and online cleaning to ensure dust removal and VOCs purification efficiency.

[0119] The above description is only a specific embodiment of the present invention and cannot be used to limit the scope of implementation of the present invention. Therefore, the replacement of equivalent components or equivalent changes and modifications made according to the protection scope of the present invention patent should still fall within the scope covered by this patent.

Claims

1. A multi-layer adsorption catalytic ceramic filter material for dust removal and VOCs purification, characterized in that: The dust removal and VOCs purification integrated multilayer adsorption catalytic ceramic filter material comprises a dense conductive metal grid, a 3D foam porous ceramic fiber filter material layer, an adsorption-catalysis-porous carrier composite material layer and a discharge electrode, wherein one side of the 3D foam porous ceramic fiber filter material layer is fixed to one side of the adsorption-catalysis-porous carrier composite material layer by coating, and the discharge electrode is fixed to the other side of the adsorption-catalysis-porous carrier composite material layer; The other side of the 3D foam porous ceramic fiber filter material layer is fixed on the dense conductive metal grid.

2. The filter material according to claim 1, characterized in that The 3D foam ceramic fiber filter material in the 3D foam porous ceramic fiber filter material layer is foam-shaped and has an asymmetric filtering structure.

3. The filter material according to claim 2, characterized in that The porosity of the 3D foam ceramic fiber filter material is 72-92%.

4. The filter material according to claim 2 or 3, characterized in that: The pore size of the internal pores of the 3D foam ceramic fiber filter material is 25-45 μm.

5. The filter material according to claim 1 or 2, characterized in that: The thickness of the 3D foam porous ceramic fiber filter material layer is 30-55 mm.

6. The filter material according to claim 1, characterized in that The adsorption-catalysis-porous carrier composite material layer comprises a porous carrier, a composite catalyst and an adsorbent, and the composite catalyst and the adsorbent are loaded on the surface of the porous carrier; The composite catalyst comprises a carrier and a metal active component, and the metal active component is loaded on the carrier.

7. The filter material according to claim 1 or 6, characterized in that: The porosity of the adsorption-catalysis-porous carrier composite material layer is 70-80%.

8. The filter material according to claim 1 or 6, characterized in that: The thickness of the adsorption-catalysis-porous carrier composite material layer is 50-90 mm.

9. The filter material according to claim 1, characterized in that The discharge electrode is a conductive metal discharge rod.

10. A flue gas dust removal and purification device, characterized in that: The flue gas dust removal and purification device comprises two pieces of dust removal and VOCs purification integrated multi-layer adsorption catalytic ceramic filter materials according to any one of claims 1 to 9, the two filter materials are arranged in the form of discharge electrodes facing each other, and a gas channel is formed between the two filter materials; The discharge electrodes in the two filter materials are electrically connected to a high voltage power supply, and the dense conductive metal grid is grounded.

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