CN109289330B - Sheet material integrating filtering, dust removal and catalytic denitration and manufacturing method thereof - Google Patents

Sheet material integrating filtering, dust removal and catalytic denitration and manufacturing method thereof Download PDF

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CN109289330B
CN109289330B CN201811355252.0A CN201811355252A CN109289330B CN 109289330 B CN109289330 B CN 109289330B CN 201811355252 A CN201811355252 A CN 201811355252A CN 109289330 B CN109289330 B CN 109289330B
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substrate
filtering
fibers
manganese
denitration
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CN109289330A (en
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刘海兵
田大春
顾军
刘卫民
张永利
张齐
韩力
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Zanhuang Jinyu Cement Co ltd
Beijing Building Materials Academy of Sciences Research
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Zanhuang Jinyu Cement Co ltd
Beijing Building Materials Academy of Sciences Research
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0001—Making filtering elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/2073—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a sheet material integrating filtration, dust removal and catalytic denitration and a manufacturing method thereof. The sheet material comprises a substrate capable of filtering flue gas, and a catalyst for denitration is attached to the substrate capable of filtering flue gas. The manufacturing method comprises the following steps: firstly, polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers are mixed to prepare a substrate; secondly, preparing part of the substrate into a viscous filter material; thirdly, preparing the viscous filter material and elements containing Mn, Ce, Zr, Ti, Fe, Cu and the like into nano-scale catalyst powder; fourthly, the prepared powder and manganese-based oxide and other element emulsion are mixed; and step five, immersing the substrate into the manganese-based oxide emulsion to prepare a sheet material. The sheet material is put into a bag-type dust remover, and the catalytic denitration treatment is carried out on the industrial flue gas while the soot in the industrial flue gas is filtered, so that the problem of occupied land is avoided, the investment is less, and the popularization and the application of the bag-type dust removal are facilitated.

Description

Sheet material integrating filtering, dust removal and catalytic denitration and manufacturing method thereof
Technical Field
The invention relates to a product for carrying out denitration and dust removal on industrial flue gas and a manufacturing method thereof, in particular to a sheet material integrating filtration and dust removal and catalytic denitration and a manufacturing method thereof.
Background
Nitrogen oxides (NOx) and fine particulate matter are major pollutants of the atmosphere. NOx is the main reason for acid rain, photochemical smog and greenhouse effect, while fine particles below PM10 are toxic and harmful to human bodies, and nitrogen oxides and dust fine particles are also important precursors of haze. Cement plants are important emission sources of nitrogen oxides and dust, and the problem of smoke pollution is more and more emphasized. The existing nitrogen oxide treatment technologies mainly comprise low-nitrogen combustion, SNCR, SCR and the like. The mature and efficient denitration technology is mainly (selective catalytic reduction) SCR technology, the denitration rate is high (more than 90 percent), the technology is mature, but the requirement of a temperature window of 270-plus-320 ℃ is met, the arrangement modes of high-temperature high-ash, low-temperature low-ash and the like are mainly adopted, the temperature interval of the cement kiln high-temperature high-ash arrangement mode is suitable, the dust concentration is high, the influences on the service life, the activity and the like of an SCR catalyst are large, and the cost of the catalyst is high. The low-temperature and low-ash mode is arranged at the rear end of the dust remover, the dust concentration is low, but the flue gas temperature is low, reheating is needed, and the operation cost is high. The dust treatment technology mainly comprises electric dust removal, bag dust removal and electric bag dust removal, wherein the bag dust remover is widely and mature in industrial furnaces and kilns, has the temperature of 160-200 ℃ and can meet the requirements of dust emission at the present stage. At present, most of SCR catalytic materials suitable for cement kilns use TiO2 as carriers, the TiO2 carriers are high in cost, so that catalytic material products are high in price, in addition, the tail gas of the cement kiln also contains a large amount of dust, and the dust and NOx are treated independently usually, so that the integration of dust removal and denitration is realized, the comprehensive cost and investment for removing pollutants are saved, and the SCR catalytic material has important significance for energy conservation and emission reduction in the cement industry.
The existing patents and technical researches are basically the compounding of single denitration and dedusting processes, and a new device is built, such as invention patents CN204469519U, CN204208445U, CN101983755A, CN1698933A and the like; other patents refer to catalysts supported on metal materials, such as patent nos. CN104190399A, 201010291794.3, CN105315000A, CN104524886A, CN205699844U, etc. The material base materials are difficult to adapt to the functional requirements of acid, alkali, oxidation, moisture, back flushing, wear resistance, replacement and the like. The service life is short, and the operating cost is high.
With the increase of the national atmospheric control requirements, the existing standards and technologies cannot adapt to new environmental protection policies. If the SCR is separately built, the problems of land occupation, influence on production operation, investment and the like are faced to the existing enterprises. And with the controlled emission of other smoke pollutant factors, the land occupation problem of environmental protection facilities is more prominent. Therefore, the development of low-temperature dust removal integrated filter materials and the like based on the improvement of the bag-type dust remover is of great significance for the implementation of ultra-low emission of the industrial furnace.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a sheet material integrating filtering, dust removal and catalytic denitration, the sheet material is placed in a bag-type dust remover, the industrial flue gas is subjected to catalytic denitration while the ash in the industrial flue gas is filtered, in addition, the floor occupation problem is avoided, the investment is less, and the popularization and the application of the bag-type dust removal are facilitated.
The second technical problem to be solved by the invention is to provide a method for manufacturing a sheet material integrating filtering, dust removal and catalytic denitration, the sheet material manufactured by the method is placed into a bag-type dust remover, and the catalytic denitration treatment is carried out on industrial flue gas while the ash in the industrial flue gas is filtered, so that the method avoids the problem of land occupation, has less investment and is beneficial to popularization and application of bag-type dust removal.
In terms of products, in order to solve the first technical problem, the invention provides a sheet material integrating filtration, dust removal and catalytic denitration, which comprises a substrate capable of filtering flue gas, wherein dust filtration air holes are densely distributed on the substrate capable of filtering flue gas, and a catalyst for denitration is attached to the substrate capable of filtering flue gas.
The substrate capable of filtering smoke is woven cloth, knitted cloth or non-woven cloth;
the non-woven fabric is prepared by opening and mixing fibers, carding into a net, cross lapping, pre-needling, spunlacing, drying and winding, pricking, singeing and heat setting, and can filter smoke;
the woven fabric is prepared by opening, carding, spinning and weaving fibers into the woven fabric capable of filtering smoke;
the knitted fabric is a knitted fabric which can filter smoke and is prepared by opening, carding, spinning, twisting and knitting fibers;
the thickness of the substrate is 1mm-3 mm;
the thickness of the substrate is 1.5mm-2 mm;
the fibers comprise polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers;
the polyphenylene sulfide (PPS) fibers and the Polytetrafluoroethylene (PTFE) fibers are mixed in a ratio of 60-70: 40-30;
the polyphenylene sulfide (PPS) fiber and the Polytetrafluoroethylene (PTFE) fiber are mixed in a ratio of 65: 35;
the catalyst is a manganese-based composite catalyst;
the manganese-based composite catalyst is formed by mixing manganese-based oxide and nano-scale catalyst powder;
the nano-scale catalyst powder contains elements such as a viscous material, manganese Mn, cerium Ce, zirconium Zr, titanium Ti, iron Fe, copper Cu and the like;
the viscous material is organosilicon modified polyurethane.
Compared with the prior art, the sheet material integrating filtering, dust removal and catalytic denitration has the following beneficial effects.
1. According to the technical scheme, as the substrate capable of filtering the flue gas is densely provided with the dust filtering air holes, and the substrate capable of filtering the flue gas is attached with the catalyst for denitration, the sheet material is placed into the bag-type dust collector, the industrial flue gas is subjected to catalytic denitration while the ash in the industrial flue gas is filtered, in addition, the occupied area problem is avoided, the investment is less, and the popularization and the application of the bag-type dust collection are facilitated. The sheet material can be directly used on the filter bag of the prior bag-type dust remover for refuse incineration, cement kiln and the like. And an SCR denitration device does not need to be separately built. Different layers can be arranged in the bag-type dust collector according to actual requirements.
2. The technical scheme adopts the technical means that the substrate capable of filtering the smoke is woven cloth or knitted cloth or non-woven cloth, so that the technical scheme is favorable for filtering and dedusting the smoke.
3. The technical scheme adopts the technical means that the non-woven fabric is made into the non-woven fabric capable of filtering smoke gas after opening and mixing, carding to form a net, cross lapping, pre-needling, spunlacing, drying and winding, pricking, singeing and heat setting, so that the manufacturing cost can be greatly reduced.
4. The technical scheme adopts the technical means that the woven fabric is made into the smoke-filterable woven fabric by opening, carding, spinning and weaving fibers, so that the strength is high, and the service life is prolonged.
5. The technical scheme adopts the technical means that the knitted fabric is made into the knitted fabric capable of filtering the smoke through opening, carding, spinning, twisting and knitting, so that the knitted fabric has good elasticity and is favorable for filtering and dedusting the smoke;
6. the technical scheme adopts the technical means that the thickness of the substrate is 1mm-3mm, so that the technical scheme is not only beneficial to filtering and dedusting the flue gas, but also beneficial to prolonging the service life of the substrate.
7. The technical scheme adopts the technical means that the thickness of the substrate is 1.5mm-2mm, so that the flue gas dust removal device has better effects on the filtration and dust removal of flue gas and the service life of the substrate.
8. The technical means that the fibers comprise polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers are adopted, so that the strength and the corrosion resistance of the substrate are improved, and the service life of the substrate is prolonged. The applicant intensively studies the preparation process of the polyphenylene sulfide (PPS) dedusting filter material supported catalyst and the denitration and dedusting performance after the supported catalyst. Firstly, soaking filter cloth into PTFE emulsion containing active components by adopting the simplest direct soaking method, discussing preparation process parameters, and optimally preparing a sample by using PTFE emulsion with the mass concentration of 4% and catalyst powder with the particle size of 200 meshes; the applicant also successfully adopts a PTFE (polytetrafluoroethylene) foaming coating to prepare the filter cloth for dust removal and denitration at the same time, selects nonionic APG as a foaming agent, and determines the optimal preparation method of the foaming coating method by adopting an orthogonal test, wherein the concentration of the APG foaming agent is 8g/L, the mixing ratio of PTFE emulsion and the foaming agent is 2: 1, the concentration dosage of a thickening stabilizer is HEC15g/L and HPMC0.5g/L, PVA5g/L, and the foaming stirring is performedThe stirring time is 15 min. The optimal foaming temperature is 30 ℃, the optimal baking mode of the foaming coating is pre-baking at the temperature of 80 ℃ for 2min, and then baking at the temperature of 140 ℃ for 5 min. Finally, based on the filter material prepared by the direct impregnation method, the reaction temperature, the filtration air speed and NH were examined3NO and oxygen content, load amount and SO2The influence on the denitration performance of the sample is compared with the change of the blank sample and the finished product in various performance indexes. The results showed that the loading was 255g/m2The catalytic activity is more than 80 percent and the highest is 91.2 percent within the temperature range of 100-200 ℃. At 160 ℃, 300ppm SO2The activity was reduced to 81% at the lowest. All indexes of the prepared filter material are qualified through detection.
9. The technical scheme is characterized in that the polyphenylene sulfide (PPS) fibers and the Polytetrafluoroethylene (PTFE) fibers are mixed according to the ratio of 60-70: 40-30, so that the strength and the corrosion resistance of the substrate can be further improved, and the service life of the substrate can be further prolonged.
10. The technical proposal adopts the polyphenylene sulfide (PPS) fiber and the Polytetrafluoroethylene (PTFE) fiber in the ratio of 65: 35, the strength and corrosion resistance of the substrate can be further improved, and the service life of the substrate can be further prolonged.
11. The technical proposal adopts the manganese-based composite catalyst as the catalyst; the manganese-based composite catalyst is formed by mixing manganese-based oxide and nano-scale catalyst powder; the nano-scale catalyst powder contains a viscous material, manganese Mn, cerium Ce, zirconium Zr, titanium Ti, iron Fe, copper Cu and other elements, so that the denitration efficiency can be greatly improved. The applicant invests a large amount of manpower, material resources and financial resources, long-term practice is carried out, finally, different single-component elements (carbon monoxide Co, iron Fe, lanthanum La, copper Cu, nickel Ni and zirconium Zr) are doped on the basis of the Mn-Ce-Ox composite oxide denitration catalyst, La and Ni with better denitration activity are selected and simultaneously doped with Mn-Ce-Ox, and the denitration performance and SO resistance of the catalyst are examined2The poisoning capacity is combined with X-ray diffraction (XRD) to carry out deep analysis on the sample, and the research result shows that when the mixture ratio is manganese Mn2When 5-La2.5-cerium Ce-Ni-Ox is used, the denitration activity is higher than that of the doped La and Ni single components; introducing SO2After 4 hours, the denitration efficiency is kept above 80%, and the SO introduction is stopped2After 2 hours, the denitration efficiency is recovered to more than 90%; under the condition of 140 ℃ for a long time, the removal efficiency of the nitrogen oxides is still kept above 96 percent after 91 days.
12. The technical scheme adopts the technical means that the viscous material is organic silicon modified polyurethane, so that the adhesive capacity of the catalyst on the substrate can be greatly improved.
As a method, in order to solve the second technical problem described above, the present invention provides a method for producing a sheet material as described above, comprising the steps of:
firstly, polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers are mixed according to the weight ratio of 60-70: 40-30, and preparing the non-woven fabric capable of filtering smoke gas by opening and mixing, carding to form a net, cross lapping, pre-needling, spunlacing, drying and winding, pricking, singeing and heat setting; or firstly, mixing polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers according to the weight ratio of 60-70: 40-30, mixing, and making the woven fabric capable of filtering smoke gas by opening, carding, spinning and weaving; or firstly, mixing polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers according to the weight ratio of 60-70: 40-30, and opening, carding, spinning, twisting and knitting to prepare a knitted fabric capable of filtering smoke;
the woven fabric capable of filtering smoke, the knitted fabric capable of filtering smoke and the non-woven fabric capable of filtering smoke are collectively called as a substrate;
secondly, immersing part of the prepared substrate into a modified polyurethane solution containing 10-15% of organic silicon, immersing for 20-30min, draining, and drying at 90-120 ℃ for 20-30min to prepare a viscous filter material;
thirdly, washing, filtering, drying and grinding the viscous filter material and salt solution containing Mn, Ce, Zr, Ti, Fe, Cu and other elements in different molar ratios to prepare nano-scale catalyst powder;
fourthly, stirring and mixing the prepared powder with water to prepare 0.04g/ml-0.1g/ml manganese-based oxide and other element emulsion;
and fifthly, immersing the substrate into the manganese-based oxide emulsion, immersing for 10-20min under the ultrasonic-assisted condition, taking out the substrate, draining, drying for 2 hours at 90-110 ℃, and drying for 20 hours at 200 ℃ of 180 ℃ to obtain the sheet material which is attached with the manganese-based composite catalyst and integrates filtration, dust removal and catalytic denitration.
The polyphenylene sulfide (PPS) fiber and the Polytetrafluoroethylene (PTFE) fiber are mixed in a ratio of 65: 35;
the thickness of the substrate 1 is 1mm-3 mm;
the thickness of the substrate 1 is 1.5mm-2 mm;
the solid content of the polyurethane solution is 10-18%;
the concentration of the salt solution containing Mn, Ce, Zr, Ti, Fe, Cu and other elements with different molar ratios is 15-25%.
The method of manufacturing the sheet material of the present invention as described above has the following advantageous effects as compared with the prior art.
1. Due to the adoption of the technical scheme
Firstly, polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers are mixed according to the weight ratio of 60-70: 40-30, and preparing the non-woven fabric capable of filtering smoke gas by opening and mixing, carding to form a net, cross lapping, pre-needling, spunlacing, drying and winding, pricking, singeing and heat setting; or firstly, mixing polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers according to the weight ratio of 60-70: 40-30, mixing, and making the woven fabric capable of filtering smoke gas by opening, carding, spinning and weaving; or firstly, mixing polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers according to the weight ratio of 60-70: 40-30, and opening, carding, spinning, twisting and knitting to prepare a knitted fabric capable of filtering smoke;
the woven fabric capable of filtering smoke, the knitted fabric capable of filtering smoke and the non-woven fabric capable of filtering smoke are collectively called as a substrate;
secondly, immersing part of the prepared substrate into a modified polyurethane solution containing 10-15% of organic silicon, immersing for 20-30min, draining, and drying at 90-120 ℃ for 20-30min to prepare a viscous filter material;
thirdly, washing, filtering, drying and grinding the viscous filter material and salt solution containing Mn, Ce, Zr, Ti, Fe, Cu and other elements in different molar ratios to prepare nano-scale catalyst powder;
fourthly, stirring and mixing the prepared powder with water to prepare 0.04g/ml-0.1g/ml manganese-based oxide and other element emulsion;
and fifthly, immersing the substrate into manganese-based oxide emulsion, immersing for 10-20min under the ultrasonic-assisted condition, taking out the substrate, draining, drying for 2 hours at 90-110 ℃, and drying for 20 hours at 200 ℃ with 180-.
The applicant invests a large amount of manpower, material resources and financial resources, long-term practice is carried out, finally, different single-component elements (carbon monoxide Co, iron Fe, lanthanum La, copper Cu, nickel Ni and zirconium Zr) are doped on the basis of the Mn-Ce-Ox composite oxide denitration catalyst, La and Ni with better denitration activity are selected and simultaneously doped with Mn-Ce-Ox, and the denitration performance and SO resistance of the catalyst are examined2The poisoning capacity is combined with X-ray diffraction (XRD) to carry out deep analysis on the sample, and research results show that when the mixture ratio is Mn (Mn2.5-La2.5) -Ce (Ce) -Ni-Ox, the denitration activity is higher than that of La and Ni single components; introducing SO2After 4 hours, the denitration efficiency is kept above 80%, and the SO introduction is stopped2After 2 hours, the denitration efficiency is recovered to more than 90%; under the condition of 140 ℃ for a long time, the removal efficiency of the nitrogen oxides is still kept above 96 percent after 91 days.
The applicant intensively studies the preparation process of the polyphenylene sulfide (PPS) dedusting filter material supported catalyst and the denitration and dedusting performance after the supported catalyst. Firstly, the simplest direct impregnation method is adopted to impregnate the filter cloth with the PTFE emulsion containing active components, the preparation process parameters, the PTFE concentration emulsion with the mass concentration of 4 percent and a particle ruler are discussedThe catalyst powder with size of 200 meshes is optimally prepared; the applicant also successfully adopts a PTFE (polytetrafluoroethylene) foaming coating to prepare the filter cloth for dust removal and denitration simultaneously, selects nonionic APG as a foaming agent, and adopts an orthogonal test to determine the optimal preparation method of the foaming coating method, wherein the concentration of the APG foaming agent is 8g/L, the mixing ratio of PTFE emulsion and the foaming agent is 2: 1, the concentration dosage of a thickening stabilizer is HEC15g/L and HPMC0.5g/L, PVA5g/L, and the foaming stirring time is 15 min. The optimal foaming temperature is 30 ℃, the optimal baking mode of the foaming coating is pre-baking at the temperature of 80 ℃ for 2min, and then baking at the temperature of 140 ℃ for 5 min. Finally, based on the filter material prepared by the direct impregnation method, the reaction temperature, the filtration air speed and NH were examined3NO and oxygen content, load amount and SO2The influence on the denitration performance of the sample is compared with the change of the blank sample and the finished product in various performance indexes. The results showed that the loading was 255g/m2The catalytic activity is more than 80 percent and the highest is 91.2 percent within the temperature range of 100-200 ℃. At 160 ℃, 300ppm SO2The activity was reduced to 81% at the lowest. All indexes of the prepared filter material are qualified through detection.
2. The technical proposal adopts the polyphenylene sulfide (PPS) fiber and the Polytetrafluoroethylene (PTFE) fiber in the ratio of 65: 35, the strength and corrosion resistance of the substrate can be further improved, and the service life of the substrate can be further prolonged.
3. The technical scheme adopts the technical means that the thickness of the substrate 1 is 1mm-3mm, so that the technical scheme is not only beneficial to filtering and dedusting smoke, but also beneficial to prolonging the service life of the substrate.
4. According to the technical scheme, the technical means that the thickness of the substrate 1 is 1.5mm-2mm is adopted, so that the flue gas dust removal device has good effects on filtering and removing dust of flue gas and prolonging the service life of the substrate.
5. The solid content of the polyurethane solution is 10-18% in the technical scheme; the concentration of the salt solution containing Mn, Ce, Zr, Ti, Fe, Cu and other elements with different molar ratios is 15-25%, so that the denitration efficiency of the sheet material can be greatly improved.
Drawings
The present invention will be described in detail with reference to the accompanying drawings and embodiments, wherein the sheet material integrates filtration, dust removal and catalytic denitration, and the manufacturing method thereof.
FIG. 1 is a schematic structural diagram of a sheet material integrating filtration, dust removal and catalytic denitration.
The reference numerals are explained below.
1. A substrate;
2. a catalyst;
3. and (5) filtering dust and air holes.
Detailed Description
As shown in fig. 1, the present embodiment provides a sheet material integrating filtration, dust removal, catalysis and denitration, comprising a substrate 1 capable of filtering flue gas, wherein dust filtration vents 3 are densely distributed on the substrate 1 capable of filtering flue gas, and a catalyst 2 for denitration is attached to the substrate 1 capable of filtering flue gas.
In the embodiment, as the substrate capable of filtering the flue gas is densely provided with the dust filtering air holes, and the substrate capable of filtering the flue gas is attached with the catalyst for denitration, the sheet material is placed into the bag-type dust collector to filter the soot in the industrial flue gas and simultaneously carry out catalytic denitration treatment on the industrial flue gas, so that the problem of occupied land is avoided, the investment is less, and the popularization and the application of the bag-type dust collection are facilitated. The sheet material can be directly used on the filter bag of the prior bag-type dust remover for refuse incineration, cement kiln and the like. And an SCR denitration device does not need to be separately built. Different layers can be arranged in the bag-type dust collector according to actual requirements.
Various modifications of the present embodiment will be described in detail below.
As shown in fig. 1, the substrate 1 capable of filtering smoke is woven fabric or knitted fabric or nonwoven fabric.
The embodiment adopts the technical means that the substrate capable of filtering the smoke is woven cloth or knitted cloth or non-woven cloth, so that the technical means is favorable for filtering and dedusting the smoke.
As shown in fig. 1, the non-woven fabric is prepared by opening and mixing fibers, carding into a web, cross lapping, pre-needling, spunlacing, drying and winding, pricking, singeing and heat setting, and then is made into the non-woven fabric capable of filtering smoke.
The embodiment adopts the technical means that the non-woven fabric is made into the non-woven fabric capable of filtering smoke gas after opening and mixing, carding and web forming, cross lapping, pre-needling, spunlacing, drying and winding, pricking, singeing and heat setting, so that the manufacturing cost can be greatly reduced.
As shown in fig. 1, the woven fabric is made by opening, carding, spinning and weaving fibers into the woven fabric capable of filtering smoke.
The embodiment adopts the technical means that the woven fabric is made into the smoke-filterable woven fabric by opening, carding, spinning and weaving, so that the strength is high, and the service life is prolonged.
As shown in fig. 1, the knitted fabric is a knitted fabric which is made by opening, carding, spinning, twisting and knitting fibers and can filter smoke.
The embodiment adopts the technical means that the knitted fabric is made into the knitted fabric capable of filtering the smoke through opening, carding, spinning, twisting and knitting, so that the elasticity is good, and the smoke is favorably filtered and dedusted;
as shown in fig. 1, the substrate 1 has a thickness of 1mm to 3 mm.
The technical means that the thickness of the substrate is 1mm-3mm is adopted, so that the method is not only beneficial to filtering and dedusting the flue gas, but also beneficial to prolonging the service life of the substrate.
As shown in fig. 1, the substrate 1 has a thickness of 1.5mm to 2 mm.
The embodiment adopts the technical means that the thickness of the substrate is 1.5mm-2mm, so that the flue gas filtering and dedusting device has better effects on the filtering and dedusting of the flue gas and the service life of the substrate.
As shown in fig. 1, the fibers include polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers.
The embodiment adopts the fiber comprising polyphenylene sulfide (PPS) fiber and polytetrafluoroethyleneThe ethylene (PTFE) fiber is technically beneficial to improving the strength and the corrosion resistance of the substrate and prolonging the service life of the substrate. The applicant intensively studies the preparation process of the polyphenylene sulfide (PPS) dedusting filter material supported catalyst and the denitration and dedusting performance after the supported catalyst. Firstly, soaking filter cloth into PTFE emulsion containing active components by adopting the simplest direct soaking method, discussing preparation process parameters, and optimally preparing a sample by using PTFE emulsion with the mass concentration of 4% and catalyst powder with the particle size of 200 meshes; the applicant also successfully adopts a PTFE (polytetrafluoroethylene) foaming coating to prepare the filter cloth for dust removal and denitration simultaneously, selects nonionic APG as a foaming agent, and adopts an orthogonal test to determine the optimal preparation method of the foaming coating method, wherein the concentration of the APG foaming agent is 8g/L, the mixing ratio of PTFE emulsion and the foaming agent is 2: 1, the concentration dosage of a thickening stabilizer is HEC15g/L and HPMC0.5g/L, PVA5g/L, and the foaming stirring time is 15 min. The optimal foaming temperature is 30 ℃, the optimal baking mode of the foaming coating is pre-baking at the temperature of 80 ℃ for 2min, and then baking at the temperature of 140 ℃ for 5 min. Finally, based on the filter material prepared by the direct impregnation method, the reaction temperature, the filtration air speed and NH were examined3NO and oxygen content, load amount and SO2The influence on the denitration performance of the sample is compared with the change of the blank sample and the finished product in various performance indexes. The results showed that the loading was 255g/m2The catalytic activity is more than 80 percent and the highest is 91.2 percent within the temperature range of 100-200 ℃. At 160 ℃, 300ppm SO2The activity was reduced to 81% at the lowest. All indexes of the prepared filter material are qualified through detection.
As shown in fig. 1, the ratio of the polyphenylene sulfide (PPS) fibers to the Polytetrafluoroethylene (PTFE) fibers is 60 to 70: 40 to 30.
In the embodiment, the polyphenylene sulfide (PPS) fibers and the Polytetrafluoroethylene (PTFE) fibers are mixed in a ratio of 60-70: 40-30, so that the strength and the corrosion resistance of the substrate can be further improved, and the service life of the substrate can be further prolonged.
As shown in fig. 1, the ratio of the polyphenylene sulfide (PPS) fibers to the Polytetrafluoroethylene (PTFE) fibers is 65: 35.
in the embodiment, the polyphenylene sulfide (PPS) fibers and the Polytetrafluoroethylene (PTFE) fibers are mixed in a ratio of 65: 35, the strength and corrosion resistance of the substrate can be further improved, and the service life of the substrate can be further prolonged.
As shown in fig. 1, the catalyst 2 is a manganese-based composite catalyst.
The manganese-based composite catalyst is formed by mixing manganese-based oxide and nano-scale catalyst powder.
The nano-scale catalyst powder contains elements such as viscous materials, manganese Mn, cerium Ce, zirconium Zr, titanium Ti, iron Fe, copper Cu and the like.
In the embodiment, the catalyst is a manganese-based composite catalyst; the manganese-based composite catalyst is formed by mixing manganese-based oxide and nano-scale catalyst powder; the nano-scale catalyst powder contains a viscous material, manganese Mn, cerium Ce, zirconium Zr, titanium Ti, iron Fe, copper Cu and other elements, so that the denitration efficiency can be greatly improved. The applicant invests a large amount of manpower, material resources and financial resources, long-term practice is carried out, finally, different single-component elements (carbon monoxide Co, iron Fe, lanthanum La, copper Cu, nickel Ni and zirconium Zr) are doped on the basis of the Mn-Ce-Ox composite oxide denitration catalyst, La and Ni with better denitration activity are selected and simultaneously doped with Mn-Ce-Ox, and the denitration performance and SO resistance of the catalyst are examined2The poisoning capacity is combined with X-ray diffraction (XRD) to carry out deep analysis on the sample, and research results show that when the mixture ratio is Mn (Mn2.5-La2.5) -Ce (Ce) -Ni-Ox, the denitration activity is higher than that of La and Ni single components; introducing SO2After 4 hours, the denitration efficiency is kept above 80%, and the SO introduction is stopped2After 2 hours, the denitration efficiency is recovered to more than 90%; under the condition of 140 ℃ for a long time, the removal efficiency of the nitrogen oxides is still kept above 96 percent after 91 days.
As shown in fig. 1, the adhesive material is silicone-modified polyurethane.
In the embodiment, the technical means that the viscous material is the organic silicon modified polyurethane is adopted, so that the adhesive capacity of the catalyst on the substrate can be greatly improved.
As shown in FIG. 1, the present embodiment provides a method of producing the sheet as described above, comprising the steps of:
firstly, polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers are mixed according to the weight ratio of 60-70: 40-30, and preparing the non-woven fabric capable of filtering smoke gas by opening and mixing, carding to form a net, cross lapping, pre-needling, spunlacing, drying and winding, pricking, singeing and heat setting; or firstly, mixing polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers according to the weight ratio of 60-70: 40-30, mixing, and making the woven fabric capable of filtering smoke gas by opening, carding, spinning and weaving; or firstly, mixing polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers according to the weight ratio of 60-70: 40-30, and opening, carding, spinning, twisting and knitting to prepare a knitted fabric capable of filtering smoke;
the woven fabric, the knitted fabric and the non-woven fabric which can filter the smoke are collectively called as a substrate 1;
secondly, immersing part of the prepared substrate 1 into a modified polyurethane solution containing 10-15% of organic silicon, immersing for 20-30min, draining, and drying at 90-120 ℃ for 20-30min to prepare a viscous filter material;
thirdly, washing, filtering, drying and grinding the viscous filter material and salt solution containing Mn, Ce, Zr, Ti, Fe, Cu and other elements in different molar ratios to prepare nano-scale catalyst powder;
fourthly, stirring and mixing the prepared powder with water to prepare 0.04g/ml-0.1g/ml manganese-based oxide and other element emulsion;
and step five, immersing the substrate 1 into the manganese-based oxide emulsion, immersing for 10-20min under the ultrasonic-assisted condition, taking out the substrate 1, draining, drying for 2 hours at 90-110 ℃, and drying for 20 hours at 200 ℃ at 180 ℃ to obtain the sheet material which is attached with the manganese-based composite catalyst and integrates filtration, dust removal and catalytic denitration.
This embodiment adopts
Firstly, polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers are mixed according to the weight ratio of 60-70: 40-30, and preparing the non-woven fabric capable of filtering smoke gas by opening and mixing, carding to form a net, cross lapping, pre-needling, spunlacing, drying and winding, pricking, singeing and heat setting; or firstly, mixing polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers according to the weight ratio of 60-70: 40-30, mixing, and making the woven fabric capable of filtering smoke gas by opening, carding, spinning and weaving; or firstly, mixing polyphenylene sulfide (PPS) fibers and Polytetrafluoroethylene (PTFE) fibers according to the weight ratio of 60-70: 40-30, and opening, carding, spinning, twisting and knitting to prepare a knitted fabric capable of filtering smoke;
the woven fabric capable of filtering smoke, the knitted fabric capable of filtering smoke and the non-woven fabric capable of filtering smoke are collectively called as a substrate;
secondly, immersing part of the prepared substrate into a modified polyurethane solution containing 10-15% of organic silicon, immersing for 20-30min, draining, and drying at 90-120 ℃ for 20-30min to prepare a viscous filter material;
thirdly, washing, filtering, drying and grinding the viscous filter material and salt solution containing Mn, Ce, Zr, Ti, Fe, Cu and other elements in different molar ratios to prepare nano-scale catalyst powder;
fourthly, stirring and mixing the prepared powder with water to prepare 0.04g/ml-0.1g/ml manganese-based oxide and other element emulsion;
and fifthly, immersing the substrate into manganese-based oxide emulsion, immersing for 10-20min under the ultrasonic-assisted condition, taking out the substrate, draining, drying for 2 hours at 90-110 ℃, and drying for 20 hours at 200 ℃ with 180-.
The applicant invests a large amount of manpower, material resources and financial resources, carries out long-term practice, and finally, based on the Mn-Ce-Ox composite oxide denitration catalyst, adds different single-component elements (carbon monoxide Co, iron Fe, lanthanum La, copper Cu, nickel Ni and zirconium Z)r), selecting La and Ni metal elements with excellent denitration activity and doping Mn-Ce-Ox at the same time, and investigating the denitration performance and SO resistance of the catalyst2The poisoning capacity is combined with X-ray diffraction (XRD) to carry out deep analysis on the sample, and research results show that when the mixture ratio is Mn (Mn2.5-La2.5) -Ce (Ce) -Ni-Ox, the denitration activity is higher than that of La and Ni single components; introducing SO2After 4 hours, the denitration efficiency is kept above 80%, and the SO introduction is stopped2After 2 hours, the denitration efficiency is recovered to more than 90%; under the condition of 140 ℃ for a long time, the removal efficiency of the nitrogen oxides is still kept above 96 percent after 91 days.
The applicant intensively studies the preparation process of the polyphenylene sulfide (PPS) dedusting filter material supported catalyst and the denitration and dedusting performance after the supported catalyst. Firstly, soaking filter cloth into PTFE emulsion containing active components by adopting the simplest direct soaking method, discussing preparation process parameters, and optimally preparing a sample by using PTFE emulsion with the mass concentration of 4% and catalyst powder with the particle size of 200 meshes; the applicant also successfully adopts a PTFE (polytetrafluoroethylene) foaming coating to prepare the filter cloth for dust removal and denitration simultaneously, selects nonionic APG as a foaming agent, and adopts an orthogonal test to determine the optimal preparation method of the foaming coating method, wherein the concentration of the APG foaming agent is 8g/L, the mixing ratio of PTFE emulsion and the foaming agent is 2: 1, the concentration dosage of a thickening stabilizer is HEC15g/L and HPMC0.5g/L, PVA5g/L, and the foaming stirring time is 15 min. The optimal foaming temperature is 30 ℃, the optimal baking mode of the foaming coating is pre-baking at the temperature of 80 ℃ for 2min, and then baking at the temperature of 140 ℃ for 5 min. Finally, based on the filter material prepared by the direct impregnation method, the reaction temperature, the filtration air speed and NH were examined3NO and oxygen content, load amount and SO2The influence on the denitration performance of the sample is compared with the change of the blank sample and the finished product in various performance indexes. The results showed that the loading was 255g/m2The catalytic activity is more than 80 percent and the highest is 91.2 percent within the temperature range of 100-200 ℃. At 160 ℃, 300ppm SO2The activity was reduced to 81% at the lowest. All indexes of the prepared filter material are qualified through detection.
Various modifications of the present embodiment will be described in detail below.
As shown in fig. 1, the ratio of the polyphenylene sulfide (PPS) fibers to the Polytetrafluoroethylene (PTFE) fibers is 65: 35.
in the embodiment, the polyphenylene sulfide (PPS) fibers and the Polytetrafluoroethylene (PTFE) fibers are mixed in a ratio of 65: 35, the strength and corrosion resistance of the substrate can be further improved, and the service life of the substrate can be further prolonged.
As shown in fig. 1, the substrate 1 has a thickness of 1mm to 3 mm.
The technical means that the thickness of the substrate 1 is 1mm-3mm is adopted, so that the method is not only beneficial to filtering and dedusting the flue gas, but also beneficial to prolonging the service life of the substrate.
As shown in fig. 1, the substrate 1 has a thickness of 1.5mm to 2 mm.
The technical means that the thickness of the substrate 1 is 1.5mm-2mm is adopted, so that the method has good effects on filtering and dedusting of smoke and the service life of the substrate.
As shown in figure 1, the solid content of the polyurethane solution is 10-18%.
The concentration of the salt solution containing Mn, Ce, Zr, Ti, Fe, Cu and other elements with different molar ratios is 15-25%.
In the embodiment, the solid content of the polyurethane solution is 10-18%; the concentration of the salt solution containing Mn, Ce, Zr, Ti, Fe, Cu and other elements with different molar ratios is 15-25%, so that the denitration efficiency of the sheet material can be greatly improved.

Claims (4)

1. The utility model provides a collect and filter dust removal and catalytic denitration in sheet stock of an organic whole which characterized in that: the denitration catalyst comprises a substrate (1) capable of filtering flue gas, dust filtering air holes (3) are densely distributed on the substrate (1) capable of filtering flue gas, and a catalyst (2) for denitration is attached to the substrate (1) capable of filtering flue gas;
the substrate (1) capable of filtering smoke is woven fabric or knitted fabric;
the woven fabric is prepared by opening, carding, spinning and weaving fibers into the woven fabric capable of filtering smoke;
the knitted fabric is a knitted fabric which can filter smoke and is prepared by opening, carding, spinning, twisting and knitting fibers;
the fibers comprise polyphenylene sulfide fibers and polytetrafluoroethylene fibers;
the ratio of the polyphenylene sulfide fibers to the polytetrafluoroethylene fibers is 60-70: 40-30;
the catalyst (2) is a manganese-based composite catalyst;
the manganese-based composite catalyst is formed by mixing manganese-based oxide and nano-scale catalyst powder;
the nano-scale catalyst powder consists of viscous materials, manganese, cerium, zirconium, titanium, iron and copper elements;
the viscous material is organosilicon modified polyurethane;
the viscous material is a viscous filter material;
the viscous filter material is prepared by immersing part of the prepared substrate (1) into a modified polyurethane solution containing 10-15% of organic silicon, soaking for 20-30min, draining, and drying at 90-120 ℃ for 20-30 min;
the nano-scale catalyst powder is prepared by washing, filtering, drying and grinding a viscous filter material and salt solutions containing manganese, cerium, zirconium, titanium, iron and copper elements in different molar ratios.
2. The sheet material integrating filtration, dust removal and catalytic denitration as claimed in claim 1, wherein:
the thickness of the substrate (1) is 1mm-3 mm.
3. A method of producing a sheet material as claimed in claim 1 or 2, wherein:
firstly, polyphenylene sulfide fibers and polytetrafluoroethylene fibers are mixed according to the weight ratio of 60-70: 40-30, mixing, and making the woven fabric capable of filtering smoke gas by opening, carding, spinning and weaving; or firstly, mixing polyphenylene sulfide fibers and polytetrafluoroethylene fibers in a weight ratio of 60-70: 40-30, and opening, carding, spinning, twisting and knitting to prepare a knitted fabric capable of filtering smoke;
the woven fabric capable of filtering smoke and the knitted fabric capable of filtering smoke are collectively called as a substrate (1);
secondly, immersing part of the prepared substrate (1) into a modified polyurethane solution containing 10-15% of organic silicon, soaking for 20-30min, draining, and drying at 90-120 ℃ for 20-30min to prepare a viscous filter material;
thirdly, washing, filtering, drying and grinding the viscous filter material and salt solutions containing manganese, cerium, zirconium, titanium, iron and copper elements in different molar ratios to prepare nano-scale catalyst powder;
fourthly, stirring and mixing the prepared powder with water to prepare 0.04g/ml-0.1g/ml manganese-based oxide element emulsion;
and fifthly, immersing the substrate (1) into the manganese-based oxide emulsion, immersing for 10-20min under the ultrasonic-assisted condition, taking out the substrate (1), draining, drying for 2 hours at 90-110 ℃, and drying for 20 hours at 200 ℃ in the presence of 180-.
4. A method of producing sheet material as defined in claim 3 wherein:
the ratio of the polyphenylene sulfide fiber to the polytetrafluoroethylene fiber is 65: 35;
the thickness of the substrate (1) is 1mm-3 mm;
the solid content of the polyurethane solution is 10-18%;
the concentration of the salt solution containing manganese, cerium, zirconium, titanium, iron and copper elements with different molar ratios is 15-25%.
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