WO2018233159A1 - Difunctional composite filter medium fiber and preparation method therefor - Google Patents

Difunctional composite filter medium fiber and preparation method therefor Download PDF

Info

Publication number
WO2018233159A1
WO2018233159A1 PCT/CN2017/106879 CN2017106879W WO2018233159A1 WO 2018233159 A1 WO2018233159 A1 WO 2018233159A1 CN 2017106879 W CN2017106879 W CN 2017106879W WO 2018233159 A1 WO2018233159 A1 WO 2018233159A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
solution
time
preparation
composite filter
Prior art date
Application number
PCT/CN2017/106879
Other languages
French (fr)
Chinese (zh)
Inventor
王栋
彭悦
韩奎华
路春美
牛胜利
张亢
司文哲
李兵
甘丽娜
Original Assignee
山东大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from CN201710488583.0A external-priority patent/CN107261644B/en
Priority claimed from CN201710486860.4A external-priority patent/CN107158799B/en
Application filed by 山东大学 filed Critical 山东大学
Publication of WO2018233159A1 publication Critical patent/WO2018233159A1/en

Links

Images

Classifications

    • 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
    • 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
    • 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
    • B01D53/46—Removing components of defined structure
    • B01D53/54—Nitrogen compounds
    • B01D53/56—Nitrogen oxides
    • 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
    • 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
    • B01D53/90—Injecting reactants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • B01J35/58—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/12—Oxidising
    • B01J37/14—Oxidising with gases containing free oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation

Definitions

  • the invention relates to the field of post-treatment of pollutant dust and nitrogen oxides in coal-fired power plants and cement, glass, ceramics and other building materials industries, and particularly relates to a dust-denitration dual-function composite filter fiber used in a bag/electric bag dust collector and Preparation.
  • Nitrogen oxides can endanger human health while causing damage to the ecological environment. It is an extremely harmful air pollutant. Among them, coal-fired boilers in the power, building materials and other industries are important sources of nitrogen oxide emissions. Selective Catalytic Reduction (SCR) is the most widely used and most mature coal-fired boiler denitration technology. It has many advantages such as high denitration efficiency, stable and reliable operation, good selectivity, etc., and its occupancy rate in practical applications is reached. More than 90. NH 3 is the most commonly used reducing agent in SCR technology. The technical characteristics of SCR determine that there will be inevitable NH3, ie ammonia escaping, in the denitration equipment outlet.
  • SCR Selective Catalytic Reduction
  • the escaping NH 3 easily reacts with the tail flue to form a highly viscous ammonium sulfate/ammonium hydrogen sulfate, causing corrosion and clogging of the tail flue.
  • the device baghouse again denitrification SCR catalyst materials, at a suitable temperature window to achieve NH 3 slip further reaction of NO x and unreduced, it is expected to escape while the effective treatment of NH 3, to further improve the System denitration efficiency.
  • bag-type dust collectors In the field of coal-fired flue gas after-treatment, bag-type dust collectors have more and more applications at home and abroad due to their high dust removal efficiency, low secondary pollution and easy recycling of dry materials, accounting for 80% of the dust removal equipment used in the market. .
  • the bag filter has a huge demand for dust filter media, especially the multifunctional composite fiber has broad market prospects.
  • China has put forward higher requirements for coal-fired boilers in various industries.
  • Coal-fired boilers in the steel, cement, glass, ceramics and other industries are the main sources of air pollution, and are also the focus of governance.
  • China's annual output of steel exceeds 900 million tons, according to Baosteel bags.
  • Bag-type dust collectors are often arranged behind the SCR device.
  • the operating temperature window is often between 150 and 250 °C, which is similar to the common low-temperature SCR technology application window.
  • the high efficiency coupling between the catalytic material and the dust filter media will effectively solve the above-mentioned ammonia slip problem and greatly improve the system denitration efficiency.
  • the composite filter material is prepared by the direct impregnation method of active oxide species.
  • the direct impregnation method is used to couple oxides of Mn, Ce, Zr and the like with fibers.
  • the fiber filter material has an active component and the fiber is not firmly bonded, and is easy to be pulverized and fallen off, and industrial production is difficult.
  • one of the objects of the present invention is to provide a method for preparing a bifunctional composite filter fiber, which can firmly bond an oxide of Mn, Ce, and Zr to a fiber, and is woven from the fiber. while the bifunctional complex filter trapping particulate matter may be implemented removal from flue gas NO x.
  • the alkali solution is first impregnated into the fiber, and the fiber is sufficiently compounded with the basic substance by ultrasonication, and then immersed in the salt solution B containing manganese ions, cerium ions and zirconium ions, the manganese ion, the cerium ion and the zirconium ion are made.
  • the salt solution B containing manganese ions, cerium ions and zirconium ions, the manganese ion, the cerium ion and the zirconium ion are made.
  • Precipitating on the surface of the fiber so that the metal atom and the fiber form a strong interaction, ensuring that the active metal oxide can be stably bonded to the surface of the fiber, not easy to fall off, and at the same time, the active metal oxide can be uniformly dispersed on the surface of the fiber, and the catalytic performance of the fiber is enhanced. .
  • the ultrasonic ion can make the metal ion enter the gap of the fiber better, so that the metal ion can be more uniformly dispersed on the fiber, and then the fiber impregnated with the metal ion is impregnated.
  • a uniformly dispersed active metal oxide can be obtained on the fiber, and the metal ions which are first impregnated enter the fiber gap, and the metal ions are precipitated, thereby not only strengthening the active metal oxide on the fiber.
  • the bonding strength and the more active dispersion of the active metal oxide on the fibers further enhance the catalytic performance of the fibers.
  • the fiber is a macromolecular organic substance which is easily degraded and dissolved under alkaline conditions, thereby impairing the structure of the fiber, and finally the composite filter fiber cannot be obtained.
  • the invention adjusts the pH of the alkaline solution A to 8-12 by a large number of experiments, and controls the infiltration or immersion time of the fiber in the alkaline solution, thereby ensuring that the fiber does not cause irreversible structural damage in the alkaline solution A, thereby finally obtaining A bifunctional composite filter fiber with a strong load of the active component.
  • Another object of the present invention is to provide a composite filter fiber prepared by the above preparation method. Filter prepared from the fiber It can remove dust and catalyze denitrification.
  • a third object of the present invention is to provide a filter material having the above composite filter fiber preparation.
  • a fourth object of the present invention is to provide an application of the above composite filter fiber or filter material in dust removal and denitrification.
  • the invention adopts a novel pre-coating precipitation process to realize the firm loading of manganese, cerium and zirconium oxide on the surface of various organic fibers.
  • the metal atom forms a strong interaction with the fiber, and the finally formed oxide It has uniform dispersion, is not easy to fall off and has stable denitration efficiency.
  • the process is simple and the cost is low, which is beneficial to the rapid production of filter material production enterprises.
  • the application of the dual-function composite filter fiber obtained by the invention can realize the integration of the dust removal and denitration process, solve the problem of ammonia escape, and greatly improve the denitration efficiency of the system, and promote the coal-fired boiler of a new round of steel, building materials and other industries. Flue gas remediation has a positive effect and has broad application prospects.
  • Example 1 is a topographical view of a polyimide fiber used in Example 1;
  • Fig. 2 is a view showing the topographical characteristics of the polyimide fiber after the treatment of Example 1.
  • the manganese salt described in the present invention is a water-soluble compound having a cation of manganese ions, such as manganese nitrate, manganese sulfate, manganese acetate or the like.
  • the onium salt described in the present invention is a water-soluble compound having a cation of cerium ions, such as cerium nitrate, cerium sulfate, cerium acetate or the like.
  • the zirconium salt described in the present invention is a water-soluble compound having a cation of zirconium ions, such as zirconium nitrate, zirconium sulfate or the like.
  • the present application proposes a bifunctional composite filter fiber. Preparation side law.
  • An exemplary embodiment of the present application provides a method for preparing a bifunctional composite filter fiber.
  • the alkali solution is first impregnated into the fiber, and the fiber is sufficiently compounded with the basic substance by ultrasonication, and then immersed in the salt solution B containing manganese ions, cerium ions and zirconium ions, the manganese ion, the cerium ion and the zirconium ion are made.
  • the salt solution B containing manganese ions, cerium ions and zirconium ions, the manganese ion, the cerium ion and the zirconium ion are made.
  • Precipitating on the surface of the fiber so that the metal atom and the fiber form a strong interaction, ensuring that the active metal oxide can be stably bonded to the surface of the fiber, not easy to fall off, and at the same time, the active metal oxide can be uniformly dispersed on the surface of the fiber, and the catalytic performance of the fiber is enhanced. .
  • the ultrasonic ion can make the metal ion enter the gap of the fiber better, so that the metal ion can be more uniformly dispersed on the fiber, and then the fiber impregnated with the metal ion is impregnated.
  • a uniformly dispersed active metal oxide can be obtained on the fiber, and the metal ions which are first impregnated enter the fiber gap, and the metal ions are precipitated, thereby not only strengthening the active metal oxide on the fiber.
  • the bonding strength and the more active dispersion of the active metal oxide on the fibers further enhance the catalytic performance of the fibers.
  • the fiber is a macromolecular organic substance which is easily degraded and dissolved under alkaline conditions, thereby impairing the structure of the fiber, and finally the composite filter fiber cannot be obtained.
  • the invention adjusts the pH of the alkaline solution A to 8-12 by a large number of experiments, and controls the infiltration or immersion time of the fiber in the alkaline solution, thereby ensuring that the fiber does not cause irreversible structural damage in the alkaline solution A, thereby finally obtaining A bifunctional composite filter fiber with a strong load of the active component.
  • the alkaline solution A is ammonia water, sodium hydroxide solution, ammonium carbonate solution or sodium carbonate solution.
  • the molar ratio of manganese ions, strontium ions and zirconium ions in the salt solution B is from 1 to 8:1 to 4:1 to 4.
  • the time of ultrasound-assisted infiltration is 5 to 30 min.
  • the ultrasonic assisted infiltration time is less than the infiltration time of the fiber immersed in the alkaline solution A; when the salt solution B is used to infiltrate the fiber, the ultrasonic assisted infiltration time is less than the fiber immersion into the salt solution B Infiltration time.
  • the time of the immersion precipitation is 30 to 80 min; when the fiber is infiltrated with the salt solution B, the infiltration time is 30 to 80 min.
  • the aging time is 2-6 hours.
  • the aging is carried out by immersing the precipitated fibers and aging them in an air atmosphere.
  • the microwave heat treatment time is 10 to 40 minutes
  • the microwave power is 100-600 W
  • the microwave generation time is 75-225 s per 300 s.
  • the microwave heat treatment is followed by drying and then activation.
  • the drying condition is drying at 105 ° C for 5 h.
  • the activation treatment is to place the fibers at a temperature of from 150 to 250 °C for a period of time.
  • the activation treatment time is 2 to 8 hours.
  • the present application also provides a composite filter fiber prepared by the above preparation method.
  • the filter material prepared from the fiber can both remove dust and catalyze denitrification.
  • the present application also provides a filter material prepared from the above composite filter media.
  • the application also provides the use of the above composite filter fiber or filter material in dust removal and denitrification.
  • the bifunctional composite filter fiber based on polyimide fiber has a morphology as shown in Figure 1.
  • the steps are as follows:
  • Step 1 Take 16 mL of a 25 wt% aqueous ammonia solution, dilute to 200 mL with deionized water, and stir to obtain a solution A (pH 10). Weighed 14.32 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate in 250 mL of deionized water, and stirred uniformly to obtain a solution B.
  • Step 2 The polyimide fiber was immersed in the A solution for 21 min, and the ultrasonic assist time was 7 min. Then, the infiltrated polyimide fiber was taken out from the solution A, drained, and then immersed in the solution B, and the fiber was taken out after being immersed for 40 minutes. The air atmosphere aged for 4 hours.
  • Step 3 The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 200 W, microwave generation time every 20 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h.
  • the dried polyimide fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #1 with a firm supported metal oxide.
  • the morphology is shown in FIG. 2 .
  • This embodiment is the same as the first embodiment except that in this embodiment, 50% by weight of a manganese nitrate solution is 3.58 g, yttrium nitrate hexahydrate is 17.36 g, and zirconium nitrate pentahydrate is 4.29 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #2.
  • This example is the same as the first embodiment except that in this embodiment, 50% by weight of a manganese nitrate solution is 3.58 g, cerium nitrate hexahydrate is 4.34 g, and zirconium nitrate pentahydrate is 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #3.
  • the bifunctional composite filter fiber based on PTFE fiber is as follows:
  • Step 1 Take 16 mL of 25 wt% aqueous ammonia solution, dilute to 200 mL with deionized water, and stir to obtain solution A (pH 11). Weighed 14.32 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate in 250 mL of deionized water, and stirred uniformly to obtain a solution B.
  • Step 2 The PTFE fiber was immersed in the A solution for 15 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated PTFE fiber was taken out from the solution A, drained, and then immersed in the solution B. After impregnation for 30 min, the fiber was taken out and placed in an air atmosphere for 4 hours.
  • Step 3 The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 200 W, microwave generation time every 20 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h.
  • the dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #4 which was firmly supported with a metal oxide.
  • This embodiment is the same as the embodiment 4 except that in this embodiment, a 50 wt% manganese nitrate solution is 3.58 g, a lanthanum nitrate hexahydrate 17.36 g, and a zirconium nitrate pentahydrate 4.29 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #5.
  • This embodiment is the same as the embodiment 4 except that in this embodiment, 50 wt% of a manganese nitrate solution is 3.58 g, bismuth nitrate hexahydrate is 4.34 g, and zirconium nitrate pentahydrate is 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #6.
  • the bifunctional composite filter fiber based on PTFE fiber is as follows:
  • Step 1 Weigh 16g of sodium hydroxide, dissolve it in deionized water and dilute to 200mL, stir until the sodium hydroxide solid is completely dissolved, and obtain a homogeneous solution A (pH 12). Weighed 14.32 g of 50 wt% manganese nitrate solution, 17.36 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate dissolved in 250 mL of deionized water, and stirred uniformly to obtain a solution B.
  • Step 2 The PTFE fiber was immersed in the A solution for 15 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated PTFE fiber was taken out from the solution A, drained, and then immersed in the solution B. After impregnation for 50 min, the fiber was taken out and placed in an air atmosphere for 4 hours.
  • Step 3 The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, reaction conditions: microwave power 400 W, microwave generation time every 30 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h.
  • the dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #7 which was firmly supported with metal oxide.
  • This embodiment is the same as the embodiment 4 except that in this embodiment, a 50 wt% manganese nitrate solution is 3.58 g, a lanthanum nitrate hexahydrate 17.36 g, and a zirconium nitrate pentahydrate 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #8.
  • This embodiment is the same as the embodiment 4 except that in this embodiment, a 50 wt% manganese nitrate solution of 14.32 g, a cerium nitrate hexahydrate of 4.34 g, and a zirconium nitrate pentahydrate of 17.16 g, a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #9.
  • the bifunctional composite filter fiber based on polyimide fiber is as follows:
  • Step 1 Weigh 19.2g of ammonium carbonate, dissolve it in deionized water and dilute to 200mL, stir until the ammonium carbonate solid is completely dissolved, and obtain a homogeneous solution A (pH 9). 3.58 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate were weighed and dissolved in 250 mL of deionized water, and stirred uniformly to obtain a solution B.
  • Step 2 The polyimide fiber was immersed in the A solution for 50 min, and the ultrasonic assist time was 20 min. Then, the infiltrated polyimide fiber was taken out from the solution A, drained, and then immersed in the solution B, and the fiber was taken out after the immersion precipitation for 60 minutes. The air atmosphere aged for 4 hours.
  • Step 3 The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 300 W, microwave generation time every 30 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h.
  • the dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #10 which was firmly supported with metal oxide.
  • This embodiment is the same as the embodiment 10 except that the infiltration time of the fiber in the A solution is 30 min, and the infiltration time in the B solution is 80 min, and the bifunctional composite fiber which is firmly loaded with the metal oxide is obtained. 11.
  • This embodiment is the same as the embodiment 10 except that the infiltration time of the fiber in the A solution is changed to 40 min, and the infiltration time in the B solution is changed to 60 min to obtain a bifunctional composite of the solid supported metal oxide. Fiber #12.
  • This embodiment is the same as that of the embodiment 10 except that 19.2 g of ammonium carbonate in the first step is changed to 21.2 g of sodium carbonate to obtain a bifunctional composite fiber #13 which is firmly supported with metal oxide.
  • the 13 catalyst samples were tested for SCR denitration activity in a laboratory fixed-bed denitration reactor.
  • the denitration reaction was tested at a reaction temperature of 125-250 ° C, a space velocity of 30 000 h -1 , a NH 3 concentration of 500 ppm, and a NO concentration of 500 ppm.
  • the O 2 concentration was 3.5%, and N 2 was a balance gas.
  • Table 1 The results are shown in Table 1.
  • a sodium hydroxide solution having a pH of 13 was prepared as the solution A, and the polyimide fiber was immersed in the A solution for 50 minutes, and the ultrasonic assist time was 20 minutes. The polyimide fiber was dissolved and could not be used.
  • This comparative example was the same as in Example 1, except that an ammonium carbonate solution having a pH of 7.5 was prepared as the solution A, and the fibers prepared by the comparative examples did not have catalytic denitration properties.
  • the bifunctional composite filter fiber based on polyimide fiber is as follows:
  • Step 1 Weigh out 14.32 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate in 250 mL of deionized water, and stir uniformly to obtain a solution A. Take 16 mL of a 25 wt% aqueous ammonia solution, dilute to 200 mL with deionized water, and stir to obtain a solution B (pH 10).
  • Step 2 The polyimide fiber was immersed in the A solution for 40 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated polyimide fiber was taken out from the solution A, drained, and then immersed in the solution B, and the fiber was taken out after being immersed for 21 minutes. The air atmosphere aged for 4 hours.
  • Step 3 The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 200 W, microwave generation time every 20 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h.
  • the dried polyimide fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #14 which was firmly supported with metal oxide.
  • This embodiment is the same as the embodiment 14, except that in this embodiment, a 50 wt% manganese nitrate solution is 3.58 g, a lanthanum nitrate hexahydrate 17.36 g, and a zirconium nitrate pentahydrate 4.29 g, and a bifunctional composite of a strongly supported metal oxide is obtained.
  • This embodiment is the same as the embodiment 14, except that in this embodiment, 50% by weight of a manganese nitrate solution is 3.58 g, bismuth nitrate hexahydrate is 4.34 g, and zirconium nitrate pentahydrate is 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #16.
  • the bifunctional composite filter fiber based on PTFE fiber is as follows:
  • Step 1 Weigh out 14.32 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate in 250 mL of deionized water, and stir uniformly to obtain a solution A. Take 16 mL of a 25 wt% aqueous ammonia solution, dilute to 200 mL with deionized water, and stir to obtain a solution B (pH 11).
  • Step 2 The PTFE fiber was immersed in the A solution for 30 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated PTFE fiber was taken out from the solution A, drained, and then immersed in the solution B. After immersing the precipitate for 15 minutes, the fiber was taken out and aged in an air atmosphere for 4 hours.
  • Step 3 The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 200 W, microwave generation time every 20 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h.
  • the dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #17 which was firmly supported with a metal oxide.
  • Example 17 This example is the same as Example 17, except that in this embodiment, 50% by weight of manganese nitrate solution is 3.58 g, strontium nitrate hexahydrate is 17.36 g, and zirconium nitrate pentahydrate is 4.29 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #18.
  • Example 17 This example is the same as Example 17, except that in this embodiment, 50% by weight of manganese nitrate solution is 3.58 g, cerium nitrate hexahydrate is 4.34 g, and zirconium nitrate pentahydrate is 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #19.
  • the bifunctional composite filter fiber based on PTFE fiber is as follows:
  • Step 1 Weigh 14.32g of 50wt% manganese nitrate solution, 17.36g of cerium nitrate hexahydrate, 4.29g of zirconium nitrate pentahydrate Dissolved in 250 mL of deionized water and stirred well to obtain solution A. 16 g of sodium hydroxide was weighed, dissolved in deionized water and made up to 200 mL, and stirred until the sodium hydroxide solid was completely dissolved to obtain a homogeneous solution B (pH 12).
  • Step 2 The PTFE fiber was immersed in the A solution for 50 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated PTFE fiber was taken out from the solution A, drained, and then immersed in the solution B. After immersing the precipitate for 15 minutes, the fiber was taken out and aged in an air atmosphere for 4 hours.
  • Step 3 The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, reaction conditions: microwave power 400 W, microwave generation time every 30 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h.
  • the dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #20 which was firmly supported with metal oxide.
  • This embodiment is the same as the embodiment 17, except that in this embodiment, a 50 wt% manganese nitrate solution is 3.58 g, a lanthanum nitrate hexahydrate 17.36 g, and a zirconium nitrate pentahydrate 17.16 g to obtain a bifunctional composite of a strongly supported metal oxide. Fiber #21.
  • This embodiment is the same as the embodiment 17, except that in this embodiment, a 50 wt% manganese nitrate solution of 14.32 g, a cerium nitrate hexahydrate of 4.34 g, and a zirconium nitrate pentahydrate of 17.16 g, a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #22.
  • the bifunctional composite filter fiber based on polyimide fiber is as follows:
  • Step 1 Weigh 3.58g of manganese nitrate solution, 4.34g of cerium nitrate hexahydrate, 4.29g of zirconium nitrate pentahydrate, dissolved in deionized water 250mL, and stir evenly to obtain solution A. 19.2 g of ammonium carbonate was weighed, dissolved in deionized water and made up to 200 mL, and stirred until the ammonium carbonate solid was completely dissolved to obtain a homogeneous solution B (pH 9).
  • Step 2 The polyimide fiber was immersed in the A solution for 60 min, and the ultrasonic assist time was 20 min. Then, the infiltrated polyimide fiber was taken out from the solution A, drained, immersed in the solution B, and the fiber was taken out after the immersion precipitation for 50 min, and placed. The air atmosphere aged for 4 hours.
  • Step 3 The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 300 W, microwave generation time every 30 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h.
  • the dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #23 which was firmly supported with metal oxide.
  • This embodiment is the same as the embodiment 23 except that the infiltration time of the fiber in the solution A is 80 min, and the infiltration time in the B solution is 30 min, and the bifunctional composite fiber with a firm metal oxide is obtained. twenty four.
  • This embodiment is the same as the embodiment 23 except that the infiltration time of the fiber in the A solution is changed to 60 min, and the infiltration time in the B solution is changed to 40 min to obtain a bifunctional composite of the solid supported metal oxide. Fiber #25.
  • This example is the same as the embodiment 23 except that 19.2 g of ammonium carbonate in the first step is changed to 21.2 g of sodium carbonate to obtain a bifunctional composite fiber #26 which is firmly supported with metal oxide.
  • the 13 catalyst samples were tested for SCR denitration activity in a laboratory fixed-bed denitration reactor.
  • the denitration reaction was tested at a reaction temperature of 125-250 ° C, a space velocity of 30 000 h -1 , a NH 3 concentration of 500 ppm, and a NO concentration of 500 ppm.
  • the O 2 concentration was 3.5%, and N 2 was a balance gas.
  • Table 2 The results are shown in Table 2.
  • This comparative example was the same as that of Example 14, except that an ammonium carbonate solution having a pH of 7.5 was prepared as the solution B, and the fibers prepared by the comparative examples did not have catalytic denitration properties.

Abstract

Disclosed are a preparation method for a difunctional composite filter medium fiber and a composite filter medium fiber prepared therefrom. The preparation method comprises: (1) preparing alkaline solution A with a pH of 8-12, and dissolving a manganese salt, a cerium salt and a zirconium salt in water to prepare salt solution B; (2) immersing a fiber in the alkaline solution A for wetting for 15-70 min and then subjecting same to ultrasound-assisted wetting for a period of time, draining the wetted fiber and then immersing same in the salt solution B for impregnation and deposition for a period of time; or immersing a fiber in the salt solution B for wetting and then subjecting same to ultrasound-assisted wetting for a period of time, draining the wetted fiber and then immersing same in the alkaline solution A for impregnation and deposition for 15-70 min; and (3) taking out the fiber after impregnation and deposition and then ageing same, then subjecting same to a microwave thermal treatment, and finally subjecting same to an activation treatment, so as to obtain the difunctional composite filter medium fiber.

Description

一种双功能复合滤料纤维及制备方法Bifunctional composite filter fiber and preparation method thereof 技术领域Technical field
本发明涉及燃煤电厂及水泥、玻璃、陶瓷等建材行业的污染物粉尘、氮氧化物后处理领域，具体涉及一种应用于布袋/电袋除尘器的除尘-脱硝双功能复合滤料纤维及制备方法。The invention relates to the field of post-treatment of pollutant dust and nitrogen oxides in coal-fired power plants and cement, glass, ceramics and other building materials industries, and particularly relates to a dust-denitration dual-function composite filter fiber used in a bag/electric bag dust collector and Preparation.
背景技术Background technique
氮氧化物可在造成生态环境破坏的同时危及人体健康，是一种危害极为广泛的大气污染物。其中电力、建材等行业的燃煤锅炉是氮氧化物排放的重要来源。选择性催化还原法(Selective Catalytic Reduction，SCR)是应用最广、技术最成熟的燃煤锅炉脱硝技术，具有脱硝效率高、运行稳定可靠、选择性好等诸多优点，在实际应用中占有率达到90％以上。NH3为目前SCR技术中应用最为普遍的还原剂，SCR的技术特点决定了脱硝设备出口将不可避免的存在未充分反应的NH3，即氨逃逸。若烟气中存在硫氧化物，逃逸的NH3易在尾部烟道与其反应生成黏结性较强的硫酸铵/硫酸氢铵，从而造成尾部烟道腐蚀、堵塞。如能在下游设备(袋式除尘器)中再次耦合SCR催化脱硝材料，在适宜的温度窗口实现逃逸NH3与未还原NOx的进一步反应，则有望在有效处理逃逸NH3的同时，进一步提高系统脱硝效率。Nitrogen oxides can endanger human health while causing damage to the ecological environment. It is an extremely harmful air pollutant. Among them, coal-fired boilers in the power, building materials and other industries are important sources of nitrogen oxide emissions. Selective Catalytic Reduction (SCR) is the most widely used and most mature coal-fired boiler denitration technology. It has many advantages such as high denitration efficiency, stable and reliable operation, good selectivity, etc., and its occupancy rate in practical applications is reached. More than 90. NH 3 is the most commonly used reducing agent in SCR technology. The technical characteristics of SCR determine that there will be inevitable NH3, ie ammonia escaping, in the denitration equipment outlet. If sulfur oxides are present in the flue gas, the escaping NH 3 easily reacts with the tail flue to form a highly viscous ammonium sulfate/ammonium hydrogen sulfate, causing corrosion and clogging of the tail flue. As can be coupled downstream of the device (baghouse) again denitrification SCR catalyst materials, at a suitable temperature window to achieve NH 3 slip further reaction of NO x and unreduced, it is expected to escape while the effective treatment of NH 3, to further improve the System denitration efficiency.
在燃煤烟气后处理领域，袋式除尘器由于具备除尘效率高、二次污染小、干料易回收等性能，在国内外的应用越来越广，约占市场应用除尘设备的80％。袋式除尘器对除尘滤料纤维的需求巨大，尤其是多功能复合纤维具有广阔的市场前景。中国对各行业燃煤锅炉排放提出了更高要求，钢铁、水泥、玻璃、陶瓷等行业燃煤锅炉是大气污染的主要来源，亦是治理重点，中国钢铁年产量超过9亿吨，按照宝钢袋式除尘器配制标准核算，共计需除尘滤料6300万平方米，每年需更换滤料1800万平方米，因此，除尘滤料纤维市场前景尤其被看好。袋式除尘器多布置于SCR装置之后，根据锅炉类型及应用领域差异，其运行温度窗口常在150～250℃之间，与常见的低温SCR技术应用窗口近似，如能在此处实现低温SCR催化材料与除尘滤料纤维的高效耦合，将有效解决上述氨逃逸问题并大幅提高系统脱硝效率。In the field of coal-fired flue gas after-treatment, bag-type dust collectors have more and more applications at home and abroad due to their high dust removal efficiency, low secondary pollution and easy recycling of dry materials, accounting for 80% of the dust removal equipment used in the market. . The bag filter has a huge demand for dust filter media, especially the multifunctional composite fiber has broad market prospects. China has put forward higher requirements for coal-fired boilers in various industries. Coal-fired boilers in the steel, cement, glass, ceramics and other industries are the main sources of air pollution, and are also the focus of governance. China's annual output of steel exceeds 900 million tons, according to Baosteel bags. The standard preparation of the type of dust collector requires a total of 63 million square meters of dust filter material and 18 million square meters of filter material per year. Therefore, the market prospect of dust filter media is particularly promising. Bag-type dust collectors are often arranged behind the SCR device. Depending on the type of boiler and the application field, the operating temperature window is often between 150 and 250 °C, which is similar to the common low-temperature SCR technology application window. The high efficiency coupling between the catalytic material and the dust filter media will effectively solve the above-mentioned ammonia slip problem and greatly improve the system denitration efficiency.
近年来，Mn、Ce、Zr等的氧化物用作低温SCR催化剂活性物种的相关研究得到了国内外学者的广泛关注，但相关载体的选择多以TiO2、Al2O3、活性炭等固体材料为主。没有Mn、Ce、Zr等的氧化物与除尘滤料纤维的耦合的相关报道。In recent years, studies on the use of oxides of Mn, Ce, Zr, etc. as active species of low-temperature SCR catalysts have attracted extensive attention from scholars at home and abroad, but the choice of related carriers is mostly TiO 2 , Al 2 O 3 , activated carbon and other solid materials. Mainly. There are no reports on the coupling of oxides of Mn, Ce, Zr, etc. with dust filter media.
发明内容 Summary of the invention
专利CN104941319A、CN103252135A、CN105315000A中均采用活性氧化物种直接浸渍负载方法制备复合滤料，然而本发明的发明人通过研究发现采用上述直接浸渍方法将Mn、Ce、Zr等的氧化物与纤维进行耦合制备的纤维滤料，其活性组分与纤维粘结不牢固，容易粉化脱落，工业生产难度较大。In the patents CN104941319A, CN103252135A, CN105315000A, the composite filter material is prepared by the direct impregnation method of active oxide species. However, the inventors of the present invention have found that the direct impregnation method is used to couple oxides of Mn, Ce, Zr and the like with fibers. The fiber filter material has an active component and the fiber is not firmly bonded, and is easy to be pulverized and fallen off, and industrial production is difficult.
为了解决现有技术的不足，本发明的目的之一是提供一种双功能复合滤料纤维的制备方法，能够使Mn、Ce、Zr的的氧化物与纤维牢固粘结，由该纤维织成的双功能复合滤料可实现捕集颗粒物的同时脱除燃煤烟气中NOx。In order to solve the deficiencies of the prior art, one of the objects of the present invention is to provide a method for preparing a bifunctional composite filter fiber, which can firmly bond an oxide of Mn, Ce, and Zr to a fiber, and is woven from the fiber. while the bifunctional complex filter trapping particulate matter may be implemented removal from flue gas NO x.
为了实现上述目的，本发明的技术方案为：In order to achieve the above object, the technical solution of the present invention is:
一种双功能复合滤料纤维的制备方法，Method for preparing bifunctional composite filter fiber,
(1)制备pH为8～12的碱性溶液A，将锰盐、铈盐和锆盐溶解于水中制备盐溶液B；(1) preparing a pH of 8 ~ 12 alkaline solution A, the manganese salt, strontium salt and zirconium salt dissolved in water to prepare a salt solution B;
(2)将纤维浸入至碱性溶液A浸润15～70min，在浸润过程中进行超声辅助浸润一段时间，将浸润后的纤维沥干后浸入盐溶液B中浸渍沉淀一段时间；或，将纤维浸入至盐溶液B浸润，在浸润过程中进行超声辅助浸润一段时间，将浸润后的纤维沥干后浸入碱性溶液A中浸渍沉淀15～70min；(2) immersing the fiber into the alkaline solution A for 15 to 70 minutes, performing ultrasonic-assisted infiltration for a period of time during the infiltration process, draining the infiltrated fiber and immersing it in the salt solution B for a period of time; or, immersing the fiber in Infiltrated into the salt solution B, ultrasonically assisted infiltration for a period of time during the infiltration process, draining the infiltrated fibers and immersing in the alkaline solution A for immersion precipitation for 15 to 70 minutes;
(3)将浸渍沉淀后的纤维取出后进行老化，将老化后的纤维进行微波热处理，最后进行活化处理即得双功能复合滤料纤维。(3) The immersed and precipitated fibers are taken out and aged, and the aged fibers are subjected to microwave heat treatment, and finally activated to obtain a bifunctional composite filter fiber.
若先将碱溶液浸渍至纤维中，并通过超声使纤维与碱性物质充分复合，然后在浸入至含有锰离子、铈离子和锆离子的盐溶液B中，使锰离子、铈离子和锆离子在纤维表面沉淀，从而使金属原子与纤维形成强相互作用，保证了活性金属氧化物能够稳定结合在纤维表面，不易脱落，同时使得活性金属氧化物能够在纤维表面均匀分散，增强纤维的催化性能。If the alkali solution is first impregnated into the fiber, and the fiber is sufficiently compounded with the basic substance by ultrasonication, and then immersed in the salt solution B containing manganese ions, cerium ions and zirconium ions, the manganese ion, the cerium ion and the zirconium ion are made. Precipitating on the surface of the fiber, so that the metal atom and the fiber form a strong interaction, ensuring that the active metal oxide can be stably bonded to the surface of the fiber, not easy to fall off, and at the same time, the active metal oxide can be uniformly dispersed on the surface of the fiber, and the catalytic performance of the fiber is enhanced. .
若先将纤维浸渍至盐溶液中，通过超声能够使得金属离子能够更好的进入至纤维的缝隙中，从而使得金属离子能够更加均匀的分散在纤维上，然后再将浸有金属离子的纤维浸渍至碱溶液中，使得在纤维上能够制得分散均匀的活性金属氧化物，由于先浸渍的金属离子进入至纤维缝隙中，再对金属离子进行沉淀，不仅能够加强活性金属氧化物在纤维上的结合强度，而且使得活性金属氧化物更加均匀的分散在纤维上，从而进一步提高了纤维的催化性能。If the fiber is first immersed in the salt solution, the ultrasonic ion can make the metal ion enter the gap of the fiber better, so that the metal ion can be more uniformly dispersed on the fiber, and then the fiber impregnated with the metal ion is impregnated. In the alkaline solution, a uniformly dispersed active metal oxide can be obtained on the fiber, and the metal ions which are first impregnated enter the fiber gap, and the metal ions are precipitated, thereby not only strengthening the active metal oxide on the fiber. The bonding strength and the more active dispersion of the active metal oxide on the fibers further enhance the catalytic performance of the fibers.
纤维是一种大分子有机物，其在碱性条件下，容易降解并溶解，从而损害了纤维的结构，最终无法得到复合滤料纤维。本发明通过大量实验，调节碱性溶液A的pH为8～12，并控制纤维在碱性溶液的浸润或浸渍时间，能够确保纤维在碱性溶液A中不产生不可逆的结构损坏，从而最终获得活性组分牢固负载的双功能复合滤料纤维。The fiber is a macromolecular organic substance which is easily degraded and dissolved under alkaline conditions, thereby impairing the structure of the fiber, and finally the composite filter fiber cannot be obtained. The invention adjusts the pH of the alkaline solution A to 8-12 by a large number of experiments, and controls the infiltration or immersion time of the fiber in the alkaline solution, thereby ensuring that the fiber does not cause irreversible structural damage in the alkaline solution A, thereby finally obtaining A bifunctional composite filter fiber with a strong load of the active component.
本发明的目的之二是提供一种上述制备方法制备的复合滤料纤维。以该纤维制备的滤 料既能除尘，还能催化脱硝。Another object of the present invention is to provide a composite filter fiber prepared by the above preparation method. Filter prepared from the fiber It can remove dust and catalyze denitrification.
本发明的目的之三是提供一种滤料，有上述复合滤料纤维制备。A third object of the present invention is to provide a filter material having the above composite filter fiber preparation.
本发明的目的之四是提供一种上述复合滤料纤维或滤料在除尘脱硝中的应用。A fourth object of the present invention is to provide an application of the above composite filter fiber or filter material in dust removal and denitrification.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
1.本发明采用全新的预涂覆沉淀工艺，实现锰、铈、锆氧化物在多种有机纤维表面的牢固负载，该工艺条件下，金属原子与纤维形成强相互作用，最终形成的氧化物分散均匀、不易脱落且具备稳定的脱硝效率；该工艺流程简单、成本低，有利于滤料生产企业迅速投入大规模生产。1. The invention adopts a novel pre-coating precipitation process to realize the firm loading of manganese, cerium and zirconium oxide on the surface of various organic fibers. Under the process condition, the metal atom forms a strong interaction with the fiber, and the finally formed oxide It has uniform dispersion, is not easy to fall off and has stable denitration efficiency. The process is simple and the cost is low, which is beneficial to the rapid production of filter material production enterprises.
2.本发明制得的双功能复合滤料纤维的应用可以实现除尘脱硝工艺上一体化，解决氨逃逸问题的同时，大幅提高系统脱硝效率，对推进新一轮钢铁、建材等行业燃煤锅炉烟气整治具有积极作用，应用前景广泛。2. The application of the dual-function composite filter fiber obtained by the invention can realize the integration of the dust removal and denitration process, solve the problem of ammonia escape, and greatly improve the denitration efficiency of the system, and promote the coal-fired boiler of a new round of steel, building materials and other industries. Flue gas remediation has a positive effect and has broad application prospects.
附图说明DRAWINGS
构成本申请的一部分的说明书附图用来提供对本申请的进一步理解，本申请的示意性实施例及其说明用于解释本申请，并不构成对本申请的不当限定。The accompanying drawings, which are incorporated in the claims of the claims
图1为实施例1采用的聚酰亚胺纤维的形貌特征图；1 is a topographical view of a polyimide fiber used in Example 1;
图2为经过实施例1处理后的聚酰亚胺纤维的形貌特征图。Fig. 2 is a view showing the topographical characteristics of the polyimide fiber after the treatment of Example 1.
具体实施方式Detailed ways
应该指出，以下详细说明都是例示性的，旨在对本申请提供进一步的说明。除非另有指明，本文使用的所有技术和科学术语具有与本申请所属技术领域的普通技术人员通常理解的相同含义。It should be noted that the following detailed description is illustrative and is intended to provide a further description of the application. All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise indicated.
需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本申请的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It is to be noted that the terminology used herein is for the purpose of describing particular embodiments, and is not intended to limit the exemplary embodiments. As used herein, the singular " " " " " " There are features, steps, operations, devices, components, and/or combinations thereof.
本发明中所述的锰盐为阳离子为锰离子的能溶于水的化合物，例如硝酸锰、硫酸锰、醋酸锰等。The manganese salt described in the present invention is a water-soluble compound having a cation of manganese ions, such as manganese nitrate, manganese sulfate, manganese acetate or the like.
本发明中所述的铈盐为阳离子为铈离子的能溶于水的化合物，例如硝酸铈、硫酸铈、醋酸铈等。The onium salt described in the present invention is a water-soluble compound having a cation of cerium ions, such as cerium nitrate, cerium sulfate, cerium acetate or the like.
本发明中所述的锆盐为阳离子为锆离子的能溶于水的化合物，例如硝酸锆、硫酸锆等。The zirconium salt described in the present invention is a water-soluble compound having a cation of zirconium ions, such as zirconium nitrate, zirconium sulfate or the like.
正如背景技术所介绍的，现有技术中存在活性组分与纤维粘结不牢固、容易粉化脱落的不足，为了解决如上的技术问题，本申请提出了一种一种双功能复合滤料纤维的制备方 法。As described in the background art, in the prior art, there is a deficiency that the active component is not firmly bonded to the fiber and is easily pulverized and detached. In order to solve the above technical problem, the present application proposes a bifunctional composite filter fiber. Preparation side law.
本申请的一种典型实施方式，提供了一种双功能复合滤料纤维的制备方法，An exemplary embodiment of the present application provides a method for preparing a bifunctional composite filter fiber.
(1)制备pH为8～12的碱性溶液A，将锰盐、铈盐和锆盐溶解于水中制备盐溶液B；(1) preparing a pH of 8 ~ 12 alkaline solution A, the manganese salt, strontium salt and zirconium salt dissolved in water to prepare a salt solution B;
(2)将纤维浸入至碱性溶液A浸润15～70min，在浸润过程中进行超声辅助浸润一段时间，将浸润后的纤维沥干后浸入盐溶液B中浸渍沉淀一段时间；或，将纤维浸入至盐溶液B浸润，在浸润过程中进行超声辅助浸润一段时间，将浸润后的纤维沥干后浸入碱性溶液A中浸渍沉淀15～70min；(2) immersing the fiber into the alkaline solution A for 15 to 70 minutes, performing ultrasonic-assisted infiltration for a period of time during the infiltration process, draining the infiltrated fiber and immersing it in the salt solution B for a period of time; or, immersing the fiber in Infiltrated into the salt solution B, ultrasonically assisted infiltration for a period of time during the infiltration process, draining the infiltrated fibers and immersing in the alkaline solution A for immersion precipitation for 15 to 70 minutes;
(3)将浸渍沉淀后的纤维取出后进行老化，将老化后的纤维进行微波热处理，最后进行活化处理即得双功能复合滤料纤维。(3) The immersed and precipitated fibers are taken out and aged, and the aged fibers are subjected to microwave heat treatment, and finally activated to obtain a bifunctional composite filter fiber.
若先将碱溶液浸渍至纤维中，并通过超声使纤维与碱性物质充分复合，然后在浸入至含有锰离子、铈离子和锆离子的盐溶液B中，使锰离子、铈离子和锆离子在纤维表面沉淀，从而使金属原子与纤维形成强相互作用，保证了活性金属氧化物能够稳定结合在纤维表面，不易脱落，同时使得活性金属氧化物能够在纤维表面均匀分散，增强纤维的催化性能。If the alkali solution is first impregnated into the fiber, and the fiber is sufficiently compounded with the basic substance by ultrasonication, and then immersed in the salt solution B containing manganese ions, cerium ions and zirconium ions, the manganese ion, the cerium ion and the zirconium ion are made. Precipitating on the surface of the fiber, so that the metal atom and the fiber form a strong interaction, ensuring that the active metal oxide can be stably bonded to the surface of the fiber, not easy to fall off, and at the same time, the active metal oxide can be uniformly dispersed on the surface of the fiber, and the catalytic performance of the fiber is enhanced. .
若先将纤维浸渍至盐溶液中，通过超声能够使得金属离子能够更好的进入至纤维的缝隙中，从而使得金属离子能够更加均匀的分散在纤维上，然后再将浸有金属离子的纤维浸渍至碱溶液中，使得在纤维上能够制得分散均匀的活性金属氧化物，由于先浸渍的金属离子进入至纤维缝隙中，再对金属离子进行沉淀，不仅能够加强活性金属氧化物在纤维上的结合强度，而且使得活性金属氧化物更加均匀的分散在纤维上，从而进一步提高了纤维的催化性能。If the fiber is first immersed in the salt solution, the ultrasonic ion can make the metal ion enter the gap of the fiber better, so that the metal ion can be more uniformly dispersed on the fiber, and then the fiber impregnated with the metal ion is impregnated. In the alkaline solution, a uniformly dispersed active metal oxide can be obtained on the fiber, and the metal ions which are first impregnated enter the fiber gap, and the metal ions are precipitated, thereby not only strengthening the active metal oxide on the fiber. The bonding strength and the more active dispersion of the active metal oxide on the fibers further enhance the catalytic performance of the fibers.
纤维是一种大分子有机物，其在碱性条件下，容易降解并溶解，从而损害了纤维的结构，最终无法得到复合滤料纤维。本发明通过大量实验，调节碱性溶液A的pH为8～12，并控制纤维在碱性溶液的浸润或浸渍时间，能够确保纤维在碱性溶液A中不产生不可逆的结构损坏，从而最终获得活性组分牢固负载的双功能复合滤料纤维。The fiber is a macromolecular organic substance which is easily degraded and dissolved under alkaline conditions, thereby impairing the structure of the fiber, and finally the composite filter fiber cannot be obtained. The invention adjusts the pH of the alkaline solution A to 8-12 by a large number of experiments, and controls the infiltration or immersion time of the fiber in the alkaline solution, thereby ensuring that the fiber does not cause irreversible structural damage in the alkaline solution A, thereby finally obtaining A bifunctional composite filter fiber with a strong load of the active component.
优选的，所述碱性溶液A为氨水、氢氧化钠溶液、碳酸铵溶液或碳酸钠溶液。Preferably, the alkaline solution A is ammonia water, sodium hydroxide solution, ammonium carbonate solution or sodium carbonate solution.
优选的，所述的盐溶液B中的锰离子、铈离子和锆离子的摩尔比为1～8:1～4:1～4。Preferably, the molar ratio of manganese ions, strontium ions and zirconium ions in the salt solution B is from 1 to 8:1 to 4:1 to 4.
优选的，超声辅助浸润的时间为5～30min。当采用碱性溶液A浸润纤维时，超声辅助浸润的时间少于纤维浸入至碱性溶液A的浸润时间；当采用盐溶液B浸润纤维时，超声辅助浸润的时间少于纤维浸入至盐溶液B的浸润时间。Preferably, the time of ultrasound-assisted infiltration is 5 to 30 min. When the alkaline solution A is used to infiltrate the fiber, the ultrasonic assisted infiltration time is less than the infiltration time of the fiber immersed in the alkaline solution A; when the salt solution B is used to infiltrate the fiber, the ultrasonic assisted infiltration time is less than the fiber immersion into the salt solution B Infiltration time.
优选的，当采用碱性溶液A浸润纤维时，所述浸渍沉淀的时间为30～80min；当采用盐溶液B浸润纤维时，所述浸润时间为30～80min。Preferably, when the fiber is infiltrated with the alkaline solution A, the time of the immersion precipitation is 30 to 80 min; when the fiber is infiltrated with the salt solution B, the infiltration time is 30 to 80 min.
优选的，所述老化的时间为2～6h。 Preferably, the aging time is 2-6 hours.
优选的，所述老化是将浸渍沉淀后的纤维取出后在空气气氛进行老化。Preferably, the aging is carried out by immersing the precipitated fibers and aging them in an air atmosphere.
优选的，所述微波热处理的时间为10～40min，微波功率100-600W，每300s微波发生时间75-225s。Preferably, the microwave heat treatment time is 10 to 40 minutes, the microwave power is 100-600 W, and the microwave generation time is 75-225 s per 300 s.
优选的，微波热处理后进行干燥后再进行活化。Preferably, the microwave heat treatment is followed by drying and then activation.
进一步优选的，所述干燥的条件为105℃烘干处理5h。Further preferably, the drying condition is drying at 105 ° C for 5 h.
优选的，所述活化处理是将纤维置于150～250℃一段时间。Preferably, the activation treatment is to place the fibers at a temperature of from 150 to 250 °C for a period of time.
进一步优选的，所述活化处理的时间为2～8h。Further preferably, the activation treatment time is 2 to 8 hours.
本申请还提供了一种上述制备方法制备的复合滤料纤维。以该纤维制备的滤料既能除尘，还能催化脱硝。The present application also provides a composite filter fiber prepared by the above preparation method. The filter material prepared from the fiber can both remove dust and catalyze denitrification.
本申请还提供了一种滤料，有上述复合滤料纤维制备。The present application also provides a filter material prepared from the above composite filter media.
本申请还提供了一种上述复合滤料纤维或滤料在除尘脱硝中的应用。The application also provides the use of the above composite filter fiber or filter material in dust removal and denitrification.
为了使得本领域技术人员能够更加清楚地了解本申请的技术方案，以下将结合具体的实施例与对比例详细说明本申请的技术方案。In order to enable those skilled in the art to more clearly understand the technical solutions of the present application, the technical solutions of the present application will be described in detail below in conjunction with specific embodiments and comparative examples.
实施例1：Example 1:
以聚酰亚胺纤维为基底的双功能复合滤料纤维，形貌如图1所示，步骤如下：The bifunctional composite filter fiber based on polyimide fiber has a morphology as shown in Figure 1. The steps are as follows:
步骤一：取25wt％的氨水溶液16mL，采用去离子水定容至200mL，搅拌均匀得到溶液A(pH为10)。称取50wt％的硝酸锰溶液14.32g、六水合硝酸铈4.34g、五水合硝酸锆4.29g溶于去离子水250mL中，搅拌均匀，得到溶液B。Step 1: Take 16 mL of a 25 wt% aqueous ammonia solution, dilute to 200 mL with deionized water, and stir to obtain a solution A (pH 10). Weighed 14.32 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate in 250 mL of deionized water, and stirred uniformly to obtain a solution B.
步骤二：将聚酰亚胺纤维浸入A溶液21min，超声辅助时间7min，之后将浸润的聚酰亚胺纤维从溶液A中取出，沥干后浸入溶液B，浸渍沉淀40min后取出纤维，置于空气气氛老化4h。Step 2: The polyimide fiber was immersed in the A solution for 21 min, and the ultrasonic assist time was 7 min. Then, the infiltrated polyimide fiber was taken out from the solution A, drained, and then immersed in the solution B, and the fiber was taken out after being immersed for 40 minutes. The air atmosphere aged for 4 hours.
步骤三：将老化后的纤维置于微波反应器中，微波热处理20min，反应条件：微波功率200W、每20s微波发生时间10s；之后置于鼓风烘干箱105℃烘干处理5h。将烘干完全的聚酰亚胺纤维置于马弗炉，在250℃条件下热处理活化4h，得到牢固负载金属氧化物的双功能复合纤维#1，形貌如图2所示。Step 3: The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 200 W, microwave generation time every 20 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h. The dried polyimide fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #1 with a firm supported metal oxide. The morphology is shown in FIG. 2 .
实施例2Example 2
本实施例与实施例1相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈17.36g、五水合硝酸锆4.29g，得到牢固负载金属氧化物的双功能复合纤维#2。This embodiment is the same as the first embodiment except that in this embodiment, 50% by weight of a manganese nitrate solution is 3.58 g, yttrium nitrate hexahydrate is 17.36 g, and zirconium nitrate pentahydrate is 4.29 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #2.
实施例3Example 3
本实施例与实施例1相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈4.34g、五水合硝酸锆17.16g，得到牢固负载金属氧化物的双功能复合纤维#3。 This example is the same as the first embodiment except that in this embodiment, 50% by weight of a manganese nitrate solution is 3.58 g, cerium nitrate hexahydrate is 4.34 g, and zirconium nitrate pentahydrate is 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #3.
实施例4：Example 4:
以PTFE纤维为基底的双功能复合滤料纤维，步骤如下：The bifunctional composite filter fiber based on PTFE fiber is as follows:
步骤一：取25wt％的氨水溶液16mL，采用去离子水定容至200mL，搅拌均匀得到溶液A(pH为11)。称取50wt％的硝酸锰溶液14.32g、六水合硝酸铈4.34g、五水合硝酸锆4.29g溶于去离子水250mL中，搅拌均匀，得到溶液B。Step 1: Take 16 mL of 25 wt% aqueous ammonia solution, dilute to 200 mL with deionized water, and stir to obtain solution A (pH 11). Weighed 14.32 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate in 250 mL of deionized water, and stirred uniformly to obtain a solution B.
步骤二：将PTFE纤维浸入A溶液15min，超声辅助时间7min，之后将浸润的PTFE纤维从溶液A中取出，沥干后浸入溶液B，浸渍沉淀30min后取出纤维，置于空气气氛老化4h。Step 2: The PTFE fiber was immersed in the A solution for 15 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated PTFE fiber was taken out from the solution A, drained, and then immersed in the solution B. After impregnation for 30 min, the fiber was taken out and placed in an air atmosphere for 4 hours.
步骤三：将老化后的纤维置于微波反应器中，微波热处理20min，反应条件：微波功率200W、每20s微波发生时间10s；之后置于鼓风烘干箱105℃烘干处理5h。将烘干完全的PTFE纤维置于马弗炉，在250℃条件下热处理活化4h，得到牢固负载金属氧化物的双功能复合纤维#4。Step 3: The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 200 W, microwave generation time every 20 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h. The dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #4 which was firmly supported with a metal oxide.
实施例5Example 5
本实施例与实施例4相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈17.36g、五水合硝酸锆4.29g，得到牢固负载金属氧化物的双功能复合纤维#5。This embodiment is the same as the embodiment 4 except that in this embodiment, a 50 wt% manganese nitrate solution is 3.58 g, a lanthanum nitrate hexahydrate 17.36 g, and a zirconium nitrate pentahydrate 4.29 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #5.
实施例6Example 6
本实施例与实施例4相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈4.34g、五水合硝酸锆17.16g，得到牢固负载金属氧化物的双功能复合纤维#6。This embodiment is the same as the embodiment 4 except that in this embodiment, 50 wt% of a manganese nitrate solution is 3.58 g, bismuth nitrate hexahydrate is 4.34 g, and zirconium nitrate pentahydrate is 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #6.
实施例7：Example 7
以PTFE纤维为基底的双功能复合滤料纤维，步骤如下：The bifunctional composite filter fiber based on PTFE fiber is as follows:
步骤一：称取氢氧化钠16g，溶于去离子水并定容至200mL，搅拌至氢氧化钠固体完全溶解，得到均匀溶液A(pH为12)。称取50wt％的硝酸锰溶液14.32g、六水合硝酸铈17.36g、五水合硝酸锆4.29g溶于去离子水250mL中，搅拌均匀，得到溶液B。Step 1: Weigh 16g of sodium hydroxide, dissolve it in deionized water and dilute to 200mL, stir until the sodium hydroxide solid is completely dissolved, and obtain a homogeneous solution A (pH 12). Weighed 14.32 g of 50 wt% manganese nitrate solution, 17.36 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate dissolved in 250 mL of deionized water, and stirred uniformly to obtain a solution B.
步骤二：将PTFE纤维浸入A溶液15min，超声辅助时间7min，之后将浸润的PTFE纤维从溶液A中取出，沥干后浸入溶液B，浸渍沉淀50min后取出纤维，置于空气气氛老化4h。Step 2: The PTFE fiber was immersed in the A solution for 15 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated PTFE fiber was taken out from the solution A, drained, and then immersed in the solution B. After impregnation for 50 min, the fiber was taken out and placed in an air atmosphere for 4 hours.
步骤三：将老化后的纤维置于微波反应器中，微波热处理20min，反应条件：微波功率400W、每30s微波发生时间10s；之后置于鼓风烘干箱105℃烘干处理5h。将烘干完全的PTFE纤维置于马弗炉，在250℃条件下热处理活化4h，得到牢固负载金属氧化物的双功能复合纤维#7。Step 3: The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, reaction conditions: microwave power 400 W, microwave generation time every 30 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h. The dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #7 which was firmly supported with metal oxide.
实施例8 Example 8
本实施例与实施例4相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈17.36g、五水合硝酸锆17.16g，得到牢固负载金属氧化物的双功能复合纤维#8。This embodiment is the same as the embodiment 4 except that in this embodiment, a 50 wt% manganese nitrate solution is 3.58 g, a lanthanum nitrate hexahydrate 17.36 g, and a zirconium nitrate pentahydrate 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #8.
实施例9Example 9
本实施例与实施例4相同，不同之处在于，本实施例50wt％的硝酸锰溶液14.32g、六水合硝酸铈4.34g、五水合硝酸锆17.16g，得到牢固负载金属氧化物的双功能复合纤维#9。This embodiment is the same as the embodiment 4 except that in this embodiment, a 50 wt% manganese nitrate solution of 14.32 g, a cerium nitrate hexahydrate of 4.34 g, and a zirconium nitrate pentahydrate of 17.16 g, a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #9.
实施例10：Example 10:
以聚酰亚胺纤维为基底的双功能复合滤料纤维，步骤如下：The bifunctional composite filter fiber based on polyimide fiber is as follows:
步骤一：称取碳酸铵19.2g，溶于去离子水并定容至200mL，搅拌至碳酸铵固体完全溶解，得到均匀溶液A(pH为9)。称取50wt％的硝酸锰溶液3.58g、六水合硝酸铈4.34g、五水合硝酸锆4.29g溶于去离子水250mL中，搅拌均匀，得到溶液B。Step 1: Weigh 19.2g of ammonium carbonate, dissolve it in deionized water and dilute to 200mL, stir until the ammonium carbonate solid is completely dissolved, and obtain a homogeneous solution A (pH 9). 3.58 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate were weighed and dissolved in 250 mL of deionized water, and stirred uniformly to obtain a solution B.
步骤二：将聚酰亚胺纤维浸入A溶液50min，超声辅助时间20min，之后将浸润的聚酰亚胺纤维从溶液A中取出，沥干后浸入溶液B，浸渍沉淀60min后取出纤维，置于空气气氛老化4h。Step 2: The polyimide fiber was immersed in the A solution for 50 min, and the ultrasonic assist time was 20 min. Then, the infiltrated polyimide fiber was taken out from the solution A, drained, and then immersed in the solution B, and the fiber was taken out after the immersion precipitation for 60 minutes. The air atmosphere aged for 4 hours.
步骤三：将老化后的纤维置于微波反应器中，微波热处理20min，反应条件：微波功率300W、每30s微波发生时间10s；之后置于鼓风烘干箱105℃烘干处理5h。将烘干完全的PTFE纤维置于马弗炉，在250℃条件下热处理活化4h，得到牢固负载金属氧化物的双功能复合纤维#10。Step 3: The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 300 W, microwave generation time every 30 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h. The dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #10 which was firmly supported with metal oxide.
实施例11Example 11
本实施例与实施例10相同，不同之处在于，本实施例改变纤维在A溶液中的浸润时间为30min，在B溶液中浸润时间为80min，得到牢固负载金属氧化物的双功能复合纤维#11。This embodiment is the same as the embodiment 10 except that the infiltration time of the fiber in the A solution is 30 min, and the infiltration time in the B solution is 80 min, and the bifunctional composite fiber which is firmly loaded with the metal oxide is obtained. 11.
实施例12Example 12
本实施例与实施例10相同，不同之处在于，本实施例改变纤维在A溶液中的浸润时间改为40min，在B溶液中浸润时间改为60min，得到牢固负载金属氧化物的双功能复合纤维#12。This embodiment is the same as the embodiment 10 except that the infiltration time of the fiber in the A solution is changed to 40 min, and the infiltration time in the B solution is changed to 60 min to obtain a bifunctional composite of the solid supported metal oxide. Fiber #12.
实施例13Example 13
本实施例与实施例10相同，不同之处在于，本实施例改变步骤一中的碳酸铵19.2g为碳酸钠21.2g，得到牢固负载金属氧化物的双功能复合纤维#13。This embodiment is the same as that of the embodiment 10 except that 19.2 g of ammonium carbonate in the first step is changed to 21.2 g of sodium carbonate to obtain a bifunctional composite fiber #13 which is firmly supported with metal oxide.
在实验室固定床脱硝反应器上对13个催化剂样品进行SCR脱硝活性测试，脱硝反应的测试条件为：反应温度125～250℃，空速30 000h-1，NH3浓度500ppm，NO浓度500ppm，O2浓度3.5％，N2为平衡气。结果如表1所示。The 13 catalyst samples were tested for SCR denitration activity in a laboratory fixed-bed denitration reactor. The denitration reaction was tested at a reaction temperature of 125-250 ° C, a space velocity of 30 000 h -1 , a NH 3 concentration of 500 ppm, and a NO concentration of 500 ppm. The O 2 concentration was 3.5%, and N 2 was a balance gas. The results are shown in Table 1.
表1双功能复合滤料纤维脱硝活性测试结果 Table 1 Test results of denitration activity of bifunctional composite filter media
Figure PCTCN2017106879-appb-000001
Figure PCTCN2017106879-appb-000001
对比例1Comparative example 1
配制pH为13的氢氧化钠溶液作为溶液A，将聚酰亚胺纤维浸入A溶液50min，超声辅助时间20min，聚酰亚胺纤维溶解，无法使用。A sodium hydroxide solution having a pH of 13 was prepared as the solution A, and the polyimide fiber was immersed in the A solution for 50 minutes, and the ultrasonic assist time was 20 minutes. The polyimide fiber was dissolved and could not be used.
对比例2Comparative example 2
本对比例与实施例1相同，不同之处在于，配制pH为7.5的碳酸铵溶液作为溶液A，通过该对比例制备的纤维并没有催化脱硝的性能。This comparative example was the same as in Example 1, except that an ammonium carbonate solution having a pH of 7.5 was prepared as the solution A, and the fibers prepared by the comparative examples did not have catalytic denitration properties.
实施例14：Example 14
以聚酰亚胺纤维为基底的双功能复合滤料纤维，步骤如下：The bifunctional composite filter fiber based on polyimide fiber is as follows:
步骤一：称取50wt％的硝酸锰溶液14.32g、六水合硝酸铈4.34g、五水合硝酸锆4.29g溶于去离子水250mL中，搅拌均匀，得到溶液A。取25wt％的氨水溶液16mL，采用去离子水定容至200mL，搅拌均匀得到溶液B(pH为10)。Step 1: Weigh out 14.32 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate in 250 mL of deionized water, and stir uniformly to obtain a solution A. Take 16 mL of a 25 wt% aqueous ammonia solution, dilute to 200 mL with deionized water, and stir to obtain a solution B (pH 10).
步骤二：将聚酰亚胺纤维浸入A溶液40min，超声辅助时间7min，之后将浸润的聚酰亚胺纤维从溶液A中取出，沥干后浸入溶液B，浸渍沉淀21min后取出纤维，置于空气气氛老化4h。 Step 2: The polyimide fiber was immersed in the A solution for 40 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated polyimide fiber was taken out from the solution A, drained, and then immersed in the solution B, and the fiber was taken out after being immersed for 21 minutes. The air atmosphere aged for 4 hours.
步骤三：将老化后的纤维置于微波反应器中，微波热处理20min，反应条件：微波功率200W、每20s微波发生时间10s；之后置于鼓风烘干箱105℃烘干处理5h。将烘干完全的聚酰亚胺纤维置于马弗炉，在250℃条件下热处理活化4h，得到牢固负载金属氧化物的双功能复合纤维#14。Step 3: The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 200 W, microwave generation time every 20 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h. The dried polyimide fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #14 which was firmly supported with metal oxide.
实施例15Example 15
本实施例与实施例14相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈17.36g、五水合硝酸锆4.29g，得到牢固负载金属氧化物的双功能复合纤维#15。This embodiment is the same as the embodiment 14, except that in this embodiment, a 50 wt% manganese nitrate solution is 3.58 g, a lanthanum nitrate hexahydrate 17.36 g, and a zirconium nitrate pentahydrate 4.29 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #15.
实施例16Example 16
本实施例与实施例14相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈4.34g、五水合硝酸锆17.16g，得到牢固负载金属氧化物的双功能复合纤维#16。This embodiment is the same as the embodiment 14, except that in this embodiment, 50% by weight of a manganese nitrate solution is 3.58 g, bismuth nitrate hexahydrate is 4.34 g, and zirconium nitrate pentahydrate is 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #16.
实施例17：Example 17
以PTFE纤维为基底的双功能复合滤料纤维，步骤如下：The bifunctional composite filter fiber based on PTFE fiber is as follows:
步骤一：称取50wt％的硝酸锰溶液14.32g、六水合硝酸铈4.34g、五水合硝酸锆4.29g溶于去离子水250mL中，搅拌均匀，得到溶液A。取25wt％的氨水溶液16mL，采用去离子水定容至200mL，搅拌均匀得到溶液B(pH为11)。Step 1: Weigh out 14.32 g of a 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate in 250 mL of deionized water, and stir uniformly to obtain a solution A. Take 16 mL of a 25 wt% aqueous ammonia solution, dilute to 200 mL with deionized water, and stir to obtain a solution B (pH 11).
步骤二：将PTFE纤维浸入A溶液30min，超声辅助时间7min，之后将浸润的PTFE纤维从溶液A中取出，沥干后浸入溶液B，浸渍沉淀15min后取出纤维，置于空气气氛老化4h。Step 2: The PTFE fiber was immersed in the A solution for 30 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated PTFE fiber was taken out from the solution A, drained, and then immersed in the solution B. After immersing the precipitate for 15 minutes, the fiber was taken out and aged in an air atmosphere for 4 hours.
步骤三：将老化后的纤维置于微波反应器中，微波热处理20min，反应条件：微波功率200W、每20s微波发生时间10s；之后置于鼓风烘干箱105℃烘干处理5h。将烘干完全的PTFE纤维置于马弗炉，在250℃条件下热处理活化4h，得到牢固负载金属氧化物的双功能复合纤维#17。Step 3: The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 200 W, microwave generation time every 20 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h. The dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #17 which was firmly supported with a metal oxide.
实施例18Example 18
本实施例与实施例17相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈17.36g、五水合硝酸锆4.29g，得到牢固负载金属氧化物的双功能复合纤维#18。This example is the same as Example 17, except that in this embodiment, 50% by weight of manganese nitrate solution is 3.58 g, strontium nitrate hexahydrate is 17.36 g, and zirconium nitrate pentahydrate is 4.29 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #18.
实施例19Example 19
本实施例与实施例17相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈4.34g、五水合硝酸锆17.16g，得到牢固负载金属氧化物的双功能复合纤维#19。This example is the same as Example 17, except that in this embodiment, 50% by weight of manganese nitrate solution is 3.58 g, cerium nitrate hexahydrate is 4.34 g, and zirconium nitrate pentahydrate is 17.16 g, and a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #19.
实施例20：Example 20
以PTFE纤维为基底的双功能复合滤料纤维，步骤如下：The bifunctional composite filter fiber based on PTFE fiber is as follows:
步骤一：称取50wt％的硝酸锰溶液14.32g、六水合硝酸铈17.36g、五水合硝酸锆4.29g 溶于去离子水250mL中，搅拌均匀，得到溶液A。称取氢氧化钠16g，溶于去离子水并定容至200mL，搅拌至氢氧化钠固体完全溶解，得到均匀溶液B(pH为12)。Step 1: Weigh 14.32g of 50wt% manganese nitrate solution, 17.36g of cerium nitrate hexahydrate, 4.29g of zirconium nitrate pentahydrate Dissolved in 250 mL of deionized water and stirred well to obtain solution A. 16 g of sodium hydroxide was weighed, dissolved in deionized water and made up to 200 mL, and stirred until the sodium hydroxide solid was completely dissolved to obtain a homogeneous solution B (pH 12).
步骤二：将PTFE纤维浸入A溶液50min，超声辅助时间7min，之后将浸润的PTFE纤维从溶液A中取出，沥干后浸入溶液B，浸渍沉淀15min后取出纤维，置于空气气氛老化4h。Step 2: The PTFE fiber was immersed in the A solution for 50 min, and the ultrasonic assisted time was 7 min. Then, the infiltrated PTFE fiber was taken out from the solution A, drained, and then immersed in the solution B. After immersing the precipitate for 15 minutes, the fiber was taken out and aged in an air atmosphere for 4 hours.
步骤三：将老化后的纤维置于微波反应器中，微波热处理20min，反应条件：微波功率400W、每30s微波发生时间10s；之后置于鼓风烘干箱105℃烘干处理5h。将烘干完全的PTFE纤维置于马弗炉，在250℃条件下热处理活化4h，得到牢固负载金属氧化物的双功能复合纤维#20。Step 3: The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, reaction conditions: microwave power 400 W, microwave generation time every 30 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h. The dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #20 which was firmly supported with metal oxide.
实施例21Example 21
本实施例与实施例17相同，不同之处在于，本实施例50wt％的硝酸锰溶液3.58g、六水合硝酸铈17.36g、五水合硝酸锆17.16g，得到牢固负载金属氧化物的双功能复合纤维#21。This embodiment is the same as the embodiment 17, except that in this embodiment, a 50 wt% manganese nitrate solution is 3.58 g, a lanthanum nitrate hexahydrate 17.36 g, and a zirconium nitrate pentahydrate 17.16 g to obtain a bifunctional composite of a strongly supported metal oxide. Fiber #21.
实施例22Example 22
本实施例与实施例17相同，不同之处在于，本实施例50wt％的硝酸锰溶液14.32g、六水合硝酸铈4.34g、五水合硝酸锆17.16g，得到牢固负载金属氧化物的双功能复合纤维#22。This embodiment is the same as the embodiment 17, except that in this embodiment, a 50 wt% manganese nitrate solution of 14.32 g, a cerium nitrate hexahydrate of 4.34 g, and a zirconium nitrate pentahydrate of 17.16 g, a bifunctional composite of a strongly supported metal oxide is obtained. Fiber #22.
实施例23：Example 23
以聚酰亚胺纤维为基底的双功能复合滤料纤维，步骤如下：The bifunctional composite filter fiber based on polyimide fiber is as follows:
步骤一：称取50wt％的硝酸锰溶液3.58g、六水合硝酸铈4.34g、五水合硝酸锆4.29g溶于去离子水250mL中，搅拌均匀，得到溶液A。称取碳酸铵19.2g，溶于去离子水并定容至200mL，搅拌至碳酸铵固体完全溶解，得到均匀溶液B(pH为9)。Step 1: Weigh 3.58g of manganese nitrate solution, 4.34g of cerium nitrate hexahydrate, 4.29g of zirconium nitrate pentahydrate, dissolved in deionized water 250mL, and stir evenly to obtain solution A. 19.2 g of ammonium carbonate was weighed, dissolved in deionized water and made up to 200 mL, and stirred until the ammonium carbonate solid was completely dissolved to obtain a homogeneous solution B (pH 9).
步骤二：将聚酰亚胺纤维浸入A溶液60min，超声辅助时间20min，之后将浸润的聚酰亚胺纤维从溶液A中取出，沥干后浸入溶液B，浸渍沉淀50min后取出纤维，置于空气气氛老化4h。Step 2: The polyimide fiber was immersed in the A solution for 60 min, and the ultrasonic assist time was 20 min. Then, the infiltrated polyimide fiber was taken out from the solution A, drained, immersed in the solution B, and the fiber was taken out after the immersion precipitation for 50 min, and placed. The air atmosphere aged for 4 hours.
步骤三：将老化后的纤维置于微波反应器中，微波热处理20min，反应条件：微波功率300W、每30s微波发生时间10s；之后置于鼓风烘干箱105℃烘干处理5h。将烘干完全的PTFE纤维置于马弗炉，在250℃条件下热处理活化4h，得到牢固负载金属氧化物的双功能复合纤维#23。Step 3: The aged fiber is placed in a microwave reactor, microwave heat treatment for 20 min, and the reaction conditions are: microwave power 300 W, microwave generation time every 30 s for 10 s; then placed in a blast drying oven at 105 ° C for 5 h. The dried PTFE fiber was placed in a muffle furnace and heat-treated at 250 ° C for 4 h to obtain a bifunctional composite fiber #23 which was firmly supported with metal oxide.
实施例24Example 24
本实施例与实施例23相同，不同之处在于，本实施例改变纤维在A溶液中的浸润时间为80min，在B溶液中浸润时间为30min，得到牢固负载金属氧化物的双功能复合纤维#24。 This embodiment is the same as the embodiment 23 except that the infiltration time of the fiber in the solution A is 80 min, and the infiltration time in the B solution is 30 min, and the bifunctional composite fiber with a firm metal oxide is obtained. twenty four.
实施例25Example 25
本实施例与实施例23相同，不同之处在于，本实施例改变纤维在A溶液中的浸润时间改为60min，在B溶液中浸润时间改为40min，得到牢固负载金属氧化物的双功能复合纤维#25。This embodiment is the same as the embodiment 23 except that the infiltration time of the fiber in the A solution is changed to 60 min, and the infiltration time in the B solution is changed to 40 min to obtain a bifunctional composite of the solid supported metal oxide. Fiber #25.
实施例26Example 26
本实施例与实施例23相同，不同之处在于，本实施例改变步骤一中的碳酸铵19.2g为碳酸钠21.2g，得到牢固负载金属氧化物的双功能复合纤维#26。This example is the same as the embodiment 23 except that 19.2 g of ammonium carbonate in the first step is changed to 21.2 g of sodium carbonate to obtain a bifunctional composite fiber #26 which is firmly supported with metal oxide.
在实验室固定床脱硝反应器上对13个催化剂样品进行SCR脱硝活性测试，脱硝反应的测试条件为：反应温度125～250℃，空速30 000h-1，NH3浓度500ppm，NO浓度500ppm，O2浓度3.5％，N2为平衡气。结果如表2所示。The 13 catalyst samples were tested for SCR denitration activity in a laboratory fixed-bed denitration reactor. The denitration reaction was tested at a reaction temperature of 125-250 ° C, a space velocity of 30 000 h -1 , a NH 3 concentration of 500 ppm, and a NO concentration of 500 ppm. The O 2 concentration was 3.5%, and N 2 was a balance gas. The results are shown in Table 2.
表2双功能复合滤料纤维脱硝活性测试结果Table 2 Test results of denitration activity of bifunctional composite filter media
Figure PCTCN2017106879-appb-000002
Figure PCTCN2017106879-appb-000002
对比例3Comparative example 3
称取50wt％的硝酸锰溶液14.32g、六水合硝酸铈4.34g、五水合硝酸锆4.29g溶于去离子水250mL中，搅拌均匀，得到溶液A。配制pH为13的氢氧化钠溶液作为溶液B，将聚酰亚 胺纤维浸入A溶液40min，超声辅助时间7min，之后将浸润的聚酰亚胺纤维从溶液A中取出，沥干后浸入溶液B，浸渍沉淀21min，聚酰亚胺纤维溶解，无法使用。Weighed 14.32 g of 50 wt% manganese nitrate solution, 4.34 g of cerium nitrate hexahydrate, and 4.29 g of zirconium nitrate pentahydrate dissolved in 250 mL of deionized water, and stirred uniformly to obtain a solution A. Prepare a sodium hydroxide solution with a pH of 13 as solution B. The amine fiber was immersed in the A solution for 40 min, and the ultrasonic assist time was 7 min. Then, the infiltrated polyimide fiber was taken out from the solution A, drained, immersed in the solution B, and impregnated and precipitated for 21 min, and the polyimide fiber was dissolved and could not be used.
对比例4Comparative example 4
本对比例与实施例14相同，不同之处在于，配制pH为7.5的碳酸铵溶液作为溶液B，通过该对比例制备的纤维并没有催化脱硝的性能。This comparative example was the same as that of Example 14, except that an ammonium carbonate solution having a pH of 7.5 was prepared as the solution B, and the fibers prepared by the comparative examples did not have catalytic denitration properties.
以上所述仅为本申请的优选实施例而已，并不用于限制本申请，对于本领域的技术人员来说，本申请可以有各种更改和变化。凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。 The above description is only the preferred embodiment of the present application, and is not intended to limit the present application, and various changes and modifications may be made to the present application. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of this application are intended to be included within the scope of the present application.

Claims (10)

  1. 一种双功能复合滤料纤维的制备方法，其特征是，(1)制备pH为8～12的碱性溶液A，将锰盐、铈盐和锆盐溶解于水中制备盐溶液B；A method for preparing a bifunctional composite filter fiber, characterized in that: (1) preparing an alkaline solution A having a pH of 8-12, and dissolving a manganese salt, a strontium salt and a zirconium salt in water to prepare a salt solution B;
    (2)将纤维浸入至碱性溶液A浸润15～70min，在浸润过程中进行超声辅助浸润一段时间，将浸润后的纤维沥干后浸入盐溶液B中浸渍沉淀一段时间；或，将纤维浸入至盐溶液B浸润，在浸润过程中进行超声辅助浸润一段时间，将浸润后的纤维沥干后浸入碱性溶液A中浸渍沉淀15～70min；(2) immersing the fiber into the alkaline solution A for 15 to 70 minutes, performing ultrasonic-assisted infiltration for a period of time during the infiltration process, draining the infiltrated fiber and immersing it in the salt solution B for a period of time; or, immersing the fiber in Infiltrated into the salt solution B, ultrasonically assisted infiltration for a period of time during the infiltration process, draining the infiltrated fibers and immersing in the alkaline solution A for immersion precipitation for 15 to 70 minutes;
    (3)将浸渍沉淀后的纤维取出后进行老化，将老化后的纤维进行微波热处理，最后进行活化处理即得双功能复合滤料纤维。(3) The immersed and precipitated fibers are taken out and aged, and the aged fibers are subjected to microwave heat treatment, and finally activated to obtain a bifunctional composite filter fiber.
  2. 如权利要求1所述的制备方法，其特征是，所述碱性溶液A为氨水、氢氧化钠溶液、碳酸铵溶液或碳酸钠溶液；The preparation method according to claim 1, wherein the alkaline solution A is ammonia water, sodium hydroxide solution, ammonium carbonate solution or sodium carbonate solution;
    或，所述的盐溶液B中的锰离子、铈离子和锆离子的摩尔比为1～8:1～4:1～4。Alternatively, the molar ratio of manganese ions, strontium ions and zirconium ions in the salt solution B is from 1 to 8:1 to 4:1 to 4.
  3. 如权利要求1所述的制备方法，其特征是，超声辅助浸润的时间为5～30min；The preparation method according to claim 1, wherein the ultrasonic assisted infiltration time is 5 to 30 min;
    或，当采用碱性溶液A浸润纤维时，所述浸渍沉淀的时间为30～80min；当采用盐溶液B浸润纤维时，所述浸润时间为30～80min。Or, when the fiber is infiltrated with the alkaline solution A, the time of the immersion precipitation is 30 to 80 min; when the fiber is infiltrated with the salt solution B, the infiltration time is 30 to 80 min.
  4. 如权利要求1所述的制备方法，其特征是，所述老化的时间为2～6h；The preparation method according to claim 1, wherein the aging time is 2 to 6 hours;
    或，所述老化是将浸渍沉淀后的纤维取出后在空气气氛进行老化。Alternatively, the aging is carried out by immersing the precipitated fibers and aging them in an air atmosphere.
  5. 如权利要求1所述的制备方法，其特征是，所述微波热处理的时间为10～40min，微波功率100-600W，每300s微波发生时间75-225s。The preparation method according to claim 1, wherein the microwave heat treatment time is 10 to 40 minutes, the microwave power is 100 to 600 W, and the microwave generation time is 75 to 225 s per 300 s.
  6. 如权利要求1所述的制备方法，其特征是，微波热处理后进行干燥后再进行活化；The preparation method according to claim 1, wherein the microwave heat treatment is followed by drying and then activation;
    优选的，所述干燥的条件为105℃烘干处理5h。Preferably, the drying condition is drying at 105 ° C for 5 h.
  7. 如权利要求1所述的制备方法，其特征是，所述活化处理是将纤维置于150～250℃一段时间；The preparation method according to claim 1, wherein the activation treatment is to place the fibers at 150 to 250 ° C for a period of time;
    优选的，所述活化处理的时间为2～8h。Preferably, the activation treatment time is 2-8 hours.
  8. 一种权利要求1～7任一所述的制备方法制备的复合滤料纤维。A composite filter fiber prepared by the preparation method according to any one of claims 1 to 7.
  9. 一种滤料，其特征是，有权利要求8所述的复合滤料纤维制备。A filter material characterized by the preparation of the composite filter fiber of claim 8.
  10. 一种权利要求8所述的复合滤料纤维或权利要求9所述的滤料在除尘脱硝中的应用。 Use of the composite filter fiber of claim 8 or the filter material of claim 9 for dust removal and denitrification.
PCT/CN2017/106879 2017-06-23 2017-10-19 Difunctional composite filter medium fiber and preparation method therefor WO2018233159A1 (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201710488583.0A CN107261644B (en) 2017-06-23 2017-06-23 A kind of difunctional composite filtering material fiber of low temperature dedusting-denitration and preparation method
CN201710486860.4 2017-06-23
CN201710486860.4A CN107158799B (en) 2017-06-23 2017-06-23 A kind of composite filtering material fiber and preparation method for SCR dedusting denitration
CN201710488583.0 2017-06-23

Publications (1)

Publication Number Publication Date
WO2018233159A1 true WO2018233159A1 (en) 2018-12-27

Family

ID=64736851

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2017/106879 WO2018233159A1 (en) 2017-06-23 2017-10-19 Difunctional composite filter medium fiber and preparation method therefor

Country Status (1)

Country Link
WO (1) WO2018233159A1 (en)

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996014153A1 (en) * 1994-11-02 1996-05-17 Bojidara Grigorova Catalyst with zirconia/ceria support
CN101518718A (en) * 2008-02-28 2009-09-02 中国纺织科学研究院 Functional filter felt for eliminating harmful constituents of fume, preparation method and application method thereof
US20140196658A1 (en) * 2011-08-22 2014-07-17 Craig GRIMES Integrated charge production architecture
CN104941319A (en) * 2015-06-19 2015-09-30 合肥工业大学 Method for preparing manganese-base dedusting and denitration integration function filter material
CN106560245A (en) * 2015-10-05 2017-04-12 通用汽车环球科技运作有限责任公司 Forming Age-suppressing Catalysts
CN107158799A (en) * 2017-06-23 2017-09-15 山东大学 A kind of composite filtering material fiber and preparation method for SCR dedusting denitrations
CN107261644A (en) * 2017-06-23 2017-10-20 山东大学 A kind of difunctional composite filtering material fiber of low temperature dedusting denitration and preparation method
CN107497440A (en) * 2017-08-17 2017-12-22 江苏天东新材料科技有限公司 The preparation method and application of tempreture organic sulphur hydrolysis, absorption and the multi-functional desulfurizing agent of deoxidation

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996014153A1 (en) * 1994-11-02 1996-05-17 Bojidara Grigorova Catalyst with zirconia/ceria support
CN101518718A (en) * 2008-02-28 2009-09-02 中国纺织科学研究院 Functional filter felt for eliminating harmful constituents of fume, preparation method and application method thereof
US20140196658A1 (en) * 2011-08-22 2014-07-17 Craig GRIMES Integrated charge production architecture
CN104941319A (en) * 2015-06-19 2015-09-30 合肥工业大学 Method for preparing manganese-base dedusting and denitration integration function filter material
CN106560245A (en) * 2015-10-05 2017-04-12 通用汽车环球科技运作有限责任公司 Forming Age-suppressing Catalysts
CN107158799A (en) * 2017-06-23 2017-09-15 山东大学 A kind of composite filtering material fiber and preparation method for SCR dedusting denitrations
CN107261644A (en) * 2017-06-23 2017-10-20 山东大学 A kind of difunctional composite filtering material fiber of low temperature dedusting denitration and preparation method
CN107497440A (en) * 2017-08-17 2017-12-22 江苏天东新材料科技有限公司 The preparation method and application of tempreture organic sulphur hydrolysis, absorption and the multi-functional desulfurizing agent of deoxidation

Similar Documents

Publication Publication Date Title
WO2020063360A1 (en) Method for preparing molecular sieve scr catalyst, and catalyst prepared thereby
WO2015161627A1 (en) Honeycomb denitration catalyst for flue gas at 400°c-600°c and preparation method therefor
CN101693192B (en) Process for preparing nitric oxide adsorbent with high adsorption capacity
CN107362807A (en) A kind of Mn/Co bases low temperature SCO catalyst and preparation method thereof
CN108816239B (en) Supported catalyst, preparation method and application thereof
CN107837826B (en) Regeneration process method of inactivated flue gas denitration catalyst
CN103433033A (en) Low-temperature denitration catalyst MnOx-CeO2-TiO2-Al2O3, and preparation method and application thereof
CN113413904A (en) g-C3N4Low-temperature NH of loaded manganese cerium composite oxide3-SCR catalyst, preparation method and application thereof
CN104138761A (en) Anti-sulfur film type low-temperature denitration catalyst and preparation method thereof
CN102764657B (en) Nano V205/activated coke denitration catalyst and preparation method of catalyst
CN105597817A (en) Low-temperature SCR (selective catalytic reduction) flue gas denitrification catalyst containing MnOx/SAPO-11 as well as preparation method and application of catalyst
CN107158799B (en) A kind of composite filtering material fiber and preparation method for SCR dedusting denitration
CN112547129A (en) Sulfur-resistant and water-resistant manganese-based low-temperature denitration catalyst and preparation method and application thereof
CN108479788B (en) Non-noble metal supported catalyst and preparation method and application thereof
CN112742413A (en) Low-temperature SCR denitration catalyst and preparation method and application thereof
CN110801848A (en) Flat plate type wide-temperature sulfur-resistant SCR denitration catalyst and preparation method thereof
CN113198529A (en) Metal carrier loaded copper-based SCR catalyst and preparation method thereof
CN110354915B (en) Recycling method of alkali metal poisoned SCR denitration catalyst
CN109821531B (en) Cerium oxide carrier-based flat plate type high-temperature sulfur-resistant SCR denitration catalyst and preparation method thereof
CN105126922A (en) Vanadium-free SCR denitration catalyst and preparation method thereof
CN104607198A (en) Vanadium-free plate-like denitration catalyst and preparation method thereof
CN107261644B (en) A kind of difunctional composite filtering material fiber of low temperature dedusting-denitration and preparation method
CN113578341A (en) Synergistic NH3Preparation method of denitration catalyst with CO
CN104998684A (en) Rare-earth modified SCR denitrification catalyst and preparation method therefor
CN108636401A (en) A kind of novel Mn, Ce codope ZrO2Aeroge low-temperature denitration catalyst

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17915128

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17915128

Country of ref document: EP

Kind code of ref document: A1

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205 DATED 13/02/2020)

122 Ep: pct application non-entry in european phase

Ref document number: 17915128

Country of ref document: EP

Kind code of ref document: A1