Porous structure glass fiber carrier and preparation method thereof

Abstract

The invention relates to the technical field of adsorption carriers, in particular to a porous structure glass fiber carrier and a preparation method thereof.Corrugated glass fiber corrugated felts and corrugated glass fiber felts are arranged in a stacked mode to obtain a fiber skeleton, then the fiber skeleton is soaked in inorganic filling slurry, and after drying and calcination, the porous structure glass fiber carrier is obtained through an immersion precipitation phase inversion method; a porous polyimide matrix is deposited on the surface of the fiber skeleton to obtain a porous structure glass fiber carrier with high mechanical strength; wherein a corrugated structure in the fiber skeleton can improve certain compressive strength and buffering capacity, and uniform distribution of inorganic filling slurry is facilitated while the specific surface area of the material is increased; moreover, the porous polymer deposited on the surface of the fiber skeleton is beneficial to further reduction of stress concentration of the glass fiber carrier, the high temperature resistance and the stability of the glass fiber carrier are improved in the denitration process, and compared with the prior art, the glass fiber carrier has a wide application prospect.

Description

Technical Field

[0001] The present invention relates to the technical field of adsorption carriers, and particularly relates to a porous structure glass fiber carrier and a preparation method thereof. Background Art

[0002] Nitric oxide (NO) is a pollutant generated in the industrial production process. After being discharged into the atmosphere, it will harm the environment. It is the main precursor of the greenhouse effect, acid rain, ozone layer depletion and photochemical smog, and even endangers human health.

[0003] Currently, the SCR denitration method widely used in the industrial field is the key technology for treating and removing this pollutant. For power plant boilers, the research and development of high-temperature SCR catalysts has been relatively mature, while there is still room for further exploration in the preparation of low-temperature SCR catalysts suitable for non-electric and low-temperature flue gas plants. Secondly, selecting catalyst carrier materials with low cost, high loading of catalyst powder and easy handling is another difficulty. The emergence of situations such as poor low-temperature activity and easy shedding of catalyst powder on the surface of the carrier often affects and shortens the service life of the catalyst under factory conditions, which will invisibly increase the factory cost.

[0004] The monolithic catalysts used in factories are usually divided into three categories: honeycomb type, plate type and corrugated plate type. The corrugated plate type catalyst is obtained by impregnating and loading the catalyst on a corrugated plate of glass fiber material. This monolithic catalyst has the advantages of strong thermal shock resistance, high specific surface area, light unit volume weight, wide application temperature range, etc., and has broad application prospects and good social and environmental benefits in the industrial application field.

[0005] Corrugated glass fiber can be used as the carrier of various catalysts, especially the carrier of various environmental protection catalysts. The corrugated glass fiber carrier has a large specific surface area, which can make the active components evenly distributed on the surface to generate more active sites. The porous structure glass fiber carrier is a glass fiber material with a special structure, and a large number of tiny pores are contained inside. These pores make the carrier have a high specific surface area and excellent adsorption performance. This carrier is widely used in the fields of catalysis, adsorption, filtration, etc., and has important application value especially in industries such as environmental protection, chemical engineering and energy.

[0006] In the prior art, the porosity of the porous structure glass fiber carrier is too high, and its mechanical strength is insufficient to withstand the external stress generated in actual applications.

[0007] Therefore, according to the above related technologies, it is urgent to develop a porous structure glass fiber carrier and a preparation method thereof. Summary of the Invention

[0008] In view of this, the purpose of the present invention is to provide a porous structure glass fiber carrier and a preparation method thereof to solve the problem of insufficient mechanical strength of the porous structure glass fiber carrier in the prior art.

[0009] For the above purposes, the present invention provides a porous structure glass fiber carrier and a preparation method thereof.

[0010] A porous structure glass fiber carrier includes a fiber skeleton, an inorganic filling slurry coated on the fiber skeleton, and a porous polymer deposited on the surface of the glass fiber carrier;

[0011] The fiber skeleton is prepared by hot pressing a corrugated glass fiber felt and a corrugated glass fiber mat;

[0012] The corrugated glass fiber felt and the corrugated glass fiber mat are arranged in a laminated manner;

[0013] The porous polymer deposited on the surface of the glass fiber is polyimide;

[0014] The inorganic filling slurry is prepared from ammonium tungstate, ammonium metatungstate, and anatase titanium dioxide.

[0015] Preferably, the preparation method of the inorganic filling slurry is as follows:

[0016] A1. Add oxalic acid, ammonium tungstate, ammonium metatungstate, and anatase titanium dioxide to deionized water, heat to 45 - 52 °C, stir evenly, dry, and then calcine in a muffle furnace to obtain compound A;

[0017] A2. Grind compound A into fine powder in a ball mill, then mix it with solvent A and deionized water, and perform ultrasonic treatment for 10 - 15 min to obtain the inorganic filling slurry.

[0018] Preferably, the mass ratio of the deionized water, oxalic acid, ammonium tungstate, ammonium metatungstate, and anatase titanium dioxide in A1 is 55 - 60:12 - 15:5.5 - 8:2.4 - 3.5:27 - 30.

[0019] Preferably, the drying temperature in A2 is 70 - 80 °C;

[0020] The calcination temperature is 520 - 550 °C and the time is 3 - 4 h.

[0021] Preferably, the mass ratio of compound A, solvent A, and deionized water in A2 is 18 - 25:8 - 13:65 - 75.

[0022] Preferably, solvent A in A2 is obtained by mixing tetraethyl orthosilicate, polyvinyl alcohol, tetrabutyl titanate, silica sol, aluminum sulfate, and deionized water in a mass ratio of 3 - 5:3 - 5:2 - 3:80 - 90:9 - 12:10 - 15.

[0023] A preparation method of a porous structure glass fiber carrier includes the following steps:

[0024] S1. Take 30 pieces each of pre-cut corrugated fiberglass felt and corrugated fiberglass mat with a size of 50*50 mm, stack them layer by layer in the order of one layer of corrugated fiberglass mat and one layer of corrugated fiberglass felt to form a cubic structure, and obtain a fiber skeleton;

[0025] S2. Place the fiber skeleton in an immersion tank filled with inorganic filling slurry. After soaking for 9 - 13 min, take out the fiber skeleton and dry it, then place it in a muffle furnace for calcination to obtain a modified fiber skeleton;

[0026] S3. Place the modified fiber skeleton in a quartz tube, and place the quartz tube on the side wall of a solution box filled with solvent B. Then place the solution box on the surface of a water tank filled with deionized water. Then take out the modified fiber skeleton from the quartz tube and immerse it in the water tank for 1 - 3 min to obtain a porous structure fiberglass carrier.

[0027] Preferably, the temperature during drying in S2 is 105 - 115 °C;

[0028] The calcination includes a first calcination, heat preservation, and a second calcination;

[0029] The heating rate during the first calcination is 1.5 - 2.5 °C / min, calcine to 280 °C, and the calcination time is 1 - 1.5 h;

[0030] The temperature during heat preservation is 280 °C, and the heat preservation time is 1 - 1.5 h;

[0031] The heating rate during the second calcination is 3 - 4 °C / min, calcine to 500 °C, and the calcination time is 2 - 3 h.

[0032] Preferably, the preparation method of solvent B in S3 is as follows:

[0033] Mix polyimide and N,N-dimethylacetamide, heat and stir, then add isopropanol, and continue to stir until dissolved to obtain solvent B.

[0034] Preferably, the mass ratio of polyimide, N,N-dimethylacetamide, and isopropanol is 16 - 22:70 - 80:4.3 - 5;

[0035] The temperature during heating and stirring is 85 - 95 °C, the stirring rate is 130 - 170 r / min, and the stirring time is 12 - 17 min.

[0036] The beneficial effects of the present invention:

[0037] The present invention provides a porous-structured glass fiber carrier and a preparation method thereof. In the present invention, a corrugated glass fiber corrugated felt and a corrugated glass fiber felt are arranged in a stacked manner to obtain a fiber skeleton, which is then immersed in an inorganic filling slurry. After drying and calcination, a porous polyimide matrix is deposited on the surface of the fiber skeleton by the immersion precipitation phase inversion method to obtain a porous-structured glass fiber carrier with high mechanical strength. Among them, the corrugated structure in the fiber skeleton can improve a certain compressive strength and buffering ability, and while increasing the specific surface area of the material, it is also beneficial to the uniform distribution of the inorganic filling slurry. Moreover, the porous polymer deposited on the surface of the fiber skeleton is conducive to further reducing the stress concentration of the glass fiber carrier. During the denitrification process, the high-temperature resistance and stability of the glass fiber carrier are improved. Compared with the prior art, it has a wide application prospect. Detailed Embodiments

[0038] To make the objectives, technical solutions and advantages of the present invention more clear and understandable, the following further elaborates on the present invention in conjunction with specific embodiments.

[0039] The sources and properties of some raw materials used in the present invention are as follows:

[0040] Isopropyl alcohol was purchased from Tianjin Fuyu Fine Chemical Co., Ltd.; quartz tubes were purchased from Yaokai Quartz Products Co., Ltd.; N,N-dimethylacetamide was purchased from Tianjin Fuyu Fine Chemical Co., Ltd.; polyimide was purchased from Shanghai Yehe Industry and Trade Co., Ltd.; ammonium tungstate was purchased from Xiamen Tungsten Co., Ltd.; ammonium metatungstate was purchased from Taizhou Yuanhang Tungsten and Molybdenum Products Co., Ltd.; anatase titanium dioxide was purchased from TCI (Shanghai) Chemical Industry Development Co., Ltd.; oxalic acid was purchased from Henan Baoxin Environmental Protection Technology Co., Ltd.; tetraethyl orthosilicate was purchased from Hubei Jianghan New Materials Co., Ltd.; polyvinyl alcohol was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd.; tetrabutyl titanate was purchased from Yunnan Lilian Biotechnology Co., Ltd.

[0041] Example 1: A preparation method of a porous-structured glass fiber carrier, comprising the following steps:

[0042] S1. Take 30 pieces each of pre-cut corrugated glass fiber corrugated felt and corrugated glass fiber felt with a size of 50*50 mm, and stack them layer by layer in the order of one layer of corrugated glass fiber felt and one layer of corrugated glass fiber corrugated felt to form a cubic structure, obtaining a fiber skeleton;

[0043] S2. Add 12 g of oxalic acid, 5.5 g of ammonium tungstate, 2.4 g of ammonium metatungstate and 27 g of anatase titanium dioxide to 55 g of deionized water, heat to 45°C and stir evenly, then dry at 70°C, and then place in a muffle furnace and calcine at 520°C for 3 h to obtain Compound A;

[0044] S3. Mix 3 g of tetraethyl orthosilicate, 3 g of polyvinyl alcohol, 2 g of tetrabutyl titanate, 80 g of silica sol, 9 g of aluminum sulfate and 10 g of deionized water, and after stirring evenly, obtain solvent A; mix 16 g of polyimide and 70 g of N,N-dimethylacetamide, heat and stir at 85 °C and a stirring rate of 130 r / min for 12 min, then add 4.3 g of isopropanol and continue to stir until dissolved to obtain solvent B;

[0045] S4. Put 18 g of compound A into a ball mill and grind it into fine powder, then mix it with 8 g of solvent A and 65 g of deionized water, and after ultrasonic treatment for 10 min, obtain an inorganic filling slurry;

[0046] S5. Place the fiber skeleton in an immersion tank filled with the inorganic filling slurry, immerse it for 9 min, take out the fiber skeleton and dry it at 105 °C, then place it in a muffle furnace for the first calcination, set the heating rate to 1.5 °C / min, calcine to 280 °C, calcine for 1 h, keep warm for 1 h, and then conduct the second calcination, with a heating rate of 3 °C / min, calcine to 500 °C, and after calcining for 2 h, obtain a modified fiber skeleton;

[0047] S6. Place the modified fiber skeleton in a quartz tube, and place the quartz tube on the side wall of a solution box filled with solvent B. Subsequently, place the solution box on the surface of a water tank filled with deionized water, and then take out the modified fiber skeleton from the quartz tube and immerse it in the water tank for 1 min to obtain a porous structure glass fiber carrier.

[0048] Example 2: A preparation method of a porous structure glass fiber carrier, comprising the following steps:

[0049] S1. Take 30 pieces each of pre-cut corrugated glass fiber felt and corrugated glass fiber mat with a size of 50*50 mm, stack them in a cubic structure in turn with one layer of corrugated glass fiber mat and one layer of corrugated glass fiber felt to obtain a fiber skeleton;

[0050] S2. Add 13 g of oxalic acid, 5.8 g of ammonium tungstate, 2.6 g of ammonium metatungstate and 27.5 g of anatase titanium dioxide to 56 g of deionized water, heat to 46 °C and stir evenly, then dry at 72 °C, and then place it in a muffle furnace and calcine at 525 °C for 3 h to obtain compound A;

[0051] S3. Mix 3.5 g of tetraethyl orthosilicate, 3.5 g of polyvinyl alcohol, 2.2 g of tetrabutyl titanate, 82 g of silica sol, 9.5 g of aluminum sulfate and 10.5 g of deionized water, and after stirring evenly, obtain solvent A; mix 17 g of polyimide and 72 g of N,N-dimethylacetamide, heat and stir at 87 °C and a stirring rate of 135 r / min for 13 min, then add 4.5 g of isopropanol and continue to stir until dissolved to obtain solvent B;

[0052] S4. Put 19 g of Compound A into a ball mill and grind it into fine powder, then mix it with 9 g of Solvent A and 67 g of deionized water. After ultrasonic treatment for 11 min, an inorganic filling slurry is obtained.

[0053] S5. Place the fiber skeleton in an immersion tank filled with the inorganic filling slurry. After soaking for 9.5 min, take out the fiber skeleton and dry it at 107 °C, then place it in a muffle furnace for the first calcination. Set the heating rate to 1.5 °C / min and calcine to 280 °C. After calcining for 1 h, keep it at a constant temperature for 1 h, and then conduct the second calcination. Its heating rate is 3 °C / min and calcine to 500 °C. After calcining for 2 h, a modified fiber skeleton is obtained.

[0054] S6. Place the modified fiber skeleton in a quartz tube, and place the quartz tube on the side wall of a solution box containing Solvent B. Then place the solution box on the surface of a water tank filled with deionized water. Then take out the modified fiber skeleton from the quartz tube and immerse it in the water tank for 1 min to obtain a porous structure glass fiber carrier.

[0055] Example 3: A method for preparing a porous structure glass fiber carrier, comprising the following steps:

[0056] S1. Take 30 pieces each of pre-cut corrugated glass fiber felt and corrugated glass fiber tile with a size of 50*50 mm, and stack them in a cubic structure in turn with one layer of corrugated glass fiber felt and one layer of corrugated glass fiber tile to obtain a fiber skeleton.

[0057] S2. Add 13.5 g of oxalic acid, 6 g of ammonium tungstate, 2.8 g of ammonium metatungstate, and 28 g of anatase titanium dioxide to 57 g of deionized water. Heat to 47 °C and stir evenly, then dry at 74 °C, and then place it in a muffle furnace and calcine at 530 °C for 3.5 h to obtain Compound A.

[0058] S3. Mix 4 g of tetraethyl orthosilicate, 4 g of polyvinyl alcohol, 2.4 g of tetrabutyl titanate, 84 g of silica sol, 10.5 g of aluminum sulfate, and 12 g of deionized water, and stir evenly to obtain Solvent A; mix 18 g of polyimide and 74 g of N,N-dimethylacetamide, heat and stir at 89 °C and a stirring rate of 140 r / min for 14 min, then add 4.5 g of isopropanol and continue to stir until dissolved to obtain Solvent B.

[0059] S4. Put 20 g of Compound A into a ball mill and grind it into fine powder, then mix it with 10 g of Solvent A and 69 g of deionized water. After ultrasonic treatment for 12 min, an inorganic filling slurry is obtained.

[0060] S5. Place the fiber skeleton in an immersion tank filled with inorganic filling slurry. After soaking for 11 min, take out the fiber skeleton and dry it at 109 °C, then place it in a muffle furnace for the first calcination. Set the heating rate to 2 °C / min and calcine to 280 °C. After calcining for 1 h, keep it at a constant temperature for 1 h, and then conduct the second calcination. Its heating rate is 3 °C / min and it is calcined to 500 °C. After calcining for 2 h, a modified fiber skeleton is obtained;

[0061] S6. Place the modified fiber skeleton in a quartz tube, and place the quartz tube on the side wall of a solution box containing solvent B. Then place the solution box on the surface of a water tank filled with deionized water. Then take out the modified fiber skeleton from the quartz tube and immerse it in the water tank for 2 min to obtain a porous structure glass fiber carrier.

[0062] Example 4: A method for preparing a porous structure glass fiber carrier, comprising the following steps:

[0063] S1. Take 30 pieces each of pre-cut corrugated glass fiber felt and corrugated glass fiber mat with a size of 50*50 mm, and stack them layer by layer in the order of one layer of corrugated glass fiber mat and one layer of corrugated glass fiber felt to form a cubic structure to obtain a fiber skeleton;

[0064] S2. Add 13.5 g of oxalic acid, 6.5 g of ammonium tungstate, 3 g of ammonium metatungstate, and 28.5 g of anatase titanium dioxide to 58 g of deionized water. After heating to 50 °C and stirring evenly, dry it at 76 °C, and then place it in a muffle furnace and calcine at 53.5 °C for 3.5 h to obtain compound A;

[0065] S3. Mix 4.5 g of tetraethyl orthosilicate, 4.5 g of polyvinyl alcohol, 2.6 g of tetrabutyl titanate, 86 g of silica sol, 11 g of aluminum sulfate, and 13 g of deionized water, and stir evenly to obtain solvent A; Mix 20 g of polyimide and 76 g of N,N-dimethylacetamide, heat and stir at 91 °C and a stirring rate of 145 r / min for 15 min, then add 4.7 g of isopropanol and continue to stir until dissolved to obtain solvent B;

[0066] S4. Put 22 g of compound A into a ball mill and grind it into fine powder, then mix it with 11.5 g of solvent A and 71 g of deionized water, and perform ultrasonic treatment for 13 min to obtain inorganic filling slurry;

[0067] S5. Place the fiber skeleton in an immersion tank filled with inorganic filling slurry. After soaking for 11 min, take out the fiber skeleton and dry it at 110 °C, then place it in a muffle furnace for the first calcination. Set the heating rate to 2 °C / min and calcine to 280 °C. After calcining for 1.5 h, keep it at a constant temperature for 1.5 h, and then conduct the second calcination. Its heating rate is 4 °C / min and it is calcined to 500 °C. After calcining for 3 h, a modified fiber skeleton is obtained;

[0068] S6. Place the modified fiber framework in a quartz tube, place the quartz tube on the side wall of a solution box containing Solvent B, then place the solution box on the surface of a water tank filled with deionized water, and then take out the modified fiber framework from the quartz tube and immerse it in the water tank for 2 min to obtain a porous structure glass fiber carrier.

[0069] Example 5: A method for preparing a porous structure glass fiber carrier, comprising the following steps:

[0070] S1. Take 30 pieces each of pre-cut corrugated glass fiber felt and corrugated glass fiber mat with a size of 50*50 mm, stack them layer by layer in the order of one layer of corrugated glass fiber mat and one layer of corrugated glass fiber felt to form a cubic structure to obtain a fiber framework;

[0071] S2. Add 14 g of oxalic acid, 7 g of ammonium tungstate, 3.3 g of ammonium metatungstate, and 29.5 g of anatase titanium dioxide to 63 g of deionized water, heat to 50 °C, stir evenly, dry at 78 °C, and then place in a muffle furnace and calcine at 540 °C for 4 h to obtain Compound A;

[0072] S3. Mix 5 g of tetraethyl orthosilicate, 5 g of polyvinyl alcohol, 3 g of tetrabutyl titanate, 88 g of silica sol, 11.5 g of aluminum sulfate, and 14 g of deionized water, stir evenly to obtain Solvent A; mix 21 g of polyimide and 78 g of N,N-dimethylacetamide, heat and stir at 93 °C and a stirring rate of 160 r / min for 16 min, then add 4.8 g of isopropanol, and continue to stir until dissolved to obtain Solvent B;

[0073] S4. Put 24 g of Compound A into a ball mill and grind it into fine powder, then mix it with 12.5 g of Solvent A and 73 g of deionized water, and perform ultrasonic treatment for 14 min to obtain an inorganic filling slurry;

[0074] S5. Place the fiber framework in an immersion tank filled with the inorganic filling slurry, soak for 12 min, take out the fiber framework and dry it at 113 °C, then place it in a muffle furnace for the first calcination, set the heating rate to 2.5 °C / min, calcine to 280 °C, calcine for 1.5 h, keep warm for 1.5 h, and then perform the second calcination, with a heating rate of 4 °C / min, calcine to 500 °C, and calcine for 3 h to obtain a modified fiber framework;

[0075] S6. Place the modified fiber framework in a quartz tube, place the quartz tube on the side wall of a solution box containing Solvent B, then place the solution box on the surface of a water tank filled with deionized water, and then take out the modified fiber framework from the quartz tube and immerse it in the water tank for 3 min to obtain a porous structure glass fiber carrier.

[0076] Example 6: A method for preparing a porous structure glass fiber carrier, comprising the following steps:

[0077] S1. Take 30 pieces each of pre-cut corrugated fiberglass felt and corrugated fiberglass mat with a size of 50*50 mm, stack them layer by layer in the order of one layer of corrugated fiberglass mat and one layer of corrugated fiberglass felt to form a cubic structure, and obtain a fiber skeleton;

[0078] S2. Add 15 g of oxalic acid, 8 g of ammonium tungstate, 3.5 g of ammonium metatungstate and 30 g of anatase titanium dioxide to 60 g of deionized water, heat to 52 °C and stir evenly, dry at 80 °C, and then place in a muffle furnace and calcine at 550 °C for 4 h to obtain Compound A;

[0079] S3. Mix 5 g of tetraethyl orthosilicate, 5 g of polyvinyl alcohol, 3 g of tetrabutyl titanate, 90 g of silica sol, 12 g of aluminum sulfate and 15 g of deionized water, stir evenly to obtain Solvent A; Mix 22 g of polyimide and 80 g of N,N-dimethylacetamide, heat and stir at 95 °C and a stirring rate of 170 r / min for 17 min, add 5 g of isopropanol, and continue to stir until dissolved to obtain Solvent B;

[0080] S4. Put 25 g of Compound A into a ball mill and grind it into fine powder, then mix it with 13 g of Solvent A and 75 g of deionized water, and perform ultrasonic treatment for 15 min to obtain an inorganic filling slurry;

[0081] S5. Place the fiber skeleton in an immersion tank filled with the inorganic filling slurry, soak for 13 min, take out the fiber skeleton and dry it at 115 °C, then place it in a muffle furnace for the first calcination, set the heating rate to 2.5 °C / min, calcine to 280 °C, calcine for 1.5 h, keep warm for 1.5 h, and then perform the second calcination, with a heating rate of 4 °C / min, calcine to 500 °C, and calcine for 3 h to obtain a modified fiber skeleton;

[0082] S6. Place the modified fiber skeleton in a quartz tube, place the quartz tube on the side wall of a solution box filled with Solvent B, then place the solution box on the surface of a water tank filled with deionized water, and then take out the modified fiber skeleton from the quartz tube and immerse it in the water tank for 3 min to obtain a porous structure fiberglass carrier.

[0083] Comparative Example 1:

[0084] In this comparative example, no porous polymer was added during the preparation process of the porous structure fiberglass carrier compared with Example 1. The remaining steps and parameters are the same. This comparative example will not be repeated here. Finally, a porous structure fiberglass carrier is obtained.

[0085] Comparative Example 2:

[0086] In this comparative example, compared with Example 1, only "corrugated fiberglass felt and corrugated fiberglass mat" was replaced with "corrugated fiberglass mat", and the remaining steps and parameters were the same. This comparative example will not be repeated here, and finally a porous structure fiberglass carrier was obtained.

[0087] Comparative Example 3:

[0088] In this comparative example, compared with Example 1, only "corrugated fiberglass felt and corrugated fiberglass mat" was replaced with "corrugated fiberglass felt", and the remaining steps and parameters were the same. This comparative example will not be repeated here, and finally a porous structure fiberglass carrier was obtained.

[0089] Comparative Example 4:

[0090] S1. Take 30 pieces each of pre-cut corrugated fiberglass felt and corrugated fiberglass mat with a size of 50*50 mm, stack them in a cube structure in turn with one layer of corrugated fiberglass mat and one layer of corrugated fiberglass felt to obtain a fiber skeleton;

[0091] S2. Add 12 g of oxalic acid, 5.5 g of ammonium tungstate, 2.4 g of ammonium metatungstate and 27 g of anatase titanium dioxide to 55 g of deionized water, heat to 45 °C and stir evenly, then dry at 70 °C, and then place in a muffle furnace and calcine at 520 °C for 3 h to obtain Compound A;

[0092] S3. Mix 3 g of tetraethyl orthosilicate, 3 g of polyvinyl alcohol, 2 g of tetrabutyl titanate, 80 g of silica sol, 9 g of aluminum sulfate and 10 g of deionized water, stir evenly to obtain Solvent A; Mix 16 g of polyimide and 70 g of N,N-dimethylacetamide, heat and stir at 85 °C and a stirring rate of 130 r / min for 12 min, then add 4.3 g of isopropanol and continue to stir until dissolved to obtain Solvent B;

[0093] S4. Put 18 g of Compound A into a ball mill and grind it into fine powder, then mix it with 8 g of Solvent A and 65 g of deionized water, and perform ultrasonic treatment for 10 min to obtain an inorganic filling slurry;

[0094] S5. Place the fiber skeleton in an immersion tank filled with the inorganic filling slurry, soak for 9 min, take out the fiber skeleton and dry it at 105 °C, then place it in a muffle furnace for calcination, set the heating rate to 3 °C / min, calcine to 500 °C, and calcine for 4 h to obtain a modified fiber skeleton;

[0095] S6. Place the modified fiber skeleton in a quartz tube, and place the quartz tube on the side wall of a solution box containing Solvent B. Then place the solution box on the surface of a water tank containing deionized water, and then take out the modified fiber skeleton from the quartz tube and immerse it in the water tank for 1 min to obtain a porous structure fiberglass carrier.

[0096] Performance Test:

[0097] Denitrification efficiency:

[0098] Refer to the test standard of GB / T 31587-2015. Use a fixed-bed quartz tube reactor to simulate the flue gas composition (SO2 concentration is 500 ppm, NH3 concentration is 200 ppm, O2 is 7%, H2O is 10%, and N2 is the balance gas), and conduct the test at an airspeed of 9000 h -1 to evaluate the denitrification efficiency of the porous structure fiberglass carriers prepared in Examples 1-6 and Comparative Examples 1-4;

[0099] Mechanical strength:

[0100] Compressive strength: Refer to the test standard of GB / T 38219-2019. Cut samples with a length of 150 mm from both ends of the porous structure fiberglass carriers prepared in Examples 1-6 and Comparative Examples 1-4 and place them in a WDW-Y300D constant stress pressure testing machine. Set the loading speed to 1.125 kN / s to test the maximum pressure that the sample can withstand per unit area;

[0101] Wear rate: Use a rotary abrasion tester with quartz sand as the abrasion agent. Place the porous structure fiberglass carriers prepared in Examples 1-6 and Comparative Examples 1-4 in the abrasion tester respectively. Set the test wind speed to 14.5 m / s and the quartz sand concentration to 52 g / m 3 . The test time is 2 hours. After the test, weigh the sample and calculate the percentage of mass loss. The wear rate is expressed as the ratio of mass loss to the consumption of the abrasion agent.

[0102] Table 1

[0103] Project Denitration efficiency (%) Compressive strength (MPa) Wear rate (% / h) Example 1 93 3.4 0.9 Example 2 95 3.1 0.8 Example 3 90 3.5 0.9 Example 4 88 3.2 1.1 Example 5 92 3.0 1.0 Example 6 91 3.1 0.8 Comparative example 1 83 2.2 1.8 Comparative example 2 79 1.9 2.3 Comparative example 3 77 2.0 2.1 Comparative example 4 84 2.7 1.3

[0104] Data analysis:

[0105] As can be seen from Table 1, the porous-structured glass fiber carrier prepared by the present invention has higher denitrification efficiency and mechanical strength. This may be because in the present invention, the corrugated glass fiber corrugated felt and the corrugated glass fiber felt are arranged in a laminated manner to obtain a fiber skeleton, which is then immersed in an inorganic filling slurry. After drying and calcination, the immersion precipitation phase inversion method is used to deposit a porous polyimide matrix on the surface of the fiber skeleton, resulting in a porous-structured glass fiber carrier with high mechanical strength. Among them, the corrugated structure in the fiber skeleton can improve a certain compressive strength and buffering capacity, and while increasing the specific surface area of the material, it is also beneficial to the uniform distribution of the inorganic filling slurry. Moreover, the porous polymer deposited on the surface of the fiber skeleton is conducive to further reducing the stress concentration of the glass fiber carrier. During the denitrification process, the high-temperature resistance and stability of the glass fiber carrier are both improved. After the fiber skeleton is immersed in the inorganic slurry, the calcination process used includes the first calcination, heat preservation, and the second calcination. Different heating rates are successively adopted and heat preservation is carried out, which can avoid cracks caused by too large a temperature gradient and further refine its microstructure, improving the overall mechanical properties and durability.

[0106] Those of ordinary skill in the art should understand that the discussion of any embodiment above is only exemplary and is not intended to imply that the scope of the present invention is limited to these examples. Under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, and the steps can be implemented in any order. There are many other variations in different aspects of the present invention as described above, and they are not provided in detail for the sake of brevity.

[0107] The present invention aims to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omission, modification, equivalent substitution, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A porous structure glass fiber carrier, characterized in that, The glass fiber carrier includes a fiber skeleton, an inorganic filling slurry coated on the fiber skeleton, and a porous polymer deposited on the surface of the glass fiber carrier; The fiber skeleton is prepared by hot pressing a corrugated glass fiber felt and a corrugated glass fiber mat; The corrugated glass fiber felt and the corrugated glass fiber mat are arranged in a laminated manner; The porous polymer deposited on the glass fiber surface is polyimide; The inorganic filling slurry is prepared from ammonium tungstate, ammonium paramolybdate, and anatase titanium dioxide.

2. The porous structure glass fiber carrier according to claim 1, wherein The preparation method of the inorganic filling slurry is as follows: A1. Add oxalic acid, ammonium tungstate, ammonium paramolybdate, and anatase titanium dioxide to deionized water, heat to 45 - 52 °C, stir evenly, dry, and then calcine in a muffle furnace to obtain compound A; A2. Grind compound A in a ball mill to fine powder, then mix it with solvent A and deionized water, and perform ultrasonic treatment for 10 - 15 min to obtain the inorganic filling slurry.

3. The porous structure glass fiber carrier according to claim 2, wherein The mass ratio of the deionized water, oxalic acid, ammonium tungstate, ammonium paramolybdate, and anatase titanium dioxide in A1 is 55 - 60:12 - 15:5.5 - 8:2.4 - 3.5:27 - 30.

4. The porous structure fiberglass carrier according to claim 2, wherein The drying temperature in A2 is 70 - 80 °C; The calcination temperature is 520 - 550 °C and the time is 3 - 4 h.

5. The porous structure fiberglass carrier according to claim 2, wherein The mass ratio of compound A, solvent A, and deionized water in A2 is 18 - 25:8 - 13:65 - 75.

6. The porous structure fiberglass carrier according to claim 2, characterized in that, Solvent A in A2 is obtained by mixing tetraethyl orthosilicate, polyvinyl alcohol, tetrabutyl titanate, silica sol, aluminum sulfate, and deionized water in a mass ratio of 3 - 5:3 - 5:2 - 3:80 - 90:9 - 12:10 - 15.

7. The preparation method of the porous structure glass fiber carrier according to any one of claims 1-6, characterized in that, It includes the following steps: S1. Take 30 pieces each of a pre - cut corrugated glass fiber felt and a corrugated glass fiber mat with a size of 50 * 50 mm, stack them layer by layer in the order of one layer of corrugated glass fiber mat and one layer of corrugated glass fiber felt to form a cubic structure to obtain the fiber skeleton; S2. Place the fiber skeleton in an immersion tank filled with the inorganic filling slurry, soak for 9 - 13 min, take out the fiber skeleton and dry it, and then calcine it in a muffle furnace to obtain a modified fiber skeleton; S3. Place the modified fiber skeleton in a quartz tube, place the quartz tube on the side wall of a solution box filled with solvent B, then place the solution box on the surface of a water tank filled with deionized water, and then take out the modified fiber skeleton from the quartz tube and immerse it in the water tank for 1 - 3 min to obtain a porous - structured glass fiber carrier.

8. The preparation method of the porous structure glass fiber carrier according to claim 7, characterized in that, The drying temperature in S2 is 105 - 115 °C; The calcination includes a first calcination, heat preservation, and a second calcination; The heating rate during the first calcination is 1.5 - 2.5 °C / min, calcine to 280 °C, and the calcination time is 1 - 1.5 h; The heat preservation temperature is 280 °C and the heat preservation time is 1 - 1.5 h; The heating rate during the second calcination is 3 - 4 °C / min, calcine to 500 °C, and the calcination time is 2 - 3 h.

9. The preparation method of the porous structure glass fiber carrier according to claim 7, characterized in that, The preparation method of solvent B in S3 is as follows: Mix polyimide and N,N - dimethylacetamide, heat and stir, then add isopropanol, and continue to stir until dissolved to obtain solvent B.

10. The preparation method of the porous structure glass fiber carrier according to claim 9, characterized in that, The mass ratio of the polyimide, N,N-dimethylacetamide and isopropanol is 16-22:70-80:4.3-5; The temperature during heating and stirring is 85-95 °C, the stirring rate is 130-170 r / min, and the stirring time is 12-17 min.