CN114130376B - Paper-based composite adsorption material and preparation method and application thereof - Google Patents
Paper-based composite adsorption material and preparation method and application thereof Download PDFInfo
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- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
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Abstract
The invention discloses a paper-based composite adsorption material and a preparation method and application thereof. The paper-based composite adsorption material is of a sandwich structure and comprises a lower fiber layer, a middle fiber + adsorbent composite layer and an upper fiber layer which are sequentially stacked; the adsorbent and the fiber in the fiber + adsorbent composite layer are uniformly dispersed. The paper-based composite adsorption material has the bursting strength of 302kPa, the filtering speed is high at normal temperature, the medium loss factor is reduced to 0.00449 percent and the volume resistivity is increased to 983.4 multiplied by 10 percent after the old transformer oil of a certain power supply department is filtered by the paper-based composite adsorption material at normal temperature 9 Omega · m is far superior to the specified index of GB/T5654-2007, and compared with the adsorption filtration performance of the commercial adsorption filtration plate, the adsorption filtration performance is obviously improved. Therefore, the paper-based composite adsorption material has a great potential application prospect in the field of transformer oil purification.
Description
Technical Field
The invention relates to the field of regeneration of waste transformer oil, in particular to a paper-based composite adsorption material for regenerating transformer oil at normal temperature and a preparation method thereof.
Background
The transformer is widely applied in the power industry as indispensable equipment in the power transmission link, and the transformer oil with the functions of cooling, arc extinction and insulation is known as the 'blood' of the transformer and mainly comprises a plurality of hydrocarbon compounds such as alkane, cyclane, aromatic hydrocarbon and the like. However, due to the introduction of various impurities including moisture, mechanical impurities, easily soluble organic small molecules and the like in the production, transportation and use processes of the transformer oil, the insulating property of the transformer oil is remarkably deteriorated, so that transformer equipment is damaged, and transformer accidents are caused.
The treatment method of the degraded transformer oil mainly comprises a filtering method and an adsorption method. The filtration method mainly utilizes the interception effect of a compact pore channel of filter paper to filter the transformer oil, thereby realizing the removal of free moisture, mechanical particles and colloid impurities. The transformer oil with high aging degree contains a large amount of organic micromolecular impurities, and the organic micromolecular impurities in the transformer oil cannot be removed by the interception effect of the filter paper. The adsorption method mainly utilizes strong interaction between the adsorption material and the organic small molecular impurities to selectively and efficiently remove the organic small molecular impurities, and has attracted extensive attention due to low cost and wide treatment range, but has the problems of large resistance, difficult cleaning of filter elements and the like.
At present, a composite filter plate combining a filtering method and an adsorption method is applied to the field of transformer oil purification, and the preparation method comprises the steps of attaching a powdery adsorption material onto cotton fibers, placing the cotton fibers between two layers of industrial oil filter paper, and finally sewing the edges to obtain the adsorption filter plate. Chinese patent No. CN 2312751Y discloses an adsorption filter plate, which is prepared by attaching activated clay and activated alumina on expanded collodion, and then packaging with fine filter paper, coarse filter paper and nylon gauze. After being filtered by the adsorption filter plate, the breakdown voltage of the transformer oil can reach more than 65kV, and the dielectric loss is reduced to be less than 0.2%. However, the adsorption filter plate contains the adsorption material attached to the cotton fibers, the particle size of the adsorption material is too small, the adsorption material is easy to agglomerate, and the edge seaming part has partial gaps, so that the adsorption filter plate has the problems of large filtration resistance, low purification efficiency and easy loss of the adsorption material from the seaming and packaging part. In addition, the viscosity and the surface tension of the transformer oil are generally reduced by adopting a heating mode at present, so that the adsorption filtration is facilitated, but the energy consumption is high, and the aging of the transformer oil is easily aggravated by the temperature rise. Therefore, research and development of a novel paper-based composite adsorption material for transformer oil regeneration at normal temperature are urgently needed, the paper-based composite adsorption material has a filtering and adsorbing function, the preparation process route is simple, the purification efficiency is high, and the filtering speed at normal temperature is high.
Disclosure of Invention
The invention aims to provide a paper-based composite adsorption material and a preparation method and application thereof aiming at the defects of the prior art. The paper-based composite adsorption material has the functions of filtration and adsorption, the bursting strength can reach 302kPa, the filtration speed is high at normal temperature, the medium loss factor is reduced to 0.00449 percent and the volume resistivity is increased to 983.4 multiplied by 10 percent after the old transformer oil of a certain power supply office is filtered by the paper-based composite adsorption material at normal temperature 9 Omega.m is far superior to the specified index of GB/T5654-2007, and the adsorption filtration performance of the filter plate is far superior to that of a commercial adsorption filter plate.
The purpose of the invention is realized by the following technical scheme.
The paper-based composite adsorption material is of a sandwich structure and comprises a lower fiber layer, a middle fiber + adsorbent composite layer and an upper fiber layer which are sequentially stacked; the adsorbent and the fiber in the fiber + adsorbent composite layer are uniformly dispersed.
Preferably, the adsorbent is a combination of activated carbon, silica gel and a metal organic framework material; wherein the dosage of the active carbon is 140g/m 2 ～200g/m 2 More preferably 160g/m 2 (ii) a The dosage of the silica gel is 80g/m 2 ～120g/m 2 More preferably 100g/m 2 (ii) a The dosage of the metal organic framework material is 20g/m 2 ～40g/m 2 More preferably 24g/m 2 。
Preferably, in the adsorbent, the activated carbon is at least one of coconut shell activated carbon, coal-based activated carbon and wood-based activated carbon, and more preferably the coal-based activated carbon and the wood-based activated carbon in a mass ratio of 1; the silica gel is at least one of column chromatography silica gel and decolorizing silica gel, and further preferably decolorizing silica gel; the metal organic framework material is at least one of MIL-101, UIO-66 and ZIF-8, and is more preferably ZIF-8.
Preferably, the mesh number of the adsorbent is 50 to 200. Mu.m, and more preferably 80 to 100. Mu.m.
Preferably, a layer of adhesive is uniformly coated on the surface of the paper-based composite adsorption material.
Preferably, the adhesive is a mixture of cationic polyacrylamide, polyamide epichlorohydrin resin and water-soluble phenolic resin; wherein, the dosage of the cationic polyacrylamide, the polyamide epichlorohydrin resin and the water-soluble phenolic resin is respectively 0.5-2 wt%, 5-10 wt%, and more preferably 1wt%, and 8wt% of the total dry weight of the fiber.
The preparation method of the paper-based composite adsorption material comprises the following steps:
(1) Soaking the fiber in an oxidizing solution, filtering, washing, then defibering and dispersing, then adding an adsorbent, uniformly mixing, and pouring the mixed solution into a paper sheet forming machine to prepare a fiber and adsorbent composite layer;
(2) Defibering and dispersing the fibers, and pouring the fiber slurry into a paper sheet forming machine to prepare a fiber layer;
(3) The fiber layer, the fiber + adsorbent composite layer and the fiber layer are sequentially attached to form a sandwich structure, and then an adhesive solution is uniformly coated on the surface of the sandwich structure to obtain a wet paper-based composite adsorption material;
(4) And (5) hot-pressing and molding the wet paper-based composite adsorption material, and drying to obtain a finished product.
Preferably, in the step (1), the types of the fibers are the combination of softwood pulp fibers, cotton linters and glass fibers, and the dosage of the fibers is 60g/m of the softwood pulp fibers respectively 2 ～100g/m 2 More preferably 80g/m 2 (ii) a Cotton linter 30g/m 2 ～50g/m 2 More preferably 40g/m 2 (ii) a Glass fiber 10g/m 2 ～20g/m 2 More preferably 15g/m 2 (ii) a The fibers are fluffed and dispersed until the beating degree is 20-40 DEG SR, and the preferable beating degree is 30 DEG SR.
Preferably, in the step (1), the oxidizing solution is at least one of hypochlorous acid, sodium hypochlorite and sodium bromide solution, and is further preferably sodium hypochlorite solution; the concentration of the oxidizing solution is 0.5 to 2mol/L, and more preferably 1mol/L.
Preferably, in the step (1), the impregnation temperature is 50-80 ℃, and more preferably 60 ℃; the impregnation time is 2 to 6 hours, and more preferably 4 hours.
Preferably, in the step (2), the type of the fibers is softwood pulp fibers, and the dosage is 80g/m 2 ～150g/m 2 More preferably 100g/m 2 (ii) a The fibers are fluffed and dispersed until the beating degree is 20-40 DEG SR, and the preferable beating degree is 30 DEG SR.
Preferably, in the step (1) and the step (2), the sheet forming machine has a forming size of a square with a side length of 10 to 30cm or a circle with a diameter of 10 to 30cm, and more preferably a square with a diameter of 20 × 20 cm.
Preferably, in the step (3), the adhesive solution is 10 to 30mL, and preferably 20mL.
Preferably, in the step (4), the temperature of the hot press molding is 80-100 ℃, and more preferably 90 ℃; the pressure is 0.5 to 1MPa, and more preferably 0.75MPa; the hot press molding time is 10 to 20min, and more preferably 15min.
Preferably, in the step (4), the drying temperature is 100 to 110 ℃, and the drying time is 3 to 8 hours, more preferably 105 ℃ and 5 hours.
The paper-based composite adsorption material is applied to regeneration of transformer oil at normal temperature.
The bursting strength of the paper-based composite adsorption material can reach more than 286kPa, the filtering speed is high at normal temperature, after old transformer oil of a certain power supply bureau is filtered by the paper-based composite adsorption material at normal temperature, the medium loss factor is reduced to be less than 0.00478%, and the volume resistivity is increased to 856.5 multiplied by 10 9 The adsorption filtration performance of the filter plate is obviously improved compared with that of a commercial adsorption filter plate.
Compared with the prior art, the invention has the following advantages and technical effects:
(1) The adsorbent powder in the commercial adsorption filter plate is attached to cotton fibers and is easy to partially agglomerate in the oil filtering process, so that a vacant area of an adsorption bed layer is generated, a fluid short circuit is easy to cause, and the adsorption efficiency of oil products is greatly reduced. The invention adopts the fiber and the adsorbent to form paper, the adsorbent is uniformly dispersed in the fiber paper, meanwhile, after the fiber is soaked in the oxidizing solution, the rich carboxyl sites on the surface and the adsorbing material form strong bonding cooperation force (such as chemical bonds, hydrogen bonds and the like), and the adsorbent in the paper-based composite adsorbing material is not easy to move and agglomerate in the oil filtering process, so the adsorption and purification efficiency is greatly improved.
(2) The paper-based composite adsorption material has a sandwich structure, the middle composite layer adsorbent adopts the combination of active carbon, silica gel and metal organic framework materials to efficiently adsorb various impurities such as metal ions, polar small molecules and the like in transformer oil, and the middle composite layer fiber adopts the combination of carboxylated softwood pulp fiber, cotton linter and glass fiber, so that the paper-based composite material is the most preferable material with high strength, large loading capacity and small resistance. The upper and lower pure fiber layers can prevent the middle composite layer adsorbent from falling off, and meanwhile, the compact fiber layers can effectively filter mechanical particles and colloid impurities to play a role in fine filtration.
(3) The paper-based composite adsorption material is formed by one-step papermaking of fibers and the adsorption material, and compared with the traditional commercial adsorption filter plate, the paper-based composite adsorption material has the advantages of simple preparation process, high filtration speed at normal temperature, no need of heating transformer oil, energy consumption reduction, avoidance of influence of temperature rise on aging of the transformer oil, and contribution to industrial popularization and application of products.
Drawings
FIG. 1 is a schematic structural diagram of a paper-based composite adsorption material prepared by the present invention.
FIG. 2 is a cross-sectional SEM representation of the paper-based composite adsorbent material prepared in the present invention.
FIG. 3 is a surface SEM representation of the paper-based composite adsorbent material prepared by the present invention.
FIG. 4 is a graph comparing the purification performance of a commercial adsorption filter plate with the paper-based composite adsorption materials of examples 1-4 of the present invention; wherein a is a dielectric loss factor comparison graph; b is a volume resistivity contrast chart.
FIG. 5 is a graph comparing the purification performance at room temperature of the paper-based composite adsorbent of example 1 and comparative examples 1 to 4.
FIG. 6 is a graph comparing the purification performance at room temperature of the paper-based composite adsorbent of example 1 and comparative examples 5 to 9.
Detailed Description
The invention is further described below with reference to the drawings and examples, but the scope of the invention as claimed is not limited to the scope of the examples.
Example 1
(1) 80g/m 2 Softwood pulp fibers of 40g/m 2 Of cotton linters and 15g/m 2 The glass fiber is soaked in 1mol/L sodium hypochlorite solution for 4 hours at the temperature of 60 ℃, filtered, washed, placed in a fluffer to be dispersed until the beating degree is 30 DEG SR, and then 80g/m of 80-100 mu m of particle size is added 2 Coal-based activated carbon 80g/m 2 Wood activated carbon, 100g/m 2 Decolorizing silica gel and 24g/m 2 Mixing ZIF-8, pouring the fiber slurry into a paper forming machine with the size of 20 multiplied by 20cm, and preparing a fiber and adsorbent composite layer for later use;
(2) 100g/m 2 The softwood pulp fibers are placed in a fluffer to be dispersed until the beating degree is 30 DEG SR, the fiber pulp is poured into a paper sheet forming machine with the size of 20 multiplied by 20cm to prepare fiber layers, and the preparation is repeated once to obtain two fiber layers for standby;
(3) The three layers of materials are laminated in sequence according to a fiber layer, a fiber + adsorbent composite layer and a fiber layer to form a sandwich structure, and then 20mL of adhesive solution is coated on the surface of the sandwich structure, wherein the dosage of the cationic polyacrylamide is 1wt% of the dry weight of the total fibers; the usage of the polyamide epichlorohydrin resin is 1wt% of the dry weight of the total fiber; the dosage of the water-soluble phenolic resin is 8wt% of the dry weight of the total fiber, so as to obtain the wet paper-based composite adsorption material;
(4) And hot-pressing the wet paper-based composite adsorption material at 90 ℃ and 0.75MPa for 15min for forming, and drying at 105 ℃ for 5h to obtain a finished product.
Example 2
(1) The mixing ratio is 100g/m 2 Softwood pulp fibers of 50g/m 2 And cotton linters of 15g/m 2 The glass fiber is soaked in 0.5mol/L hypochlorous acid solution for 2 hours at the temperature of 50 ℃, filtered, washed, placed in a fluffer to be dispersed until the beating degree is 20 DEG SR, and then 160g/m with the particle size of 50-100 mu m is added 2 Coal-based activated carbon of 100g/m 2 Silica gel column chromatography and 20g/m 2 UIO-66, pouring the fiber slurry into a paper forming machine with the size of 20 multiplied by 20cm, and preparing a fiber and adsorbent composite layer for later use;
(2) 80g/m 2 The softwood pulp fibers are placed in a fluffer to be dispersed until the beating degree is 40 DEG SR, the fiber pulp is poured into a paper sheet forming machine with the size of 20 x 20cm, a fiber layer is prepared, and two fiber layers are obtained by repeating the steps for standby;
(3) The three layers of materials are laminated in sequence according to a fiber layer, a fiber + adsorbent composite layer and a fiber layer to form a sandwich structure, and then 30mL of adhesive solution is coated on the surface of the sandwich structure, wherein the dosage of the cationic polyacrylamide is 0.5wt% of the dry weight of the total fibers; the dosage of the polyamide epichlorohydrin resin is 1.2wt% of the dry weight of the total fiber; the dosage of the water-soluble phenolic resin is 5wt% of the dry weight of the total fiber, so as to obtain the wet paper-based composite adsorption material;
(4) And (3) hot-pressing the wet paper-based composite adsorption material at 80 ℃ and 0.5MPa for 10min for molding, and drying at 100 ℃ for 3h to obtain a finished product.
Example 3
(1) 60g/m 2 Softwood pulp fibers of 40g/m 2 Of cotton linters and 20g/m 2 The glass fiber is soaked in 0.8mol/L sodium bromide solution for 4 hours at the temperature of 50 ℃, filtered, washed, placed in a fluffer to be dispersed until the beating degree is 40 DEG SR, and then 200g/m of particles with the size of 150-200 mu m is added 2 Coconut shell activated carbon, 80g/m 2 Column chromatography silica gel and 40g/m 2 UIO-66, pouring the fiber slurry into a paper sheet forming machine with the size of 20 multiplied by 20cm, and preparing a fiber and adsorbent composite layer for later use;
(2) The mixing ratio is 100g/m 2 The softwood pulp fibers are placed in a fluffer to be dispersed until the beating degree is 30 DEG SR, and the fiber pulp is poured into a paper forming machine with the size of 20 multiplied by 20cmPreparing a fiber layer, and repeating the steps once to obtain two fiber layers for later use;
(3) The three layers of materials are laminated in sequence according to a fiber layer, a fiber + adsorbent composite layer and a fiber layer to form a sandwich structure, and then 20mL of adhesive solution is coated on the surface of the sandwich structure, wherein the dosage of the cationic polyacrylamide is 2wt% of the dry weight of the total fibers; the usage amount of the polyamide epichlorohydrin resin is 2wt% of the dry weight of the total fiber; the dosage of the water-soluble phenolic resin is 6wt% of the dry weight of the total fiber, so as to obtain the wet paper-based composite adsorption material;
(4) And hot-pressing the wet paper-based composite adsorption material at 100 ℃ and 1MPa for 15min for forming, and drying at 110 ℃ for 3h to obtain a finished product.
Example 4
(1) 70g/m 2 Softwood pulp fibers of 40g/m 2 Of cotton linters and 10g/m 2 The glass fiber is soaked in 2mol/L sodium hypochlorite solution for 6 hours at the temperature of 80 ℃, filtered, washed, placed in a fluffer to be dispersed until the beating degree is 35 DEG SR, and then 140g/m with the particle size of 50-100 mu m is added 2 Coal-based activated carbon of 120g/m 2 Decolorized silica gel and 20g/m 2 MIL-101, pouring the fiber slurry into a paper forming machine with the size of 20 multiplied by 20cm, and preparing a fiber and adsorbent composite layer for later use;
(2) 150g/m 2 The softwood pulp fibers are placed in a fluffer to be dispersed until the beating degree is 20 DEG SR, the fiber pulp is poured into a paper sheet forming machine with the size of 20 multiplied by 20cm to prepare fiber layers, and the preparation is repeated once to obtain two fiber layers for standby;
(3) The three layers of materials are laminated in sequence according to a fiber layer, a fiber + adsorbent composite layer and a fiber layer to form a sandwich structure, and then 10mL of adhesive solution is coated on the surface of the sandwich structure, wherein the dosage of the cationic polyacrylamide is 0.5wt% of the dry weight of the total fibers; the usage amount of the polyamide epichlorohydrin resin is 0.5wt% of the dry weight of the total fiber; the dosage of the water-soluble phenolic resin is 10wt% of the dry weight of the total fiber, so as to obtain the wet paper-based composite adsorption material;
(4) And (3) hot-pressing the wet paper-based composite adsorption material at 90 ℃ and 0.5MPa for 20min for molding, and drying at 100 ℃ for 8h to obtain a finished product.
Comparative example 1
The adsorbent with the same type and quality as those in the example 1, the particle size of 80-100 meshes, 3.2g of coal-based activated carbon, 3.2g of wood-based activated carbon, 4g of decolorizing silica gel and 0.96g of ZIF-8 are mixed, directly added into 300mL of old transformer oil, stirred and soaked for 15min at normal temperature and then filtered, and the dielectric loss factor and the volume resistivity of the transformer oil are tested.
Comparative example 2
The adsorbent mixed in the paper-based composite adsorption material is 284g/m 2 The other steps of the preparation of the coal-based activated carbon of (1) were the same as those of example 1.
Comparative example 3
The adsorbent mixed in the paper-based composite adsorption material is 284g/m 2 The procedure of the preparation of the decolorized silica gel was the same as in example 1.
Comparative example 4
The adsorbent mixed in the paper-based composite adsorption material is 284g/m 2 The other preparation steps of ZIF-8 were the same as in example 1.
Comparative example 5
(1) 80g/m 2 Softwood pulp fibers of 40g/m 2 And cotton linters of 15g/m 2 The glass fiber is soaked in 1mol/L sodium hypochlorite solution for 4 hours at the temperature of 60 ℃, filtered, washed, placed in a fluffer to be dispersed until the beating degree is 30 DEG SR, and then 80g/m of 80-100 mu m of particle size is added 2 Coal-based activated carbon 80g/m 2 Wood activated carbon, 100g/m 2 Decolorizing silica gel and 24g/m 2 ZIF-8, pouring the fiber slurry into a paper sheet forming machine with the size of 20 multiplied by 20cm, and preparing a fiber and adsorbent composite layer for later use;
(2) Coating 20mL of adhesive solution on the surface of the fiber and adsorbent composite layer, wherein the dosage of the cationic polyacrylamide is 1wt% of the dry weight of the total fiber; the usage amount of the polyamide epichlorohydrin resin is 1wt% of the dry weight of the total fiber; the dosage of the water-soluble phenolic resin is 8wt% of the dry weight of the total fiber, so as to obtain the wet paper-based composite adsorption material;
(3) And hot-pressing the wet paper-based composite adsorption material at 90 ℃ and 0.75MPa for 15min for forming, and drying at 105 ℃ for 5h to obtain a finished product.
Comparative example 6
The cationic polyacrylamide, the polyamide epichlorohydrin resin and the water-soluble phenol resin were used in amounts of 0.3wt%, 4wt%, respectively, based on the total fiber, and other preparation steps were the same as in example 1.
Comparative example 7
The cationic polyacrylamide, the polyamide epichlorohydrin resin and the water-soluble phenol resin were used in amounts of 3wt%, 3wt% and 12wt%, respectively, based on the total fiber, and the other preparation steps were the same as in example 1.
Comparative example 8
The cationic polyacrylamide, the polyamide epichlorohydrin resin and the water-soluble phenol resin were used in amounts of 0.3wt%, 0.3wt% and 12wt%, respectively, based on the total fiber, and the other preparation steps were the same as in example 1.
Comparative example 9
The cationic polyacrylamide, the polyamide epichlorohydrin resin and the water-soluble phenol resin were used in amounts of 3wt%, 3wt% and 4wt%, respectively, based on the total fiber, and the other preparation steps were the same as in example 1.
Scanning Electron Microscope (SEM) analysis
SEM adopts JEC JEOL JSM-35C Scanning Microscope manufactured by Nissan electric company, and the working conditions of the Scanning electron Microscope are as follows: acceleration voltage 10kV and vacuum degree 10 -5 Pa。
FIG. 1 is a schematic structural diagram of the paper-based composite adsorption material prepared by the invention, which is a sandwich structure, the middle of the paper-based composite adsorption material is a composite layer of fiber and the adsorption material, and the upper layer and the lower layer are compact fiber fine filtration layers. Fig. 2 is a cross-sectional SEM characterization diagram of the paper-based composite adsorption material prepared by the present invention, and it can be seen from fig. 2 that there is no significant gap between layers after the paper-based composite adsorption material with 3-layer structure is subjected to bonding, hot pressing, and drying treatment, which indicates that the interlayer composite state is good and the lamination is not easy to occur during transformer oil purification. Fig. 3 is a surface SEM representation of the paper-based composite adsorbent material prepared by the present invention, and it can be seen from fig. 3 that the fiber surface has filiform bonds formed by adhesives, which is the main reason for its high burst strength, and meanwhile, the pure fiber layer surface has no adsorbent material. The paper-based composite adsorption material disclosed by the invention has the advantages that the adsorbent is not easy to run off under the coverage of the outer pure fiber layer, secondary pollution to transformer oil is avoided, and the paper-based composite adsorption material has practical application value.
Filter performance test
Commercial adsorption filter plates of Shenyang Sida filter plate factory, paper-based composite adsorption materials of examples 1-4 and comparative examples 2-9 were fixed on a 20X 20cm suction head, and 300mL old transformer oil from a power supply bureau was filtered through filter paper for performance test. The test conditions were as follows: the system temperature is room temperature, and the vacuum degree of the oil pump is 0.1MPa. And then the purification performance of the paper-based composite adsorption material is evaluated through the filtration time and the insulation performance parameters of the filtered transformer oil.
TABLE 1
| Normal temperature filtration time | Total mass of adsorbent | Total mass of fiber | |
| Commercial adsorption filter plate | 30min | 50g | 20g |
| Example 1 | 72s | 11.36g | 13.4g |
| Example 2 | 78s | 11.2g | 14.6g |
| Example 3 | 78s | 12.8g | 12.8g |
| Example 4 | 78s | 11.2g | 14g |
Table 1 is a table comparing the filtration time and the amount of raw materials used for commercial adsorption filter plates and the paper-based composite adsorption materials of examples 1-4. Fig. 4 is a graph comparing the purification performance at normal temperature of a commercial adsorption filter plate and the paper-based composite adsorption materials of examples 1 to 4, in which the dielectric loss factor and the volume resistivity of the transformer oil were measured by the BURA dielectric tester. From the results, it can be seen that the paper-based composite adsorption material of the present invention has excellent filtration performance, and the filtration time is much shorter than that of a commercial adsorption filter plate, and the amount of the adsorbent and the fiber used per unit area is less than that of the commercial adsorption filter plate, which is mainly attributed to the optimization of the formulation of the adsorbent and the optimization of the particle size of the adsorbent. After the purification of the paper-based composite adsorbing material in the embodiment 1, the dielectric loss factor is reduced to 0.00449 percent, and the volume resistivity reaches 983.4 multiplied by 10 9 Omega.m. The purifying performance of the paper-based composite adsorbing material is obviously superior to that of a commercial adsorbing filter plate and is far higher than GB/T5654-2007 standard (the dielectric loss factor is lower than 0.5%, and the volume resistivity is higher than 60 multiplied by 10) 9 Ω·m)。
FIG. 5 is a graph comparing the purification performance at room temperature of the paper-based composite adsorbent of example 1 and comparative examples 1 to 4. As can be seen from fig. 5, comparative example 1, in which the purification performance was decreased without using the adsorbent directly but forming the paper, fully demonstrates that the filtration of the fibers after the paper base composite forming also increases the purification performance. Comparative examples 2 to 4 use single materials of active carbon, silica gel and metal organic framework materials, and the purification performance of the single materials is lower than that of the single materials after the single materials are molded by papermaking, which is mainly attributed to the differential adsorption of the three materials on various impurities in the transformer oil, so that the purification effect of the three materials is greatly improved.
TABLE 2
| Example 1 | Comparative example 5 | |
| Volume resistivity x 10 10 (Ω·m) | 98.34 | 5.23 |
| Dielectric loss factor x 10 -2 (％) | 0.449 | 15.21 |
Comparative example 5 is a paper-based composite adsorbent material without upper and lower layers of fibers, and the other conditions are the same as in example 1. As can be seen from table 2, compared to the paper-based composite adsorbent material of example 1, the volume resistivity of the paper-based composite adsorbent material without the upper and lower fibers is significantly reduced, and the dielectric loss factor is very high. When the upper and lower layers of fibers are absent, a small amount of adsorbing materials in the composite layer fall off in the transformer oil, and the compact structure of the pure fiber layer can play a fine filtration role, so that the purification performance of the paper-based composite adsorbing materials without the upper and lower layers of fibers is greatly reduced.
FIG. 6 is a graph comparing the purification performance at room temperature of the paper-based composite adsorbent of example 1 and comparative examples 6 to 9. As can be seen from FIG. 6, the cleaning performance of the paper-based composite adsorption material obtained by adding less adhesive in comparative example 6 is not much different from that of the paper-based composite adsorption material obtained in example 1, while the cleaning performance of the paper-based composite adsorption material obtained by adding more adhesive in any kind in comparative examples 7-9 is greatly reduced.
Burst test
In the actual working condition of transformer oil purification, in order to increase the filtering speed, the filtering instrument usually applies a pressure of 0.1-0.3 MPa to the outside, so that the filtering material needs to have higher strength in order to prevent the filtering material from being damaged and losing the purification effect.
TABLE 3
| Examples | Example 1 | Example 2 | Example 3 | Example 4 | |
| Burst strength (kPa) | 302 | 295 | 286 | 287 | |
| Comparative example | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 |
| Burst strength (kPa) | 236 | 253 | 286 | 263 | 267 |
The bursting strength test results of the paper-based composite adsorbing materials in the examples 1 to 4 and the comparative examples 5 to 9 are shown in table 3, the bursting strength of the paper-based composite adsorbing materials in the examples can reach 302kPa at most, and the bursting strength requirements under common filtering working conditions are met (the bursting strength is not less than 265kPa in Q/SZR01 to 2018). Compared with the prior art, the bursting strength of the paper-based composite adsorption material is greatly reduced when the upper and lower layers of fibers are absent in the comparative example 5, so that the overall strength is greatly improved by the upper and lower layers of fibers, and the supporting effect is achieved. The burst strength of the paper-based composite adsorbent material to which the binder of the example was added was greatly reduced by adding less binder in comparative example 6, and thus the type and amount of the binder of the present invention were the most preferable for the comprehensive evaluation of strength and cleaning performance.
Claims (7)
1. The paper-based composite adsorption material is characterized in that the paper-based composite adsorption material is of a sandwich structure and comprises a lower fiber layer, a middle fiber + adsorbent composite layer and an upper fiber layer which are sequentially stacked; the adsorbent and the fibers in the fiber + adsorbent composite layer are uniformly dispersed;
a layer of adhesive is uniformly coated on the surface of the paper-based composite adsorption material;
the adhesive is a mixture of cationic polyacrylamide, polyamide epichlorohydrin resin and water-soluble phenolic resin; wherein the dosage of the cationic polyacrylamide, the dosage of the polyamide epichlorohydrin resin and the dosage of the water-soluble phenolic resin are respectively 0.5 to 2wt%, 0.5 to 2wt% and 5 to 10wt% of the dry weight of the total fiber;
the adsorbent is a combination of activated carbon, silica gel and a metal organic framework material;
the fiber of the middle layer adopts the combination of carboxylated softwood pulp fiber, cotton linter and glass fiber.
2. The paper-based composite adsorption material according to claim 1, wherein in the adsorbent, the activated carbon is at least one of coconut shell activated carbon, coal-based activated carbon and wood-based activated carbon, the silica gel is at least one of column chromatography silica gel and decolorizing silica gel, and the metal organic framework material is at least one of MIL-101, UIO-66 and ZIF-8; in the fiber + adsorbent composite layer, the dosage of the active carbon is 140g/m 2 ~200 g/m 2 The dosage of the silica gel is 80g/m 2 ~120 g/m 2 The dosage of the metal organic framework material is 20g/m 2 ~40 g/m 2 (ii) a The particle size of the adsorbent is 50-200 mu m.
3. A method of making a paper-based composite adsorbent material according to any one of claims 1-2, comprising the steps of:
(1) Soaking the fiber in an oxidizing solution, filtering, washing, then defibering and dispersing, then adding an adsorbent, uniformly mixing, and pouring the mixed solution into a paper sheet forming machine to prepare a fiber and adsorbent composite layer;
(2) Defibering and dispersing the fibers, and pouring the fiber slurry into a paper sheet forming machine to prepare a fiber layer;
(3) The fiber layer, the fiber + adsorbent composite layer and the fiber layer are sequentially attached to form a sandwich structure, and then an adhesive solution is uniformly coated on the surface of the sandwich structure to obtain a wet paper-based composite adsorption material;
(4) And (5) hot-pressing and molding the wet paper-based composite adsorption material, and drying to obtain a finished product.
4. The production method according to claim 3, wherein in the step (1), the kind of the fiber is a combination of softwood pulp fiber, cotton linter and glass fiber; in the fiber and adsorbent composite layer, the dosage of the softwood pulp fiber is 60g/m 2 ~100 g/m 2 The dosage of the cotton linters is 30g/m 2 ~50 g/m 2 The dosage of the glass fiber is 10g/m 2 ~20 g/m 2 (ii) a The fibers are loosened and dispersed until the beating degree is 20 to 40 DEG SR; the oxidizing solution is at least one of hypochlorous acid, sodium hypochlorite and sodium bromide solution; the concentration of the oxidizing solution is 0.5 to 2 mol/L; the temperature of the impregnation is 50 to 80 ℃; the dipping time is 2 to 6 hours.
5. The method according to claim 3, wherein in the step (2), the type of the fibers is softwood pulp fibers, and the amount of the fibers in the fiber layer is 80g/m 2 ~150 g/m 2 (ii) a The fibers are loosened and dispersed until the beating degree is 20 to 40 DEG SR; in the step (1) and the step (2), the forming size of the paper sheet forming machine is a square with the side length of 10-30 cm or a circle with the diameter of 10-30 cm.
6. The preparation method according to claim 3, wherein in the step (4), the hot press molding is carried out at a temperature of 80 to 100 ℃, under a pressure of 0.5 to 1MPa, and for a time of 10 to 20 min; the drying temperature is 100 to 110 ℃, and the drying time is 3 to 8 hours.
7. Use of a paper-based composite adsorbent material according to any one of claims 1-2 for regenerating transformer oil at room temperature.
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