A glass fiber water purifying agent and its application

Abstract

The present invention provides a glass fiber water purifying agent and its application. The glass fiber water purifying agent comprises the following components by weight parts: CaAl@C 70 15 - 25 parts of core - shell material, 15 - 25 parts of calcium fluoride crystal nuclei, 10 - 20 parts of calcium ion suspension, 10 - 25 parts of aluminum ion aging reagent, and 1 - 3 parts of anionic polyacrylamide; the calcium ion suspension comprises calcium hydroxide and calcium chloride, and the aluminum ion aging reagent comprises polyaluminum chloride and aluminum sulfate; CaAl@C 70 The preparation method of the core - shell material is as follows: S1. Put 0.2 mol of organic acid, 0.04 mol of CaO, 0.04 mol of Al2O3 and 1 L of C 70 saturated solution into a glass tube, displace the air in the tube with nitrogen to obtain a sealed tube; S2. Put the sealed tube obtained in S1 into an oven, heat it to 210 - 225 °C, keep it for 50 - 90 h, and then cool it to room temperature at a rate of 8 °C / h; S3. Filter the solid product in the glass tube, and then rinse it 3 times with the organic solvent for preparing C 70 saturated solution, and dry it to obtain CaAl@C 70 core - shell material. The glass fiber water purifying agent of the present invention has strong adaptability to the treatment of different types of glass fiber wastewater and strong comprehensive ability to remove COD, SS and fluoride ions.

Description

Technical Field

[0001] The present invention belongs to the technical field of wastewater treatment, and particularly relates to a glass fiber water purifying agent and its application. Background Art

[0002] The wastewater generated in the production process of the glass fiber industry mainly includes the sizing agent flushing water discharged during the wire drawing process, the binder-containing flushing water in the felt-making process, a small amount of resin-containing wastewater discharged in the production of fiberglass, and suspended substances such as fine glass fibers. The sizing agent-containing wastewater discharged from the wire drawing workshop accounts for about 80%-90% of the fiberglass wastewater. Therefore, the wire drawing wastewater is the main pollution source of the fiberglass industrial wastewater.

[0003] The main components of the sizing agent are epoxy emulsion, polyurethane lactic acid, lubricants, antistatic agents, various coupling agents, etc. Except for the solvent, most of them are high-molecular organic substances with high thermal stability and poor water solubility, and their properties are related to the types of sizing agents contained. Usually, the sizing agents can be divided into three categories: starch type, reinforcing type, and paraffin type. The chemical compositions of these three types of sizing agents vary greatly. Even for the same type of sizing agent, due to different uses of the products, the chemical composition formulations also have great differences. Summarizing the chemical compositions of various sizing agent formulations, the following types of substances can be classified:

[0004] (1) Oils: mainly include paraffin, stearic acid, vaseline, machine oil, etc. These oily substances are all solid organic substances insoluble in water at room temperature. In the paraffin sizing agent formulation, the oily substances account for more than 50% of the total solid content. In the other two types of sizing agents, the content of solid organic substances is also relatively high.

[0005] (2) Emulsifiers: A certain amount of emulsifiers are added to various sizing agents. There are many types of emulsifiers, which vary with the uses of the sizing agents. Most of these emulsifiers contain surface active substances, including ionic and non-ionic types. Almost most of the sizing agents contain surfactants.

[0006] (3) Water-soluble organic substances: There are many types of water-soluble organic substances in the fiberglass wire drawing wastewater, including various coupling agents and film-forming agents, such as soluble epoxy resin, water-soluble polyester resin, soluble starch, etc. The content of water-soluble organic substances varies greatly in different types of sizing agents. Among them, the content of soluble organic substances in the starch type sizing agent wastewater is the highest, followed by the reinforcing type, and the paraffin type is the smallest.

[0007] (4) Toxic substances: mainly formaldehyde, which is usually released from the color fixing agent. The color fixing agent accounts for a large proportion in the paraffin type sizing agent, so formaldehyde is one of the pollutants in the wire drawing wastewater. The wastewater also contains a small amount of glass fibers and residues. The above several types of substances are the main pollutants in the fiberglass wire drawing wastewater, and most of them are high-molecular organic substances with high thermal stability and poor water solubility.

[0008] The glass fiber drawing wastewater is an organic wastewater. However, due to the different types of sizing agents, the characteristics shown are quite different. The BOD5 / COD Cr value can be used to judge its biodegradability. The starch-type glass fiber wastewater has good biodegradability, and its BOD5 / COD Cr is about 0.5 - 0.25; for the enhanced wastewater, the BOD5 / COD Cr is about 0.22 - 0.1; for the paraffin-type wastewater, the BOD5 / COD Cr is about 0.08 - 0.45. According to the generally accepted biodegradability identification data at home and abroad: BOD5 / COD Cr >0.45 indicates good biodegradability; BOD5 / COD Cr >0.3 means it can be biodegraded; BOD5 / COD Cr <0.3 means it is difficult to be biodegraded; BOD5 / COD Cr <0.25 means it is very difficult to be biodegraded. It is not difficult to see that the starch-type is relatively easy to be biochemically treated, the enhanced type is the second, and the paraffin-type is difficult to be biochemically treated.

[0009] The existing water purification agents have unstable treatment effects on different types and batches of glass fiber wastewater, and the removal rates of suspended solids, COD, SS, and fluoride ions in water all need to be improved. Summary of the Invention

[0010] To solve the problems existing in the background technology, the present invention provides a glass fiber water purification agent and its application to improve the treatment adaptability to different types of glass fiber wastewater and enhance the comprehensive ability to remove COD, SS, and fluoride ions.

[0011] To achieve the above object, the present invention provides the following technical solutions:

[0012] A glass fiber water purification agent, by weight, comprises the following components: CaAl@C 70 core-shell material 15 - 25 parts, calcium fluoride crystal nucleus 15 - 25 parts, calcium ion suspension 10 - 20 parts, aluminum ion curing reagent 10 - 25 parts, and anionic polyacrylamide 1 - 3 parts; the calcium ion suspension comprises calcium hydroxide and calcium chloride, and the aluminum ion curing reagent comprises polyaluminum chloride and aluminum sulfate;

[0013] The preparation method of the CaAl@C 70 core-shell material is as follows:

[0014] S1. Put 0.2 mol of organic acid, 0.04 mol of CaO, 0.04 mol of Al2O3, and 1 L of C 70 saturated solution into a glass tube, displace the air in the tube with nitrogen to obtain a sealed tube;

[0015] S2. Put the sealed tube obtained in S1 into an oven, heat it to 210 - 225 °C, keep it for 50 - 90 h, and then cool it to room temperature at a rate of 8 °C / h;

[0016] S3. Filter the solid product in the glass tube, and then rinse it 3 times with the organic solvent for preparing saturated solution C 70 and dry it to obtain the CaAl@C 70 core - shell material.

[0017] Furthermore, the preparation method of the calcium fluoride crystal nuclei is as follows: Sodium fluoride and calcium chloride are configured into a saturated solution according to a molar ratio of 2:1, and reacted at a stirring intensity of 200 s -1 for 60 minutes, then filtered to obtain crystals, and dried at 120 °C for 2 hours to obtain the calcium fluoride crystal nuclei.

[0018] Furthermore, the preparation method of the calcium ion suspension is as follows: Calcium hydroxide and calcium chloride are mixed according to an equal weight ratio, and water is added and stirred until a suspension is obtained, thus obtaining the calcium ion suspension.

[0019] Furthermore, the preparation method of the aluminum ion aging reagent is as follows: Poly aluminum chloride and aluminum sulfate are mixed according to an equal weight ratio, water is added at room temperature, and stirred at a rotation speed of 100 - 150 r / min for 2 - 5 days to obtain the aluminum ion aging reagent.

[0020] Furthermore, the organic solvent for preparing saturated solution C 70 is chlorobenzene and / or toluene.

[0021] Furthermore, the organic acid is tartaric acid and / or glutaric acid.

[0022] The application of a glass fiber water purifying agent, the glass fiber water purifying agent is the above - mentioned glass fiber water purifying agent, and is used for treating glass fiber wastewater, including the steps:

[0023] A1. Add the CaAl@C 70 core - shell material and calcium fluoride crystal nuclei into mixing tank 1, stir, and keep the reagent for 4 to 8 min;

[0024] A2. Intercept the CaAl@C 70 core - shell material and calcium fluoride crystal nuclei from the wastewater discharged from mixing tank 1 through a filter, and replenish them back to mixing tank 1;

[0025] A3. Discharge the wastewater into mixing tank 2, add the calcium ion suspension, stir, and keep the reagent for 10 to 20 min;

[0026] A4. Discharge the wastewater into mixing tank 3, add the aluminum ion aging reagent and anionic polyacrylamide, stir, and keep the reagent for 5 to 10 min;

[0027] A5. The wastewater enters the sedimentation area for sediment - water separation.

[0028] Further, the stirring intensity in mixing tank 1 is 250 - 350 s -1 ; the stirring intensity in mixing tank 2 is 250 - 350 s -1 ; the stirring intensity in mixing tank 3 is 50 - 100 s -1 .

[0029] This application has the following beneficial effects:

[0030] 1. The CaAl@C 70 core - shell material prepared by the present invention has strong adsorption capacity. When mixed with calcium fluoride crystal nuclei, it accelerates the formation of flocs, provides favorable conditions for subsequent floc separation, reduces the moisture content of sludge, can remove suspended solids, COD, SS and fluoride ions simultaneously, has strong adaptability to the treatment of different types of fiberglass wastewater, and has strong comprehensive ability to remove COD, SS and fluoride ions;

[0031] 2. Compared with existing aluminum salts and calcium salts, the fiberglass water purifying agent of the present invention can reduce the content of dissolved aluminum and calcium in water; the use of calcium chloride can reduce the sludge production; the mixed use of polyaluminum chloride and aluminum sulfate can reduce the pH impact on water, enabling it to be used in a wider pH range with strong adaptability. Description of the Drawings

[0032] Figure 1 It is a graph showing the change of COD removal concentration and removal rate of the corresponding batches of sewage after treatment in Examples 1 - 4;

[0033] Figure 2 It is a graph showing the change of SS removal concentration and removal rate of the corresponding batches of sewage after treatment in Examples 1 - 4;

[0034] Figure 3 It is a graph showing the change of fluoride ion removal concentration and removal rate of the corresponding batches of sewage after treatment in Examples 1 - 4; Detailed Embodiments

[0035] The following further elaborates on this application with reference to examples.

[0036] Unless otherwise specified, the raw materials in the examples and comparative examples of this application are all commercially available.

[0037] Example 1

[0038] CaAl@C 70 The preparation method of the core - shell material is as follows:

[0039] S1. Put 0.2 mol of organic acid, 0.04 mol of CaO, 0.04 mol of Al2O3 and 1 L of C 70 saturated solution into a glass tube, displace the air in the tube with nitrogen to obtain a sealed tube; prepare C70 The organic solvent of the saturated solution is an equal mixture of chlorobenzene and toluene; the organic acid is glutaric acid;

[0040] S2. Place the sealed tube obtained in S1 into an oven, heat it to 210 - 225 °C, keep it for 50 - 90 h, and then cool it to room temperature at a rate of 8 °C / h;

[0041] S3. Filter the solid product in the glass tube, and then rinse it 3 times with the organic solvent of the saturated solution for the preparation of C 70 and dry it to obtain the CaAl@C 70 core - shell material.

[0042] The preparation method of calcium fluoride crystal nuclei is as follows: Sodium fluoride and calcium chloride are configured into a saturated solution according to a molar ratio of 2:1, react for 60 minutes at a stirring intensity of 200 s -1 and then filter to obtain crystals, and dry them at 120 °C for 2 hours to obtain calcium fluoride crystal nuclei.

[0043] The preparation method of calcium ion suspension is as follows: Calcium hydroxide and calcium chloride are mixed in equal weight ratio, and water is added and stirred until a suspension is obtained, thus obtaining a calcium ion suspension.

[0044] The preparation method of aluminum ion aging reagent is as follows: Poly aluminum chloride and aluminum sulfate are mixed in equal weight ratio, water is added at room temperature, and stirred at a rotation speed of 100 - 150 r / min for aging for 2 - 5 days to obtain an aluminum ion aging reagent.

[0045] When the glass fiber water purifying agent is used to treat glass fiber wastewater, for one ton of wastewater, the dosage amounts are 30 kg of CaAl@C 70 core - shell material, 30 kg of calcium fluoride crystal nuclei, 20 kg of calcium ion suspension, 20 kg of aluminum ion aging reagent, and 2 kg of anionic polyacrylamide.

[0046] The specific steps are as follows:

[0047] A1. Add the CaAl@C 70 core - shell material and calcium fluoride crystal nuclei into mixing tank 1, the stirring intensity in mixing tank 1 is 300 s -1 , the volume circulation times are greater than 10, the mixing uniformity is greater than 99%, and the residence time of the reagent is 6 min;

[0048] A2. Intercept the CaAl@C 70 core - shell material and calcium fluoride crystal nuclei from the wastewater discharged from mixing tank 1 through a filter, and replenish them back to mixing tank 1;

[0049] A3. Discharge the wastewater into mixing tank 2, add the calcium ion suspension, the stirring intensity is 300 s -1 , the volume circulation times are greater than 10, the mixing uniformity is greater than 99%, and the residence time of the reagent is 15 min;

[0050] A4. The discharged wastewater enters the mixing tank 3, and the aluminum ion ripening reagent and anionic polyacrylamide are added. The stirring intensity is 70 s -1 , the volume circulation times are more than 10, the mixing uniformity is more than 99%, and the reagent residence time is 7 min;

[0051] A5. The wastewater enters the sedimentation area for sediment-water separation, and the water quality purification process is completed.

[0052] Example 2

[0053] The difference between this example and Example 1 is only that: in the preparation process of the CaAl@C 70 core-shell material, the organic solvent for preparing the C 70 saturated solution is chlorobenzene; the organic acid is tartaric acid. When the glass fiber water purification agent is used to treat glass fiber wastewater, for one ton of wastewater, the dosage amounts are 40 kg of CaAl@C 70 core-shell material, 40 kg of calcium fluoride crystal nuclei, 30 kg of calcium ion suspension, 30 kg of aluminum ion ripening reagent, and 4 kg of anionic polyacrylamide.

[0054] The specific steps are the same as those in Example 1, as follows:

[0055] A1. Add the CaAl@C 70 core-shell material and calcium fluoride crystal nuclei to the mixing tank 1. The stirring intensity in the mixing tank 1 is 300 s -1 , the volume circulation times are more than 10, the mixing uniformity is more than 99%, and the reagent residence time is 6 min;

[0056] A2. Intercept the CaAl@C 70 core-shell material and calcium fluoride crystal nuclei from the wastewater discharged from the mixing tank 1 and replenish them back to the mixing tank 1;

[0057] A3. The discharged wastewater enters the mixing tank 2, and the calcium ion suspension is added. The stirring intensity is 300 s -1 , the volume circulation times are more than 10, the mixing uniformity is more than 99%, and the reagent residence time is 15 min;

[0058] A4. The discharged wastewater enters the mixing tank 3, and the aluminum ion ripening reagent and anionic polyacrylamide are added. The stirring intensity is 70 s -1 , the volume circulation times are more than 10, the mixing uniformity is more than 99%, and the reagent residence time is 7 min;

[0059] A5. The wastewater enters the sedimentation area for sediment-water separation, and the water quality purification process is completed.

[0060] Example 3

[0061] The difference between this embodiment and Embodiment 1 is only that when the glass fiber water purifying agent is used to treat glass fiber wastewater, for one ton of wastewater, the dosage is respectively CaAl@C 70 core-shell material 50 kg, calcium fluoride crystal nucleus 40 kg, calcium ion suspension 40 kg, aluminum ion aging reagent 50 kg, and anionic polyacrylamide 6 kg.

[0062] The specific steps are the same as those in Embodiment 1, as follows:

[0063] A1. Add the CaAl@C 70 core-shell material and calcium fluoride crystal nucleus to Mixing Tank 1. The stirring intensity in Mixing Tank 1 is 300 s -1 , the volume circulation times are greater than 10, the mixing uniformity is greater than 99%, and the residence time of the reagent is 6 min;

[0064] A2. Intercept the CaAl@C 70 core-shell material and calcium fluoride crystal nucleus from the wastewater discharged from Mixing Tank 1 through a filter, and replenish it back to Mixing Tank 1;

[0065] A3. Discharge the wastewater into Mixing Tank 2, add the calcium ion suspension, and the stirring intensity is 300 s -1 , the volume circulation times are greater than 10, the mixing uniformity is greater than 99%, and the residence time of the reagent is 15 min;

[0066] A4. Discharge the wastewater into Mixing Tank 3, add the aluminum ion aging reagent and anionic polyacrylamide, and the stirring intensity is 70 s -1 , the volume circulation times are greater than 10, the mixing uniformity is greater than 99%, and the residence time of the reagent is 7 min;

[0067] A5. The wastewater enters the sedimentation area for sedimentation separation, and the water purification process is completed.

[0068] Embodiment 4

[0069] The difference between this embodiment and Embodiment 1 is only that when the glass fiber water purifying agent is used to treat glass fiber wastewater, the specific steps are as follows:

[0070] A1. Add the CaAl@C 70 core-shell material and calcium fluoride crystal nucleus to Mixing Tank 1. The stirring intensity in Mixing Tank 1 is 350 s -1 , the volume circulation times are greater than 10, the mixing uniformity is greater than 99%, and the residence time of the reagent is 8 min;

[0071] A2. Intercept the CaAl@C 70 core-shell material and calcium fluoride crystal nucleus from the wastewater discharged from Mixing Tank 1 through a filter, and replenish it back to Mixing Tank 1;

[0072] A3. The discharged wastewater enters the mixing tank 2, and a calcium ion suspension is added. The stirring intensity is 350 s -1 , the volume circulation times are more than 10, the mixing uniformity is more than 99%, and the reagent residence time is 20 min;

[0073] A4. The discharged wastewater enters the mixing tank 3, and a reagent for alumin ion ripening and anionic polyacrylamide are added. The stirring intensity is 100 s -1 , the volume circulation times are more than 10, the mixing uniformity is more than 99%, and the reagent residence time is 10 min;

[0074] A5. The wastewater enters the sedimentation area for sediment-water separation, and the water purification process is completed.

[0075] Comparative Example 1

[0076] The difference between this comparative example and Example 1 is only that: the glass fiber water purifying agent does not include the CaAl@C 70 core-shell material.

[0077] Specifically, when the glass fiber water purifying agent is used to treat glass fiber wastewater, the specific steps are as follows:

[0078] A1. Add calcium fluoride crystal nuclei to the mixing tank 1. The stirring intensity in the mixing tank 1 is 350 s -1 , the volume circulation times are more than 10, the mixing uniformity is more than 99%, and the reagent residence time is 8 min;

[0079] A2. Intercept the calcium fluoride crystal nuclei from the wastewater discharged from the mixing tank 1 through a filter and replenish it back to the mixing tank 1;

[0080] A3. The discharged wastewater enters the mixing tank 2, and a calcium ion suspension is added. The stirring intensity is 350 s -1 , the volume circulation times are more than 10, the mixing uniformity is more than 99%, and the reagent residence time is 20 min;

[0081] A4. The discharged wastewater enters the mixing tank 3, and a reagent for alumin ion ripening and anionic polyacrylamide are added. The stirring intensity is 100 s -1 , the volume circulation times are more than 10, the mixing uniformity is more than 99%, and the reagent residence time is 10 min;

[0082] A5. The wastewater enters the sedimentation area for sediment-water separation, and the water purification process is completed.

[0083] Comparative Example 2

[0084] The difference between this comparative example and Example 1 is only that: the glass fiber water purifying agent does not include calcium fluoride crystal nuclei.

[0085] Specifically, when the glass fiber water purifying agent is used to treat glass fiber wastewater, the specific steps are as follows:

[0086] A1. Add the CaAl@C 70 core-shell material to mixing tank 1, with a stirring intensity of 350 s -1 in mixing tank 1, a volume circulation times greater than 10, a mixing uniformity greater than 99%, and a residence time of the reagent of 8 min;

[0087] A2. Intercept the CaAl@C 70 core-shell material from the wastewater discharged from mixing tank 1 and replenish it back to mixing tank 1;

[0088] A3. Discharge the wastewater into mixing tank 2, add the calcium ion suspension, with a stirring intensity of 350 s -1 in mixing tank 2, a volume circulation times greater than 10, a mixing uniformity greater than 99%, and a residence time of the reagent of 20 min;

[0089] A4. Discharge the wastewater into mixing tank 3, add the aluminum ion ripening reagent and anionic polyacrylamide, with a stirring intensity of 100 s -1 in mixing tank 3, a volume circulation times greater than 10, a mixing uniformity greater than 99%, and a residence time of the reagent of 10 min;

[0090] A5. The wastewater enters the sedimentation area for sedimentation separation, and thus the water purification process is completed.

[0091] Comparative Example 3

[0092] The difference between this comparative example and Example 1 is only that: the glass fiber water purifying agent does not include the CaAl@C 70 core-shell material and calcium fluoride crystal nuclei.

[0093] Specifically, when the glass fiber water purifying agent is used to treat glass fiber wastewater, the specific steps are as follows:

[0094] The wastewater enters mixing tank 2, add the calcium ion suspension, with a stirring intensity of 350 s -1 in mixing tank 2, a volume circulation times greater than 10, a mixing uniformity greater than 99%, and a residence time of the reagent of 20 min;

[0095] The wastewater enters mixing tank 3, add the aluminum ion ripening reagent and anionic polyacrylamide, with a stirring intensity of 100 s -1 in mixing tank 3, a volume circulation times greater than 10, a mixing uniformity greater than 99%, and a residence time of the reagent of 10 min;

[0096] The wastewater enters the sedimentation area for sedimentation separation, and thus the water purification process is completed.

[0097] Comparative Example 4

[0098] This comparative example uses an existing ordinary commercially available water purifying agent.

[0099] Test Example

[0100] I. Test method: A total of 32 batches of fiberglass wastewater of different types were marked as batches 1 - 32. These 32 batches of fiberglass wastewater were evenly divided into 4 parts (8 batches each). The first part (fiberglass wastewater of batches 1 - 8) was treated using Example 1; the second part (fiberglass wastewater of batches 9 - 16) was treated using Example 2; the third part (fiberglass wastewater of batches 17 - 24) was treated using Example 3; the fourth part (fiberglass wastewater of batches 24 - 32) was treated using Example 4. Record the COD, SS, and the removal concentration and removal rate of fluoride ions before and after the treatment of the fiberglass wastewater in batches 1 - 32. The water quality of the 32 batches of fiberglass wastewater is shown in Table 1.

[0101] Table 1. Water quality of 32 batches of fiberglass wastewater

[0102]

[0103]

[0104] Calculation method of removal rate:

[0105]

[0106] The precipitation time was set at 60 min, and the supernatant was taken for measurement.

[0107] Test results: As shown in Tables 2 - 4 and Figures 1-3 as follows.

[0108] Table 2. Record of COD removal effect of the corresponding batches of sewage after treatment with Examples 1 - 4

[0109]

[0110]

[0111] Table 3. Record of SS removal effect of the corresponding batches of sewage after treatment with Examples 1 - 4

[0112] Batch Raw water Residual SS SS removal rate 1 226 56 75％ 2 284 78 73％ 3 239 65 73％ 4 273 41 85％ 5 240 42 83％ 6 298 60 80％ 7 279 49 82％ 8 241 70 71％ 9 233 65 72％ 10 273 80 71％ 11 244 47 81％ 12 300 79 74％ 13 255 74 71％ 14 206 60 71％ 15 210 60 72％ 16 220 58 73％ 17 275 62 77％ 18 284 75 74％ 19 300 80 73％ 20 218 58 73％ 21 284 70 75％ 22 262 70 73％ 23 248 59 76％ 24 260 68 74％ 25 222 56 75％ 26 240 47 80％ 27 276 55 80％ 28 270 62 77％ 29 299 69 77％ 30 283 74 74％ 31 255 56 78％ 32 261 45 83％

[0113] Table 4. Record of fluoride ion removal effect of the corresponding batches of sewage after treatment with Examples 1 - 4

[0114]

[0115]

[0116] II. Test method: Randomly select 8 batches from the 32 batches of fiberglass wastewater, namely batch 1, batch 5, batch 8, batch 14, batch 17, batch 23, batch 28, and batch 32;

[0117] Batch 1 and Batch 5 were treated with Comparative Example 1;

[0118] Batch 8 and Batch 14 were treated with Comparative Example 2;

[0119] Batch 17 and Batch 23 were treated with Comparative Example 3;

[0120] Batch 28 and Batch 32 were treated with Comparative Example 4;

[0121] Record the COD, SS, fluoride ion removal concentration and removal rate before and after the treatment of the glass fiber wastewater in the above 8 batches respectively.

[0122] Test results: as shown in Table 5-7.

[0123] Table 5. Record of COD removal effect of sewage in corresponding batches after treatment with Comparative Examples 1-4

[0124] Batch Raw water Residual COD COD removal rate 1 2032 1095 46％ 5 1980 1038 48％ 8 1983 982 50％ 14 1998 988 51％ 17 1992 1203 40％ 23 1980 1234 38％ 28 2008 1070 47％ 32 1991 998 50％

[0125] Table 6. Record of SS removal effect of sewage in corresponding batches after treatment with Comparative Examples 1-4

[0126] Batch Raw water Residual SS SS removal rate 1 226 108 52％ 5 240 119 50％ 8 241 125 48％ 14 206 98 52％ 17 275 159 42％ 23 248 140 44％ 28 270 130 52％ 32 261 125 52％

[0127] Table 7. Record of fluoride ion removal effect of sewage in corresponding batches after treatment with Comparative Examples 1-4

[0128] Batch Raw water <![CDATA[Remaining F - > <![CDATA[F - Removal rate]]> 1 52 28 46％ 5 35 20 43％ 8 40 19 53％ 14 57 29 49％ 17 80 48 40％ 23 68 40 41％ 28 59 32 46％ 32 67 40 40％

[0129] Result analysis: From Table 2-7 and Figures 1-3 it can be seen that the glass fiber water purifying agent of the present invention has strong adaptability to the treatment of different types of glass fiber wastewater and strong comprehensive ability to remove COD, SS and fluoride ions.

[0130] In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without conflict. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0131] In addition, any combination can be made between various different embodiments of the present invention, as long as it does not violate the idea of the present invention, it should also be regarded as the content disclosed by the present invention.

Claims

1. A glass fiber water purifying agent, characterized in that, By weight parts, it includes the following components: CaAl@C 70 15-25 parts of core-shell material, 15-25 parts of calcium fluoride crystal nuclei, 10-20 parts of calcium ion suspension, 10-25 parts of aluminum ion curing reagent, and 1-3 parts of anionic polyacrylamide; the calcium ion suspension includes calcium hydroxide and calcium chloride, and the aluminum ion curing reagent includes polyaluminum chloride and aluminum sulfate; The CaAl@C 70 The preparation method of the core-shell material is as follows: S1. Put 0.2 mol of organic acid, 0.04 mol of CaO, 0.04 mol of Al2O3 and 1 L of saturated solution of C into a glass tube, purge the air in the tube with nitrogen, and obtain a sealed tube; 70 ​ S2. Place the sealed tube obtained in S1 into an oven, heat it to 210 - 225 °C, maintain for 50 - 90 h, and then cool it to room temperature at a rate of 8 °C / h; S3. Filter the solid product in the glass tube, and then rinse it three times with the organic solvent for preparing the C 70 saturated solution, and dry it to obtain the CaAl@C 70 core-shell material; Preparation of C 70 The organic solvent for preparing the saturated solution is chlorobenzene and / or toluene; The organic acid is tartaric acid and / or glutaric acid; A saturated solution is prepared by mixing sodium fluoride and calcium chloride in a molar ratio of 2:1, and the reaction is carried out at a stirring intensity of -1 for 60 minutes. After filtration, the crystals are obtained and dried at 120 °C for 2 hours to obtain calcium fluoride crystal nuclei. -1 ​ 2. The fiberglass water purifying agent according to claim 1, characterized in that, The preparation method of the calcium ion suspension is as follows: Calcium hydroxide and calcium chloride are mixed in an equal weight ratio, and water is added and stirred until a suspension is obtained, thus obtaining the calcium ion suspension.

3. The fiberglass water purifying agent according to claim 1, characterized in that, The preparation method of the aluminum ion curing reagent is as follows: Polyaluminum chloride and aluminum sulfate are mixed in an equal weight ratio, water is added at room temperature, and it is stirred at a rotation speed of 100 - 150 revolutions per minute and cured for 2 - 5 days, thus obtaining the aluminum ion curing reagent.

4. Application of a glass fiber water purifying agent, characterized in that, The glass fiber water purifying agent is the glass fiber water purifying agent according to any one of claims 1 - 3, and is used for treating glass fiber wastewater, including the steps: A1. Add CaAl@C 70 core-shell material and calcium fluoride crystal nuclei into mixing tank 1, stir, and let the reagent stay for 4 to 8 minutes; A2. Intercept the CaAl@C core-shell material and calcium fluoride crystal nuclei from the wastewater discharged from the mixing tank 1 through a filter, and replenish it back into the mixing tank 1; 70 ​ A3. Drain the wastewater into mixing tank 2, add the calcium ion suspension, stir, and let the reagent stay for 10 to 20 min; A4. Drain the wastewater into mixing tank 3, add the aluminum ion curing reagent and anionic polyacrylamide, stir, and let the reagent stay for 5 to 10 min; A5. The wastewater enters the sedimentation area for sediment - water separation.

5. The application of the glass fiber water purifying agent according to claim 4, wherein The stirring intensity in mixing tank 1 is 250 - 350 s -1 ; The stirring intensity in mixing tank 2 is 250 - 350 s -1 ; The stirring intensity in mixing tank 3 is 50 - 100 s -1 .

Images