Water purifying agent composite material and preparation method thereof

Abstract

The invention discloses a composite material for a water purifying agent. The composite material for the water purifying agent comprises activated carbon, a zeolite-doped synergistic additive and a modified long-acting liquid, wherein the substance mass ratio of the activated carbon to the additive compounded by the doped zeolite to the modified long-acting liquid is (7-9): (4-6): 3. According to the water purifying agent composite material disclosed by the invention, the activated carbon is adopted as a matrix, and is matched with the zeolite-doped synergistic additive and the modified long-acting liquid, and the obtained water purifying agent composite material has excellent COD (Chemical Oxygen Demand) removal efficiency through uniform stirring and mixing, ball-milling improvement and best compression molding, and meanwhile, ammonia nitrogen and heavy metals are harmoniously removed; and the product has corrosion resistance to different degrees and high-temperature stability, and is durable and excellent in use.

Description

Technical Field

[0001] The present invention relates to the technical field of water purifying agent materials, and particularly relates to a composite water purifying agent and a preparation method thereof. Background Art

[0002] Water purifying agents are mainly chemicals that can react with other impurities in water when put into water. Their main methods are aggregation and adsorption. Activated carbon is a commonly used adsorption material, a black powdery or granular porous crystal. For existing composite water purifying agents using activated carbon as the matrix, the efficiency of removing COD in wastewater is poor. At the same time, it is difficult to achieve a coordinated removal effect on ammonia nitrogen and heavy metals, and the product has poor corrosion resistance at different levels and stability at high temperatures. At the same time, the durability of the product is poor, which limits the use efficiency of the product. Based on this, the present invention makes further improvement treatments. Summary of the Invention

[0003] Aiming at the defects of the prior art, the purpose of the present invention is to provide a composite water purifying agent and a preparation method thereof to solve the problems raised in the above background art.

[0004] The present invention adopts the following technical solutions to solve the technical problems:

[0005] The present invention provides a composite water purifying agent, which includes activated carbon, an additive coordinated with doped zeolite, and a modified long-acting liquid; wherein the mass ratio of activated carbon, the additive coordinated with doped zeolite, and the modified long-acting liquid is (7-9):(4-6):3.

[0006] Preferably, the mass ratio of activated carbon, the additive coordinated with doped zeolite, and the modified long-acting liquid is 8:5:3.

[0007] Preferably, the preparation method of the additive coordinated with doped zeolite is as follows:

[0008] S01: Stir and mix zeolite in a sufficient amount of 5% hydrogen peroxide solution, then wash with water, filter by suction, and dry. Then preheat the dried zeolite at 60-65°C for 1 h and keep warm.

[0009] S02: Mix 3-5 parts of nano-titanium dioxide, 5-8 parts of 5% lanthanum nitrate solution, and 2-4 parts of 6% hydrochloric acid dopamine solution to obtain a nano-titanium dioxide solution.

[0010] Ultrasonically treat 4-7 parts of the zeolite treated in S01 and 6-9 parts of the nano-titanium dioxide solution. After the ultrasonic treatment ends, a zeolite coordination solution is obtained.

[0011] S03: Preparation of the modified additive:

[0012] S031: Add 2 - 3 parts of nano-aluminum oxide and 1 - 2 parts of silane coupling agent into 5 - 8 parts of a 5% sodium dodecyl sulfate solution, and stir evenly to obtain the first modified liquid;

[0013] S032: Blend 3 - 5 parts of kaolin, 2 - 4 parts of boron nitride and 5 - 8 parts of yttrium nitrate solution thoroughly to obtain the second modified liquid;

[0014] The first modified liquid and the second modified liquid are blended and modified according to a weight ratio of 2:5. After the modification is completed, filter by suction and dry to obtain the modified additive;

[0015] S04: Mix the zeolite synergistic liquid and the modified additive according to a weight ratio of 5:3, and perform ball milling treatment at 1000 r / min for 1 h. After the ball milling is completed, filter by suction and dry to obtain the additive doped with zeolite synergist.

[0016] Preferably, the blending rotation speed for the blending and modification treatment is 750 - 850 r / min for 1 h; the ultrasonic power for the ultrasonic treatment is 350 - 400 W for 20 min.

[0017] Preferably, the mass fraction of the yttrium nitrate solution is 4 - 7%; the silane coupling agent is silane coupling agent KH550.

[0018] Preferably, the preparation method of the modified long-acting liquid is as follows:

[0019] S11: Add 2 - 3 parts of wood cellulose and 1 - 3 parts of nano-silica sol into 4 - 7 parts of a 2 - 5% chitosan solution, and perform blending and ball milling treatment at a ball milling speed of 1000 r / min for 2 h. After the ball milling is completed, obtain the modified chitosan agent;

[0020] S12: Blend 3 - 5 parts of fly ash, 2 - 3 parts of the modified chitosan agent and 5 - 8 parts of sodium alginate solution thoroughly, then filter by suction and dry to obtain the filler modifier;

[0021] S13: Blend the filler modifier, sodium dodecylbenzenesulfonate solution and sodium carboxymethylcellulose according to a weight ratio of (4 - 5):(5 - 8):2 thoroughly to obtain the modified long-acting liquid.

[0022] Preferably, the mass fraction of the sodium alginate solution is 4 - 6%; the mass fraction of the sodium dodecylbenzenesulfonate solution is 3 - 5%.

[0023] Preferably, the wood cellulose is also treated by immersion in a sodium silicate solution. The specific immersion method is as follows:

[0024] Stir and immerse the wood cellulose, sodium silicate solution and silicon carbide powder according to a weight ratio of 2:5:1. The stirring and immersion rotation speed is 150 - 200 r / min for 1 h. That's it.

[0025] Preferably, the mass fraction of the sodium silicate solution is 4-7%.

[0026] The present invention provides a preparation method of a water purifying agent composite material, comprising the following steps:

[0027] Mix activated carbon, an additive with doped zeolite in coordination, and a modified long-acting liquid evenly, then ball mill sufficiently in a ball mill at a ball mill speed of 1500 r / min for 1 h. After the ball milling is completed, carry out suction filtration and drying, and finally carry out molding for 10 min under a pressure of 30-35 Mpa to obtain the water purifying agent composite material of the present invention.

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] The water purifying agent composite material of the present invention uses activated carbon as the matrix, and is combined with an additive with doped zeolite in coordination and a modified long-acting liquid. Through even mixing, then ball milling improvement, and finally pressing and molding, the obtained water purifying agent composite material has excellent COD removal efficiency, and at the same time realizes coordinated removal of ammonia nitrogen and heavy metals, as well as the corrosion resistance of the product to different degrees and the stability at high temperature, and the product has excellent durability in use; the additive with doped zeolite in coordination is optimized and improved by zeolite through hydrogen peroxide solution and preheating to improve its activity efficiency, and then is ultrasonically treated with nano-titanium dioxide solution. The nano-titanium dioxide in the nano-titanium dioxide solution, a lanthanum nitrate solution with a mass fraction of 5%, and a hydrochloric acid dopamine solution with a mass fraction of 6% are blended and improved together. Through the coordinated co-effect between the raw materials, the blending effect of nano-titanium dioxide and zeolite is improved. At the same time, it is further improved by a modified additive. The first modified liquid and the second modified liquid in the modified additive are blended and improved together. The first modified liquid uses nano-aluminum oxide as the matrix material, and is coordinated and optimized by a silane coupling agent and a sodium dodecyl sulfate solution with a mass fraction of 5%, and the second modified liquid is obtained by co-adjusting and improving kaolin, boron nitride and a yttrium nitrate solution. By the mutual adjustment and coordination optimization between the first modified liquid and the second modified liquid, the coordinated removal of COD, ammonia nitrogen and heavy metals in the system is optimized, and at the same time, the corrosion resistance of the product to different degrees and the stability at high temperature, as well as the excellent durability of the product in use are achieved; the modified long-acting liquid is mutually adjusted and coordinated with a filler modifier, a sodium dodecyl benzene sulfonate solution and sodium carboxymethyl cellulose. The filler modifier is sufficiently blended and stirred with fly ash, a modified chitosan agent and a sodium alginate solution. At the same time, the chitosan solution, wood cellulose and nano-silica sol in the modified chitosan agent are blended and ball milled. Wood cellulose, a sodium silicate solution and silicon carbide powder are further stirred and immersed. Through the co-allocation and co-effect between the raw materials, they are jointly blended and optimized into the system medium, thereby further improving the performance effect of the system. Specific embodiments

[0030] The following describes the technical solutions in the embodiments of the present invention clearly and completely in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0031] A water purifying agent composite material in this embodiment, the water purifying agent composite material includes activated carbon, an additive coordinated by doped zeolite, and a modified long-acting liquid; wherein the mass ratio of activated carbon, the additive coordinated by doped zeolite, and the modified long-acting liquid is (7-9):(4-6):3.

[0032] In this embodiment, the mass ratio of activated carbon, the additive coordinated by doped zeolite, and the modified long-acting liquid is 8:5:3.

[0033] The preparation method of the additive coordinated by doped zeolite in this embodiment is as follows:

[0034] S01: Stir and mix zeolite in a sufficient amount of 5% hydrogen peroxide solution, then wash with water, filter by suction, and dry. Then preheat the dried zeolite at 60-65°C for 1 h and keep warm.

[0035] S02: Mix 3-5 parts of nano-titanium dioxide, 5-8 parts of 5% lanthanum nitrate solution by mass, and 2-4 parts of 6% hydrochloric acid dopamine solution by mass to obtain a nano-titanium dioxide solution.

[0036] Ultrasonically process 4-7 parts of zeolite treated by S01 and 6-9 parts of nano-titanium dioxide solution. After the ultrasonic treatment, a zeolite coordination solution is obtained.

[0037] S03: Preparation of the modified additive:

[0038] S031: Add 2-3 parts of nano-aluminum oxide and 1-2 parts of silane coupling agent to 5-8 parts of 5% sodium dodecyl sulfate solution by mass and stir evenly to obtain a first modified liquid.

[0039] S032: Mix 3-5 parts of kaolin, 2-4 parts of boron nitride, and 5-8 parts of yttrium nitrate solution by mass to obtain a second modified liquid.

[0040] The first modified liquid and the second modified liquid are blended and modified according to a weight ratio of 2:5. After the modification, filter by suction and dry to obtain the modified additive.

[0041] S04: Mix the zeolite coordination solution and the modified additive according to a weight ratio of 5:3, perform ball milling treatment at 1000 r / min for 1 h. After the ball milling, filter by suction and dry to obtain the additive coordinated by doped zeolite.

[0042] The blending speed for the blending modification treatment in this example is 750 - 850 r / min, and the blending is carried out for 1 h; the ultrasonic power for the ultrasonic treatment is 350 - 400 W, and the ultrasonic treatment is carried out for 20 min.

[0043] In this example, the mass fraction of the yttrium nitrate solution is 4 - 7%; the silane coupling agent is silane coupling agent KH550.

[0044] The preparation method of the modified long - acting liquid in this example is as follows:

[0045] S11: Add 2 - 3 parts of wood cellulose and 1 - 3 parts of nano - silica sol blended balls to 4 - 7 parts of a chitosan solution with a mass fraction of 2 - 5%, and carry out a co - blending ball - milling treatment. The ball - milling speed is 1000 r / min, and the ball - milling is carried out for 2 h. After the ball - milling is completed, a modified chitosan agent is obtained.

[0046] S12: Thoroughly blend 3 - 5 parts of fly ash, 2 - 3 parts of the modified chitosan agent, and 5 - 8 parts of sodium alginate solution, then carry out suction filtration and drying to obtain a filler modifier.

[0047] S13: Blend the filler modifier, sodium dodecyl benzene sulfonate solution, and sodium carboxymethyl cellulose in a weight ratio of (4 - 5):(5 - 8):2 to obtain the modified long - acting liquid.

[0048] In this example, the mass fraction of the sodium alginate solution is 4 - 6%; the mass fraction of the sodium dodecyl benzene sulfonate solution is 3 - 5%.

[0049] In this example, the wood cellulose is also treated by immersion in a sodium silicate solution. The specific immersion method is as follows:

[0050] Stir and immerse the wood cellulose, sodium silicate solution, and silicon carbide powder in a weight ratio of 2:5:1. The stirring and immersion speed is 150 - 200 r / min, and the stirring is carried out for 1 h.

[0051] In this example, the mass fraction of the sodium silicate solution is 4 - 7%.

[0052] The preparation method of a water - purifying agent composite material in this example includes the following steps:

[0053] Stir and mix the activated carbon, the additive with doped zeolite co - coordination, and the modified long - acting liquid evenly, then carry out sufficient ball - milling in a ball mill. The ball - milling speed is 1500 r / min, and the ball - milling is carried out for 1 h. After the ball - milling is completed, carry out suction filtration and drying, and finally carry out molding at a pressure of 30 - 35 Mpa for 10 min to obtain the water - purifying agent composite material of the present invention.

[0054] Example 1.

[0055] A water purification agent composite material in this embodiment, the water purification agent composite material includes activated carbon, an additive composed of doped zeolite in coordination, and a modified long-acting liquid; among them, the mass ratio of activated carbon, the additive composed of doped zeolite in coordination, and the modified long-acting liquid is 7:4:3.

[0056] The preparation method of the additive composed of doped zeolite in coordination in this embodiment is as follows:

[0057] S01: Stir and mix zeolite in a sufficient amount of 5% hydrogen peroxide solution, then wash with water, filter by suction, and dry. Preheat the dried zeolite at 60 °C for 1 h and keep warm;

[0058] S02: Mix 3 parts of nano-titanium dioxide, 5 parts of 5% lanthanum nitrate solution by mass fraction, and 2 parts of 6% hydrochloric acid dopamine solution by mass fraction to obtain a nano-titanium dioxide solution;

[0059] Ultrasonically treat 4 parts of the zeolite treated in S01 and 6 parts of the nano-titanium dioxide solution. After the ultrasonic treatment ends, obtain a zeolite coordination solution;

[0060] S03: Preparation of the modified additive:

[0061] S031: Add 2 parts of nano-aluminum oxide and 1 part of silane coupling agent to 5 parts of 5% sodium dodecyl sulfate solution by mass fraction and stir evenly to obtain a first modified liquid;

[0062] S032: Mix 3 parts of kaolin, 2 parts of boron nitride and 5 parts of yttrium nitrate solution by mass fraction to obtain a second modified liquid;

[0063] The first modified liquid and the second modified liquid are blended and modified according to the weight ratio of 2:5. After the modification ends, filter by suction and dry to obtain the modified additive;

[0064] S04: Mix the zeolite coordination solution and the modified additive according to the weight ratio of 5:3, perform ball milling treatment at 1000 r / min for 1 h. After the ball milling ends, filter by suction and dry to obtain the additive composed of doped zeolite in coordination.

[0065] The blending rotation speed of the blending and modification treatment in this embodiment is 750 r / min for 1 h; the ultrasonic power of the ultrasonic treatment is 350 W for 20 min.

[0066] The mass fraction of the yttrium nitrate solution in this embodiment is 4%; the silane coupling agent is silane coupling agent KH550.

[0067] The preparation method of the modified long-acting liquid in this embodiment is as follows:

[0068] S11: adding 2 parts of wood cellulose and 1 part of nano-silica sol to 4 parts of chitosan solution with a mass fraction of 2%, and ball milling the mixture at a speed of 1000 r / min for 2 h to obtain a modified chitosan agent;

[0069] S12: 3 parts of fly ash, 2 parts of modified chitosan agent and 5 parts of sodium alginate solution are mixed and stirred thoroughly, and then filtered and dried to obtain a filler modifier;

[0070] S13: The filler modifier, sodium dodecylbenzene sulfonate solution and sodium carboxymethyl cellulose are mixed in a weight ratio of 4:5:2 to obtain a modified long-acting liquid.

[0071] The mass fraction of the sodium alginate solution in this embodiment is 4%; the mass fraction of the sodium dodecylbenzene sulfonate solution is 3%.

[0072] The lignocellulose of this embodiment is also treated by immersion in a sodium silicate solution, and the specific immersion method is as follows:

[0073] The wood cellulose, sodium silicate solution and silicon carbide powder are stirred and immersed in a weight ratio of 2:5:1 at a stirring speed of 150 r / min for 1 hour.

[0074] The mass fraction of the sodium silicate solution in this embodiment is 4%.

[0075] A method for preparing a water purifier composite material of this embodiment comprises the following steps:

[0076] The activated carbon, the additive doped with zeolite and the modified long-acting liquid are stirred and mixed, and then fully ball-milled in a ball mill at a ball milling speed of 1500r / min for 1h. After the ball milling is completed, the mixture is filtered and dried, and finally formed at a pressure of 30Mpa for 10min to obtain the water purifier composite material of the present invention.

[0077] Example 2.

[0078] A water purifier composite material of this embodiment includes activated carbon, an additive doped with zeolite, and a modified long-acting liquid; wherein the mass ratio of the activated carbon, the additive doped with zeolite, and the modified long-acting liquid is 9:6:3.

[0079] The preparation method of the additive doped with zeolite in this embodiment is:

[0080] S01: Stir and mix the zeolite in a sufficient amount of 5% by mass hydrogen peroxide solution, then wash, filter and dry. Preheat the dried zeolite at 65°C for 1 hour and keep warm.

[0081] S02: 5 parts of nano titanium dioxide, 8 parts of 5% by mass lanthanum nitrate solution, and 4 parts of 6% by mass dopamine hydrochloride solution are mixed to obtain a nano titanium dioxide liquid;

[0082] 7 parts of S01 treated zeolite and 9 parts of nano titanium dioxide liquid were ultrasonically treated, and the ultrasonic treatment was terminated to obtain a zeolite coordinated liquid;

[0083] S03: Preparation of modified additives:

[0084] S031: adding 3 parts of nano-alumina and 2 parts of silane coupling agent to 8 parts of 5% by mass sodium dodecyl sulfate solution and stirring evenly to obtain a first modified solution;

[0085] S032: 5 parts of kaolin, 4 parts of boron nitride and 8 parts of yttrium nitrate solution are fully mixed to obtain a second modified solution;

[0086] The first modified liquid and the second modified liquid are mixed and modified in a weight ratio of 2:5, and after the modification is completed, the modified liquid is filtered and dried to obtain a modified additive;

[0087] S04: The zeolite co-formulation liquid and the modified additive are mixed in a weight ratio of 5:3, and the mixture is ball-milled at 1000 r / min for 1 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the zeolite-doped co-formulation additive.

[0088] The blending speed of the blending modification treatment in this embodiment is 850r / min, and the blending is 1h; the ultrasonic power of the ultrasonic treatment is 400W, and the ultrasonic treatment is 20min.

[0089] The mass fraction of the yttrium nitrate solution in this embodiment is 7%; the silane coupling agent is silane coupling agent KH550.

[0090] The preparation method of the modified long-acting liquid of this embodiment is:

[0091] S11: adding 3 parts of wood cellulose and 3 parts of nano-silica sol to 7 parts of 5% chitosan solution by mass, and mixing and ball milling at a speed of 1000 r / min for 2 h to obtain a modified chitosan agent;

[0092] S12: 5 parts of fly ash, 3 parts of modified chitosan agent and 8 parts of sodium alginate solution are mixed and stirred thoroughly, and then filtered and dried to obtain a filler modifier;

[0093] S13: The filler modifier, sodium dodecylbenzene sulfonate solution and sodium carboxymethyl cellulose are mixed in a weight ratio of 5:8:2 to obtain a modified long-acting liquid.

[0094] The mass fraction of the sodium alginate solution in this embodiment is 6%; the mass fraction of the sodium dodecylbenzene sulfonate solution is 5%.

[0095] In this embodiment, the lignocellulose is also treated by immersion in a sodium silicate solution. The specific immersion method is as follows:

[0096] The lignocellulose, sodium silicate solution and silicon carbide powder are stirred and immersed in a weight ratio of 2:5:1. The stirring and immersion speed is 200 r / min, and stirring is carried out for 1 h. That's it.

[0097] The mass fraction of the sodium silicate solution in this embodiment is 7%.

[0098] A preparation method of a water purifying agent composite material in this embodiment includes the following steps:

[0099] The activated carbon, the additive with doped zeolite in coordination, and the modified long-acting liquid are stirred and mixed evenly, and then ball-milled sufficiently in a ball mill. The ball-milling speed is 1500 r / min, and ball-milling is carried out for 1 h. After ball-milling is completed, filtration and drying are carried out, and finally molding is carried out at a pressure of 35 Mpa for 10 min to obtain the water purifying agent composite material of the present invention.

[0100] Example 3.

[0101] A water purifying agent composite material in this embodiment, the water purifying agent composite material includes activated carbon, an additive with doped zeolite in coordination, and a modified long-acting liquid; among them, the mass ratio of the activated carbon, the additive with doped zeolite in coordination, and the modified long-acting liquid is 8:5:3.

[0102] The preparation method of the additive with doped zeolite in coordination in this embodiment is as follows:

[0103] S01: Stir and mix the zeolite evenly in a sufficient amount of hydrogen peroxide solution with a mass fraction of 5%, then wash with water, filter and dry. Then preheat the dried zeolite at 62.5 °C for 1 h and keep warm;

[0104] S02: Mix 4 parts of nano-titanium dioxide, 6.5 parts of lanthanum nitrate solution with a mass fraction of 5%, and 3 parts of dopamine hydrochloride solution with a mass fraction of 6% evenly to obtain a nano-titanium dioxide liquid;

[0105] Ultrasonically treat 5.5 parts of the zeolite treated in S01 and 7.5 parts of the nano-titanium dioxide liquid. After ultrasonic treatment is completed, a zeolite coordination liquid is obtained;

[0106] S03: Preparation of the modified additive:

[0107] S031: Add 2.5 parts of nano-aluminum oxide and 1.5 parts of silane coupling agent to 6.5 parts of sodium dodecyl sulfate solution with a mass fraction of 5% and stir evenly to obtain a first modified liquid;

[0108] S032: Mix 4 parts of kaolin, 3 parts of boron nitride and 6.5 parts of yttrium nitrate solution evenly to obtain a second modified liquid;

[0109] The first modified liquid and the second modified liquid are mixed and modified in a weight ratio of 2:5, and after the modification is completed, the modified liquid is filtered and dried to obtain a modified additive;

[0110] S04: The zeolite co-formulation liquid and the modified additive are mixed in a weight ratio of 5:3, and the mixture is ball-milled at 1000 r / min for 1 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the zeolite-doped co-formulation additive.

[0111] The blending speed of the blending modification treatment in this embodiment is 800r / min, and the blending is 1h; the ultrasonic power of the ultrasonic treatment is 375W, and the ultrasonic treatment is 20min.

[0112] The mass fraction of the yttrium nitrate solution in this embodiment is 5.5%; the silane coupling agent is silane coupling agent KH550.

[0113] The preparation method of the modified long-acting liquid of this embodiment is:

[0114] S11: adding 2.5 parts of wood cellulose and 2 parts of nano-silica sol to 5.5 parts of chitosan solution with a mass fraction of 3.5%, and then ball milling the mixture at a speed of 1000 r / min for 2 h to obtain a modified chitosan agent;

[0115] S12: 4 parts of fly ash, 2.5 parts of modified chitosan agent and 6.5 parts of sodium alginate solution are mixed and stirred thoroughly, and then filtered and dried to obtain a filler modifier;

[0116] S13: The filler modifier, sodium dodecylbenzene sulfonate solution and sodium carboxymethyl cellulose are mixed in a weight ratio of 4.5:6.5:2 to obtain a modified long-acting liquid.

[0117] The mass fraction of the sodium alginate solution in this embodiment is 5%; the mass fraction of the sodium dodecylbenzene sulfonate solution is 4%.

[0118] The lignocellulose of this embodiment is also treated by immersion in a sodium silicate solution, and the specific immersion method is as follows:

[0119] The wood cellulose, sodium silicate solution and silicon carbide powder are stirred and immersed in a weight ratio of 2:5:1 at a stirring speed of 175 r / min for 1 hour.

[0120] The mass fraction of the sodium silicate solution in this embodiment is 5.5%.

[0121] A method for preparing a water purifier composite material of this embodiment comprises the following steps:

[0122] Mix the activated carbon, the additive co - formulated with doped zeolite, and the modified long - acting liquid evenly, and then ball - mill them sufficiently in a ball mill at a ball - mill speed of 1500 r / min for 1 h. After the ball - milling is completed, filter by suction and dry, and finally form at a pressure of 32.5 Mpa for 10 min to obtain the water - purifying agent composite material of the present invention.

[0123] Comparative Example 1.

[0124] It is different from Example 3 in that the additive co - formulated with doped zeolite is not added.

[0125] Comparative Example 2.

[0126] It is different from Example 3 in that nano - titanium dioxide liquid is not added for ultrasonic treatment in the preparation of the additive co - formulated with doped zeolite.

[0127] Comparative Example 3.

[0128] It is different from Example 3 in that nano - titanium dioxide and a 5% lanthanum nitrate solution by mass are not added to the nano - titanium dioxide liquid.

[0129] Comparative Example 4.

[0130] It is different from Example 3 in that the modified additive is not added in the preparation of the additive co - formulated with doped zeolite.

[0131] Comparative Example 5.

[0132] It is different from Example 3 in that the first modification liquid is not added to the modified additive.

[0133] Comparative Example 6.

[0134] It is different from Example 3 in that nano - aluminum oxide and silane coupling agent are not added to the first modification liquid.

[0135] Comparative Example 7.

[0136] It is different from Example 3 in that the second modification liquid is not added to the modified additive.

[0137] Comparative Example 8.

[0138] It is different from Example 3 in that kaolin and boron nitride are not added to the second modification liquid.

[0139] Comparative Example 9.

[0140] It is different from Example 3 in that the modified long - acting liquid is not added.

[0141] Comparative Example 10.

[0142] It is different from Example 3 in that the filler modifier is not used for treatment in the modified long - acting liquid.

[0143] Comparative Example 11.

[0144] It is different from Example 3 in that fly ash is not added during the treatment of the filler modifier.

[0145] Comparative Example 12.

[0146] It is different from Example 3 in that the modified chitosan agent is not added during the treatment of the filler modifier.

[0147] Comparative Example 13.

[0148] It is different from Example 3 in that lignocellulose and nano-silica sol are not added to the modified chitosan agent.

[0149] Comparative Example 14.

[0150] It is different from Example 3 in that lignocellulose is not treated by immersion in sodium silicate solution.

[0151] Comparative Example 15.

[0152] It is different from Example 3 in that silicon carbide powder is not added during the immersion treatment with sodium silicate solution.

[0153] The products of Examples 1 to 3 and Comparative Examples 1 to 15 were subjected to performance tests, and the performance test results are as follows:

[0154]

[0155]

[0156] It can be obtained from Examples 1 to 3 and Comparative Examples 1 to 15 that the products of Example 3 of the present invention can achieve coordinated improvement in COD removal rate, ammonia nitrogen removal rate, and heavy metal Cr removal rate;

[0157] The products of Examples 1 to 3 and Comparative Examples 1 to 10 of the present invention were placed at 70 °C for 24 h, then placed under 2% hydrochloric acid mist conditions for 12 h, and then placed under 5% hydrochloric acid corrosion conditions for 12 h. The above is one cycle, and the cycle was repeated 10 times to test the corrosion resistance of the products to different degrees and the stability at high temperature. The test results are as follows:

[0158]

[0159]

[0160] It can be seen from the above performance tests that the product of Example 3 not only has recyclability, but also has corrosion resistance to different degrees and stability at high temperature;

[0161] It can be seen from Comparative Examples 1-15 and Example 3 that when the additives doped with zeolite are not added or one of the modified long-acting liquids is not added to the product, the product performance deteriorates significantly. Only when the two are coordinated and synergistic, the performance effect of the product is the most significant;

[0162] During the preparation of the additive coordinated with doped zeolite, ultrasonic treatment was not carried out after adding nano-titanium dioxide solution, nano-titanium dioxide was not added to the nano-titanium dioxide solution, a lanthanum nitrate solution with a mass fraction of 5% was not added, and a modified additive was not added during the preparation of the additive coordinated with doped zeolite. The performance of the product showed an obvious trend of deterioration;

[0163] When the first modification liquid was not added to the modified additive, nano-aluminum oxide and silane coupling agent were not added to the first modification liquid, the second modification liquid was not added to the modified additive, and kaolin and boron nitride were not added to the second modification liquid, the performance of the product showed a trend of deterioration to varying degrees. Only the modified additive obtained by the specific method of the present invention in combination with the nano-titanium dioxide solution and the additive coordinated with doped zeolite obtained by a specific process had the most significant performance effect. Replacing with other methods was not as obvious as the effect of the present invention;

[0164] When the filler modifier was not used to treat the modified long-acting liquid, fly ash was not added during the treatment with the filler modifier, and the modified chitosan agent was not added during the treatment with the filler modifier, the performance of the product showed a trend of deterioration to varying degrees. Also, when wood cellulose, nano-silica sol were not added to the modified chitosan agent, the wood cellulose was not immersed in a sodium silicate solution, and silicon carbide powder was not added during the immersion treatment with the sodium silicate solution, the performance of the product showed a trend of deterioration. The performance effect of the modified long-acting liquid prepared by the process of the wood cellulose immersed in the specific sodium silicate solution and the specific modified chitosan agent of the present invention was the most obvious.

[0165] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and without departing from the spirit or basic characteristics of the present invention, the present invention can be implemented in other specific forms. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

[0166] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A water purifier composite material, characterized in that: The water purifier composite material includes activated carbon, additives doped with zeolite, and modified long-acting liquid; wherein the mass ratio of the activated carbon, additives doped with zeolite, and modified long-acting liquid is (7-9):(4-6):

3.

2. A water purification agent composite material according to claim 1, characterized in that: The mass ratio of the activated carbon, the additive doped with zeolite and the modified long-acting liquid is 8:5:

3.

3. The water purification agent composite material according to claim 1, characterized in that: The preparation method of the additive doped with zeolite is as follows: S01: Stir and mix the zeolite in a sufficient amount of 5% by mass hydrogen peroxide solution, then wash, filter and dry. Preheat the dried zeolite at 60-65°C for 1h and keep warm. S02: 3 to 5 parts of nano titanium dioxide, 5 to 8 parts of 5% by mass lanthanum nitrate solution, and 2 to 4 parts of 6% by mass dopamine hydrochloride solution are mixed to obtain a nano titanium dioxide solution; 4-7 parts of S01 treated zeolite and 6-9 parts of nano titanium dioxide liquid are ultrasonically treated, and the ultrasonic treatment is terminated to obtain a zeolite coordinated liquid; S03: Preparation of modified additives: S031: adding 2 to 3 parts of nano-alumina and 1 to 2 parts of silane coupling agent to 5 to 8 parts of 5% by mass sodium dodecyl sulfate solution and stirring evenly to obtain a first modified solution; S032: 3 to 5 parts of kaolin, 2 to 4 parts of boron nitride and 5 to 8 parts of yttrium nitrate solution are mixed to obtain a second modified solution; The first modified liquid and the second modified liquid are mixed and modified in a weight ratio of 2:5, and after the modification is completed, the modified liquid is filtered and dried to obtain a modified additive; S04: The zeolite co-formulation liquid and the modified additive are mixed in a weight ratio of 5:3, and the mixture is ball-milled at 1000 r / min for 1 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the zeolite-doped co-formulation additive.

4. The water purification agent composite material according to claim 3, characterized in that: The blending speed of the blending modification treatment is 750-850 r / min, and the blending is for 1 hour; the ultrasonic power of the ultrasonic treatment is 350-400 W, and the ultrasonic treatment is for 20 minutes.

5. The water purifier composite material according to claim 3, characterized in that: The mass fraction of the yttrium nitrate solution is 4-7%; the silane coupling agent is silane coupling agent KH550.

6. The water purification agent composite material according to claim 1, characterized in that: The preparation method of the modified long-acting liquid is: S11: adding 2 to 3 parts of lignocellulose and 1 to 3 parts of nano-silica sol to 4 to 7 parts of chitosan solution with a mass fraction of 2 to 5%, and mixing and ball milling at a speed of 1000 r / min for 2 hours to obtain a modified chitosan agent; S12: 3-5 parts of fly ash, 2-3 parts of modified chitosan agent and 5-8 parts of sodium alginate solution are mixed and stirred thoroughly, and then filtered and dried to obtain a filler modifier; S13: The filler modifier, sodium dodecylbenzene sulfonate solution and sodium carboxymethyl cellulose are mixed in a weight ratio of (4-5):(5-8):2 to obtain a modified long-acting liquid.

7. The water purification agent composite material according to claim 6, characterized in that: The mass fraction of the sodium alginate solution is 4-6%; the mass fraction of the sodium dodecylbenzene sulfonate solution is 3-5%.

8. The water purification agent composite material according to claim 6, characterized in that: The wood cellulose is also treated by immersion in a sodium silicate solution, and the specific immersion method is: The wood cellulose, sodium silicate solution and silicon carbide powder are stirred and immersed in a weight ratio of 2:5:1 at a stirring and immersion speed of 150-200 r / min for 1 hour.

9. The water purification agent composite material according to claim 8, characterized in that: The mass fraction of the sodium silicate solution is 4-7%.

10. The method for preparing a water purifier composite material according to any one of claims 1 to 9, characterized in that: The following steps are involved: The activated carbon, the additive doped with zeolite and the modified long-acting liquid are stirred and mixed, and then fully ball-milled in a ball mill at a ball milling speed of 1500r / min for 1h. After the ball milling is completed, the mixture is filtered and dried, and finally formed at a pressure of 30-35Mpa for 10min to obtain the water purifier composite material of the present invention.

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