A submerged plant planting matrix for water treatment and preparation method thereof

Abstract

The present application relates to the technical field of water treatment, and specifically discloses a submerged plant planting matrix for water treatment and a preparation method thereof. A submerged plant planting matrix for water treatment includes the following components in parts by weight: 30-40 parts of Fe3O4 particles; 15-20 parts of TiO2-loaded tourmaline; 100-120 parts of ore particles; 20-25 parts of graphene hollow activated carbon fibers; 10-15 parts of water; 1-3 parts of binder; and its preparation method is: first, TiO2-loaded tourmaline is mixed with graphene hollow activated carbon fibers, impregnated, dried, and a mixed material is obtained, and then blended with other raw materials, rolled, distributed holes, fired, cooled, and a submerged plant planting matrix is ​​obtained. Submerged plants are planted in the planting matrix of the present application, and the ecological floating bed formed by the two can effectively purify water and efficiently remove pollutants.

Description

Technical Field

[0001] The present application relates to the technical field of water treatment, and in particular to a submerged plant planting matrix for water treatment and a preparation method thereof. Background Art

[0002] Ecological floating bed is a new type of highly efficient and environmentally friendly in-situ ecological restoration technology for water bodies. It uses hydroponics to fix aquatic plants on the planting matrix to form an ecological floating bed. It effectively removes nitrogen and phosphorus pollutants in the water through plant absorption, root adsorption and attached microbial metabolism, thereby achieving the effect of purifying water quality. Compared with other water environment restoration technologies, ecological floating beds have the advantages of low cost and simple operation, and have been widely used in the treatment of eutrophic water bodies. As a type of aquatic plants, submerged plants can efficiently absorb nutrients in water and sediments, inhibit eutrophication of water bodies, and control the occurrence of algal blooms to a certain extent. They are important pollution purifiers in the water environment. At present, they are mostly combined with planting matrices and used for water treatment.

[0003] Antibiotics are a new type of water pollutant that can enter the environment in a variety of ways, from the production of active pharmaceutical ingredients to the discharge of residues after use or the discarding of unused drugs. After entering the human or animal body, these different stages of antibiotics will be excreted in the form of parent structures or metabolites (such as urine or feces). These different forms of antibiotics will enter and accumulate in the water environment through indirect or direct pathways, thereby affecting the water environment to varying degrees. Antibiotics have very severe toxic effects on aquatic plants, including interfering with metabolism, damaging the oxidation process, damaging the photosynthetic system, and inhibiting growth. What's more tricky is that submerged plants are more sensitive to antibiotics than other aquatic plants (such as emergent plants, floating plants, etc.), and their growth is more restricted. Therefore, the technology of applying submerged plants to ecological floating beds is facing severe tests. Summary of the invention

[0004] In order to reduce the impact of antibiotics in water bodies on submerged plants, the present application provides a submerged plant planting matrix for water treatment and a preparation method thereof.

[0005] In the first aspect, the present application provides a submerged plant planting matrix for water treatment, wherein the raw materials used include the following components in parts by weight: 30-40 parts of Fe3O4 particles; 15-20 parts of TiO2-loaded tourmaline; 100-120 parts of ore particles; 20-25 parts of graphene hollow activated carbon fibers; 10-15 parts of water; 1-3 parts of a binder;

[0006] The preparation method of the TiO2-loaded tourmaline comprises the following steps: dispersing tourmaline and tetrabutyl titanate in a weight ratio of 5:(5-20) in an organic solvent, aging to obtain a dry gel, and then heating the dry gel overnight, calcining, and cooling to obtain the TiO2-loaded tourmaline.

[0007] Preferably, the raw materials used include the following components in parts by weight: 35 parts of Fe3O4 particles; 18 parts of TiO2-loaded tourmaline; 110 parts of ore particles; 24 parts of graphene hollow activated carbon fibers; 12 parts of water; and 2 parts of a binder.

[0008] By adopting the above technical scheme, in the TiO2-loaded tourmaline, the tourmaline itself has the ability to catalyze the decomposition of organic matter, adsorb nitrogen and phosphorus, and promote the proliferation of microalgae in the water body. The present application utilizes this characteristic, and then the TiO2 with the ability to catalyze the degradation of antibiotics is loaded on the surface of the tourmaline by the gel method, and finally the TiO2-loaded tourmaline that can adsorb and degrade a large number of pollutants in the water body is obtained. After adding it to the submerged plant planting matrix, the antibiotic content in the water body can be reduced, and the good growth of submerged plants can be maintained, thereby ensuring the long-term water purification effect of the ecological floating bed. The present application controls the weight ratio of tourmaline and tetrabutyl titanate, thereby controlling the ratio of TiO2 to tourmaline in the final TiO2-loaded tourmaline, and finally obtains a TiO2-loaded tourmaline with good antibiotic degradation effect. If the amount of tetrabutyl titanate is too small, the catalytic activity of the TiO2-loaded tourmaline itself will be reduced; if the amount of tetrabutyl titanate is too large, the surface of the tourmaline will be over-coated by TiO2 particles, resulting in the damage of the adsorption effect of the tourmaline itself.

[0009] In addition, the present application utilizes ultrasonic impregnation to prepare graphene hollow activated carbon fibers, which have excellent adsorption capacity and can effectively adsorb antibiotic molecules in water bodies, and then uses vacuum impregnation to fill TiO2-loaded tourmaline into the hollow pores of the graphene hollow activated carbon fibers, thereby increasing the intensity of the adsorption and degradation behavior of TiO2-loaded tourmaline on antibiotic molecules in water bodies, promoting the degradation of antibiotics by the planting matrix, and maintaining good growth conditions for submerged plants; and the outer surface of the graphene hollow activated carbon fibers has a layered graphene structure, which can not only enhance the surface adsorption force of the graphene hollow activated carbon fibers, thereby effectively adsorbing a variety of pollutants in the water body, but also enhance the surface roughness. After being blended with other raw materials, they can be more closely combined with each other, effectively enhancing the stability of the planting matrix for submerged plants.

[0010] Finally, the Fe3O4 particles of the present application have good adsorption and catalytic effects, and can effectively adsorb organic pollutants and microorganisms in the water; the mineral particles can effectively adsorb nitrogen and phosphorus in the water, thereby improving the absorption and utilization rate of nitrogen and phosphorus by submerged plants; water and binders can bond a variety of solid materials into one, and finally a variety of substances play a synergistic role, resulting in a submerged plant planting matrix that can effectively degrade antibiotics, adsorb pollutants in the water and assist submerged plants to grow well.

[0011] The binder may be any one or more of those known to those skilled in the art, such as one or more of gypsum, silica sol, water glass, silicate cement and mortar. In the specific implementation of the present application, only silica sol is used as an example for illustration, and those skilled in the art may make adjustments according to actual conditions.

[0012] Preferably, in the method for preparing TiO2-loaded tourmaline, the weight ratio of tourmaline to tetrabutyl titanate is 5:(10-15).

[0013] By adopting the above technical scheme, the present application further controls the weight ratio of tourmaline and tetrabutyl titanate. At this time, the degradation effect of TiO2-loaded tourmaline is optimal. Experimental data show that the ecological floating bed obtained by planting matrix and submerged plants can increase the COD removal rate to 56.9-57.2%, the nitrogen and phosphorus removal rate to 93.4-93.6%, and the antibiotic removal rate to 71.1-71.3%.

[0014] Preferably, the tourmaline is also pretreated, specifically comprising the following steps: mixing Fe(NO3)3·9H2O, Zn(NO3)2·6H2O and tourmaline in a weight ratio of (1.8-2):(0.7-0.8):5, heat treating at a temperature of 85-95°C, followed by cooling, drying, calcining at 500-520°C, and cooling to obtain pretreated tourmaline.

[0015] Preferably, the weight ratio of Fe(NO3)3·9H2O, Zn(NO3)2·6H2O and tourmaline is 1.9:0.75:5.

[0016] By adopting the above technical solution, the present application uses Fe(NO3)3·9H2O and Zn(NO3)2·6H2O to pretreat tourmaline, and obtains pretreated tourmaline with spinel structure zinc ferrite on the surface, which can form a heterojunction after combining with TiO2, enhancing the charge transfer ability and migration ability, reducing the aggregation between particles, and further improving the catalytic activity and catalytic stability of TiO2-loaded tourmaline. In addition, the present application strictly controls the weight ratio of Fe(NO3)3·9H2O, Zn(NO3)2·6H2O and tourmaline, so that the catalytic effect of TiO2-loaded tourmaline is optimal at this time. Experimental data show that the adsorption and degradation effect of the planting matrix on COD, nitrogen, phosphorus and antibiotics are significantly improved at this time.

[0017] Preferably, the ore particles include vermiculite, medical stone and volcanic stone in a weight ratio of 60:(15-20):(20-25).

[0018] By adopting the above-mentioned technical scheme, the present application utilizes vermiculite, medical stone and volcanic rock in a certain proportion to obtain mineral particles that can not only effectively absorb nitrogen and phosphorus, but also promote the absorption of nutrients by submerged plants and the growth of microalgae in the water body, thereby improving the diversity and richness of microorganisms in the water body. In addition, the mineral particles of the present application have a certain mechanical strength. The planting matrix prepared by mixing it as the main supporting material with other components has a high cylinder pressure strength, thereby improving the service life of the overall ecological floating bed and protecting the stable growth of submerged plants in the planting matrix.

[0019] In a second aspect, the present application provides a method for preparing a submerged plant planting substrate for water treatment, comprising the following steps:

[0020] I. Ultrasonic dispersion of TiO2-loaded tourmaline in a polyvinyl alcohol aqueous solution, followed by mixing with graphene hollow activated carbon fibers, impregnating for 5 min under a vacuum environment, drying, and repeating the impregnation and drying operations 1-6 times to finally obtain a mixed material;

[0021] II. Evenly mix Fe3O4 particles, ore particles, binder and water, grind them, add the mixed material obtained in step I and blend them, then roll them into planting bodies, distribute holes, burn them, and naturally cool them to obtain submerged plant planting substrates.

[0022] By adopting the above technical scheme, the present application first mixes TiO2-loaded tourmaline with graphene hollow activated carbon fibers, and obtains graphene hollow activated carbon fibers with hollow pores filled with TiO2-loaded tourmaline by vacuum impregnation, and effectively controls the filling amount by controlling the number of impregnation and drying times, and then mixes with ground Fe3O4 particles, ore particles, binder and water, rolls, distributes holes, burns, and naturally cools to obtain a submerged plant planting matrix, which has multiple advantages of degrading antibiotics, adsorbing pollutants in water bodies, assisting the good growth of submerged plants, and having good mechanical stability. The preparation method of the present application can effectively enhance the adsorption and degradation intensity of antibiotic molecules in water bodies by TiO2-loaded tourmaline, and promote the degradation of antibiotics by the planting matrix.

[0023] Preferably, in step I, the dipping and drying operations are repeated 4-5 times.

[0024] By adopting the above technical scheme, the present application further controls the number of impregnation and drying in step I, thereby further controlling the filling amount of TiO2-loaded tourmaline, so as to achieve an optimal balance between the effects of improving the adsorption and degradation of antibiotic molecules in water by TiO2-loaded tourmaline and improving the surface adsorption force and surface roughness of graphene hollow activated carbon fibers, thereby achieving a higher level of water purification effect of the planting matrix and the growth of submerged plants.

[0025] In a third aspect, the present application provides an application of a submerged plant planting matrix for water treatment, comprising the following steps: planting submerged plants into the holes of the above-mentioned submerged plant planting matrix to obtain an ecological floating bed.

[0026] By adopting the above technical solution, the present application plants submerged plants into the holes of the above submerged plant planting matrix to obtain an ecological floating bed, which is placed in the water body to be treated, which can effectively reduce the COD, nitrogen and phosphorus content and antibiotic content in the water body. At the same time, the submerged plants can grow well and play a long-term and efficient water purification effect. The submerged plants in this application take Vallisneria as an example, and the planting density is 100 plants / m 2 For example, in actual use, technicians in this field can reasonably replace different submerged plants and / or reasonably adjust different planting densities according to actual conditions.

[0027] In summary, this application has the following beneficial technical effects:

[0028] 1. The planting matrix of the present application contains TiO2-loaded tourmaline that can adsorb and catalytically degrade a large number of pollutants in water bodies, and graphene hollow activated carbon fibers that have excellent adsorption capacity and can enhance the effect of TiO2-loaded tourmaline in degrading antibiotics. The two play a synergistic effect with each other, and are supplemented by mineral particles, Fe3O4 particles and other substances with good adsorption capacity. The multiple substances cooperate with each other to jointly enhance the effect of the planting matrix in degrading antibiotics, adsorbing pollutants in water bodies and assisting the good growth of submerged plants;

[0029] 2. The preparation method of the present application can effectively improve the severity of the adsorption and degradation behavior of TiO2-loaded tourmaline on antibiotic molecules in water bodies, promote the degradation of antibiotics by planting substrates, and at the same time control the number of immersion and drying in step I, thereby controlling the filling amount of TiO2-loaded tourmaline, so that the effects of improving the adsorption and degradation of antibiotic molecules in water bodies by TiO2-loaded tourmaline and improving the surface adsorption force and surface roughness of graphene hollow activated carbon fibers tend to be optimally balanced, thereby improving the water purification effect of the planting substrate and optimizing the growth of submerged plants;

[0030] 3. After the ecological floating bed of the present application is placed in the water body to be treated, it can effectively reduce the COD, nitrogen and phosphorus content and antibiotic content in the water body. At the same time, submerged plants can grow well, achieving a long-term and efficient water purification effect. DETAILED DESCRIPTION

[0031] Material Source

[0032] Unless otherwise specified, the raw materials used in this application are all commercially available products, specifically:

[0033] Tourmaline was purchased from Hengluan Mining in Shijiazhuang, Hebei Province, with a particle size of 2±0.05um;

[0034] Tetrabutyl titanate was purchased from Shandong Jibei New Materials Co., Ltd., with an effective ingredient of 99 wt%;

[0035] Fe(NO3)3·9H2O was purchased from Tianjin Fuchen Chemical Reagent Factory;

[0036] Zn(NO3)2·6H2O was purchased from Guangzhou Chemical Reagent Factory

[0037] Citric acid monohydrate was purchased from Tianjin Damao Chemical Reagent Factory;

[0038] Graphene was graphene oxide purchased from Aladdin Chemical Co., Ltd.

[0039] 60 wt % polytetrafluoroethylene solution was purchased from Shanghai Fengguang Plastic Technology Co., Ltd.;

[0040] Polyvinyl alcohol aqueous solution was purchased from Jinan Century Tongda Chemical Co., Ltd., with a content of 40wt%, and diluted to 0.5wt% for later use;

[0041] The quartz stone was purchased from Lingshou County Chenyang Mineral Products Co., Ltd., with a whiteness of 90%, a density of 2.46 g / cm³, and a hardness of 7 HB;

[0042] Basalt was purchased from Henan Landa Water Treatment Materials Co., Ltd., with a pressure resistance of 743 MPa, a porosity of 82%, and an adsorption rate of 98%;

[0043] Silica sol was purchased from Heyuan Sodium Silicate Factory, Duruan Town, Pengjiang District, Jiangmen City, with an effective ingredient of 30wt% and a density of 1.2kg / m³;

[0044] Fe3O4 particles were purchased from Shijiazhuang Dongming New Materials Technology Co., Ltd. with a purity of 99.9%;

[0045] Hollow activated carbon fibers were purchased from Suzhou Kaifa New Material Technology Co., Ltd.;

[0046] Activated carbon fiber was purchased from Anhui Xinran Carbon Fiber Environmental Protection Technology Co., Ltd.

[0047] The present application is further described in detail below in combination with preparation examples, embodiments, application examples and comparative examples.

[0048] Preparation Example 1.1

[0049] The preparation method of TiO2 supported tourmaline adopts the following steps:

[0050] 5 kg of tourmaline, 10 L of acetic acid and 20 L of anhydrous ethanol were mixed and stirred for 1 hour, then 5 kg of tetrabutyl titanate was added into the system and aged to obtain a dry gel. The dry gel was then heated at 90°C overnight, then calcined at 450°C for 3 hours, and naturally cooled to room temperature to obtain TiO2-loaded tourmaline.

[0051] Preparation Example 1.2

[0052] The preparation method of TiO2 supported tourmaline adopts the following steps:

[0053] 5 kg of tourmaline, 10 L of acetic acid and 20 L of anhydrous ethanol were mixed and stirred for 1 hour, then 20 kg of tetrabutyl titanate was added into the system and aged to obtain a dry gel. The dry gel was then heated at 90°C overnight, then calcined at 450°C for 3 hours, and naturally cooled to room temperature to obtain TiO2-loaded tourmaline.

[0054] Preparation Example 1.3

[0055] The preparation method of TiO2-loaded tourmaline is different from that of Preparation Example 1.1 in that the amount of tetrabutyl titanate used is 10 kg, and the rest is the same as that of Preparation Example 1.1.

[0056] Preparation Example 1.4

[0057] The preparation method of TiO2-loaded tourmaline is different from that of Preparation Example 1.1 in that the amount of tetrabutyl titanate used is 12.5 kg, and the rest is the same as that of Preparation Example 1.1.

[0058] Preparation Example 1.5

[0059] The preparation method of TiO2-loaded tourmaline is different from that of Preparation Example 1.1 in that the amount of tetrabutyl titanate used is 15 kg, and the rest is the same as that of Preparation Example 1.1.

[0060] Preparation Example 1.6

[0061] The preparation method of TiO2-loaded tourmaline is different from that of Preparation Example 1.1 in that the amount of tetrabutyl titanate used is 7.5 kg, and the rest is the same as that of Preparation Example 1.1.

[0062] Preparation Example 1.7

[0063] The preparation method of TiO2-loaded tourmaline is different from that of Preparation Example 1.1 in that the amount of tetrabutyl titanate used is 17.5 kg, and the rest is the same as that of Preparation Example 1.1.

[0064] Preparation Example 2.1

[0065] The preparation method of TiO2-loaded tourmaline is different from that of Preparation Example 1.3 in that the tourmaline is also pretreated, specifically:

[0066] 1.8kg Fe(NO3)3·9H2O and 0.8kg Zn(NO3)2·6H2O were dissolved in 30L water, and then 1.5kg citric acid monohydrate and 5kg tourmaline were mixed and added into the system. After stirring for 0.5h, the mixture was heat treated at 95°C for 2h, cooled, dried, and calcined at 500°C for 3h. The mixture was cooled to room temperature to obtain pretreated tourmaline. 5kg pretreated tourmaline, 10L acetic acid and 20L anhydrous ethanol were blended, stirred for 1h, and then 5kg tetrabutyl titanate was added into the system. The dry gel was aged to obtain a dry gel. The dry gel was then heated at 90°C overnight, calcined at 450°C for 3h, and naturally cooled to room temperature to obtain TiO2-loaded tourmaline.

[0067] Preparation Example 2.2

[0068] The preparation method of TiO2-loaded tourmaline is different from that of Preparation Example 1.3 in that the tourmaline is also pretreated, specifically:

[0069] 2kg Fe(NO3)3·9H2O and 0.7kg Zn(NO3)2·6H2O were dissolved in 30L water, and then 1.5kg citric acid monohydrate and 5kg tourmaline were mixed and added into the system. After stirring for 0.5h, the mixture was heat treated at 85°C for 2h, cooled, dried, and calcined at 520°C for 3h. The mixture was cooled to room temperature to obtain pretreated tourmaline. 5kg pretreated tourmaline, 10L acetic acid and 20L anhydrous ethanol were blended, stirred for 1h, and then 5kg tetrabutyl titanate was added into the system. The dry gel was aged to obtain a dry gel. The dry gel was then heated at 90°C overnight, calcined at 450°C for 3h, and naturally cooled to room temperature to obtain TiO2-loaded tourmaline.

[0070] Preparation Example 2.3

[0071] The preparation method of TiO2-loaded tourmaline is different from that of Preparation Example 2.1 in that the amount of Fe(NO3)3·9H2O used is 1.9 kg, the amount of Zn(NO3)2·6H2O used is 0.75 kg, and the rest is the same as Preparation Example 2.1.

[0072] Preparation Example 3

[0073] The preparation method of graphene hollow activated carbon fiber adopts the following steps:

[0074] 2.2 kg of graphene and 0.88 kg of sodium bicarbonate were added to 100 L of anhydrous ethanol, and ultrasonic treatment was performed for 15 min to uniformly disperse it to obtain a graphene slurry. The ultrasonic treatment was continued for 15 min and 8.8 kg of a 60 wt% polytetrafluoroethylene solution was slowly added dropwise. Then 10 kg of hollow activated carbon fibers were immersed in the graphene slurry and ultrasonically treated for 60 min. The hollow activated carbon fibers with graphene attached were then taken out and calcined at a temperature of 360 ° C. The heating rate was 10 ° C / min. After calcination for 10 min, graphene hollow activated carbon fibers were obtained.

[0075] Comparative Preparation Example 1.1

[0076] The difference from Preparation Example 1.1 is that the amount of tetrabutyl titanate used is 3 kg, and the rest is the same as Preparation Example 1.1.

[0077] Comparative Preparation Example 1.2

[0078] The difference from Preparation Example 1.1 is that the amount of tetrabutyl titanate used is 25 kg, and the rest is the same as Preparation Example 1.1.

[0079] Comparative Example 2

[0080] The preparation method of graphene activated carbon fiber adopts the following steps:

[0081] 2.2 kg of graphene and 0.88 kg of sodium bicarbonate were added to 100 L of anhydrous ethanol, and ultrasonic treatment was performed for 15 min to uniformly disperse the graphene slurry. The ultrasonic treatment was continued for 15 min and 8.8 kg of 60 wt% polytetrafluoroethylene solution was slowly added dropwise. Then 10 kg of activated carbon fiber was immersed in the graphene slurry and ultrasonically treated for 60 min. The activated carbon fiber with graphene attached was then taken out and calcined at a temperature of 360 ° C. The heating rate was 10 ° C / min. After calcination for 10 min, graphene activated carbon fiber was obtained.

[0082] Example 1.1

[0083] A method for preparing a submerged plant planting matrix for water treatment comprises the following steps:

[0084] I. Ultrasonic dispersion of 2 kg of TiO2-loaded tourmaline obtained in Preparation Example 1.1 in 10 kg of 0.5 wt% polyvinyl alcohol aqueous solution, followed by addition of 2 kg of graphene hollow activated carbon fibers obtained in Preparation Example 3, impregnation for 5 min under vacuum, drying at 85° C., and repeating the impregnation and drying operations for 6 times to finally obtain a mixed material;

[0085] II. Evenly mix 3kg of Fe3O4 particles, 10kg of ore particles (quartz), 0.3kg of binder and 1kg of water, grind to 200 mesh, add all the mixed materials obtained in step I, blend, and then roll into a planting body, shape, and evenly distribute holes. Sinter at 650℃ for 80h, cool naturally, and cut according to the specification to obtain a submerged plant planting matrix with a size of 0.5m×0.5m×0.4m.

[0086] Example 1.2

[0087] A method for preparing a submerged plant planting matrix for water treatment comprises the following steps:

[0088] I. 1.5 kg of the TiO2-loaded tourmaline obtained in Preparation Example 1.2 was ultrasonically dispersed in 10 kg of a 0.5 wt% polyvinyl alcohol aqueous solution, and then 2.5 kg of the graphene hollow activated carbon fiber obtained in Preparation Example 3 was added, and the mixture was impregnated for 5 min under a vacuum environment, dried at a temperature of 85° C., and the impregnation and drying operations were repeated once to finally obtain a mixed material;

[0089] II. Evenly mix 4 kg of Fe3O4 particles, 12 kg of ore particles (basalt), 0.1 kg of binder and 1.5 kg of water, grind to 200 mesh, add all the mixed materials obtained in step I, blend, and then roll into a planting body, shape it, and evenly distribute holes. Sinter it at 650°C for 80 hours, cool it naturally, and cut it according to the specification to obtain a submerged plant planting matrix with a size of 0.5m×0.5m×0.4m.

[0090] Example 1.3

[0091] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that the amount of TiO2-loaded tourmaline obtained in Preparation Example 1.1 in step I is 1.8 kg, the amount of graphene hollow activated carbon fiber obtained in Preparation Example 3 is 2.4 kg, the amount of Fe3O4 particles in step II is 3.5 kg, the amount of ore particles is 11 kg, the amount of binder is 0.2 kg, the amount of water is 1.2 kg, and the rest is the same as Example 1.1.

[0092] Examples 2.1-2.5

[0093] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that, in step I, the TiO2-loaded tourmaline obtained in Preparation Example 1.1 is replaced by the TiO2-loaded tourmaline obtained in Preparation Examples 1.3-1.7 respectively, and the rest is the same as Example 1.1.

[0094] Examples 3.1-3.3

[0095] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 2.1 in that, in step I, the TiO2-loaded tourmaline obtained in Preparation Example 1.1 is replaced by the TiO2-loaded tourmaline obtained in Preparation Examples 2.1-2.3 respectively, and the rest is the same as Example 2.1.

[0096] Example 4.1

[0097] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step II, 10 kg of quartz stone is replaced by 6 kg of vermiculite, 1.5 kg of medical stone and 2.5 kg of volcanic stone, and the rest is the same as Example 1.1.

[0098] Example 4.2

[0099] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step II, 10 kg of quartz stone is replaced by 6 kg of vermiculite, 2 kg of medical stone and 2 kg of volcanic stone, and the rest is the same as Example 1.1.

[0100] Example 4.3

[0101] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step II, 10 kg of quartz stone is replaced by 6 kg of vermiculite, 1.7 kg of medical stone and 2.3 kg of volcanic stone, and the rest is the same as Example 1.1.

[0102] Example 4.4

[0103] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step II, 10 kg of quartz stone is replaced by 5 kg of vermiculite, 4 kg of medical stone and 1 kg of volcanic stone, and the rest is the same as Example 1.1.

[0104] Example 4.5

[0105] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step II, 10 kg of quartz stone is replaced by 8 kg of vermiculite, 0.5 kg of medical stone and 1.5 kg of volcanic stone, and the rest is the same as Example 1.1.

[0106] Example 4.6

[0107] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step II, 10 kg of quartz stone is replaced by 4 kg of vermiculite, 1 kg of medical stone and 5 kg of volcanic stone, and the rest is the same as Example 1.1.

[0108] Example 4.7

[0109] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 2.1 in that in step II, 10 kg of quartz stone is replaced by 6 kg of vermiculite, 1.7 kg of medical stone and 2.3 kg of volcanic stone, and the rest is the same as Example 2.1.

[0110] Example 5.1

[0111] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step I, the immersion and drying operations are repeated twice, and the rest are the same as Example 1.1.

[0112] Example 5.2

[0113] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step I, the immersion and drying operations are repeated 3 times, and the rest are the same as Example 1.1.

[0114] Example 5.3

[0115] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step I, the immersion and drying operations are repeated 4 times, and the rest are the same as Example 1.1.

[0116] Example 5.4

[0117] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 1.1 in that in step I, the immersion and drying operations are repeated 5 times, and the rest are the same as Example 1.1.

[0118] Example 5.5

[0119] A method for preparing a submerged plant planting matrix for water treatment, which is different from Example 2.1 in that in step I, the immersion and drying operations are repeated 4 times, and the rest are the same as Example 2.1.

[0120] Comparative Example 1

[0121] The difference from Example 1.1 is that step I is removed, specifically: 2kg of TiO2-loaded tourmaline obtained in Preparation Example 1.1, 2kg of graphene hollow activated carbon fiber obtained in Preparation Example 3, 3kg of Fe3O4 particles, 10kg of ore particles (quartz stone), 0.3kg of binder and 1kg of water are evenly mixed, ground to 200 mesh, and then rolled into a planting body, shaped, and evenly distributed with holes, fired at 650°C for 80h, naturally cooled, and cut according to the specification to obtain a submerged plant planting matrix with a size of 0.5m×0.5m×0.4m.

[0122] Comparative Example 2.1

[0123] The difference from Example 1.1 is that the amount of TiO2-loaded tourmaline obtained in Preparation Example 1.1 in step I is 2.5 kg, the amount of graphene hollow activated carbon fiber obtained in Preparation Example 3 is 1.5 kg, the amount of Fe3O4 particles in step II is 4.5 kg, the amount of ore particles is 15 kg, and the rest is the same as Example 1.1.

[0124] Comparative Example 2.2

[0125] The difference from Example 1.1 is that the amount of TiO2-loaded tourmaline obtained in Preparation Example 1.1 in step I is 1.2 kg, the amount of graphene hollow activated carbon fiber obtained in Preparation Example 3 is 3 kg, the amount of Fe3O4 particles in step II is 2.5 kg, the amount of ore particles is 8 kg, and the rest is the same as Example 1.1.

[0126] Comparative Example 3.1

[0127] The difference from Example 1.1 is that the TiO2-loaded tourmaline obtained in Preparation Example 1.1 in step I is replaced by tourmaline particles, and the rest is the same as Example 1.1.

[0128] Comparative Examples 3.2-3.3

[0129] The difference from Example 1.1 is that the TiO2-loaded tourmaline obtained in Preparation Example 1.1 in Step I is replaced by the TiO2-loaded tourmaline obtained in Comparative Preparation Examples 1.1-1.2 respectively, and the rest is the same as Example 1.1.

[0130] Comparative Example 4

[0131] The difference from Example 1.1 is that the graphene hollow activated carbon fiber prepared in Preparation Example 3 in Step I is replaced by the graphene activated carbon fiber prepared in Comparative Preparation Example 2, and the rest is the same as Example 1.1.

[0132] Comparative Example 5

[0133] The difference from Example 1.3 is that all the Fe3O4 particles in step II are removed, and their amounts are added to other raw materials used in proportion. Specifically, the amount of TiO2-loaded tourmaline obtained in Preparation Example 1.1 in step I is 2.21 kg, the amount of graphene hollow activated carbon fibers obtained in Preparation Example 3 is 2.96 kg, the amount of ore particles is 13.53 kg, and the rest is the same as Example 1.3.

[0134] Application Example 1-23

[0135] An application of a submerged plant planting substrate for water treatment comprises the following steps:

[0136] Vallisneria was planted into the holes of the submerged plant planting matrix prepared in Examples 1.1-5.5, with a planting density of 100 plants / m 2 , and obtain an ecological floating bed.

[0137] Comparative Application Examples 1-8

[0138] The following steps are involved:

[0139] Vallisneria was planted into the holes of the submerged plant planting substrates prepared in Comparative Examples 1-5, with a planting density of 100 plants / m 2 , and obtain an ecological floating bed.

[0140] Performance Testing

[0141] 1. Water purification capacity test: The ecological floating bed obtained in each application example is placed in the water body to be treated for 1 month. The water body to be treated is a flowing water body. The COD is 25 mg / L, the total nitrogen and phosphorus content is 25 mg / L, and the total amount of antibiotics (mainly norfloxacin and oxytetracycline hydrochloride) is 11.5 mg / L. According to the records in GB 8978-2002, the water quality indicators of each application example are measured, the removal rate is calculated, and the results are recorded in Table 1;

[0142] 2. Stability test: The cylinder compressive strength (MPa) of the submerged plant planting matrix filler prepared in each example was measured according to the record in GB / T 17431.1-2010, and the results were recorded in Table 1;

[0143] 3. Plant growth detection (chlorophyll content change): According to the article "Zhou Jinbo, Jin Shuquan, Bao Weihong, et al. Comparative study on the effects of different concentrations of ammonia nitrogen on the growth of four submerged plants [J / OL]. Journal of Agricultural Resources and Environment, 2018, 35(1): 74-81.", the chlorophyll content of Vallisneria was determined. 0.2g of Vallisneria leaf was taken for each measurement. The measurement was performed once a day, and the average value of the difference between the daily chlorophyll content and the first day's chlorophyll content was calculated (mg·g -1 ), recorded in Table 1.

[0144] Table 1 Performance test table

[0145]

[0146] Data Analysis:

[0147] As can be seen from Table 1, the COD removal rate of the ecological floating bed of Application Examples 1-3 of this application can reach 56.4-56.8%, the nitrogen and phosphorus removal rate can reach 92.6-92.7%, the antibiotic removal rate can reach 68.6-68.9%, the cylinder pressure strength can reach 7.5-7.9MPa, and the average value μ1 of the difference between the daily chlorophyll content and the first day chlorophyll content can reach 0.085-0.086mg·g -1 , it is proved that the various substances of the present application exert a synergistic effect, and a submerged plant planting matrix that can effectively degrade antibiotics, adsorb pollutants in the water body and assist the good growth of submerged plants is obtained. Submerged plants are planted in the holes of the above-mentioned submerged plant planting matrix to obtain an ecological floating bed, which is placed in the water body to be treated, which can effectively reduce the COD, nitrogen and phosphorus content and antibiotic content in the water body. At the same time, the submerged plants can grow well, achieving a long-term and efficient water purification effect;

[0148] The COD removal rate, nitrogen and phosphorus removal rate, and antibiotic removal rate of Application Example 4-5 in Application Example 4-8 are significantly higher than those of Application Example 1 and Application Example 6-8, proving that the present application can optimize the degradation effect of TiO2-loaded tourmaline by controlling the weight ratio of tourmaline and tetrabutyl titanate;

[0149] The COD removal rate, nitrogen and phosphorus removal rate, antibiotic removal rate and μ1 of application examples 9-11 are better than those of application example 4, proving that the present application obtains pretreated tourmaline with spinel-structured zinc ferrite on the surface by pretreating tourmaline with Fe(NO3)3·9H2O and Zn(NO3)2·6H2O, which can form a heterojunction after combining with TiO2, thereby enhancing the charge transfer ability and migration ability, reducing the aggregation between particles, and further improving the catalytic activity and catalytic stability of TiO2-loaded tourmaline. Among them, the various data of application example 11 are better than those of application examples 9-10, proving that the present application strictly controls the weight ratio of Fe(NO3)3·9H2O, Zn(NO3)2·6H2O and tourmaline, so that the catalytic effect of TiO2-loaded tourmaline can be optimized at this time;

[0150] The COD removal rate, nitrogen and phosphorus removal rate, antibiotic removal rate and μ1 of application examples 12-17 are better than those of application example 1, and the data of application examples 12-14 are better than those of application examples 15-17, which proves that the mineral particles obtained by compounding vermiculite, medical stone and volcanic stone in a certain proportion in this application can not only effectively adsorb nitrogen and phosphorus, but also promote the absorption of nutrients by submerged plants and the growth of microalgae in the water body, and improve the diversity and richness of microorganisms in the water body. In addition, the mineral particles of this application have a certain mechanical strength. The planting matrix prepared by mixing it as the main supporting material with other components has a high cylinder pressure strength, thereby improving the service life of the overall ecological floating bed and protecting the stable growth of submerged plants in the planting matrix.

[0151] In Application Examples 19-22, the data of Application Examples 21-22 are better than those of Application Examples 19-20 and Application Example 1, proving that the present application effectively controls the filling amount by controlling the number of immersion and drying, so as to achieve an optimal balance between the effects of improving the adsorption and degradation of antibiotic molecules in the water by TiO2-loaded tourmaline and improving the surface adsorption force and surface roughness of the graphene hollow activated carbon fibers, thus achieving a higher level of water purification effect of the planting matrix and the growth of submerged plants;

[0152] The data of Application Example 1 are obviously inferior to those of Application Example 1, which proves that the graphene hollow activated carbon fiber of the present application combined with the TiO2-loaded tourmaline by vacuum impregnation can enhance the adsorption and degradation of antibiotic molecules in the water by the TiO2-loaded tourmaline, promote the degradation of antibiotics by the planting matrix, and maintain the good growth of submerged plants.

[0153] The data of application examples 2-3 are obviously inferior to those of application example 1, which proves that the present application can achieve a higher level of water purification effect of the planting matrix and the growth of submerged plants by controlling the ratio of various substances;

[0154] The data of application examples 4-6 are obviously inferior to those of application example 1, which proves that the TiO2-loaded tourmaline of the present application can reduce the antibiotic content in the water body and maintain the good growth of submerged plants, thereby ensuring the water purification effect of the ecological floating bed;

[0155] The data of Application Example 7 are obviously inferior to those of Application Example 1, which proves that the graphene hollow activated carbon fiber of the present application can effectively adsorb antibiotics and accommodate TiO2-loaded tourmaline into the hollow pores, thereby increasing the intensity of the adsorption and degradation behavior of TiO2-loaded tourmaline on antibiotic molecules in the water, promoting the degradation of antibiotics by the planting matrix, and maintaining good growth conditions of submerged plants.

[0156] The data of Application Example 8 are obviously inferior to those of Application Example 1 and Application Example 3, which means that even if the Fe3O4 particles are removed under the premise of achieving the optimal ratio between other components, the water purification effect of the ecological floating bed is still far lower than that of the ecological floating bed containing Fe3O4 particles. This proves that the TiO2-loaded tourmaline, graphene hollow activated carbon fiber and Fe3O4 particles in this application do have a good synergistic effect, which can promote the degradation of antibiotics by the planting matrix and maintain good growth conditions of submerged plants.

[0157] The embodiments of this specific implementation method are all preferred embodiments of the present application, and are not intended to limit the protection scope of the present application. Therefore, all equivalent changes made based on the structure, shape, and principle of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a submerged plant planting matrix for water treatment, characterized in that: The raw materials used include the following components in parts by weight: 30-40 parts of Fe3O4 particles; 15-20 parts of TiO2-loaded tourmaline; 100-120 parts of ore particles; 20-25 parts of graphene hollow activated carbon fibers; Water 10-15 parts; Binder 1-3 parts; The preparation method comprises the following steps: I. Ultrasonic dispersion of TiO2-loaded tourmaline in a polyvinyl alcohol aqueous solution, followed by mixing with graphene hollow activated carbon fibers, impregnating for 5 min under a vacuum environment, drying, and repeating the impregnation and drying operations 1-6 times to finally obtain a mixed material; II. Evenly mix Fe3O4 particles, ore particles, a binder and water, grind them, add the mixed material obtained in step I, blend them, and then press them into a planting body, distribute holes, burn them, and naturally cool them to obtain a submerged plant planting matrix; The preparation method of the TiO2-loaded tourmaline comprises the following steps: dispersing tourmaline and tetrabutyl titanate in a weight ratio of 5:(5-20) in an organic solvent, aging to obtain a dry gel, and then heating the dry gel overnight, calcining, and cooling to obtain the TiO2-loaded tourmaline.

2. The method for preparing a submerged plant planting matrix for water treatment according to claim 1, characterized in that: The raw materials used include the following components in parts by weight: 35 parts of Fe3O4 particles; 18 parts of TiO2-loaded tourmaline; 110 parts of ore particles; 24 parts of graphene hollow activated carbon fibers; 12 parts of water; and 2 parts of a binder.

3. The method for preparing a submerged plant planting matrix for water treatment according to claim 1, characterized in that: In the preparation method of the TiO2-loaded tourmaline, the weight ratio of tourmaline to tetrabutyl titanate is 5:(10-15).

4. The method for preparing a submerged plant planting matrix for water treatment according to claim 1, characterized in that: The tourmaline is also pre-treated, the specific steps are: Fe(NO3)3·9H2O, Zn(NO3)2·6H2O and tourmaline in a weight ratio of (1.8-2):(0.7-0.8):5 are mixed, heat treated at a temperature of 85-95°C, then cooled, dried, calcined at 500-520°C, and cooled to obtain pretreated tourmaline.

5. The method for preparing a submerged plant planting matrix for water treatment according to claim 4, characterized in that: The weight ratio of Fe(NO3)3·9H2O, Zn(NO3)2·6H2O and tourmaline is 1.9:0.75:

5.

6. The method for preparing a submerged plant planting matrix for water treatment according to claim 1, characterized in that: The ore particles include vermiculite, medical stone and volcanic stone in a weight ratio of 60:(15-20):(20-25).

7. The method for preparing a submerged plant planting matrix for water treatment according to claim 1, characterized in that: In the step I, the dipping and drying operations are repeated 4-5 times.

8. An application of a submerged plant planting substrate for water treatment, characterized in that: The method comprises the following steps: planting submerged plants into the holes of the submerged plant planting matrix according to any one of claims 1 to 7 to obtain an ecological floating bed.

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