CN110479226B - A clay mineral/agricultural and forestry waste biomass composite sewage treatment agent, its preparation method and application - Google Patents

Abstract

The invention discloses a clay mineral/agricultural and forestry waste biomass composite sewage treatment agent, and a preparation method and application thereof. Taking clay minerals naturally existing in nature, renewable agricultural and forestry waste biomass and organic binder as raw materials, performing ball milling, mixing uniformly, performing superfine treatment, adding hot water for wetting and performing ageing treatment to obtain slurry; and mixing the materials by an open mill, tabletting and forming, drying, crushing and grading to prepare the clay mineral/biomass composite sewage treating agent. The sewage treatment agent obtained by the invention has the capability of simultaneously adsorbing and removing organic dyes, heavy metal ions, fluorine ions and the like. The composite sewage treatment agent prepared by using the natural clay minerals and the agricultural and forestry waste biomass as raw materials has the characteristics of low price, high yield, greenness, low carbon, pollution control by using waste, high performance and the like, and the preparation method has the advantages of simple process, environmental protection, energy conservation, easiness in mass production and the like, and has wide application prospect in sewage treatment application.

Description

A clay mineral/agricultural and forestry waste biomass composite sewage treatment agent and preparation method thereof and application

technical field

The invention belongs to the field of mineral-based composite materials and sewage treatment, and particularly relates to a clay mineral/agricultural and forestry waste biomass composite sewage treatment agent, a preparation method and application thereof.

Background technique

Rapid social and economic development (industrialization, urbanization) has brought serious environmental problems such as water pollution. Water pollution treatment and prevention technology is a global common topic, and it is also a major demand in my country at this stage. However, according to the "Water Pollution Prevention and Control Plan for Key River Basins", nearly 10% of the surface water in the country has a sub-category V water quality, and the pollution of nitrogen, phosphorus and heavy metals is becoming more and more prominent. Even trace heavy metals are harmful to human health, aquatic systems and the environment. Great threat (Environ. Technol. 2018, 11, 187). The Ministry of Industry and Information Technology's "Guiding Opinions on Accelerating the Development of Environmental Protection Equipment Manufacturing Industry" requires focusing on the research and development of "new high-efficiency water treatment materials and agents", "nanomaterials and agents for ecological restoration and environmental protection", and the development of multi-pollutant collaborative treatment and in-depth treatment technologies. It can be seen that the development of new composite adsorbents for the adsorption and removal of water-soluble pollutants with high efficiency, low cost, and ecological environmental protection is in line with the development trend and meets the major needs of the country.

Water-soluble pollutants, including heavy metal ions, organic dyes, agricultural and pharmaceutical intermediates and residues, are complex and diverse, with different properties, and often coexist at the same time, which is a challenge to purification technology. Commonly used treatment methods include precipitation, incineration, flocculation, coagulation, ion exchange, reverse osmosis, membrane filtration, electrochemistry, photochemistry, advanced oxidation, biological methods, etc. (App. Clay Sci. 2016, 123, 239), but some of the disadvantages of these methods are: low removal efficiency, high sludge yield, low cost, generation of toxic by-products, and the use of large amounts of chemicals (J. Environ. Manage. 2016, 179, 20). Adsorption removal method is currently the most cost-effective wastewater treatment method (Environ. Technol. 2009, 6, 583), and its core technical bottleneck lies in the design and macro-production of high-efficiency, low-cost, eco-friendly adsorbents. Common adsorbents include synthetic polymers (such as PAM), clay, biomass, etc., but most of them have problems such as large particles, single function, low adsorption capacity, and poor environmental compatibility, which are difficult to meet the water treatment of large quantities and complex and diverse pollution sources. Require. In addition, the price of chemical synthetic adsorbents used in industry is relatively expensive, which increases the cost of sewage treatment.

SUMMARY OF THE INVENTION

The purpose of the present invention is to aim at the deficiencies of the prior art, provide a kind of clay mineral/agricultural and forestry waste biomass composite sewage treatment agent, its preparation method and application: with cheap and abundant, ecologically friendly layered clay, agricultural and forestry biomass etc. Natural resources are used as raw materials, asymmetric ultra-fine exfoliation of clay, biomass and other blocks into two-dimensional clay nanosheets and one-dimensional biomass nanofibers, and hybrid embedding of clay nanosheets and biomass nanofibers to construct "clay" Nanosheet/biomass nanofiber" multi-level hybrid nanostructure; through the synergy between multi-component, multi-level structure and various functional groups, one-time adsorption and removal of complex and diverse soluble pollutants in sewage. The invention has the advantages of abundant quantity and low price, ecological environment protection, good sewage treatment effect, simple preparation process, easy batch production and the like.

In order to achieve the above purpose, the present invention adopts the following technical scheme: take natural clay minerals, renewable agricultural and forestry waste biomass, and organic binders as raw materials, after ball milling, mixing and ultra-fine, heating water to wet and stale treatment. Slurry is prepared; the clay mineral/biomass composite sewage treatment agent is prepared after kneading in an open mill, tableting, drying, crushing and grading treatment. A clay mineral/agricultural and forestry waste biomass composite sewage treatment agent and a preparation method thereof, comprising the following steps:

(1) Using agricultural and forestry waste biomass, clay minerals and binders as raw materials, according to the mass ratio of clay minerals, agricultural and forestry waste biomass and binders = (1~5):10:(2~6) ball milling;

(2) adding the mixed powder obtained in the step (1) into hot water, fully stirring and mixing, the temperature of the hot water is 40～95 ℃, and the mass ratio of the hot water and the mixed powder is (2.5～5): 1;

(3) The material obtained in step (2) is sealed and then placed in a set temperature for stale treatment, and the stale condition is kept at 40~100ºC for 5~48 h;

(4) The mixed slurry obtained in step (3) is kneaded, tableted and dried;

(5) The dry block material obtained in step (4) is crushed, sieved and classified to obtain a composite sewage treatment agent mainly composed of clay minerals and biomass.

As a preference of the above technical solution, the agricultural and forestry waste biomass is a mixture of jute straw and one or more of leaves, straw, corncob, bagasse, rice husk, fruit peel, and algae in any proportion.

As the preference of the above technical scheme, the clay mineral is one of bentonite, kaolin, attapulgite, sepiolite, montmorillonite, halloysite, vermiculite, smectite, palygorskite, illite or A mixture of two or more in any ratio.

As a preference of the above technical scheme, the binder is starch, protein, animal glue, sodium alginate, sodium carboxymethyl cellulose, polyacrylamide, sodium polyacrylate, polyvinylpyridinium salt, polyethyleneimine, A mixture of one or more of polydimethyldiallyl ammonium chloride in any proportion.

As the preference of the above-mentioned technical scheme, the used grinding ball is a mixture of one or more arbitrary proportions of alumina balls, zirconia balls, mullite balls and stainless steel balls, and the mass ratio of the grinding balls to the material is (3 ~ 6): 1, the diameter of the grinding ball is 3~15mm, the ball milling speed is 50~600 rpm, and the ball milling time is 1~20 h.

As the optimization of the above-mentioned technical scheme, the kneading and tableting are processed by an open mill, the front wheel speed of the mill is 5 to 20 rpm, the rear wheel speed of the mill is 5 to 20 rpm, and the temperature of the front wheel is 40 to 100 rpm. ºC, the rear wheel temperature is 40~100ºC, and the distance between the front and rear wheels is 0.5~5mm.

As a preference of the above technical solution, the drying refers to drying at 80-150° C. for 2-16 h, and the moisture content is (2-10)%.

As a preference of the above technical solution, after crushing and sieving in the step (5), the particle size range of the obtained composite treatment agent is 0.1-1 mm.

The clay mineral/agricultural and forestry waste biomass composite sewage treatment agent prepared by the above preparation method.

The application of the above clay mineral/agricultural and forestry waste biomass composite sewage treatment agent in adsorbing heavy metal ions in sewage, the heavy metal ions are preferably copper ions.

The application of the above clay mineral/agricultural and forestry waste biomass composite sewage treatment agent in adsorbing organic dyes in sewage, the organic dyes are preferably methylene blue.

The present invention has the following beneficial effects:

The invention combines the abundant functional groups of renewable biomass with the low-dimensional lamellar or fibrous structure of natural clay minerals, and utilizes their synergistic effect to improve the ability of the complex to adsorb and remove harmful ions such as organic dyes, heavy metal ions, and fluoride ions at the same time. , with stronger adaptability than existing commercial sewage treatment agents.

In addition, the composite sewage treatment agent prepared by the method provided by the invention using natural clay minerals and agricultural and forestry waste biomass as raw materials has the characteristics of low price, abundant, green and low carbon, pollution control with waste, and high performance, and the preparation method has the advantages of simple process, The advantages of environmental protection, energy saving, easy mass production, etc., have broad application prospects in sewage treatment applications.

The invention breaks through the key technologies for the design and preparation of new water treatment agents with high efficiency, ecology, low price and abundance, and realizes the high-value utilization of natural resources such as layered clay and biomass, and the improvement of the green and low-carbon water treatment technology of "waste control". Sustainable development, enrich and improve the theoretical system and cases of the preparation and application of mineral materials.

Description of drawings

Fig. 1 is the experimental flow chart of the preparation of the example.

Fig. 2 is the XRD pattern of the prepared sample of embodiment 1;

Fig. 3 is the SEM image of the prepared sample of embodiment 1;

Fig. 4 is the XRD pattern of the prepared sample of embodiment 2;

Fig. 5 is the SEM image of the prepared sample of embodiment 2;

Fig. 6 is the XRD pattern of the prepared sample of embodiment 3;

Fig. 7 is the SEM image of the prepared sample of Example 3;

Fig. 8 is the XRD pattern of the prepared sample of embodiment 4;

Fig. 9 is the SEM image of the prepared sample of embodiment 4;

Figure 10 is the XRD pattern of the sample prepared in Example 5;

Figure 11 is the SEM image of the sample prepared in Example 5;

Figure 12 is the XRD pattern of the sample prepared in Example 6;

FIG. 13 is a SEM image of the sample prepared in Example 6. FIG.

Figure 14 is a graph showing the performance of the composite sewage treatment agent on Cu ²⁺ adsorption.

Figure 15 is a graph of the performance of the unmodified raw material for Cu ²⁺ adsorption.

Figure 16 is a performance diagram of the adsorption of methylene blue by the composite sewage treatment agent.

Figure 17 is a graph showing the performance of the unmodified raw material on the adsorption of methylene blue.

Figure 18 shows the effect of the samples prepared in Example 2 on the adsorption performance and removal rate of different Cu ²⁺ concentrations.

Figure 19 shows the effect of the samples prepared in Example 2 on the adsorption performance and removal rate of different methylene blue concentrations.

Detailed ways

In order to better understand the present invention, the present invention will be further illustrated below through the examples using jute, bentonite, kaolin, attapulgite, anionic polyacrylamide, etc. as raw materials. The examples are only used to explain the present invention and will not constitute any limit.

Example 1

Mix 15 g of jute powder (leaf powder), 4.5 g of bentonite, and 3 g of anionic polyacrylamide (APAM) and put them into a polytetrafluoroethylene ball mill. %, 50% of medium balls with a diameter of 5 mm, and 30% of small balls with a diameter of 3 mm) and the composite raw materials in a mass ratio of 6:1. Put the above mixed powder into an agate mortar, add 90 g of warm water at 50ºC, stir evenly, wrap it with plastic wrap, and put it in an oven at 50ºC for 10 hours to obtain a composite slurry. The composite slurry was put into an open mill for kneading treatment. The front wheel speed of the open mill was 4 rpm, the rear wheel speed was 2 rpm, the temperature of the front and rear wheels were both 50ºC, and the distance between the front and rear wheels was 1 mm; fully mixed After pressing into tablets, the clay mineral/biomass composite tablets were obtained by drying in an oven at 80ºC for 12 h. Then, after being crushed by a crusher, the composite flakes pass through a 60-mesh sieve, and the material under the sieve is the clay mineral/biomass composite sewage treatment agent.

The obtained clay mineral/biomass composite sewage treatment agent adsorbs Cu ²⁺ under the following conditions: initial concentration of 2 g/L, dosage of sewage treatment agent 2 g/L, pH= 5, temperature of 55ºC, and adsorption time of 60 min. See Figure 14 for details.

The conditions for the adsorption of methylene blue by the obtained clay mineral/biomass composite sewage treatment agent were: initial concentration of 500 mg/L, dosage of sewage treatment agent 1.6 g/L, pH = 6, temperature of 60ºC, and adsorption time of 150 min. The adsorption capacity was tested.

Figure 1 is the preparation flow chart of the experiment, which introduces the preparation process of the composite sewage treatment agent in detail.

Figure 2 is the XRD of jute leaf powder, bentonite, jute leaf powder/bentonite composite sewage treatment agent, the XRD pattern of the composite sewage treatment agent is basically consistent with that of bentonite, but the intensity of the peak is relatively low, which is the jute powder intercalated bentonite and reduce its long-range order.

Figure 3 is the SEM image of the jute powder/bentonite composite sewage treatment agent. It can be seen from the figure that the surface of the bentonite is wrapped with jute powder, and there is also jute powder between the layers. This structure shows that the bentonite and the jute powder are closely combined. When the composite sewage treatment agent adsorbs Cu ²⁺ or methylene blue, it can promote the synergistic effect of jute powder and bentonite.

The adsorption performance of the composite sewage treatment agent obtained in Example 1 on Cu ²⁺ is shown in Figure 14. It can be seen that the adsorption amount of Cu ²⁺ by the product of Example 1 is 257.3 mg/g.

Figure 15 is a performance diagram of the adsorption of Cu ²⁺ by the unmodified raw materials. Combined with the adsorption amounts of Cu ²⁺ in Example 1 and Example 7 in Figure 14, it can be concluded that the adsorption of Cu ²⁺ by the composite sewage treatment agent The amount of Cu 2+ is much larger than that of the unmodified raw material, and the adsorption amount of Cu ²⁺ by the composite sewage treatment agent after adding bentonite is greater than that without the addition of the bentonite composite sewage treatment agent (ie Example 7).

The adsorption performance of the composite sewage treatment agent obtained in Example 1 on methylene blue is shown in Figure 16. It can be seen that the adsorption capacity of the product in Example 1 on methylene blue is 155 mg/g.

Figure 17 is a graph showing the adsorption performance of unmodified raw materials on methylene blue. Combining the adsorption capacity of methylene blue in Example 1 and Example 7 in Figure 16, it can be concluded that the adsorption capacity of methylene blue by the composite sewage treatment agent is much larger than that of the unmodified raw material. The adsorption capacity of the sample, and the adsorption capacity of the composite sewage treatment agent after adding bentonite to methylene blue is greater than that without adding the bentonite composite sewage treatment agent.

Example 2

Put 15 g of jute powder (leaf powder), 4.5 g of bentonite, and 9 g of anionic polyacrylamide (APAM) into a polytetrafluoroethylene ball mill. 20%, 50% of the balls with a diameter of 5 mm, and 30% of the small balls with a diameter of 3mm) and the composite raw materials, the mass ratio is 6:1, the speed of the ball mill is 500 rpm, and the ball is milled for 4 h, and the mixed powder is obtained after ball milling. Other treatment methods are the same as in Example 1.

The obtained clay mineral/biomass composite sewage treatment agent adsorbed Cu ²⁺ under the following conditions: initial test concentration 2 g/L, sewage treatment agent dosage 2 g/L, pH=5, temperature 55ºC, adsorption time 60 min, and the adsorption capacity was tested.

The conditions for the effect of different Cu ²⁺ concentrations on the adsorption performance of the clay mineral/biomass composite sewage treatment agent are: initial concentration 1 g/L, 1.2 g/L, 1.4 g/L, 1.6 g/L, 1.8 g/L, 2 g/L, 2.2 g/L, sewage treatment agent dosage 2 g/L, pH=5, temperature 55ºC, adsorption time 60 min, test the adsorption capacity, the results are shown in Figure 18.

The conditions for the adsorption of methylene blue by the obtained clay mineral/biomass composite sewage treatment agent were: initial concentration of 500 mg/L, dosage of sewage treatment agent 1.6 g/L, pH = 6, temperature of 60ºC, and adsorption time of 150 min. The adsorption capacity was tested.

The conditions for the effect of different methylene blue concentrations on the adsorption performance of the clay mineral/biomass composite sewage treatment agent are: initial test concentrations of 100 mg/L, 200 mg/L, 300 mg/L, 400 mg/L, 500 mg/L, 600 mg/L L, 700 mg/L, sewage treatment agent dosage 1.6 g/L, pH= 6, temperature 60ºC, adsorption time 150 min, test the adsorption capacity, the results are shown in Figure 19.

Figure 4 is the XRD of the jute leaf powder, bentonite, and the jute leaf powder/bentonite composite sewage treatment agent. The XRD pattern of the composite sewage treatment agent is basically consistent with that of the bentonite.

Figure 5 is the SEM image of the jute powder/bentonite composite sewage treatment agent. It can be seen from the figure that the surface of the bentonite is wrapped with jute powder, and there is also jute powder between the layers. This structure shows that the bentonite and the jute powder are closely combined. When the composite sewage treatment agent adsorbs Cu ²⁺ or methylene blue, it can promote the synergistic effect of jute powder and bentonite.

The adsorption performance of the composite sewage treatment agent obtained in Example 2 on Cu ²⁺ is shown in Figure 14. It can be seen that the adsorption amount of Cu ²⁺ by the product of Example 2 is 327.3 mg/g

Figure 15 is a performance diagram of the adsorption of Cu ²⁺ by the unmodified raw materials. Combined with the adsorption amounts of Cu ²⁺ in Example 2 and Example 7 in Figure 14, it can be concluded that the adsorption of Cu ²⁺ by the composite sewage treatment agent The adsorption capacity of the composite sewage treatment agent after adding ^bentonite is much greater than that of the unmodified raw material.

The adsorption performance of the composite sewage treatment agent obtained in Example 2 on methylene blue is shown in Figure 16, and it can be seen that the adsorption capacity of the product in Example 2 on methylene blue is 169.4 mg/g.

Figure 17 is a graph showing the adsorption performance of unmodified raw materials on methylene blue. Combining with the adsorption capacity of methylene blue in Example 2 and Example 7 in Figure 16, it can be concluded that the adsorption capacity of methylene blue by the composite sewage treatment agent is much larger than that of the unmodified raw material. The adsorption capacity of the sample, and the adsorption capacity of the composite sewage treatment agent after adding bentonite to methylene blue is greater than that without adding the bentonite composite sewage treatment agent.

Figure 18 shows the effect of Example 2 on the adsorption performance and removal rate of different Cu ²⁺ concentrations. It can be seen from the figure that with the increase of Cu ²⁺ concentration, the adsorption amount of Cu ²⁺ by the composite sewage treatment agent gradually increases and then approaches equilibrium. Correspondingly, the removal rate gradually decreased.

Figure 19 shows the effect of Example 2 on the adsorption performance and removal rate of different methylene blue concentrations. It can be seen from the figure that with the increase of methylene blue concentration, the adsorption capacity of the composite sewage treatment agent to methylene blue gradually increased and then approached equilibrium, and the corresponding removal rate Gradually decreases.

Example 3

Put 15 g of jute powder (rod powder), 7.5 g of kaolin, and 9 g of anionic polyacrylamide (APAM) into a PTFE ball milling jar. 20%, 50% of the balls with a diameter of 5 mm, and 30% of the small balls with a diameter of 3 mm) and the composite raw materials, the mass ratio is 6:1, the speed of the ball mill is 500 rpm, and the ball is milled for 4 h. Other treatment methods are the same as in Example 1.

The conditions for adsorbing Cu ²⁺ and methylene blue by the obtained clay mineral/biomass composite sewage treatment agent are the same as those in Example 1.

Figure 6 is the XRD of jute stem powder, kaolin, jute stem powder/kaolin composite sewage treatment agent, and the XRD pattern of the composite sewage treatment agent is basically consistent with that of kaolin.

Figure 7 is the SEM image of the jute stem powder/kaolin composite sewage treatment agent. It can be seen from the figure that the surface of the kaolin is wrapped with jute powder, and there is also jute powder between the layers. This structure illustrates the comparison of the combination of kaolin and jute powder. Tightly, when the composite sewage treatment agent adsorbs Cu ²⁺ or methylene blue, it can promote the synergistic effect of jute powder and kaolin.

The adsorption performance of the composite sewage treatment agent obtained in Example 3 on Cu ²⁺ is shown in Figure 14. It can be seen that the adsorption amount of Cu ²⁺ by the product of Example 3 is 270 mg/g.

Figure 15 is a graph showing the performance of the unmodified raw materials on the adsorption of Cu ²⁺ . Combining with the adsorption amounts of Cu ²⁺ in Example 3 and Example 7 in Figure 14, it can be concluded that the composite sewage treatment agent has a better effect on Cu ²⁺ . The adsorption capacity is much greater than that of the unmodified raw materials, and the adsorption capacity of Cu ²⁺ by the composite sewage treatment agent after adding kaolin is greater than that of the composite sewage treatment agent without kaolin.

The adsorption performance of the composite sewage treatment agent obtained in Example 3 on methylene blue is shown in Figure 16. It can be seen that the adsorption capacity of the product in Example 3 on methylene blue is 123.3 mg/g.

Figure 17 is a graph showing the adsorption performance of unmodified raw materials on methylene blue. Combining the adsorption capacity of methylene blue in Example 3 and Example 7 in Figure 16, it can be concluded that the adsorption capacity of methylene blue by the composite sewage treatment agent is much larger than that of the unmodified raw material. The adsorption capacity of the sample, and the adsorption capacity of methylene blue by the composite sewage treatment agent after adding kaolin is greater than the adsorption capacity of the composite sewage treatment agent without kaolin.

Example 4

Put 15 g of jute leaf stem powder (the mass ratio of leaf powder and stem powder is 1:1), 7.5 g of kaolin, and 9 g of anionic polyacrylamide (APAM) into a polytetrafluoroethylene ball mill. Mass ratio meter, the mass ratio of large balls with a diameter of 10 mm is 20%, the medium balls with a diameter of 5 mm is 50%, and the small balls with a diameter of 3 mm are 30%) and the mass ratio of the composite raw material is 6:1, and the speed of the ball mill is 500 rpm , ball-milled for 4 h, and the mixed powder was obtained after ball-milling. Other treatment methods are the same as in Example 1.

The conditions for adsorbing Cu ²⁺ and methylene blue by the obtained clay mineral/biomass composite sewage treatment agent are the same as those in Example 1.

Figure 8 is the XRD of the jute leaf stem powder, kaolin, jute leaf stem powder/bentonite composite sewage treatment agent, the XRD pattern of the composite sewage treatment agent is basically consistent with that of kaolin, but the intensity of the peaks is relatively low, which is jute Powder wrapped sake.

Figure 9 is the SEM image of the jute leaf pole powder/kaolin composite sewage treatment agent. It can be seen from the figure that the surface of the kaolin is wrapped with the jute powder. This structure shows that the kaolin and the jute powder are closely combined. When the agent adsorbs Cu ²⁺ or methylene blue, it can promote the synergistic effect of jute flour and kaolin.

The adsorption performance of the composite sewage treatment agent obtained in Example 4 on Cu ²⁺ is shown in Figure 14. It can be seen that the adsorption amount of Cu ²⁺ by the product of Example 4 is 239.5 mg/g.

Figure 15 is the performance diagram of the adsorption of Cu ²⁺ by the unmodified raw materials. Combined with the adsorption amounts of Cu ²⁺ in Example 4 and Example 7 in Figure 14, it can be concluded that the adsorption of Cu ²⁺ by the composite sewage treatment agent The amount of Cu 2+ adsorption is much greater than that of the unmodified raw material, and the adsorption amount of Cu ²⁺ by the composite sewage treatment agent after adding kaolin is greater than that without the addition of kaolin.

The adsorption performance of the composite sewage treatment agent obtained in Example 4 on methylene blue is shown in Figure 16. It can be seen that the adsorption capacity of the product in Example 4 on methylene blue is 188.9 mg/g.

Figure 17 is a graph showing the adsorption performance of unmodified raw materials on methylene blue. Combining with the adsorption capacity of methylene blue in Example 4 and Example 7 in Figure 16, it can be concluded that the adsorption capacity of methylene blue by the composite sewage treatment agent is much larger than that of the unmodified raw material. The adsorption capacity of the sample, and the adsorption capacity of methylene blue by the composite sewage treatment agent after adding kaolin is greater than the adsorption capacity of the composite sewage treatment agent without kaolin.

Example 5

Put 15 g of jute powder (rod powder), 1.5 g of attapulgite, and 3 g of anionic polyacrylamide (APAM) into a polytetrafluoroethylene ball milling jar. The mass ratio of 20%, 50% of the balls with a diameter of 5 mm, and 30% of the small balls with a diameter of 3mm) and the composite raw material is 6:1, the speed of the ball mill is 500 rpm, and the ball is milled for 4 hours. . Other treatment methods are the same as in Example 1.

The conditions for adsorbing Cu ²⁺ and methylene blue by the obtained clay mineral/biomass composite sewage treatment agent are the same as those in Example 1.

In this embodiment, the jute powder is jute straw powder, and the polyacrylamide is anionic polyacrylamide (APAM).

Figure 10 shows the XRD of jute rod powder, attapulgite, and jute powder/attapulgite composite sewage treatment agent. The XRD pattern of the composite sewage treatment agent is basically consistent with that of attapulgite, but the peak intensity is relatively low.

Figure 11 is the SEM image of the jute powder/attapulgite composite sewage treatment agent. It can be seen from the figure that the attapulgite is wrapped on the outside of the jute powder. This structure shows that the attapulgite and the jute powder are closely combined. When the sewage treatment agent adsorbs Cu ²⁺ or methylene blue, it can promote the synergistic effect of jute powder and attapulgite.

Fig. 14 is a performance diagram of the adsorption of Cu ²⁺ by the composite sewage treatment agent. It can be seen from the figure that the adsorption amount of Cu ²⁺ in Example 5 is 246.8 mg/g.

Figure 15 is a performance diagram of the adsorption of Cu ²⁺ by the unmodified raw materials. Combined with the adsorption amounts of Cu ²⁺ in Example 5 and Example 7 in Figure 14, it can be concluded that the adsorption of Cu ²⁺ by the composite sewage treatment agent The amount of Cu 2+ is much larger than that of the unmodified raw material, and the adsorption amount of Cu ²⁺ by the composite sewage treatment agent after adding attapulgite is greater than that without the attapulgite composite sewage treatment agent.

The adsorption performance of the sewage treatment agent obtained in Example 5 on methylene blue is shown in Figure 16. It can be seen that the adsorption capacity of the product in Example 5 on methylene blue is 132.3 mg/g.

Figure 17 is a graph showing the adsorption performance of unmodified raw materials on methylene blue. Combining the adsorption capacity of methylene blue in Example 5 and Example 7 in Figure 16, it can be concluded that the adsorption capacity of methylene blue by the composite sewage treatment agent is much larger than that of the unmodified raw material. The adsorption amount of the sample, and the adsorption amount of methylene blue by the composite sewage treatment agent after adding attapulgite is greater than the adsorption amount of the composite sewage treatment agent without adding attapulgite.

Example 6

Put 15 g of jute powder (rod powder), 1.5 g of attapulgite, and 9 g of polyacrylamide into a polytetrafluoroethylene ball mill jar. The mass ratio of balls with a diameter of 5 mm is 50% and that of small balls with a diameter of 3 mm is 30%) and the composite material is 6:1. The speed of the ball mill is 500 rpm, and the ball is milled for 4 h. Other treatment methods are the same as in Example 1.

The conditions for adsorbing Cu ²⁺ and methylene blue by the obtained clay mineral/biomass composite sewage treatment agent are the same as those in Example 1.

In this embodiment, the jute powder is jute straw powder, and the polyacrylamide is anionic polyacrylamide (APAM).

Figure 12 is the XRD of jute powder, attapulgite, jute powder/attapulgite composite sewage treatment agent, the XRD pattern of the composite sewage treatment agent is basically consistent with that of attapulgite, but the peak intensity is relatively low.

Figure 13 is the SEM image of the jute stick powder/attapulgite composite sewage treatment agent. It can be seen from the figure that the surface of the attapulgite is wrapped with jute powder, and there is also jute powder between the layers. This structure shows that the attapulgite and the jute powder are combined It is relatively close, and when the composite sewage treatment agent adsorbs Cu ²⁺ or methylene blue, it can promote the synergistic effect of jute powder and attapulgite.

The adsorption performance of the sewage treatment agent obtained in Example 6 on Cu ²⁺ is shown in Figure 14, and it can be seen that the adsorption capacity of the product in Example 6 on Cu ²⁺ is 272.9 mg/g.

Figure 15 is the performance diagram of the adsorption of Cu ²⁺ by the unmodified raw materials. Combined with the adsorption amounts of Cu ²⁺ in Example 6 and Example 7 in Figure 14, it can be concluded that the adsorption of Cu ²⁺ by the composite sewage treatment agent The amount of Cu 2+ is much larger than that of the unmodified raw material, and the adsorption amount of Cu ²⁺ by the composite sewage treatment agent after adding attapulgite is greater than that without the attapulgite composite sewage treatment agent.

The adsorption performance of the composite sewage treatment agent obtained in Example 6 on methylene blue is shown in Figure 16. It can be seen that the adsorption capacity of the product in Example 6 on methylene blue is 157.3 mg/g.

Figure 17 is a graph showing the adsorption performance of unmodified raw materials on methylene blue. Combining the adsorption capacity of methylene blue in Example 6 and Example 7 in Figure 16, it can be concluded that the adsorption capacity of methylene blue by the composite sewage treatment agent is much larger than that of the unmodified sample. The adsorption capacity of the composite sewage treatment agent after adding attapulgite to methylene blue is greater than the adsorption capacity of the composite sewage treatment agent without attapulgite.

Example 7

Put 15 g of jute powder and 9 g of polyacrylamide into a PTFE ball mill jar, alumina balls (in terms of mass ratio, large balls with a diameter of 10 mm account for 20%, and medium balls with a diameter of 5 mm account for 50%. The mass ratio of the balls with a diameter of 3 mm (30%) and the composite raw materials is 6:1, the speed of the ball mill is 500 rpm, and the ball milling is performed for 4 h. Other treatment methods are the same as in Example 1.

The conditions for adsorbing Cu ²⁺ and methylene blue by the obtained clay mineral/biomass composite sewage treatment agent are the same as those in Example 1.

In this embodiment, the jute powder is jute leaf powder, and the polyacrylamide is anionic polyacrylamide (APAM).

The adsorption performance of the sewage treatment agent obtained in Example 7 on Cu ²⁺ is shown in Figure 14. It can be seen that the adsorption amount of Cu ²⁺ by the product of Example 7 is 124.4 mg/g.

The adsorption performance of the sewage treatment agent obtained in Example 7 on methylene blue is shown in Figure 16. It can be seen that the adsorption capacity of the product in Example 7 on methylene blue is 106.3 mg/g.

Claims (6)

1. A preparation method of a clay mineral/agricultural and forestry waste biomass composite sewage treatment agent is characterized by comprising the following steps:

(1) taking agricultural and forestry waste biomass, clay minerals and a binder as raw materials, and performing ball milling according to the mass ratio of the clay minerals, the agricultural and forestry waste biomass to the binder (1-5): 10: (2-6);

(2) adding the mixed powder obtained in the step (1) into hot water at the temperature of 40-95 ℃, fully stirring and uniformly mixing, wherein the mass ratio of the hot water to the mixed powder is (2.5-5): 1;

(3) sealing the material obtained in the step (2) and then carrying out staling treatment; the aging condition is that the temperature is kept at 40-100 ℃ for 5-48 h;

(4) mixing, tabletting and drying the mixed slurry obtained in the step (3);

(5) crushing and sieving the dried block material obtained in the step (4) to prepare the composite sewage treatment agent; the agricultural and forestry waste biomass is jute stalks and leaves;

the clay mineral is one or a mixture of more than two of bentonite, kaolin and attapulgite in any proportion;

the binder is polyacrylamide.

2. The preparation method of the clay mineral/agriculture and forestry waste biomass composite sewage treatment agent according to claim 1, wherein a grinding ball used in ball milling is one or more of an alumina ball, a zirconia ball, a mullite ball and a stainless steel ball, the mass ratio of the grinding ball to a material is (3-6): 1, the grinding ball has a diameter of 3-15 mm, the ball milling speed is 50-600 rpm, and the ball milling time is 1-20 hours.

3. The preparation method of the clay mineral/agricultural and forestry waste biomass composite sewage treatment agent according to claim 1, wherein the drying is drying at 80-150 ℃ for 2-16 h, and the water content is (2-10)%; after crushing and sieving in the step (5), the particle size range of the obtained composite treating agent is 0.1-1 mm.

4. The clay mineral/agricultural and forestry waste biomass composite sewage treatment agent prepared by the preparation method of any one of claims 1 to 3.

5. The application of the clay mineral/agriculture and forestry waste biomass composite sewage treatment agent in adsorption of heavy metal ions in sewage as claimed in claim 4, wherein the heavy metal ions are copper ions.

6. The use of the clay mineral/agricultural and forestry waste biomass composite sewage treatment agent in adsorbing organic dye in sewage, wherein the organic dye is methylene blue.

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