CN110479226B - Clay mineral/agriculture and forestry waste biomass composite sewage treatment agent, and preparation method and application thereof - Google Patents

Clay mineral/agriculture and forestry waste biomass composite sewage treatment agent, and preparation method and application thereof Download PDF

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CN110479226B
CN110479226B CN201910816199.8A CN201910816199A CN110479226B CN 110479226 B CN110479226 B CN 110479226B CN 201910816199 A CN201910816199 A CN 201910816199A CN 110479226 B CN110479226 B CN 110479226B
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sewage treatment
treatment agent
composite sewage
forestry waste
composite
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CN110479226A (en
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陈德良
李佳衡
李涛
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Zhengzhou University
Dongguan University of Technology
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Zhengzhou University
Dongguan University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/12—Naturally occurring clays or bleaching earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/485—Plants or land vegetals, e.g. cereals, wheat, corn, rice, sphagnum, peat moss
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/40—Organic compounds containing sulfur

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

Clay mineral/agriculture and forestry waste biomass composite sewage treatment agent, and preparation method and application thereof
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, and a preparation method and application thereof.
Background
The rapid development (industrialization and urbanization) of social economy brings serious environmental problems such as water pollution, and water pollution treatment and prevention science and technology are global common problems and are important requirements in the current stage of China. However, according to the program for preventing and treating water pollution of key drainage basins, the cross-section water quality of surface water of the whole country is poor in class V, the pollution of nitrogen, phosphorus, heavy metals and the like is increasingly prominent, and even trace heavy metals have huge threats to human health, aquatic systems and environment (environ, technol. 2018,11, 187). The Ministry of industry and belief that "guidance opinions about accelerating the development of the environmental protection equipment manufacturing industry" requires the intensive research and development of "novel efficient water treatment materials and agents", "ecological remediation, environmental protection nano materials and agents", and the development of multi-pollutant cooperative treatment and deep treatment technologies. Therefore, the novel composite adsorbent for adsorbing and removing the water-soluble pollutants, which is efficient, low in cost, ecological and environment-friendly, is developed, accords with the development trend and meets the national important requirements.
The water-soluble pollutants comprise heavy metal ions, organic dyes, agricultural and pharmaceutical intermediates, residual substances and the like, are complex and various in types and different in properties, often coexist at the same time, and are a challenge to the purification treatment technology. The commonly used treatment methods are precipitation, incineration, flocculation, coagulation, ion exchange, reverse osmosis, membrane filtration, electrochemistry, photochemistry, advanced oxidation, biological methods etc. (app. Clay sci. 2016,123,239), but these methods have some disadvantages of 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). The adsorption removal method is the current sewage treatment method with the highest cost performance (environ. technol.2009,6,583), and the core technical bottleneck of the adsorption removal method lies in the design and macro-preparation of the efficient, low-cost and eco-friendly adsorbent. Common adsorbents comprise synthetic polymers (such as PAM), clay, biomass and the like, but most of the adsorbents have the problems of large particles, single function, low adsorption capacity, poor environmental compatibility and the like, and are difficult to meet the water treatment requirements of large enough amount and complex and various pollution sources. In addition, the chemical synthetic adsorbents used in industry are expensive, which increases the cost of sewage treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a clay mineral/agricultural and forestry waste biomass composite sewage treatment agent, a preparation method and application thereof: taking cheap, abundant, ecological and environment-friendly natural resources such as layered clay, agriculture and forestry biomass and the like as raw materials, asymmetrically and superfinely stripping the bulk such as clay, biomass and the like into two-dimensional clay nanosheets and one-dimensional biomass nanofibers, and embedding the clay nanosheets and the biomass nanofibers in a hybridization manner to construct a 'clay nanosheets/biomass nanofibers' multi-level hybrid nanostructure; by means of the synergistic effect of the multi-component, multi-stage structure and various functional groups, the complex and various soluble pollutants in the sewage are removed by one-time adsorption. The invention has the advantages of abundant and cheap quantity, ecological environmental protection, good sewage treatment effect, simple preparation process, easy mass production and the like.
In order to achieve the purpose, the invention adopts the following technical scheme: 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. A clay mineral/agriculture and forestry waste biomass composite sewage treatment agent and a preparation method thereof comprise the following steps:
(1) taking agricultural and forestry waste biomass, clay minerals and a binder as raw materials, and 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 hot water into the mixed powder obtained in the step (1), fully stirring and uniformly mixing, wherein the temperature of the hot water is 40-95 ℃, and 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 placing the material under a set temperature condition for ageing treatment, wherein the ageing condition is that the temperature is kept for 5-48 h at 40-100 ℃;
(4) mixing, tabletting and drying the mixed slurry obtained in the step (3);
(5) and (4) crushing, screening and grading the dried block material obtained in the step (4) to obtain the composite sewage treatment agent with clay minerals and biomass as main components.
Preferably, the agriculture and forestry waste biomass is a mixture of jute stalks and one or more than two of leaves, straws, corncobs, bagasse, rice hulls, fruit peels and algae in any proportion.
Preferably, the clay mineral is one or a mixture of more than two of bentonite, kaolin, attapulgite, sepiolite, montmorillonite, halloysite, vermiculite, smectite, palygorskite and illite in any proportion.
Preferably, the binder is one or a mixture of two or more of starch, protein, gelatin, sodium alginate, sodium carboxymethylcellulose, polyacrylamide, sodium polyacrylate, polyvinyl pyridinium, polyethyleneimine and polydimethyldiallylammonium chloride in any ratio.
Preferably, the grinding balls are one or a mixture of more than two of alumina balls, zirconia balls, mullite balls and stainless steel balls in any proportion, the mass ratio of the grinding balls to the materials is (3-6): 1, the diameter of the grinding balls is 3-15 mm, the rotation speed of the ball mill is 50-600 rpm, and the ball milling time is 1-20 hours.
Preferably, the mixing and tabletting are processed by an open mill, the rotating speed of front wheels of the open mill is 5-20 rpm, the rotating speed of rear wheels of the open mill is 5-20 rpm, the temperature of the front wheels is 40-100 ℃, the temperature of the rear wheels is 40-100 ℃, and the distance between the front wheels and the rear wheels is 0.5-5 mm.
Preferably, the drying is carried out at 80-150 ℃ for 2-16 h, and the water content is (2-10)%.
Preferably, in the step (5), after crushing and sieving, the particle size range of the obtained composite treating agent is 0.1-1 mm.
The clay mineral/agricultural and forestry waste biomass composite sewage treatment agent prepared by the preparation method.
The clay mineral/agriculture and forestry waste biomass composite sewage treatment agent is applied to adsorption of heavy metal ions in sewage, and the heavy metal ions are preferably copper ions.
The clay mineral/agriculture and forestry waste biomass composite sewage treatment agent is applied to adsorption of organic dye in sewage, and the organic dye is preferably methylene blue.
The invention has the following beneficial effects:
according to the invention, rich functional groups of renewable biomass are combined with low-dimensional lamellar or fiber structures of natural clay minerals, and the synergistic effect of the functional groups and the fiber structures is utilized to improve the capability of the compound for simultaneously adsorbing and removing harmful ions such as organic dyes, heavy metal ions and fluorine ions, so that the compound has stronger adaptability than the existing commercial sewage treatment agent.
In addition, 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.
The invention breaks through the key technology of designing and preparing a novel water treatment agent with high efficiency, ecology, low price and high yield, realizes the high-value utilization of natural resources such as layered clay, biomass and the like and the sustainable development of a green low-carbon water treatment technology for treating waste by using waste to treat sewage, and fills and perfects a theoretical system and a case for preparing and applying mineral materials.
Drawings
FIG. 1 is a flow chart of an experiment of example preparation.
FIG. 2 is an XRD pattern of a sample prepared in example 1;
FIG. 3 is an SEM photograph of a sample prepared in example 1;
FIG. 4 is an XRD pattern of a sample prepared in example 2;
FIG. 5 is an SEM photograph of a sample prepared in example 2;
FIG. 6 is an XRD pattern of a sample prepared in example 3;
FIG. 7 is an SEM photograph of a sample prepared in example 3;
FIG. 8 is an XRD pattern of a sample prepared in example 4;
FIG. 9 is an SEM photograph of a sample prepared in example 4;
FIG. 10 is an XRD pattern of a sample prepared in example 5;
FIG. 11 is an SEM photograph of a sample prepared in example 5;
FIG. 12 is an XRD pattern of a sample prepared in example 6;
FIG. 13 is an SEM photograph of a sample prepared in example 6.
FIG. 14 shows the combination of sewage treatment agents for Cu 2+ Performance graph of adsorption.
FIG. 15 shows a pair of unmodified raw materials Cu 2+ Performance graph of adsorption.
FIG. 16 is a graph of the performance of the composite wastewater treatment agent on methylene blue adsorption.
Fig. 17 is a graph of the performance of unmodified starting material on methylene blue adsorption.
FIG. 18 shows the results of the samples obtained in example 2 for different Cu 2+ Influence of concentration adsorption performance and removal rate.
FIG. 19 is a graph showing the effect of the samples prepared in example 2 on the adsorption performance and removal rate for different methylene blue concentrations.
Detailed Description
In order to better understand the present invention, the present invention is further illustrated by the following examples using jute, bentonite, kaolin, attapulgite, anionic polyacrylamide, etc. as raw materials, which are only used for explaining the present invention and do not constitute any limitation to the present invention.
Example 1
Mixing 15 g of jute powder (leaf powder), 4.5 g of bentonite and 3 g of Anionic Polyacrylamide (APAM), putting the mixture into a polytetrafluoroethylene ball milling tank, wherein the mass ratio of alumina balls (by mass ratio, 20% of large balls with the diameter of 10 mm, 50% of medium balls with the diameter of 5mm and 30% of small balls with the diameter of 3 mm) to the composite raw materials is 6:1, the rotation speed of ball milling treatment is 500 rpm, and ball milling is carried out for 4 hours to obtain mixed powder. And putting the mixed powder into an agate mortar, adding 90 g of warm water at 50 ℃, uniformly stirring, wrapping with a preservative film, and putting into an oven for aging at 50 ℃ for 10 hours to obtain the composite slurry. Putting the composite slurry into an open mill for mixing treatment, wherein the rotating speed of a front wheel of the open mill is 4 rpm, the rotating speed of a rear wheel of the open mill is 2 rpm, the temperatures of the front wheel and the rear wheel are both 50 ℃, and the distance between the front wheel and the rear wheel is 1 mm; and fully mixing, pressing into sheets, and drying in an oven at 80 ℃ for 12 hours to obtain the clay mineral/biomass composite sheet. And then crushing the composite sheet by a crusher, and screening the crushed composite sheet by a 60-mesh screen to obtain undersize products, namely the clay mineral/biomass composite sewage treatment agent.
The obtained clay mineral/biomass composite sewage treatment agent adsorbs Cu 2+ The conditions are as follows: the initial test concentration is 2 g/L, the dosage of the sewage treatment agent is 2 g/L, pH = 5, the temperature is 55 ℃, the adsorption time is 60 min, and the adsorption amount is tested, and the result is shown in detail in figure 14.
The condition that the obtained clay mineral/biomass composite sewage treatment agent absorbs methylene blue is as follows: the initial test concentration is 500 mg/L, the dosage of the sewage treatment agent is 1.6 g/L, pH = 6, the temperature is 60 ℃, the adsorption time is 150 min, and the adsorption quantity is tested.
Fig. 1 is a flow chart of the preparation of the experiment, and details the preparation process of the composite sewage treatment agent.
FIG. 2 is XRD of jute leaf powder, bentonite and composite sewage treating agent of jute leaf powder/bentonite, the XRD pattern of the composite sewage treating agent is basically identical to that of bentonite, but the peak intensity is relatively low, which is the reason that jute powder intercalates with bentonite to reduce the degree of long-range order.
FIG. 3 is an SEM image of a jute powder/bentonite composite sewage treatment agent, wherein the surface of the bentonite is wrapped by jute powder, and the jute powder is arranged between the layers of the bentonite, and the structure shows that the bentonite and the jute powder are combined closely, and the composite sewage treatment agent adsorbs Cu 2+ Or methylene blue can promote the synergistic effect of jute powder and bentonite.
Example 1 composite Sewage treatment agent for Cu 2+ The adsorption performance is shown in FIG. 14, and it can be seen that the product of example 1 has Cu adsorption 2+ The amount of adsorbed was 257.3 mg/g.
FIG. 15 shows a pair of unmodified raw materials Cu 2+ Performance of adsorption combining Cu from example 1 and example 7 in FIG. 14 2+ The adsorption capacity of the composite sewage treatment agent can be concluded to be Cu 2+ The adsorption capacity of the bentonite is far larger than that of unmodified raw materials, and the bentonite-added composite sewage treatment agent can treat Cu 2+ The adsorption amount of (a) is larger than that of the bentonite-free composite sewage treatment agent (i.e., example 7).
The performance of the composite sewage treatment agent obtained in example 1 on methylene blue adsorption is shown in fig. 16, and it can be seen that the adsorption amount of the product of example 1 on methylene blue is 155 mg/g.
Fig. 17 is a performance graph of an unmodified raw material on methylene blue, and by combining the adsorption amounts of example 1 and example 7 in fig. 16 on methylene blue, it can be concluded that the adsorption amount of the composite sewage treatment agent on methylene blue is far greater than that of an unmodified sample, and the adsorption amount of the composite sewage treatment agent after bentonite is added on methylene blue is greater than that of the composite sewage treatment agent without bentonite.
Example 2
Placing 15 g of jute powder (leaf powder), 4.5 g of bentonite and 9 g of Anionic Polyacrylamide (APAM) into a polytetrafluoroethylene ball milling tank, wherein the mass ratio of alumina balls (by mass ratio, large balls with the diameter of 10 mm account for 20%, medium balls with the diameter of 5mm account for 50% and small balls with the diameter of 3mm account for 30%) to composite raw materials is 6:1, the rotation speed of the ball mill is 500 rpm, and ball milling is carried out for 4 h to obtain mixed powder after ball milling. The other treatment methods were the same as in example 1.
The obtained clay mineral/biomass composite sewage treatment agent adsorbs Cu 2+ The conditions are as follows: the initial test concentration is 2 g/L, the dosage of the sewage treatment agent is 2 g/L, pH = 5, the temperature is 55 ℃, the adsorption time is 60 min, and the adsorption capacity is tested.
Different Cu 2+ The conditions of the influence of the concentration on the adsorption performance of the clay mineral/biomass composite sewage treatment agent are as follows: the initial test concentration is 1 g/L, 1.2 g/L, 1.4 g/L, 1.6 g/L, 1.8 g/L, 2 g/L and 2.2 g/L, the dosage of the sewage treatment agent is 2 g/L, pH = 5, the temperature is 55 ℃, the adsorption time is 60 min, the adsorption capacity is tested, and the result is shown in figure 18.
The condition that the obtained clay mineral/biomass composite sewage treatment agent absorbs methylene blue is as follows: the initial test concentration is 500 mg/L, the dosage of the sewage treatment agent is 1.6 g/L, pH = 6, the temperature is 60 ℃, the adsorption time is 150 min, and the adsorption capacity is tested.
The conditions of the influence of different methylene blue concentrations on the adsorption performance of the clay mineral/biomass composite sewage treatment agent are as follows: the initial concentration is 100 mg/L, 200 mg/L, 300 mg/L, 400 mg/L, 500 mg/L, 600 mg/L and 700 mg/L, the dosage of the sewage treatment agent is 1.6 g/L, pH = 6, the temperature is 60 ℃, the adsorption time is 150 min, the adsorption capacity is tested, and the result is shown in detail in figure 19.
FIG. 4 is XRD of jute leaf powder, bentonite and jute leaf powder/bentonite composite sewage treatment agent, and the XRD pattern of the composite sewage treatment agent is basically identical to that of bentonite.
FIG. 5 is an SEM image of a jute powder/bentonite composite sewage treatment agent, from which it can be seen that the surface of the bentonite is coated with jute powder, and the jute powder is also arranged between the layers, and the structure shows that the bentonite and the jute powder are combined closely, and the composite sewage treatment agent adsorbs Cu 2+ Or methylene blue can promote the synergistic effect of jute powder and bentonite.
Example 2 composite Sewage treatment agent for Cu 2+ The adsorption performance is shown in FIG. 14, and it can be seen that the product of example 2 has Cu adsorption 2+ Has an adsorption amount of 327.3 mg/g
FIG. 15 shows a pair of unmodified raw materials Cu 2+ Performance of adsorption combining Cu from example 2 and example 7 in FIG. 14 2+ The adsorption capacity of the composite sewage treatment agent can be concluded to be Cu 2+ The adsorption capacity of the bentonite is far larger than that of unmodified raw materials, and the bentonite-added composite sewage treatment agent can treat Cu 2+ The adsorption capacity of the bentonite-containing composite sewage treatment agent is larger than that of the bentonite-containing composite sewage treatment agent.
The adsorption performance of the composite sewage treatment agent obtained in example 2 on methylene blue is shown in FIG. 16, and it can be seen that the adsorption amount of the product of example 2 on methylene blue is 169.4 mg/g.
Fig. 17 is a performance graph of an unmodified raw material on methylene blue, and by combining the adsorption amounts of example 2 and example 7 in fig. 16, it can be concluded that the adsorption amount of the composite sewage treatment agent on methylene blue is far greater than that of an unmodified sample, and the adsorption amount of the composite sewage treatment agent after bentonite is added on methylene blue is greater than that of the composite sewage treatment agent without bentonite.
FIG. 18 shows the results of example 2 on different Cu 2+ The influence of the concentration adsorption performance and the removal rate, and it is understood from the graph that Cu is included 2+ Concentration increase of composite sewage treatment agent to Cu 2+ Gradually increases in the amount of adsorption and then approaches equilibrium, corresponding to its removalThe rate gradually decreases.
Fig. 19 shows the influence of example 2 on the adsorption performance and removal rate of different methylene blue concentrations, and it can be seen from the graph that the adsorption amount of the composite sewage treatment agent to methylene blue gradually increases and then approaches the equilibrium with the increase of the methylene blue concentration, and the removal rate gradually decreases correspondingly.
Example 3
Placing 15 g of jute powder (straw powder), 7.5 g of kaolin and 9 g of Anionic Polyacrylamide (APAM) into a polytetrafluoroethylene ball milling tank, wherein the mass ratio of alumina balls (by mass ratio, 20% of large balls with the diameter of 10 mm, 50% of medium balls with the diameter of 5mm and 30% of small balls with the diameter of 3 mm) to the composite raw materials is 6:1, the rotating speed of the ball mill is 500 rpm, and ball milling is carried out for 4 hours to obtain mixed powder after ball milling. The other treatment methods were the same as in example 1.
The obtained clay mineral/biomass composite sewage treatment agent adsorbs Cu 2+ The conditions of methylene blue were the same as in example 1.
FIG. 6 is XRD of jute straw powder, kaolin, jute straw powder/kaolin composite sewage treatment agent, and XRD pattern of the composite sewage treatment agent is basically identical to that of kaolin.
FIG. 7 is an SEM image of a sewage treatment agent made of jute straw powder/kaolin composite material, from which it can be seen that the surface of kaolin is wrapped with jute powder and the jute powder is between the layers, and this structure shows that the kaolin and jute powder are combined more closely and Cu is adsorbed by the composite sewage treatment agent 2+ Or methylene blue can promote the synergistic effect of jute powder and kaolin.
Example 3 composite Sewage treatment agent for Cu 2+ The adsorption performance is shown in FIG. 14, and it can be seen that the product of example 3 has Cu adsorption 2+ The amount of adsorption of (A) was 270 mg/g.
FIG. 15 shows a pair of unmodified raw materials Cu 2+ Performance of adsorption combining Cu from example 3 and example 7 in FIG. 14 2+ The adsorption amount of the composite sewage treatment agent can be concluded to be Cu 2+ The adsorption capacity of the composite sewage treatment agent is far greater than that of the unmodified raw material, and the composite sewage treatment agent added with kaolin is used for treating Cu 2+ Is greater than that ofAdding the adsorption capacity of the kaolin composite sewage treatment agent.
The performance of the composite sewage treatment agent obtained in example 3 on methylene blue adsorption is shown in fig. 16, and it can be seen that the adsorption amount of the product of example 3 on methylene blue is 123.3 mg/g.
Fig. 17 is a performance graph of an unmodified raw material on methylene blue, and by combining the adsorption amounts of example 3 and example 7 in fig. 16 on methylene blue, it can be concluded that the adsorption amount of the composite sewage treatment agent on methylene blue is much larger than that of an unmodified sample, and the adsorption amount of the composite sewage treatment agent on methylene blue after kaolin is added is larger than that of the composite sewage treatment agent without kaolin.
Example 4
15 g of jute leaf and stem powder (the mass ratio of leaf powder to stem powder is 1: 1), 7.5 g of kaolin and 9 g of Anionic Polyacrylamide (APAM) are put into a polytetrafluoroethylene ball milling tank, the mass ratio of alumina balls (in terms of mass ratio, 20% of large balls with the diameter of 10 mm, 50% of medium balls with the diameter of 5mm and 30% of small balls with the diameter of 3 mm) to the composite raw material is 6:1, the rotation speed of the ball mill is 500 rpm, ball milling is carried out for 4 hours, and mixed powder is obtained after ball milling. The other treatment methods were the same as in example 1.
The obtained clay mineral/biomass composite sewage treatment agent adsorbs Cu 2+ The conditions of methylene blue were the same as in example 1.
FIG. 8 is an XRD of the jute straw powder, kaolin and jute straw powder/bentonite composite sewage treatment agent, the XRD of the composite sewage treatment agent is basically identical to that of kaolin, but the peak intensity is relatively low, which is caused by jute powder coating.
FIG. 9 is an SEM image of a composite sewage treatment agent of jute straw powder/kaolin, from which it can be seen that the kaolin is coated with jute powder, and the structure shows that the kaolin and jute powder are combined closely, and Cu is adsorbed by the composite sewage treatment agent 2+ Or methylene blue can promote the synergistic effect of jute powder and kaolin.
Example 4 composite Sewage treatment agent for Cu 2+ The performance of the adsorption is shown in FIG. 14, and can beIt is seen that the product of example 4 is paired with Cu 2+ The adsorption amount of (B) was 239.5 mg/g.
FIG. 15 shows a pair of unmodified raw materials Cu 2+ Performance of adsorption combining Cu from example 4 and example 7 in FIG. 14 2+ The adsorption capacity of the composite sewage treatment agent can be concluded to be Cu 2+ The adsorption capacity of the composite sewage treatment agent is far greater than that of the unmodified raw material, and the composite sewage treatment agent added with kaolin is used for treating Cu 2+ The adsorption capacity of the composite sewage treatment agent is larger than that of the composite sewage treatment agent without kaolin.
The performance of the composite sewage treatment agent obtained in example 4 on methylene blue adsorption is shown in fig. 16, and it can be seen that the adsorption amount of the product of example 4 on methylene blue is 188.9 mg/g.
Fig. 17 is a performance graph of an unmodified raw material on methylene blue, and by combining the adsorption amounts of example 4 and example 7 in fig. 16 on methylene blue, it can be concluded that the adsorption amount of the composite sewage treatment agent on methylene blue is much larger than that of an unmodified sample, and the adsorption amount of the composite sewage treatment agent on methylene blue after kaolin is added is larger than that of the composite sewage treatment agent without kaolin.
Example 5
Placing 15 g of jute powder (rod powder), 1.5 g of attapulgite and 3 g of Anionic Polyacrylamide (APAM) into a polytetrafluoroethylene ball milling tank, wherein the mass ratio of alumina balls (by mass ratio, large balls with the diameter of 10 mm account for 20%, medium balls with the diameter of 5mm account for 50% and small balls with the diameter of 3mm account for 30%) to composite raw materials is 6:1, the rotating speed of the ball mill is 500 rpm, and ball milling is carried out for 4 h to obtain mixed powder after ball milling. The other treatment methods were the same as in example 1.
The obtained clay mineral/biomass composite sewage treatment agent adsorbs Cu 2+ The conditions of methylene blue were the same as in example 1.
In this example, the jute powder was jute straw powder and the polyacrylamide was Anionic Polyacrylamide (APAM).
FIG. 10 is XRD of jute stalk powder, attapulgite, jute powder/attapulgite composite sewage treatment agent, the XRD pattern of the composite sewage treatment agent is basically identical to that of attapulgite, but the peak intensity is relatively low.
FIG. 11 is SEM image of jute powder/attapulgite composite sewage treatment agent, from which it can be seen that attapulgite is wrapped outside jute powder, and this structure illustrates that the combination of attapulgite and jute powder is relatively tight, and Cu is adsorbed by the composite sewage treatment agent 2+ Or methylene blue can promote the synergistic effect of jute powder and attapulgite.
FIG. 14 shows the combination of sewage treatment agents for Cu 2+ The performance of adsorption is shown, and the graph shows that the Cu is adsorbed in the example 5 2+ The amount of adsorbed was 246.8 mg/g.
FIG. 15 shows a pair of unmodified raw materials Cu 2+ Performance of adsorption combining Cu from example 5 and example 7 in FIG. 14 2+ The adsorption capacity of the composite sewage treatment agent can be concluded to be Cu 2+ The adsorption capacity of the composite sewage treatment agent is far greater than that of the unmodified raw material, and the composite sewage treatment agent added with the attapulgite is used for treating Cu 2+ The adsorption capacity of the attapulgite composite sewage treatment agent is larger than that of the sewage treatment agent without the attapulgite composite sewage treatment agent.
The performance of the sewage treatment agent obtained in example 5 on methylene blue adsorption is shown in FIG. 16, and it can be seen that the adsorption amount of the product of example 5 on methylene blue is 132.3 mg/g.
Fig. 17 is a performance diagram of adsorption of unmodified raw materials to methylene blue, and by combining the adsorption amounts of example 5 and example 7 in fig. 16 to methylene blue, it can be concluded that the adsorption amount of the composite sewage treatment agent to methylene blue is much larger than that of an unmodified sample, and the adsorption amount of the composite sewage treatment agent to methylene blue after the attapulgite is added is larger than that of the composite sewage treatment agent without the attapulgite.
Example 6
Placing 15 g of jute powder (rod powder), 1.5 g of attapulgite and 9 g of polyacrylamide into a polytetrafluoroethylene ball milling tank, wherein the mass ratio of alumina balls (in terms of mass ratio, 20% of large balls with the diameter of 10 mm, 50% of medium balls with the diameter of 5mm and 30% of small balls with the diameter of 3 mm) to the composite raw material is 6:1, the rotating speed of a ball mill is 500 rpm, and ball milling is carried out for 4 hours to obtain mixed powder after ball milling. The other treatment methods were the same as in example 1.
The obtained clay mineral/biomass composite sewage treatment agent adsorbs Cu 2+ The conditions of methylene blue were the same as in example 1.
In this example, the jute powder was jute straw powder and the polyacrylamide was Anionic Polyacrylamide (APAM).
FIG. 12 is XRD of jute powder, attapulgite, jute powder/attapulgite composite sewage treatment agent, the XRD pattern of the composite sewage treatment agent is basically identical to that of attapulgite, but the peak intensity is relatively low.
FIG. 13 is an SEM image of a jute stalk powder/attapulgite composite sewage treatment agent, from which it can be seen that the surface of the attapulgite is wrapped by jute powder, and jute powder is also arranged between the layers, and this structure shows that the combination of attapulgite and jute powder is relatively tight, and the composite sewage treatment agent adsorbs Cu 2+ Or methylene blue can promote the synergistic effect of jute powder and attapulgite.
Example 6 Sewage treatment agent for Cu 2+ The adsorption performance is shown in FIG. 14, and it can be seen that the product of example 6 has Cu 2+ The adsorbed amount of (A) was 272.9 mg/g.
FIG. 15 shows a pair of unmodified raw materials Cu 2+ Performance of adsorption combining Cu from example 6 and example 7 in FIG. 14 2+ The adsorption capacity of the composite sewage treatment agent can be concluded to be Cu 2+ The adsorption capacity of the composite sewage treatment agent is far greater than that of the unmodified raw material, and the composite sewage treatment agent added with the attapulgite is used for treating Cu 2+ The adsorption capacity of the attapulgite composite sewage treatment agent is larger than that of the sewage treatment agent 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 fig. 16, and it can be seen that the adsorption amount of the product of example 6 on methylene blue is 157.3 mg/g.
Fig. 17 is a graph showing the adsorption performance of an unmodified raw material on methylene blue, and by combining the adsorption amounts of example 6 and example 7 in fig. 16, it can be concluded that the adsorption amount of the composite sewage treatment agent on methylene blue is far greater than that of an unmodified sample, and the adsorption amount of the composite sewage treatment agent after the attapulgite is added on methylene blue is greater than that of the composite sewage treatment agent without the attapulgite.
Example 7
Placing 15 g of jute powder and 9 g of polyacrylamide into a polytetrafluoroethylene ball milling tank, wherein the mass ratio of alumina balls (by mass ratio, the mass ratio of large balls with the diameter of 10 mm to 20 percent, the mass ratio of medium balls with the diameter of 5mm to 50 percent and the mass ratio of small balls with the diameter of 3mm to 30 percent) to the composite raw materials is 6:1, the rotating speed of the ball mill is 500 rpm, and the ball milling is carried out for 4 hours. The other treatment methods were the same as in example 1.
The obtained clay mineral/biomass composite sewage treatment agent adsorbs Cu 2+ The conditions of methylene blue were the same as in example 1.
In this example, the jute powder was jute leaf powder and the polyacrylamide was Anionic Polyacrylamide (APAM).
Example 7 Sewage treatment agent for Cu 2+ The adsorption performance is shown in FIG. 14, and it can be seen that the product of example 7 has Cu 2+ The amount of adsorbed was 124.4 mg/g.
The performance of the sewage treatment agent obtained in example 7 on methylene blue adsorption is shown in FIG. 16, and it can be seen that the adsorption amount of the product of 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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CN102614851A (en) * 2012-04-09 2012-08-01 西北师范大学 Preparation of palygorskite clay/plant stalk composite adsorbent and application of composite adsorbent in treating printing and dyeing wastewater
CN108689407A (en) * 2018-06-26 2018-10-23 中国科学院生态环境研究中心 A kind of technique that binder pressed active carbon is exempted from abandoned biomass preparation

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CN102614851A (en) * 2012-04-09 2012-08-01 西北师范大学 Preparation of palygorskite clay/plant stalk composite adsorbent and application of composite adsorbent in treating printing and dyeing wastewater
CN108689407A (en) * 2018-06-26 2018-10-23 中国科学院生态环境研究中心 A kind of technique that binder pressed active carbon is exempted from abandoned biomass preparation

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