CN113773846A - Method for preparing agricultural water-retaining agent by using waste green algae - Google Patents

Method for preparing agricultural water-retaining agent by using waste green algae Download PDF

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CN113773846A
CN113773846A CN202111056249.0A CN202111056249A CN113773846A CN 113773846 A CN113773846 A CN 113773846A CN 202111056249 A CN202111056249 A CN 202111056249A CN 113773846 A CN113773846 A CN 113773846A
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water
retaining agent
green alga
carbon
based material
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CN113773846B (en
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彭红波
林俊健
杨雯雯
许志敏
杨杰
王思瑶
牛一帆
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Kunming University of Science and Technology
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    • Y02P60/20Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
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Abstract

The invention relates to a method for preparing an agricultural water-retaining agent by using waste green algae, belonging to the technical field of water-retaining agent preparation. The water-retaining agent prepared by the invention has high water absorption multiple and good water-retaining effect, has high saline-alkali resistance, and has the characteristics of low temperature resistance and no ice formation by adding an antifreezing agent; the microwave heating method is adopted in the aspect of efficiency, and the limitation of high temperature and high time is broken through compared with the traditional process; in addition, aiming at the characteristic of high extraction difficulty of freshwater green algae cellulose, the yield of green algae cellulose raw materials is greatly improved by adopting a three-stage extraction process combining a biological enzyme method and a chemical method, and the carbon-based material inoculated with a degradation strain, the active clay adsorbent loaded with green algae fiber and the water-retaining agent are coupled by an ultrasonic technology, so that the improvement and purification of the crop soil environment are facilitated while water is retained, the complete degradation is easy, the secondary pollution is avoided, and the efficient utilization of waste resources is realized.

Description

Method for preparing agricultural water-retaining agent by using waste green algae
Technical Field
The invention belongs to the technical field of water-retaining agent preparation, and particularly relates to a method for preparing an agricultural water-retaining agent by using waste green algae.
Background
With the vigorous development of agricultural and industrial related industrial chains in recent years, a lot of sewage is derived while economic value is created, and the water quality of a lot of fresh water systems is gradually developed towards eutrophication due to high nitrogen phosphorus and potassium content, so that disasters such as water bloom are caused. In the past, most of the overflowed green algae are salvaged and buried or low-valued, so that resource waste is caused, and the green algae do not have a relatively mature clean subsequent treatment process. In the market of the existing water-retaining agent, a cellulose efficient extraction process and a subsequent related preparation process designed for freshwater green algae are not provided, and the water-retaining agent has great market potential.
The water-retaining agent is developed rapidly and is diversified, the water-retaining technology mainly used by most environmental protection companies is still a common polyacrylamide technology, and the finished product produced by the technology is difficult to degrade due to the stability of the polymer, so that the synthesized water-retaining agent mainly has the problems of high cost, poor salt resistance, difficult biodegradation and the like, the icing problem of the water-retaining agent brought by a low-temperature environment is not improved, and the application range and seasons have serious limitations.
The traditional water-retaining agent preparation process is commonly an acrylic acid self-crosslinking technology, the final gel production process of the technology is often accompanied by high-temperature and high-pressure, nitrogen protection and other process requirements with high risk coefficient and high operation difficulty, and the gel can be formed only after a long time of several hours by means of water bath without heating, so that the efficiency is very low.
Most of the water retention agents sold in the current market only have the single water retention effect or are applied in combination with water and fertilizer, and the application mode is not convenient and fast and is easy to cause the phenomenon of seedling burning caused by excessive application. Aiming at the defect of functional diversity of the water-retaining agent, a multifunctional integrated agricultural water-retaining agent which has the functions of water retention, heat preservation, fertilizer increase, soil quality improvement and pollution purification is needed to be developed.
For example, CN105085828A discloses a preparation method of a flax scrap fiber water-retaining agent, which comprises washing flax scraps with deionized water, filtering, naturally drying at normal temperature, putting the dried flax scraps into a beaker, adding a sodium hydroxide solution with the mass fraction of 15%, transferring into an oil bath pan, heating to 150-170 ℃, wherein the temperature in the process is high, the production difficulty is high, the cost is high, and the produced water-retaining agent cannot retain water for a long time. In addition, the water-retaining agent mainly absorbs saline water instead of deionized water in the application process, and the salt tolerance of the water-retaining agent is not verified, but most of the water-retaining agents sold in the market at present have higher deionized water absorption capacity but only absorb a small amount of saline water, so that the water-retaining agent is not suitable for application.
For example, CN103864980A discloses a method for preparing a water retention agent, which comprises using methacrylic acid, acrylic acid and acrylamide as monomers, adding potassium persulfate as an initiator and N, N-methylene bisacrylamide as a cross-linking agent into the monomer mixture, and carrying out polymerization reaction under the condition of introducing nitrogen. In the preparation method, the filling of nitrogen is not easy to control, and the heating ring is energy-saving and time-consuming, so that the energy consumption is large and the comprehensive investment cost is high.
For example, CN104892824A discloses a method for preparing a water-retaining agent, which comprises, first, adding acrylic acid into a reaction kettle, mixing, then neutralizing with sodium hydroxide, cooling, then adding N, N-methylene bisacrylamide, disodium EDTA, and carboxymethyl cellulose into the cooled solution, mixing uniformly, and then charging nitrogen gas and the like. The water-retaining agent obtained by the preparation method only has a single function of water retention and cannot meet the current market requirements.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preparing an agricultural water-retaining agent by using waste green algae. The abused and waste fresh water green algae are used as the raw material for preparing the water-retaining agent, so that the waste resources are recycled. The three-stage green algae cellulose extraction process combining the biological method with the chemical method can greatly improve the hydrolysis rate of the green algae cellulose, thereby improving the yield of the water-retaining agent; the water-retaining agent is prepared by the steps of 6 and 7, the green alga fiber and N, N '-methylene bisacrylamide are subjected to graft copolymerization reaction under the action of an initiator potassium persulfate, then the green alga fiber and N, N' -methylene bisacrylamide are tightly combined with a carbon-based material in an ultrasonic reaction kettle, and finally the relatively low temperature of 70-75 ℃ is kept by a microwave heating technology, so that the water-retaining agent prepared by the scheme has high water absorption multiple, good water-retaining effect, high saline-alkali resistance and low temperature resistance, and can be degraded into carbon dioxide, water, free nitrogen, phosphorus and sylvite after completing the task of a water-retaining period because the main raw material component contained in the water-retaining agent is fresh water green alga, no harmful substance is left, and the water-retaining agent can be completely degraded by inoculating a degrading strain, and because the carbon-based material is added for optimization, the carbon-based material can also increase a soil carbon source and is beneficial to the growth and the propagation of soil microorganisms, and the added activated clay composite adsorbent greatly improves the capacity of adsorbing heavy metals and part of organic pollutants in the soil under the loading action of the green alga fibers, so that the biological effectiveness of improving the soil environment, reducing the stress of the pollutants and promoting the growth of crops are achieved, the environment is protected, and considerable economic benefits are created.
In order to achieve the purpose, the invention is implemented according to the following technical scheme:
the method specifically comprises the following steps:
1) taking a certain amount of fresh green algae, cleaning, drying, crushing by a crusher, and sieving to obtain green algae dry powder;
2) pouring the green algae dry powder into a lyase tank for hydrolysis, and performing centrifugation and membrane separation to obtain a green algae extract I;
3) after the green alga extract is sieved and washed, alkaline pretreatment is carried out by using alkaline solution, then green alga cellulose in the green alga extract I is extracted by using nitric acid-ethanol in a combined mode, and then the green alga cellulose is subjected to centrifugation, grinding, sieving and washing in sequence to obtain a green alga extract II;
4) adding an initiator potassium persulfate, activated clay and deionized water into the second green alga extract, uniformly stirring, and then carrying out microwave heating by using a microwave device to obtain a green alga fiber mixed solution;
5) neutralizing acrylic acid and sodium hydroxide under the ice-water bath condition, adding the neutralized acrylic acid and sodium hydroxide into the green alga fiber mixed solution, and adding N, N' -methylene bisacrylamide serving as a cross-linking agent into the green alga fiber mixed solution to obtain a reaction solution;
6) placing the reaction liquid in a container, adding the carbon-based material inoculated with the degrading bacteria and the anti-freezing agent, fully and uniformly mixing, placing the mixture into an ultrasonic reaction kettle, and reacting for a period of time to obtain a mixed material reaction liquid;
7) putting the reaction solution into a microwave device, and heating with medium fire to obtain a gel-state primary product;
8) and washing the gel-state primary product, drying to constant mass, grinding and crushing to obtain the water-retaining agent.
The method for preparing the algae water-retaining agent optimized by the carbon-based material according to claim 1, wherein the method comprises the following steps: in the step 2), the lyase is a mixture of alginate lyase and chlorella polysaccharide lyase, the enzymolysis time is 3h, and the enzymolysis temperature is 40 ℃.
Preferably, in the step 3), the alkali liquor is a sodium hydroxide solution with the mass fraction of 30%, and the mass ratio of the green alga extract I to the alkali liquor is 1:3, the ratio of the first green alga extract to the nitric acid ethanol feed liquid is 1:43 g/ml.
Preferably, in the step 4), the activated clay is montmorillonite activated by sulfuric acid, and the ratio of the added amount of the activated clay to the liquid-material ratio of the green alga extract II is 1: 10.
preferably, in the step 5, the mass ratio of the added amount of the acrylic acid to the green alga dry powder is 7: 1, the neutralization degree of the acrylic acid and the sodium hydroxide is 60-70%, a sodium hydroxide solution with the mass fraction of 30% is adopted, and the neutralization temperature of the acrylic acid and the sodium hydroxide is controlled at 15-45 ℃.
Preferably, in the step 5, the adding amount of the N, N-methylene-bisacrylamide is 0.5-1% of the mass of the acrylic acid.
Preferably, in step 6, the degrading bacteria are chlorella polysaccharide degrading strains, and the degrading bacteria suspension and the biochar are mixed in a liquid-to-material ratio of 3: 1 (V: W) and shaking at 200rpm for 24 hr to inoculate the degrading flora onto the carbon-based material.
Preferably, in step 6, the antifreeze comprises the following components in parts by weight: 100 portions of water, 200 portions of glacial acetic acid, 35 portions to 45 portions of hydrogen peroxide and 20 portions to 30 portions of hydrogen peroxide.
The invention has the beneficial effects that:
(1) the extraction process can hydrolyze the cellulose to the maximum extent by the green algae with low cellulose content, improves the production efficiency, ensures the yield of the water-retaining agent by increasing the yield of the green algae cellulose which is a main raw material, breaks through the current situations that the low value of the freshwater green algae is utilized and the green algae is not applied as the raw material in the preparation process of the water-retaining agent, recycles the waste resources and creates the economic value.
(2) Improve the salt resistance and have low temperature resistance. The water-retaining agent prepared by using fresh water green algae as a main raw material is an irregular solid after absorbing water, is mostly of a net structure after absorbing water compared with the water-retaining agents sold in the market, is easy to discharge water by extrusion, is not easy to swell after being applied to soil, and is more beneficial to use; in addition, the application scene of the water-retaining agent is mainly saline water absorption rather than deionized water, and the rate of the water-retaining agent in the scheme for absorbing normal saline water can reach 100-200 times, so that the water-retaining agent is more suitable for practical farmland application; the antifreezing agent is added, the problem of water retention property failure caused by icing of the water retention agent brought by low-temperature environment is improved, the applicable geographical range and seasonal limitation are broken through, even under the low-temperature environment of 0 ℃, the multiplying power of the water retention agent in the scheme for absorbing normal saline can reach about 100 times, and the large-area popularization is more suitable.
(3) Simplifying conditions and reducing cost. The final gel forming stage is placed in a microwave device for reaction, the temperature is controlled in real time through a temperature control device, the whole process temperature is 70-75 ℃, the gel can be formed only in 10min due to the high dielectric body heating effect of the microwave, compared with the requirement of high temperature and high time of 2-3h at 90 ℃ of the traditional water bath heating process, the process is simplified, the heat source consumption is greatly reduced, the restriction on reaction conditions such as air isolation and nitrogen protection is not needed to be compromised, and the cost is reduced in the aspects of time, money and the like.
(4) Environment protection, easy complete degradation and multifunction integration. The water-retaining agent in the technical scheme has high water absorption multiple and good water-retaining effect, and the main raw material component contained in the water-retaining agent is fresh water green algae, so that the water-retaining agent can be degraded into carbon dioxide, water, free nitrogen, phosphorus and potassium salt after completing a water-retaining period task, no harmful substance is left, and the water-retaining agent can be completely degraded by inoculating degradation strains; the degrading strain is a green alga polysaccharide degrading flora for producing alginic acid lyase and green alga polysaccharide lyase, and can be used for a second time after hydrolyzing cellulose in the early stage; the carbon-based material is optimized by adding the carbon-based material, so that the carbon-based material can also increase a soil carbon source and is beneficial to the growth and the propagation of soil microorganisms; the added activated clay and the green algae cellulose are loaded and combined under the stirring condition, a compound with a stable structure can be formed, so that the green algae cellulose is filled into an interlayer structure of the activated clay, the adsorption performance is improved, and even heavy metals and partial organic pollutants in soil can be adsorbed, so that the biological effectiveness of improving the soil environment, reducing the stress of the pollutants and promoting the growth of crops are achieved, the environment is protected, considerable economic benefits are created, and the multifunction and the simplicity of application of one agent are realized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a flow chart of the preparation process of the water-retaining agent of the present invention;
FIG. 2 is a diagram of a microwave reaction device for water-retaining agent of the present invention;
in the figure, 1-a heat insulation layer, 2-a material cylinder, 3-a microwave emitter, 4-a microwave power controller, 5-a temperature control system, 6-a switch and 7-a stirring device.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings to facilitate understanding of the skilled person.
The mechanism of the invention is as follows: 1. the fresh green algae is cleaned, and can be better crushed and sieved after being conveniently dried, so that the subsequent efficiency of extracting cellulose is guaranteed; 2. the green alga dry powder is biologically hydrolyzed by using lyase, alginic lyase and green alga polysaccharide lyase are selected as lyase, the hydrolysis process is mild, no damage is caused to cellulose, side reactions are few, the hydrolysis degree is easy to control under the conditions of proper temperature and pH, and higher hydrolysis degree can be obtained with lower production cost; 3. the swelling and breaking effects of sodium hydroxide on cellulose and hemicellulose hydrogen bonds are utilized, alkali liquor is added to accelerate the cracking of green alga polysaccharide cell walls under a high-temperature environment, so that a polysaccharide substance, namely green alga cellulose, which is one of main raw materials of the water retaining agent is obtained, then the green alga cellulose (in a microcrystalline form) is extracted by a nitric acid-ethanol method, the finished product extraction rate of hydrolysate green alga polysaccharide is ensured to the maximum extent, and the resource utilization is maximized; 4. adding an initiator to generate free radicals on a cellulose macromolecular skeleton, and reacting the free radicals with acrylic acid to form a graft copolymer; the added activated clay and the green algae cellulose are subjected to load combination under the stirring condition to form a compound with a stable structure, so that the green algae cellulose is filled into an interlayer structure of the activated clay, the interlayer spacing of the activated clay is enlarged, the specific surface area of the activated clay is increased, and the pore channel quantity of the activated clay is greatly increased, so that the adsorption performance of the water-retaining agent is improved, and even heavy metals and partial organic pollutants in soil can be adsorbed, thereby improving the soil environment, reducing the biological effectiveness of pollutant stress, promoting the growth of crops, protecting the environment, creating considerable economic benefits, and realizing the multifunction of one dose and simplification of application; 5. the initiator potassium persulfate and the green alga cellulose are mixed and preheated in advance, so that the initiator and the green alga cellulose can be uniformly mixed (artificial physical interference cannot be carried out in subsequent microwaves), the device can be prevented from being opened in the subsequent microwave process (the microwave device is not required to be opened for adding the initiator, danger is avoided), the microwave device is utilized for preheating, the dissolution of the potassium persulfate is accelerated, the potassium persulfate is enabled to form a free radical on a cellulose framework, the subsequent graft polymerization is facilitated, and the efficiency is improved; 6. the biochar is prepared by burning waste melon, fruit, vegetable and livestock manure, is rich in nitrogen, phosphorus and potassium, has unique characteristics such as high specific surface area, cation exchange capacity and porosity, changes pH value and a large number of functional groups, becomes an effective material, can be used for fixing trace elements in soil to improve soil fertility, adsorbs heavy metals and organic pollutants, and achieves functional diversity; the biochar can promote the propagation of soil microorganisms, so that the degradation rate of the water-retaining agent can be accelerated through microbial decomposition, and the water-retaining agent is more easily decomposed because cellulose is used as a raw material; the ultrasonic reaction kettle is used for closely and uniformly coupling the biochar and the water-retaining agent raw materials, and a large number of biochar particles are uniformly distributed on the surface of the water-retaining agent through observation of an electron microscope, so that the advantage of the biochar can be grafted into the water-retaining agent generated after reaction;
the water-retaining agent is polymerized by free radicals, under the action of an initiator potassium persulfate, free radicals are firstly generated on a cellulose macromolecular skeleton and react with acrylic acid to form a cross-linking agent N, N' -methylene bisacrylamide added into a graft copolymer, so that a cellulose main chain and an acrylic acid branched chain can be cross-linked with each other to form a complex three-dimensional network structure, the water absorption rate of the water-retaining agent is favorably improved, and biochar is adsorbed in gel by virtue of the grafting process to be favorable for function diversification; the invention utilizes the dielectric body heating effect of microwave energy to lead positive and negative electrons in the raw material to generate a large amount of heat energy through the friction of high-frequency microwave, thereby achieving the effect of rapid gelation; the water-retaining agent is prepared by adopting a microwave radiation method, and the water absorption rate of the water-retaining agent mainly depends on the crosslinking degree of ionized carboxyl groups and a copolymerization chain, so that compared with the traditional method, the method has the advantages that the rapid polymerization of acrylic acid can be promoted, the crosslinking level can be controlled (the temperature can be controlled after a microwave device is modified), the temperature rise is fast, the heating is uniform, the reaction speed can be improved, and the polymerization time can be shortened.
The reaction carrier in the whole process of the water-retaining agent prepared by the invention is completely replaced by natural green algae cellulose, in the degradation process of the water-retaining agent, a green algae fiber extract can slowly release abundant nutrients such as lignin, hemicellulose, amino acid, phytohormone, free nitrogen phosphorus potassium salt and the like contained in the green algae fiber extract, the coupled carbon-based material inoculated with degradation strains can promote the propagation of soil microorganisms so as to ensure and accelerate the complete degradation of the water-retaining agent, the added activated clay composite adsorbent can adsorb heavy metals and organic pollutants in the soil so as to improve the soil environment, and the added antifreezing agent breaks through the geographic range and seasonal limitation of the application of the water-retaining agent, so that the water-retaining agent is more suitable for large-area popularization. Therefore, the water-retaining agent of the invention is a multifunctional integrated agricultural easily-degradable 'algae-made water-retaining fertilizer' with the functions of soil water retention, heat preservation, fertilizer increase, soil quality improvement and pollution purification.
Example 1:
selecting 1kg of fresh green algae, cleaning, drying, crushing by using a crusher, and sieving by using a 60-mesh sieve to obtain 100g of green algae dry powder; pouring 100g of green algae dry powder into a lyase pool (water with a feed liquid ratio of 1:20 is added into the pool) for hydrolysis, wherein the lyase is a mixture of alginic lyase and green algae polysaccharide lyase, the enzymolysis time is 3h, the enzymolysis temperature is 40 ℃, and the green algae extract I is obtained by centrifugation (the centrifugation speed is 7000r/min, the centrifugation time is 10 min) and membrane separation (a semi-permeable membrane adopted in the membrane separation is an ultrafiltration membrane (UF)); the first green alga extract is subjected to 60-mesh sieve and washing, then is subjected to alkalization pretreatment by using alkali liquor, wherein the alkali liquor adopts 10% by mass of sodium hydroxide solution, the addition amount of the alkali liquor is 300g, the first green alga extract is further hydrolyzed, after alkali treatment is carried out for 1 hour at 90 ℃, nitric acid ethanol (mixed solution of nitric acid and 95% ethanol, V/V =1: 3) is added, the material-liquid ratio is 1:43g/ml, reflux extraction is carried out for 1.5h under 90 ℃ water bath, centrifugation (centrifugal rotation speed of 7000r/min and centrifugal time of 10 min) is carried out, water washing is carried out until the mixture is neutral, and then centrifugation, pulp grinding, sieving (60-mesh sieve) and washing are sequentially carried out to obtain a second green alga extract. Adding 14g of initiator potassium persulfate, 10g of activated clay and 350g of deionized water into the second green alga extract, uniformly stirring for 30min to enable the activated clay and the green alga cellulose to be loaded and combined to form a compound with a stable structure, and then carrying out low-fire-level microwave heating by using a microwave device, wherein the temperature is controlled to be about 45 ℃ to obtain a green alga fiber mixed solution. Under the condition of ice-water bath, 1400g of acrylic acid solution with the mass fraction of 50% and 700g of sodium hydroxide solution with the mass fraction of 30% are neutralized, the neutralization temperature is controlled to be below 45 ℃, the neutralization degree is about 60%, the acrylic acid solution is added into mixed solution which is heated by microwave and then cooled to room temperature, 3.5g of N, N' -methylene bisacrylamide is added into the mixed solution to be used as a cross-linking agent, and the mixture is fully mixed to obtain reaction liquid; placing the reaction liquid in a container, adding 1g of carbon-based material (biochar formed by firing waste melon, fruit and vegetable and livestock feces) which is sieved by a 200-mesh sieve and inoculated with degradation strains and 1g of antifreeze (the antifreeze comprises the following components, by weight, 200 parts of water, 35-45 parts of glacial acetic acid and 20-30 parts of hydrogen peroxide), fully mixing uniformly, then placing into an ultrasonic reaction kettle, and carrying out ultrasonic reaction at the set temperature of 50 ℃ for 5min to obtain mixed material reaction liquid; pouring the carbon-based material reaction liquid into a stainless steel plate, uniformly spreading a layer, putting the stainless steel plate into a microwave device, heating with medium fire for about 10 minutes, and keeping the whole temperature at 70-75 ℃ until the reaction liquid forms a gel-state primary product; and (3) taking the gel out of a stainless steel disc, washing, drying to constant mass, grinding and crushing to obtain the algae water-retaining agent optimized by the carbon-based material.
Example 2: (Low degree of neutralization)
A multifunctional integrated agricultural water-retaining agent prepared by combining cellulose extracted from waste green algae and a carbon-based material is different from the agricultural water-retaining agent prepared in example 1 in that the neutralization degree of an acrylic acid solution and a sodium hydroxide solution in a neutralization process is controlled to be 60%.
Example 3: (in degree of neutralization)
A multifunctional integrated agricultural water-retaining agent prepared by combining cellulose extracted from waste green algae and a carbon-based material is different from the agricultural water-retaining agent prepared in example 1 in that the neutralization degree of an acrylic acid solution and a sodium hydroxide solution in a neutralization process is controlled to be 65%.
Example 4: (high amount of crosslinking agent)
A multifunctional integrated agricultural water-retaining agent prepared by combining cellulose extracted from waste green algae and a carbon-based material is different from the agricultural water-retaining agent prepared in example 1 in that the addition amount of an N, N' -methylenebisacrylamide cross-linking agent is 7 g.
Example 5: (Water bath heating for 1 h)
A multifunctional integrated agricultural water-retaining agent prepared by combining cellulose extracted from waste green algae and a carbon-based material is different from the water-retaining agent prepared in the embodiment 1 in that a carbon-based material reaction solution is poured into a stainless steel disc and uniformly paved into a layer, the stainless steel disc is placed into a water bath heating device, the reaction time is about 1 hour, and the whole temperature is kept at 70-75 ℃.
Example 6: (obtaining Chlorella cellulose by hydrolysis with alkali only)
A multifunctional integrated agricultural water-retaining agent prepared by combining cellulose extracted from waste green algae and a carbon-based material is different from the water-retaining agent in example 1 in that alkalization hydrolysis is carried out only by using alkaline solution, 300g of sodium hydroxide solution with the mass fraction of 10% is added into the green algae extract I for alkalization, and alkali treatment is carried out for 1 hour at 90 ℃.
Example 7: (without adding activated clay)
The difference between the multifunctional integrated agricultural water-retaining agent prepared by extracting green alga cellulose from waste green alga and combining the green alga cellulose with a carbon-based material and the embodiment 1 is that 0g of activated clay and 350g of deionized water are added, and after the mixture is uniformly stirred for 30min, the activated clay and the green alga cellulose are combined.
Example 8: (activated Clay was added, and stirring was not carried out sufficiently)
The difference between the multifunctional integrated agricultural water-retaining agent prepared by extracting green alga cellulose from waste green alga and combining the green alga cellulose with a carbon-based material is that 10g of activated clay and 350g of deionized water are added, and the activated clay and the green alga cellulose are combined without uniform stirring.
Example 9: (without addition of carbon-based materials)
A multifunctional integrated agricultural water-retaining agent prepared by combining cellulose extracted from waste green algae and a carbon-based material is different from the agricultural water-retaining agent prepared in example 1 in that 0g of the carbon-based material which is sieved by a 200-mesh sieve and inoculated with a degradation strain is added.
Example 10: (carbon-based material added, not inoculated with degrading bacteria)
A multifunctional integrated agricultural water-retaining agent prepared by combining cellulose extracted from waste green algae and a carbon-based material is different from the agricultural water-retaining agent prepared in example 1 in that 1g of the carbon-based material which is sieved by a 200-mesh sieve and is not inoculated with a degradation strain is added.
Example 11: (without addition of antifreeze)
A multifunctional integrated agricultural water-retaining agent prepared by combining cellulose extracted from waste green algae and a carbon-based material is different from the agricultural water-retaining agent prepared in example 1 in that 0g of an antifreezing agent is added.
The water release rate, water absorption time and water retention days of the water retention agents prepared in the above examples 1 and 2 to 11 are tested, and the finished product yield of the water retention agents prepared in the above examples 1 and 2 and 3 to 6 is tested, wherein the test methods are as follows:
(1) taking the resin which absorbs saturated water, accurately weighing the resin, placing the resin into a 8000r/min centrifuge for centrifuging for 10 minutes, taking the resin out, pouring out water, and weighing, wherein the water release rate = water weight/total weight;
(2) water absorption multiple, namely accurately weighing the water-retaining agent, putting the water-retaining agent into sufficient distilled water for 24 hours, filtering the water-retaining agent by using 30-mesh filter cloth, and weighing the water-retaining agent;
(3) adding a fixed amount of water-retaining agent into a sufficient amount of distilled water, weighing once every 10 minutes until the weight change is less than 5% after 3 times, and recording the time when the weight is unchanged for the first time, namely the water absorption time;
(4) and (4) water retention days, namely taking a fixed amount of water retention agent to absorb water in a saturated way, placing the water retention agent in a ventilated place, and recording the weight of the water retention agent every day until the weight of the water retention agent is 50 percent less than the saturated weight of the water retention agent.
(5) Yield of finished products: accurately weighing 100g of green alga dry powder, obtaining a finished product water-retaining agent according to the process flow, accurately recording the quality of the finished product water-retaining agent, recording as Mg, and calculating the yield of the water-retaining agent according to the following formula:
yield (%) = M/100x100%
The test results are shown in table 1 below:
Figure 583248DEST_PATH_IMAGE001
TABLE 1 Water retention Properties and product yields of the Water-retaining Agents
The water retention agents prepared in the above examples 1, 7 and 8 were subjected to Cu-conditioning2+、Cr3+、Pb2+The detection method of the adsorption rate of (2) is as follows:
Cu2+adsorption ratio of (2): to dispose the same concentration of copper ions (Cu)2+) Using the solution as adsorption liquid, using sufficient water-retaining agent as adsorbent, and using element absorption instrument to detect Cu in the adsorption liquid after adsorption2+Calculated as adsorption rate.
Cr3+Adsorption ratio of (2): to dispose copper ions (Cr) with the same concentration3+) Using the solution as adsorption liquid, using enough water-retaining agent as adsorbent, and using element absorption instrument to detect Cr in the adsorption liquid3+Calculated as adsorption rate.
Pb2+Adsorption ratio of (2): to dispose the same concentration of copper ions (Pb)2+) Using the solution as adsorption liquid, using sufficient water-retaining agent as adsorbent, and using element absorption instrument to detect Pb in the adsorption liquid2+Calculated as adsorption rate. The test results are shown in table 2 below.
TABLE 2 Water-retaining Agents heavy metals (Cu)2+) Adsorption rate
Figure 890602DEST_PATH_IMAGE003
The degradation performance of the water-retaining agents prepared in the above examples 1, 9 and 10 is tested by the following methods:
10g of the water-retaining agent prepared in each example and comparative example was completely buried in natural soil having water retention capacity and humidity of 50% in a constant temperature and humidity chamber (GB/T192752003), and after 60 days, the water-retaining agent was taken out, washed, dried and weighed as m, and the degradation rate and degradation rate of the water-retaining agent were calculated according to the following formulas, and the results are shown in Table 3:
A=(10-m)/10*100
B=(10-m)/60
in the formula: a: degradation rate,%, of water-retaining agent; b: degradation rate of the water-retaining agent, g/d, m: water-retaining agent quality after 60 days.
TABLE 3 degradability and Plastic degradation Rate of the Water-retaining Agents
Item Example 1 Example 9 Example 10
Degradation Rate (%) 47.2 21.7 29.1
Degradation Rate (g/d) 0.079 0.036 0.049
The water-retaining agents prepared in the above examples 1 and 11 were tested for freezing resistance and water retention property by the following methods:
anti-freezing and water retention properties: multiple water absorption (g/g): the water-retaining agent is accurately weighed, put into a sufficient amount of distilled water (the temperature of the distilled water is 0 ℃) for 24 hours, filtered by 30-mesh filter cloth, weighed, and the test results are shown in the following table 4.
TABLE 4 Freeze resistance and Water retention Properties of the Water-retaining Agents
Figure 608022DEST_PATH_IMAGE004
Finally, it is noted that the above-mentioned preferred embodiments illustrate rather than limit the invention, and that, while the invention has been described in detail with reference to the foregoing preferred embodiments, it will be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the scope of the invention as defined by the appended claims; the size of the attached figure is irrelevant to the specific real object, and the size of the real object can be changed at will.

Claims (9)

1. A method for preparing an agricultural water-retaining agent by using waste green algae is characterized by comprising the following steps:
1) taking a certain amount of fresh green algae, cleaning, drying, crushing by a crusher, and sieving to obtain green algae dry powder;
2) pouring the green algae dry powder into a lyase tank for hydrolysis, and performing centrifugation and membrane separation to obtain a green algae extract I;
3) after the green alga extract is sieved and washed, alkaline pretreatment is carried out by using alkaline solution, then green alga cellulose in the green alga extract I is extracted by using nitric acid-ethanol in a combined mode, and then the green alga cellulose is subjected to centrifugation, grinding, sieving and washing in sequence to obtain a green alga extract II;
4) adding an initiator potassium persulfate, activated clay and deionized water into the second green alga extract, uniformly stirring, and then carrying out microwave heating by using a microwave device to obtain a green alga fiber mixed solution;
5) neutralizing acrylic acid and sodium hydroxide under the ice-water bath condition, adding the neutralized acrylic acid and sodium hydroxide into the green alga fiber mixed solution, and adding N, N' -methylene bisacrylamide serving as a cross-linking agent into the green alga fiber mixed solution to obtain a reaction solution;
6) placing the reaction liquid in a container, adding the carbon-based material inoculated with the degrading bacteria and the anti-freezing agent, fully and uniformly mixing, placing the mixture into an ultrasonic reaction kettle, and reacting for a period of time to obtain a mixed material reaction liquid;
7) putting the reaction solution into a microwave device, and heating with medium fire to obtain a gel-state primary product;
8) and washing the gel-state primary product, drying to constant mass, grinding and crushing to obtain the water-retaining agent.
2. The method for preparing the algae water-retaining agent optimized by the carbon-based material according to claim 1, wherein the method comprises the following steps: in the step 2), the lyase is a mixture of alginate lyase and chlorella polysaccharide lyase, the enzymolysis time is 3h, and the enzymolysis temperature is 40 ℃.
3. The method for preparing the algae water-retaining agent optimized by the carbon-based material according to claim 1, wherein the method comprises the following steps: in the step 3), the alkali liquor is a sodium hydroxide solution with the mass fraction of 30%, and the mass ratio of the green alga extract I to the alkali liquor is 1:3, the ratio of the first green alga extract to the nitric acid ethanol feed liquid is 1:43 g/ml.
4. The method for preparing the algae water-retaining agent optimized by the carbon-based material according to claim 1, wherein the method comprises the following steps: in the step 4), the activated clay is montmorillonite activated by sulfuric acid, and the ratio of the addition amount of the activated clay to the liquid-material ratio of the green alga extract II is 1: 10.
5. the method for preparing the algae water-retaining agent optimized by the carbon-based material according to claim 1, wherein the method comprises the following steps: in the step 5, the mass ratio of the addition amount of the acrylic acid to the green alga dry powder is 7: 1, the neutralization degree of the acrylic acid and the sodium hydroxide is 60-70%, a sodium hydroxide solution with the mass fraction of 30% is adopted, and the neutralization temperature of the acrylic acid and the sodium hydroxide is controlled at 15-45 ℃.
6. The method for preparing the algae water-retaining agent optimized by the carbon-based material according to claim 1, wherein the method comprises the following steps: in the step 5, the adding amount of the N, N-methylene bisacrylamide is 0.5 to 1 percent of the mass of the acrylic acid.
7. The method for preparing the algae water-retaining agent optimized by the carbon-based material according to claim 1, wherein the method comprises the following steps: in step 6, the biochar is prepared by burning waste melons, fruits, vegetables and livestock manure.
8. The method for preparing the algae water-retaining agent optimized by the carbon-based material according to claim 7, wherein the method comprises the following steps: in the step 6, the degrading bacteria are green alga polysaccharide degrading strains, and the degrading flora suspension and the biochar are mixed according to a liquid-material ratio of 3: 1 (V: W) and shaking at 200rpm for 24 hr to inoculate the degrading flora onto the carbon-based material.
9. The method for preparing the algae water-retaining agent optimized by the carbon-based material according to claim 1, wherein the method comprises the following steps: in the step 6, the antifreezing agent comprises the following components in parts by weight: 100 portions of water, 200 portions of glacial acetic acid, 35 portions to 45 portions of hydrogen peroxide and 20 portions to 30 portions of hydrogen peroxide.
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