Preparation method of graphene-based degradable high-strength dust fixing agent
阅读说明：本技术 一种石墨烯基可降解高强型固尘剂的制备方法 (Preparation method of graphene-based degradable high-strength dust fixing agent ) 是由 孙友谊 杨贵焱 于 2021-08-03 设计创作，主要内容包括：一种石墨烯基可降解高强型固尘剂的制备方法,属于碳材料石墨烯与固尘剂的交叉技术领域,可解决现有固尘剂的降解、环保和固尘效果难以同时优化的问题,首先,设计合成一种可化学交联氧化面粉中蛋白的多臂交联剂,其次,对含有可降解蛋白和淀粉的面粉进行氧化改性,得到水溶性稳定好的氧化面粉,最后,将上述自制交联剂、氧化面粉加入水中溶解,而后依次加入PVA、石墨烯和硼酸,通过机械搅拌均匀,形成一种石墨烯基可降解高强固尘剂。相对传统固尘剂,不仅绿色环保,固尘效果好,且含有的石墨烯和硼酸对土壤具有优异的改良效果和肥效,同时制造成本低,制备过程简单,易于工业化生产和规模化推广。(A preparation method of a graphene-based degradable high-strength dust fixing agent belongs to the technical field of intersection of carbon material graphene and the dust fixing agent, and can solve the problems that the degradation, environmental protection and dust fixing effects of the existing dust fixing agent are difficult to optimize simultaneously. Compared with the traditional dust fixing agent, the dust fixing agent is green and environment-friendly, has a good dust fixing effect, contains graphene and boric acid, has excellent improvement effect and fertilizer effect on soil, and is low in manufacturing cost, simple in preparation process, and easy for industrial production and large-scale popularization.)
1. A preparation method of a graphene-based degradable high-strength dust-fixing agent is characterized by comprising the following steps: the method comprises the following steps:
first step, preparation of oxidized flour cross-linking agent
Adding 1, 6-hexanediol glycidyl ether and triethylene tetramine serving as raw materials into a three-necked flask, continuously stirring, and then heating to 60 ℃ under the stirring condition and keeping for 30min to obtain an oxidized flour cross-linking agent;
second step, preparation of oxidized flour
Adding water and flour into a device provided with a mechanical stirrer, a thermometer and a condenser pipe, uniformly stirring to obtain flour water dispersion solution, and adding H2O2Heating the reaction temperature to 60 ℃, preserving heat and oxidizing for 0.3h, then continuously heating to 85 ℃, preserving heat and oxidizing for 1.0h, and cooling to room temperature after oxidation to obtain oxidized flour;
thirdly, preparing graphene-based degradable high-strength dust-fixing agent slurry
Adding water and PVA into a device provided with a mechanical stirrer, a thermometer and a condenser pipe, heating to 70 ℃, mechanically stirring and dissolving to obtain a PVA aqueous solution, adding oxidized flour, heating to 80 ℃, mechanically stirring for 0.5h, cooling to room temperature, sequentially adding an oxidized flour cross-linking agent, graphene and boric acid, and mechanically stirring for 0.5h to obtain graphene-based degradable high-strength dust-fixing agent slurry;
fourthly, preparing the graphene-based degradable high-strength dust fixing agent
Adding water into the graphene-based degradable high-strength dust-fixing agent slurry to adjust solid content to obtain a graphene-based degradable high-strength dust-fixing agent water dispersion solution, then adding alkaline rose essence, and mechanically stirring for 1h at room temperature to obtain the green graphene-based degradable high-strength dust-fixing agent.
2. The preparation method of the graphene-based degradable high-strength dust-fixing agent according to claim 1, wherein the preparation method comprises the following steps: in the first step, the mass ratio of the 1, 6-hexanediol glycidyl ether to the triethylene tetramine is 10: 0.5-2.
3. The preparation method of the graphene-based degradable high-strength dust-fixing agent according to claim 1, wherein the preparation method comprises the following steps: in the second step, the mass concentration of the flour water dispersion solution is 5-40%, and the mass ratio of flour to hydrogen peroxide is 100: 2-10.
4. The preparation method of the graphene-based degradable high-strength dust-fixing agent according to claim 1, wherein the preparation method comprises the following steps: in the third step, the mass concentration of the PVA aqueous solution is 5-15%, and the mass ratio of PVA to oxidized flour is 100: 20-50.
5. The preparation method of the graphene-based degradable high-strength dust-fixing agent according to claim 1, wherein the preparation method comprises the following steps: in the third step, the mass ratio of the oxidized flour to the oxidized flour cross-linking agent is 100: 2-5, and the mass ratio of PVA to boric acid is 100: 2-10, wherein the mass ratio of PVA to graphene is 100: 0.5 to 2.0.
6. The preparation method of the graphene-based degradable high-strength dust-fixing agent according to claim 1, wherein the preparation method comprises the following steps: in the fourth step, the solid content of the water dispersion solution is adjusted to be 0.1-5%, and the adding amount of the alkaline rose essence is 1-5% of the solid content of the water solution.
Technical Field
The invention belongs to the technical field of intersection of carbon material graphene and a dust fixing agent, and particularly relates to a preparation method of a graphene-based degradable high-strength dust fixing agent.
Background
In recent years, dust control of dust fixation is an important subject of air pollution prevention in various countries, and many dust problems are caused by artificial emission, such as building construction site dust emission, mine mining dust emission, road transportation dust emission, industrial production dust emission and the like. The hydraulic dust settling and fixing method is the most common and simple dust removal method at present, but the water has large surface tension, poor dust infiltration effect and easy volatilization, so that the efficiency of dust settling by simply watering is low, the action time is short, and the current environment-friendly requirement is difficult to meet. At present, a green dense mesh net is mainly adopted to prevent dust from flying, but most of the dense mesh nets are non-degradable materials, secondary pollution is brought to the environment, and the dense mesh nets are difficult to fix in the environment with high wind ratio, so that danger is brought to surrounding implementation and equipment.
Recently, a dust fixing agent is developed, after the dust fixing agent is sprayed on the surface of bare soil, the dust fixing agent can be rapidly combined with sandy soil and solidified into a semi-permanent dust-proof shell, the dust is inhibited from flying, the dust-proof effect can reach over 90 percent, the dust-fixing effect is far stronger than that of a dense mesh net, and no dust is generated through an 8-level wind dust blowing test, so that the dust fixing agent becomes the most effective method for preventing dust from flying in the future. At present, some researches and reports about dust-fixing agents are available, for example, CN200810057756.4 uses silica gel as a main raw material to prepare the dust-fixing agent, and in order to improve the dust-fixing effect, the proportion of silica gel in the raw material is more than eighty percent, but the dust-fixing agent has the problem of difficult degradation; CN201110160998.8 uses natural latex, natural plant fiber, glycerol, surfactant and water to prepare dust suppressant, the cost is high, and the problem of difficult degradation exists. In conclusion, the existing dust fixing agent also has the problems of degradation, environmental protection and difficulty in simultaneously optimizing the dust fixing effect.
Disclosure of Invention
The invention provides a preparation method of a graphene-based degradable high-strength dust-fixing agent, aiming at the problems of degradation, environmental protection and difficulty in simultaneous optimization of dust-fixing effects of the existing dust-fixing agent.
The invention adopts the following technical scheme:
a preparation method of a graphene-based degradable high-strength dust-fixing agent comprises the following steps:
first step, preparation of oxidized flour cross-linking agent
Adding 1, 6-hexanediol glycidyl ether and triethylene tetramine serving as raw materials into a three-necked flask, continuously stirring, and then heating to 60 ℃ under the stirring condition and keeping for 30min to obtain an oxidized flour cross-linking agent;
second step, preparation of oxidized flour
Adding water and flour into a device provided with a mechanical stirrer, a thermometer and a condenser pipe, uniformly stirring to obtain flour water dispersion solution, and adding H2O2Heating the reaction temperature to 60 ℃, preserving heat and oxidizing for 0.3h, then continuously heating to 85 ℃, preserving heat and oxidizing for 1.0h, and cooling to room temperature after oxidation to obtain oxidized flour;
thirdly, preparing graphene-based degradable high-strength dust-fixing agent slurry
Adding water and PVA into a device provided with a mechanical stirrer, a thermometer and a condenser pipe, heating to 70 ℃, mechanically stirring and dissolving to obtain a PVA aqueous solution, adding oxidized flour, heating to 80 ℃, mechanically stirring for 0.5h, cooling to room temperature, sequentially adding an oxidized flour cross-linking agent, graphene and boric acid, and mechanically stirring for 0.5h to obtain graphene-based degradable high-strength dust-fixing agent slurry;
fourthly, preparing the graphene-based degradable high-strength dust fixing agent
Adding water into the graphene-based degradable high-strength dust-fixing agent slurry to adjust solid content to obtain a graphene-based degradable high-strength dust-fixing agent water dispersion solution, then adding alkaline rose essence, and mechanically stirring for 1h at room temperature to obtain the green graphene-based degradable high-strength dust-fixing agent.
In the first step, the mass ratio of the 1, 6-hexanediol glycidyl ether to the triethylene tetramine is 10: 0.5-2.
In the second step, the mass concentration of the flour water dispersion solution is 5-40%, and the mass ratio of the flour to the hydrogen peroxide is 100: 2-10.
In the third step, the mass concentration of the PVA aqueous solution is 5-15%, and the mass ratio of PVA to oxidized flour is 100: 20-50.
In the third step, the mass ratio of the oxidized flour to the oxidized flour cross-linking agent is 100: 2-5, and the mass ratio of PVA to boric acid is 100: 2-10, wherein the mass ratio of PVA to graphene is 100: 0.5 to 2.0.
In the fourth step, the solid content of the water dispersion solution is adjusted to be 0.1-5%, and the adding amount of the alkaline rose essence is 1-5% of the solid content of the water solution.
The invention has the following beneficial effects:
the invention discloses a novel graphene-based degradable high-strength dust-fixing agent, which is prepared by taking a low-cost, green and environment-friendly degradable material as a main component (such as flour and PVA), and simultaneously combining a cross-linking agent (such as boric acid and a multi-arm cross-linking agent) and a reinforcing agent (graphene) to improve the dust-fixing effect, and more importantly, the added low-content graphene and boric acid can effectively improve the soil fertilizer efficiency. Compared with the existing dust fixing agent, the newly designed dust fixing agent is green, environment-friendly, degradable, good in dust fixing effect, free of secondary pollution and beneficial to soil.
Detailed Description
A preparation method of a graphene-based degradable high-strength dust-fixing agent comprises the following steps:
first step, preparation of oxidized flour cross-linking agent
Adding 1, 6-hexanediol glycidyl ether and triethylene tetramine serving as raw materials into a three-necked flask, continuously stirring, and then heating to 60 ℃ under the stirring condition and keeping for 30min to obtain an oxidized flour cross-linking agent;
second step, preparation of oxidized flour
Adding water and flour into a device provided with a mechanical stirrer, a thermometer and a condenser pipe, uniformly stirring to obtain flour water dispersion solution, and adding H2O2Heating the reaction temperature to 60 ℃, preserving heat and oxidizing for 0.3h, then continuously heating to 85 ℃, preserving heat and oxidizing for 1.0h, and cooling to room temperature after oxidation to obtain oxidized flour;
thirdly, preparing graphene-based degradable high-strength dust-fixing agent slurry
Adding water and PVA into a device provided with a mechanical stirrer, a thermometer and a condenser pipe, heating to 70 ℃, mechanically stirring and dissolving to obtain a PVA aqueous solution, adding oxidized flour, heating to 80 ℃, mechanically stirring for 0.5h, cooling to room temperature, sequentially adding an oxidized flour cross-linking agent, graphene and boric acid, and mechanically stirring for 0.5h to obtain graphene-based degradable high-strength dust-fixing agent slurry;
fourthly, preparing the graphene-based degradable high-strength dust fixing agent
Adding water into the graphene-based degradable high-strength dust-fixing agent slurry to adjust solid content to obtain a graphene-based degradable high-strength dust-fixing agent water dispersion solution, then adding alkaline rose essence, and mechanically stirring for 1h at room temperature to obtain the green graphene-based degradable high-strength dust-fixing agent.
Example 1
20g of 1, 6-hexanediol glycidyl ether and 2.0g of triethylene tetramine were added to a three-necked flask and stirred continuously. The temperature is raised to 60 ℃, and the reaction is carried out for 30 minutes under the condition of stirring. Adding 200ml of water and 20g of flour into a device provided with a mechanical stirring device, a thermometer and a condenser pipe, uniformly stirring, and then adding 10.0g H2O2And raising the reaction temperature to 60 ℃, preserving heat and oxidizing for 0.3h, then continuously raising the temperature to 85 ℃, preserving heat and oxidizing for 1.0h, and cooling to room temperature after the oxidation is finished.
Adding 200ml of water and 15.0g of PVA into a device provided with a mechanical stirring device, a thermometer and a condenser, heating to 70 ℃, after the mixture is mechanically stirred and dissolved, adding 40ml of oxidized flour aqueous solution, heating to 80 ℃, after the mixture is mechanically stirred for 0.5h, cooling to room temperature, sequentially adding 0.2g of oxidized flour cross-linking agent, 0.3g of graphene and 1.0g of boric acid, after the mixture is mechanically stirred for 0.5h, adding 300ml of water, mechanically stirring for 0.5h, adding 6g of rose essence, and continuously mechanically stirring for 1.0h at room temperature to obtain a green graphene-based degradable high-strength dust-fixing agent sample 1.
Example 2
10g of 1, 6-hexanediol glycidyl ether and 2.0g of triethylene tetramine were added to a three-necked flask and stirred continuously. The temperature is raised to 60 ℃, and the reaction is carried out for 30 minutes under the condition of stirring. Adding 200ml of water and 20g of flour into a device provided with a mechanical stirring device, a thermometer and a condenser pipe, uniformly stirring, and then adding 10.0g H2O2On the contraryHeating to 60 deg.C, maintaining the temperature, oxidizing for 0.3h, then heating to 85 deg.C, maintaining the temperature, oxidizing for 1.0h, and cooling to room temperature.
Adding 200ml of water and 15.0g of PVA into a device provided with a mechanical stirring device, a thermometer and a condenser, heating to 70 ℃, mechanically stirring for dissolving, adding 40ml of oxidized flour aqueous solution, heating to 80 ℃, mechanically stirring for 0.5h, cooling to room temperature, sequentially adding 0.2g of oxidized flour cross-linking agent, 0.3g of graphene and 1.0g of boric acid, mechanically stirring for 0.5h, adding 300ml of water, mechanically stirring for 0.5h, adding 6g of rose essence, and continuously mechanically stirring for 1.0h at room temperature to obtain a green graphene-based degradable high-strength dust-fixing agent sample 2.
Example 3
20g of 1, 6-hexanediol glycidyl ether and 2.0g of triethylene tetramine were added to a three-necked flask and stirred continuously. The temperature is raised to 60 ℃, and the reaction is carried out for 30 minutes under the condition of stirring. Adding 200ml of water and 20g of flour into a device provided with a mechanical stirring device, a thermometer and a condenser pipe, uniformly stirring, and then adding 10.0g H2O2And raising the reaction temperature to 60 ℃, preserving heat and oxidizing for 0.3h, then continuously raising the temperature to 85 ℃, preserving heat and oxidizing for 1.0h, and cooling to room temperature after the oxidation is finished.
Adding 200ml of water and 10.0g of PVA into a device provided with a mechanical stirring device, a thermometer and a condenser, heating to 70 ℃, mechanically stirring for dissolving, adding 40ml of oxidized flour aqueous solution, heating to 80 ℃, mechanically stirring for 0.5h, cooling to room temperature, sequentially adding 0.2g of oxidized flour cross-linking agent, 0.3g of graphene and 1.0g of boric acid, mechanically stirring for 0.5h, adding 300ml of water, mechanically stirring for 0.5h, adding 6g of rose essence, and continuously mechanically stirring for 1.0h at room temperature to obtain a green graphene-based degradable high-strength dust-fixing agent sample 3.
Example 4
20g of 1, 6-hexanediol glycidyl ether and 2.0g of triethylene tetramine were added to a three-necked flask and stirred continuously. The temperature is raised to 60 ℃, and the reaction is carried out for 30 minutes under the condition of stirring. Adding 200ml of water and 20g of flour into a device provided with a mechanical stirring device, a thermometer and a condenser pipe, uniformly stirring, and then adding 10.0g H2O2The reaction temperature is raised to 60 ℃ and the temperature is keptAnd (4) oxidizing for 0.3h at a warm temperature, then continuously heating to 85 ℃, preserving heat and oxidizing for 1.0h, and cooling to room temperature after the oxidation is finished.
Adding 200ml of water and 15.0g of PVA into a device provided with a mechanical stirring device, a thermometer and a condenser, heating to 70 ℃, mechanically stirring for dissolving, adding 40ml of oxidized flour aqueous solution, heating to 80 ℃, mechanically stirring for 0.5h, cooling to room temperature, sequentially adding 0.2g of oxidized flour cross-linking agent, 0.5g of graphene and 2.0g of boric acid, mechanically stirring for 0.5h, adding 300ml of water, mechanically stirring for 0.5h, adding 6g of rose essence, and continuously mechanically stirring for 1.0h at room temperature to obtain a green graphene-based degradable high-strength dust-fixing agent sample 4.
Example 5
20g of 1, 6-hexanediol glycidyl ether and 2.0g of triethylene tetramine were added to a three-necked flask and stirred continuously. The temperature is raised to 60 ℃, and the reaction is carried out for 30 minutes under the condition of stirring. Adding 200ml of water and 20g of flour into a device provided with a mechanical stirring device, a thermometer and a condenser pipe, uniformly stirring, and then adding 10.0g H2O2And raising the reaction temperature to 60 ℃, preserving heat and oxidizing for 0.3h, then continuously raising the temperature to 85 ℃, preserving heat and oxidizing for 1.0h, and cooling to room temperature after the oxidation is finished.
Adding 200ml of water and 15.0g of PVA into a device provided with a mechanical stirring device, a thermometer and a condenser, heating to 70 ℃, after the mixture is mechanically stirred and dissolved, adding 40ml of oxidized flour aqueous solution, heating to 80 ℃, after the mixture is mechanically stirred for 0.5h, cooling to room temperature, sequentially adding 0.2g of oxidized flour cross-linking agent, 0.5g of graphene and 2.0g of boric acid, after the mixture is mechanically stirred for 0.5h, adding 300ml of water, mechanically stirring for 0.5h, adding 6g of rose essence, and continuously mechanically stirring for 1.0h at room temperature to obtain a green graphene-based degradable high-strength dust-fixing agent sample 5.
TABLE 1 dust-fixing agent Properties of different formulations