CN108262029B - Preparation method of organic-inorganic composite modified straw dephosphorization adsorbing material - Google Patents

Preparation method of organic-inorganic composite modified straw dephosphorization adsorbing material Download PDF

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CN108262029B
CN108262029B CN201810066936.2A CN201810066936A CN108262029B CN 108262029 B CN108262029 B CN 108262029B CN 201810066936 A CN201810066936 A CN 201810066936A CN 108262029 B CN108262029 B CN 108262029B
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钱程
刘兴勇
曹洪岩
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Sichuan University of Science and Engineering
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Abstract

The invention belongs to the technical field of environment adsorbing materials, and particularly relates to a preparation method of an organic-inorganic composite modified straw phosphorus removal adsorbing material. The method takes crop straws as raw materials, takes cheap and nontoxic organic acid and calcium salt as modifiers, prepares the organic-inorganic composite modified straw phosphorus removal adsorbing material through processes of stirring, refluxing, dipping and the like under certain conditions, and simultaneously realizes the reutilization of organic and non-modified reagents. The process is simple, green and environment-friendly, can effectively remove phosphorus in sewage, and improves the practical value of the invention.

Description

Preparation method of organic-inorganic composite modified straw dephosphorization adsorbing material
Technical Field
The invention belongs to the technical field of environment adsorbing materials, and particularly relates to a preparation method of an organic-inorganic composite modified straw phosphorus removal adsorbing material.
Background
With the economic development of China and the improvement of the urban living standard, the problem of water pollution is more serious, and eutrophication phenomena of different degrees appear in a plurality of rivers and lakes, and the over-standard phosphorus is a main factor for causing eutrophication of water bodies. Therefore, how to effectively remove the phosphorus in the sewage is one of the problems which need to be solved in the environmental protection and eutrophication water body treatment of China at present. At present, common methods for removing phosphorus mainly comprise a biological method, a chemical precipitation method, a membrane separation method, an adsorption method and the like, wherein the adsorption method is concerned about due to the advantages of simple equipment, convenient operation, higher treatment speed and the like. The key point of adopting the adsorption method to remove phosphorus is the selection of the adsorption material. As an efficient dephosphorization adsorption material, the material has the characteristics of environmental friendliness, good stability, easy regeneration and low price. Crop straws are widely concerned due to wide sources, special chemical structures and potential of waste reutilization.
As a big agricultural country, China produces a large amount of straws every year, and the treatment mode of the straws is mainly direct returning or burning at present. Although a large amount of straws can be consumed by straw incineration, a large amount of fly ash and inhalable particles can be generated, and a large amount of toxic and harmful gas is generated at the same time, so that environmental pollution is caused, therefore, a new application way of crop straws is developed, waste is changed into wealth, resource utilization is realized, the urgent need of sustainable development is met, and the straws are prepared into efficient adsorption materials and are applied to the field of water treatment, so that the economic and social values are high.
The straw is the residual part of crops such as rice, wheat, corn, cotton and the like after seeds are harvested, and is a type of agricultural waste which mainly comprises lignin, cellulose, hemicellulose and the like, and the straw has a structure which contains rich active groups such as hydroxyl and the like and has functionalization capability. However, at present, the adsorption material prepared by crop straws mostly focuses on removing heavy metal ions, and is less used for removing phosphorus. The method for preparing the phosphorus removal adsorption material by using the straws mainly comprises the following steps: (1) the method adopts an organic synthesis method to graft amino, and uses toxic substances such as epoxy chloropropane, and the process is not environment-friendly enough (Xing Xu, Baoyu Gao, WenyiWang, et al.Adsoration of phosphate from aqueous solutions on to modified leather, namely, Characteristics, kinetic and column students [ J ]. colloid and surface B: biointerface, 2009,70: 46-52); (2) the straw is converted into the biological activated carbon by adopting a high-temperature carbonization method, and the rare earth cerium is modified, so that the method has high early treatment energy consumption, expensive modification reagent and relatively poor economy (CN 103877937B); (3) lanthanum zirconium inorganic salt is used as a modifier, an inorganic modified rape straw (CN107126935) is prepared by a microwave activation-precipitation method, and a small amount of straw phosphorus removal adsorbent is prepared by an organic-inorganic composite modification method.
Disclosure of Invention
The invention aims to provide a preparation method of an organic-inorganic composite modified straw dephosphorization adsorbing material aiming at the technical problems. The method takes crop straws as raw materials to prepare the organic-inorganic composite modified straw phosphorus removal adsorption material, and the organic-inorganic composite modified straw phosphorus removal adsorption material is used for removing phosphate radicals in sewage, so that cyclic utilization of modified filtrate is realized, a method is provided for resource utilization of straws and development of novel phosphorus adsorption materials, and an effective way is provided for treatment of phosphorus-containing wastewater.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a preparation method of an organic-inorganic composite modified straw dephosphorization adsorption material comprises the following steps:
1) any one of wheat and rice straws is taken as a raw material, and after being crushed, 60-120 meshes of straw powder is collected, washed and dried for 12 hours at 80 ℃ for standby.
2) Taking any one of oxalic acid, malonic acid, succinic acid and citric acid as an organic modification reagent, taking water as a solvent, and preparing an aqueous solution with the concentration range of 0.2-2.0mol/L, which is marked as a solution A; and (3) preparing a calcium ion solution with the calcium ion concentration range of 0.1-1.0mol/L by taking any one of calcium chloride or calcium nitrate as an inorganic modification reagent, and marking as a solution B.
3) Weighing 5g of straws, carrying out constant-temperature stirring reflux reaction on the straws and 100ml of the solution A obtained in the step 2 at 135 ℃ for 3-12h, filtering under normal pressure, marking a liquid phase as modified filtrate I, and storing for later use after detecting the content of organic acid; solid phase and 50ml 0.1mol/LNa2CO3The solution was stirred at room temperature for 1 h. And (4) carrying out suction filtration on the obtained product, washing, drying at the constant temperature of 80 ℃ for 12 hours for later use, and marking as the organic modified straw.
4) Putting 100mL of the organic modified straw obtained in the step 3) into the solution B obtained in the step 2), stirring and reacting for 2-6h at room temperature, performing suction filtration, recording a filtrate as a modified filtrate II, and storing for later use after calcium ion concentration detection; and drying the solid phase at the constant temperature of 80 ℃ for 12 hours to obtain the organic-inorganic composite modified straw.
5) And (4) measuring the saturated adsorption amount of phosphorus. Weighing 0.1g of organic-inorganic composite modified straw and 25mL of NaH with certain concentration2PO4And (5) oscillating the solution in a conical flask for 12 hours at room temperature to adsorb, and measuring and calculating the saturated adsorption quantity of phosphorus.
The method can also comprise 6) respectively supplementing a certain amount of organic acid and a certain amount of calcium salt into the modified filtrate I obtained in the step 3) and the modified filtrate II obtained in the step 4) to prepare aqueous solutions, and repeating the operation according to the steps 2) to 5) to realize the recycling of the modified filtrate I and the modified filtrate II.
The positive effects of the invention are as follows:
the organic-inorganic composite modified straw phosphorus removal adsorbing material is prepared by taking crop straws as raw materials and cheap and nontoxic organic acid and calcium salt as modifiers through processes of refluxing, dipping and the like under certain conditions, and the organic and inorganic modified reagents are recycled.
And (II) the process is simple, green and environment-friendly, and can effectively remove phosphorus in the sewage, thereby improving the practical value of the invention.
Description of the figures and accompanying tables
FIG. 1 is a process flow diagram of a preparation method of an organic-inorganic composite modified straw phosphorus removal adsorption material
FIG. 2-1 is an electron microscope (SEM) picture of the organic-inorganic composite modified straw prepared in example 3
FIG. 2-2 is the spectrum (EDS) of the organic-inorganic composite modified straw prepared in example 3
FIGS. 2-3 are electron micrographs (SEM) of phosphorus-adsorbed straw
FIGS. 2-4 are the energy spectrum (EDS) of the phosphorus-adsorbed straw
FIGS. 2-5 are electron micrographs (SEM) of organic-inorganic composite modified straw phosphorus adsorbed straw prepared by recycling filtrate for the 3 rd time
FIG. 2-6 is the spectrum (EDS) of the organic-inorganic composite modified straw after phosphorus adsorption prepared by recycling the filtrate for the 3 rd time
Detailed Description
The present invention will be further illustrated below with reference to specific examples and comparative examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes and modifications of the present invention may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1:
a preparation method of an organic-inorganic composite modified straw dephosphorization adsorption material comprises the following steps:
1) wheat straw is used as a raw material, and after being crushed, 60-120 meshes of straw powder is washed and dried for 12 hours at 80 ℃ for later use.
2) Preparing oxalic acid aqueous solution with the concentration of 0.5mol/L by taking oxalic acid as a modifying reagent, and marking as solution A; calcium chloride is used as an inorganic modification reagent to prepare a calcium ion solution with the calcium ion concentration of 0.4mol/L, and the solution is marked as solution B.
3) Weighing 5g of straw, carrying out reflux reaction with 100ml of the solution A obtained in the step 2 at 105 ℃, stirring at constant temperature for 10 hours, filtering under normal pressure, and mixing the solid phase with 100ml of 0.1mol/L Na2CO3The solution was stirred at room temperature for 1 h. Carrying out suction filtration on the obtained product, washing, drying at the constant temperature of 80 ℃ for 12h for later use, and marking as organic modified straws;
4) putting 100mL of the solution B obtained in the step 2) into the organic modified straw obtained in the step 3), stirring and reacting for 2h at room temperature, performing suction filtration and washing, and drying the solid phase at the constant temperature of 80 ℃ for 12h to obtain the organic-inorganic composite modified straw.
5) Respectively supplementing a certain amount of organic acid and a certain amount of calcium salt into the modified filtrate I obtained in the step 3) and the modified filtrate II obtained in the step 4) to prepare aqueous solutions, and repeatedly operating according to the steps 2) -5) to realize the recycling of the modified filtrate I and the modified filtrate II.
0.1g of organic-inorganic composite modified straw is weighed and mixed with NaH2PO4Solution (NaH)2PO4The concentration of the solution is 10-150mg/L, the same applies below), and the solution is vibrated and adsorbed in a conical flask at room temperature for 12 hours, and the phosphorus saturation adsorption capacity of the adsorbing material is measured. Through detection, the saturated phosphorus adsorption capacity of the organic-inorganic composite modified straw is 23.8 mg/g. The saturated adsorption capacity of the modified straws prepared by the 3 rd circulation on the phosphorus is 22.6 mg/g.
Example 2:
a preparation method of an organic-inorganic composite modified straw dephosphorization adsorption material comprises the following steps:
1) taking rice straws as raw materials, crushing, washing 60-120 meshes of straw powder, and drying at 80 ℃ for 12 hours for later use.
2) Succinic acid is used as an organic modification reagent, and a succinic acid aqueous solution with the concentration of 0.8mol/L is prepared and marked as a solution A; calcium nitrate is used as an inorganic modification reagent to prepare a calcium ion solution with the calcium ion concentration of 0.2mol/L, and the solution is marked as solution B.
3) Weighing 5g of straw, carrying out reflux reaction with 100ml of the solution A obtained in the step 2 at 120 ℃, stirring at constant temperature for 6 hours, filtering under normal pressure, and mixing the solid phase with 100ml of 0.1mol/L Na2CO3The solution was stirred at room temperature for 1 h. Carrying out suction filtration on the obtained product, washing, drying at the constant temperature of 80 ℃ for 12h for later use, and marking as organic modified straws;
4) and (3) putting 100mL of the solution B obtained in the step 2 into the organic modified straw, stirring and reacting for 1-4h at room temperature, performing suction filtration and washing, and drying the solid phase at the constant temperature of 80 ℃ for 12h to obtain the organic-inorganic composite modified straw.
5) And (3) respectively supplementing a certain amount of organic acid and a certain amount of calcium salt into the modified filtrate I obtained in the step (3) and the modified filtrate II obtained in the step (4) to prepare aqueous solutions, and repeating the steps 2) -5) to realize the recycling of the modified filtrate I and the modified filtrate II. Through detection, the saturated phosphorus adsorption capacity of the organic-inorganic composite modified straw is 22.1 mg/g. The saturated adsorption capacity of the modified straws prepared by the 3 rd circulation on the phosphorus is 21.0 mg/g.
Example 3:
a preparation method of an organic-inorganic composite modified straw dephosphorization adsorption material comprises the following steps:
1) taking wheat straws as raw materials, crushing, washing 60-120 meshes of straw powder, and drying at 80 ℃ for 12 hours for later use.
2) Citric acid is taken as an organic modification reagent, and a citric acid aqueous solution with the concentration of 1.0mol/L is prepared and is marked as a solution A; calcium chloride is used as an inorganic modification reagent to prepare a calcium ion solution with the calcium ion concentration of 0.6mol/L, and the solution is marked as solution B.
3) Weighing 5g of straw and 100 g of strawml of the solution A obtained in the step 2 is stirred and refluxed at the temperature of 125 ℃ for 6 hours, and after filtration under normal pressure, the solid phase is mixed with 100ml of 0.1mol/L Na2CO3The solution was stirred at room temperature for 1 h. And (4) carrying out suction filtration on the obtained product, washing, drying at the constant temperature of 80 ℃ for 12 hours for later use, and marking as the organic modified straw.
4) And (3) putting 100mL of the solution B obtained in the step 2 into the organic modified straw, stirring and reacting for 5h at room temperature, performing suction filtration and washing, and drying the solid phase at the constant temperature of 80 ℃ for 12h to obtain the organic-inorganic composite modified straw.
5) And (3) respectively supplementing a certain amount of organic acid and a certain amount of calcium salt into the modified filtrate I obtained in the step (3) and the modified filtrate II obtained in the step (4) to prepare aqueous solutions, and repeating the steps 2) -5) to realize the recycling of the modified filtrate I and the modified filtrate II. Through detection, the saturated phosphorus adsorption capacity of the organic-inorganic composite modified straw is 28.6 mg/g. The saturated adsorption capacity of the modified straws prepared by the 3 rd circulation on the phosphorus is 27.2 mg/g.
Example 4:
a preparation method of an organic-inorganic composite modified straw dephosphorization adsorption material comprises the following steps:
1) taking rice straws as raw materials, crushing, washing 60-120 meshes of straw powder, and drying at 80 ℃ for 12 hours for later use.
2) Preparing a malonic acid aqueous solution with the concentration of 1.0mol/L by taking malonic acid as a modifying reagent and water as a solvent, and marking as a solution A; calcium nitrate is used as an inorganic modification reagent to prepare a calcium ion solution with the calcium ion concentration of 0.3mol/L, and the solution is marked as solution B.
3) Weighing 5g of straws, carrying out reflux reaction on the straws and 100ml of the solution A obtained in the step 2) at 135 ℃ under constant temperature stirring for 3 hours, and filtering the mixture under normal pressure to obtain a solid phase and 100ml of 0.1mol/L Na2CO3The solution was stirred at room temperature for 1 h. Carrying out suction filtration on the obtained product, washing, drying at the constant temperature of 80 ℃ for 12h for later use, and marking as organic modified straws;
4) and (3) putting 100mL of the solution B obtained in the step 2 into the organic modified straw, stirring and reacting for 6h at room temperature, performing suction filtration and washing, and drying the solid phase at the constant temperature of 80 ℃ for 12h to obtain the organic-inorganic composite modified straw.
5) Respectively supplementing a certain amount of organic acid and a certain amount of calcium salt into the modified filtrate I obtained in the step 3) and the modified filtrate II obtained in the step 4 to prepare aqueous solutions, and repeatedly operating according to the steps 2) -5) to realize the recycling of the modified filtrate I and the modified filtrate II. Through detection, the saturated phosphorus adsorption capacity of the organic-inorganic composite modified straw is 23.6 mg/g. The saturated adsorption capacity of the modified straws prepared by the 3 rd circulation on the phosphorus is 23.3 mg/g.
Comparative example 1:
taking the example 3 as reference, preparing single organic modified straws by the following specific steps:
1) taking wheat straws as raw materials, crushing, washing 60-120 meshes of straw powder, and drying at 80 ℃ for 12 hours for later use.
2) Citric acid is used as an organic modification reagent, and a citric acid aqueous solution with the concentration of 1.0mol/L is prepared and is marked as a solution A.
3) Weighing 5g of straw, carrying out reflux reaction with 100ml of the solution A obtained in the step 2 at 125 ℃, stirring at constant temperature for 6 hours, filtering under normal pressure, and mixing the solid phase with 100ml of 0.1mol/L Na2CO3The solution was stirred at room temperature for 1 h. And (4) carrying out suction filtration on the obtained product, washing, drying at the constant temperature of 80 ℃ for 12 hours for later use, and marking as the organic modified straw.
Through detection, the saturated phosphorus adsorption amount of the organic modified straws is equal to 0.8 mg/g.
Comparative example 2:
taking example 3 as a reference, preparing single inorganic modified wheat straw, wherein the specific conditions are as follows:
a preparation method of an organic-inorganic composite modified straw dephosphorization adsorption material comprises the following steps:
1) taking wheat straws as raw materials, crushing, washing 60-120 meshes of straw powder, and drying at 80 ℃ for 12 hours for later use.
2) Calcium chloride is used as an inorganic modification reagent to prepare a calcium ion solution with the calcium ion concentration of 0.6mol/L, and the solution is marked as solution B.
3) And (3) putting the straw into 100mL of the solution B obtained in the step (2), stirring and reacting for 5h at room temperature, performing suction filtration and washing, and drying the solid phase at the constant temperature of 80 ℃ for 12h to obtain the inorganic modified straw.
The detection shows that the saturated adsorption capacity of the inorganic modified straws to phosphorus is 1.1 mg/g.
Comparative example 3
Taking example 3 as a reference, preparing organic-inorganic composite modified wheat straw, wherein the specific conditions are as follows:
1) taking wheat straws as raw materials, crushing, washing 60-120 meshes of straw powder, and drying at 80 ℃ for 12 hours for later use.
2) Citric acid is taken as an organic modification reagent, and a citric acid aqueous solution with the concentration of 0.01mol/L is prepared and is marked as a solution A; calcium chloride is used as an inorganic modification reagent to prepare a calcium ion solution with the calcium ion concentration of 0.6mol/L, and the solution is marked as solution B.
3) Weighing 5g of straw, carrying out reflux reaction with 100ml of the solution A obtained in the step 2 at 125 ℃, stirring at constant temperature for 6 hours, filtering under normal pressure, and mixing the solid phase with 100ml of 0.1mol/L Na2CO3The solution was stirred at room temperature for 1 h. And (4) carrying out suction filtration on the obtained product, washing, drying at the constant temperature of 80 ℃ for 12 hours for later use, and marking as the organic modified straw.
4) And (3) putting 100mL of the solution B obtained in the step 2 into the organic modified straw, stirring and reacting for 5h at room temperature, carrying out suction filtration and washing, and drying the solid phase at the constant temperature of 80 ℃ for 12h to obtain the organic-inorganic composite modified straw.
5) And (4) respectively supplementing a certain amount of organic acid and a certain amount of calcium salt into the modified filtrate I obtained in the step (3) and the modified filtrate II obtained in the step (4) to prepare aqueous solutions, and repeating the operation according to the steps 2-5 to realize the recycling of the modified filtrate I and the modified filtrate II. Through detection, the saturated phosphorus adsorption capacity of the organic-inorganic composite modified straw is 3.8 mg/g.
Comparative example 4
Taking example 3 as a reference, preparing organic-inorganic composite modified wheat straw, wherein the specific conditions are as follows:
1) taking wheat straws as raw materials, crushing, washing 60-120 meshes of straw powder, and drying at 80 ℃ for 12 hours for later use.
2) Citric acid is taken as an organic modification reagent, and a citric acid aqueous solution with the concentration of 1.0mol/L is prepared and is marked as a solution A; calcium chloride is used as an inorganic modification reagent to prepare a calcium ion solution with the calcium ion concentration of 0.01mol/L, and the solution is marked as solution B.
3) Weighing 5g of straw, carrying out reflux reaction with 100ml of the solution A obtained in the step 2 at 125 ℃, stirring at constant temperature for 6 hours, filtering under normal pressure, and mixing the solid phase with 100ml of 0.1mol/L Na2CO3The solution was stirred at room temperature for 1 h. And (4) carrying out suction filtration on the obtained product, washing, drying at the constant temperature of 80 ℃ for 12 hours for later use, and marking as the organic modified straw.
4) And (3) putting 100mL of the solution B obtained in the step 2 into the organic modified straw, stirring and reacting for 5h at room temperature, performing suction filtration and washing, and drying the solid phase at the constant temperature of 80 ℃ for 12h to obtain the organic-inorganic composite modified straw.
5) And (4) respectively supplementing a certain amount of organic acid and a certain amount of calcium salt into the modified filtrate I obtained in the step (3) and the modified filtrate II obtained in the step (4) to prepare aqueous solutions, and repeating the operation according to the steps 2-5 to realize the recycling of the modified filtrate I and the modified filtrate II. Through detection, the saturated phosphorus adsorption capacity of the organic-inorganic composite modified straw is 4.5 mg/g.
The saturated adsorption amounts of the straws to phosphorus in examples 1 to 4 and comparative documents 1 to 4 are summarized as follows, and are shown in Table 1:
TABLE 1 saturated phosphorus adsorption by straw in examples and comparative examples
Figure BDA0001556938850000101
The above examples are only preferred embodiments of the patent, but the scope of protection of the patent is not limited thereto. It should be noted that, for those skilled in the art, without departing from the principle of this patent, several improvements and modifications can be made according to the patent solution and its patent idea, and these improvements and modifications should also be regarded as the protection scope of this patent.

Claims (3)

1. A preparation method of an organic-inorganic composite modified straw dephosphorization adsorption material is characterized by comprising the following steps:
1) any one of wheat and rice straws is taken as a raw material, and after being crushed, 60-120 meshes of straw powder is collected, washed and dried for standby;
2) taking any one of oxalic acid, malonic acid, succinic acid and citric acid as an organic modification reagent, taking water as a solvent, and preparing an aqueous solution with the concentration range of 0.5-2.0 mol/L, which is marked as a solution A; preparing a calcium ion solution with the calcium ion concentration range of 0.1-1.0mol/L by taking any one of calcium chloride or calcium nitrate as an inorganic modification reagent, and marking as a solution B;
3) weighing 5g of straws, carrying out constant-temperature stirring reflux reaction with 100mL of solution A at the temperature of 105-135 ℃, reacting for 3-12h, filtering under normal pressure, marking a liquid phase as modified filtrate I, and storing for later use after detecting the content of organic acid; solid phase and 50mL of 0.2mol/L Na2CO3Stirring the solution at room temperature for 1h, carrying out suction filtration on the obtained product, washing, drying at the constant temperature of 80 ℃ for 12h for later use, and marking as organic modified straws;
4) putting 100mL of the organic modified straw obtained in the step 3) into the solution B obtained in the step 2), stirring and reacting for 2-6h at room temperature, performing suction filtration, recording a filtrate as a modified filtrate II, and storing for later use after calcium ion concentration detection; and drying the solid phase at the constant temperature of 80 ℃ for 12 hours to obtain the organic-inorganic composite modified straw.
2. The preparation method of the organic-inorganic composite modified straw phosphorus removal adsorption material of claim 1, characterized in that the method further comprises: respectively supplementing a certain amount of organic acid and a certain amount of calcium salt into the modified filtrate I obtained in the step 3) and the modified filtrate II obtained in the step 4) to prepare aqueous solutions, and repeatedly operating according to the steps 2) to 5) to realize the recycling of the modified filtrate I and the modified filtrate II.
3. The method for removing phosphorus from the organic-inorganic composite modified straw phosphorus removal adsorption material prepared by the method according to claim 1 is characterized by comprising the following steps of:
0.1g of organic-inorganic composite modified straw is weighed and mixed with NaH2PO4Oscillating and adsorbing the solution in a conical flask for 12 hours at room temperature, and measuring the phosphorus saturation adsorption quantity of the adsorbing material; NaH2PO4The concentration of the solution is 10-150 mg/L.
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