CN110743513A - Preparation method of cellulose sponge for copper ion adsorption - Google Patents
Preparation method of cellulose sponge for copper ion adsorption Download PDFInfo
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Abstract
The invention discloses a preparation method of cellulose sponge for copper ion adsorption, which comprises the steps of putting 0.1-1 part of cellulose sponge into 8-12 parts of quinizarine acetone solution with the concentration of 200-1000ppm, mixing and stirring for 30-60min, then drying for 30-60min at 50-60 ℃, then putting into deionized water after drying, stirring for 10-20min, and finally air-drying to obtain quinizarine modified cellulose sponge. The invention has excellent copper ion adsorption capacity, can be recycled or naturally degraded, and does not cause pollution to the environment; in addition, the invention has simple and convenient processing and low cost.
Description
Technical Field
The invention relates to the field of sponge preparation, in particular to a preparation method of cellulose sponge for copper ion adsorption.
Background
The sponge is a general term for the foam, and various sponge products with different properties can be produced according to different materials. The traditional sponge product is mainly a synthetic resin sponge which is made of polyurethane foam and similar materials through foaming, the chemical name of the sponge is polyurethane foam, and the sponge is divided into soft foam for furniture and hard foam for heat preservation. Also has sponge materials with special purposes, such as hemostatic sponge, sewage treatment sponge, etc. Metal contamination is a main form of water contamination, and for metal-contaminated sewage, how to remove metal ions in the sewage is a key problem. The sewage treatment sponge is an excellent sewage treatment material due to the strong adsorbability. The existing sewage treatment sponge has weak adsorption performance on metal ions in sewage, and most of the sewage treatment sponge is made of polymer chemical materials, so that the sponge has certain environmental pollution on the product itself, cannot be regenerated, is difficult to treat after sewage is adsorbed and used, is easy to cause secondary pollution, and has a slightly complex preparation method and higher cost.
Disclosure of Invention
The invention aims to provide a preparation method of cellulose sponge for copper ion adsorption. The invention has excellent copper ion adsorption capacity, can be recycled or naturally degraded, and does not cause pollution to the environment; in addition, the invention has convenient processing and production and low cost.
In order to solve the technical problems, the technical scheme provided by the invention is as follows: a preparation method of cellulose sponge for copper ion adsorption comprises the steps of putting 0.1-1 part of cellulose sponge into 8-12 parts of quinizarine acetone solution with the concentration of 200-1000ppm, mixing and stirring for 30-60min, drying at 50-60 ℃ for 30-60min, then putting into deionized water after drying, stirring for 10-20min, and finally drying in the air to obtain quinizarine modified cellulose sponge.
The preparation method of the cellulose sponge for copper ion adsorption comprises the steps of putting 0.5 part of cellulose sponge into 10 parts of quinizarine acetone solution with the concentration of 500ppm, mixing and stirring for 45min, then drying for 45min at 55 ℃, then putting into deionized water for stirring for 15min after drying, and finally air-drying to obtain quinizarine-modified cellulose sponge.
The preparation method of the cellulose sponge for copper ion adsorption comprises the following steps:
a. alkalization: mixing 0.5-2 parts of oven-dried cotton linters and 3-8 parts of NaOH solution with the concentration of 17.5-25% by mass, and reacting at room temperature for 3-6h to obtain sodium cellulose;
b. yellowing: 0.8-1.5 parts of CS2Reacting with sodium cellulose at room temperature for 1.5-4h to obtain cellulose sulfonate;
c. dissolving and aging: adding 4-6 parts of water into cellulose sulfonate, and mixing for 48-72 hours to obtain a sodium cellulose sulfonate solution;
d. mixing the nano-cellulose with a sodium cellulose sulfonate solution: taking 1-5 parts of 0.2-1% nano cellulose solution and sodium cellulose sulfonate solution, and mixing for 0.5-2h in a rotating manner;
e. sponge forming: uniformly mixing the mixed solution obtained in the step d with sodium phosphate according to the mass ratio of 1:1-2, pouring the mixture into a mold, putting the mold into an oven, reacting for 6-24 hours at the temperature of 65-90 ℃, and fully rinsing to obtain cellulose sponge;
the preparation method of the cellulose sponge for copper ion adsorption comprises the following steps:
a. alkalization: mixing 1 part of oven-dried cotton linter and 5 parts of NaOH solution with the concentration of 20% in parts by mass, and reacting at room temperature for 4 hours to obtain sodium cellulose;
b. yellowing: taking 1 part of CS2Reacting with sodium cellulose at room temperature for 2h to obtain cellulose sulfonate;
c. dissolving and aging: adding 4 parts of water into cellulose sulfonate, and mixing for 60 hours to obtain a sodium cellulose sulfonate solution;
d. mixing the nano-cellulose with a sodium cellulose sulfonate solution: taking 2 parts of nano cellulose solution with the concentration of 0.5 percent and sodium cellulose sulfonate solution, and rotationally mixing for 1 hour;
e. sponge forming: and d, uniformly mixing the mixed solution obtained in the step d and sodium phosphate according to the mass ratio of 1:1.5, pouring the mixture into a mold, putting the mold into an oven, reacting for 12 hours at the temperature of 80 ℃, and fully rinsing to obtain the cellulose sponge.
In the preparation method of the cellulose sponge for copper ion adsorption, the oven-dried cotton linters are crushed into the particle size of 40-300 meshes.
According to the preparation method of the cellulose sponge for copper ion adsorption, the nano-cellulose solution is prepared by taking bleached bamboo pulp with the concentration of 10% as a raw material, grinding the bleached bamboo pulp by using a PFI mill to obtain pulp, diluting the pulp to 0.5-1%, and then circularly homogenizing the pulp for 30-60 times by using a high-pressure homogenizer with the homogenizing pressure of 80-120MPa, thus obtaining the nano-cellulose solution.
The preparation method of the cellulose sponge for copper ion adsorption comprises the steps of air-drying slurry obtained when the beating degree reaches 85-95 DEG SR, mixing and defibering NaOH solution with the mass ratio of 1:4-6 and the concentration of 2-10%, soaking at normal temperature for 4-24h, sending into a reaction kettle, heating to 110-130 ℃ with saturated steam, controlling the pressure to be 1-4MPa, keeping the temperature for 30-120min, then instantly discharging pressure to explode the slurry in the reaction kettle, fully washing and air-drying the slurry, and fully washing and air-drying the slurry with HNO with the mass ratio of 1:4-6 and the concentration of 5-10%3Mixing and defibering the solution, soaking for 4-24h at normal temperature, then sending into the reaction kettle again, heating to 110-130 ℃ with saturated steam, controlling the pressure to be 1-4MPa, keeping the temperature for 30-120min, then instantly discharging the pressure again to explode the slurry in the reaction kettle again, finally diluting the slurry to 0.5-1%, then circularly homogenizing for 30-60 times with a high-pressure homogenizer at 80-120MPa, and finally obtaining the nano-cellulose solution.
In the preparation method of the cellulose sponge for copper ion adsorption, in the step e, the cellulose sponge is fully rinsed by hot water at 40-60 ℃.
Compared with the prior art, the cellulose sponge is modified by quinizarine acetone solution, the modified cellulose sponge has extremely strong copper ion adsorption performance, the copper ion adsorption capacity of the modified cellulose sponge reaches 120-160mg/g, and the adsorption capacity of the modified cellulose sponge is enhanced by 3-4 times compared with that of the existing sewage treatment sponge. The invention can remove the adsorption of copper ions by soaking in nitric acid solution for several minutes after adsorbing the copper ions, and can be reused, thereby having good recycling property. In addition, the invention optimizes the preparation process of the cellulose sponge, sodium cellulose is prepared by NaOH solution and cotton wool, sodium cellulose sulfonate solution is prepared by taking the sodium cellulose as the raw material, the sodium cellulose sulfonate solution and the nano-cellulose are mixed and then react with sodium phosphate to prepare the cellulose sponge, the preparation process of the cellulose sponge is simple, the temperature requirement is low, the preparation process can be carried out in a closed environment, the control of the reaction and the recycling of the raw material are facilitated, the preparation process and the flow of the cellulose sponge are greatly simplified, the production cost is reduced, the nano-cellulose and the sodium cellulose sulfonate solution are creatively combined for preparing the cellulose sponge, the strength performance of the cellulose sponge is greatly improved, the strength performance of the cellulose sponge is improved by 5-7 times compared with the common cellulose sponge, and the cellulose sponge has very superior strength effect, and the cellulose sponge can be degraded, and has the function of environmental protection. The invention adopts the method of firstly crushing (namely, adopting the cotton velvet) and then reacting, thereby facilitating the reaction rate between the NaOH solution and the cotton velvet and improving the production speed; the invention also optimizes the preparation process of the nano-cellulose, and after the nano-cellulose is prepared by taking the bamboo pulp as the raw material through a physical method, the cellulose sponge can form small holes on the basis of conventional large holes, thereby being beneficial to improving the specific surface area, greatly improving the adsorption capacity of the cellulose sponge and having better advantages and development and application potentials. Furthermore, the invention carries out steam explosion treatment on the pulp prepared from the bamboo pulp, so that the plant fiber raw material with a cell structure is steamed in a vapor phase under a high-temperature and high-pressure medium, high-pressure steam permeates into gaps in the material, and hemicellulose and lignin generate a plurality of acidic substances to degrade the hemicellulose into soluble sugar; meanwhile, lignin in the composite intercellular layer is softened and partially degraded, so that the bonding strength of the fiber is reduced, and the generated cellulose chain is subjected to acid-like degradation, thermal degradation and physical exercise. In the blasting stage, under the combined action of 2 media of vapor phase saturated steam and high-temperature liquid water, the media and the materials complete physical energy release together by suddenly releasing pressure, and the process is an instant adiabatic process and does work outwards; the softened material generates water shearing force deformation movement under the impact of expansion gas and is separated, in the process, steam water spoons which have penetrated into microfibril crystal bundles in the cellulose and air flow are released instantly at high speed, so that friction and collision are generated between microfibrils and unit cells of the cellulose, a crystal area is reduced, the surface of an accessible crystal area is increased, and hydrogen bonds in an amorphous area are broken and rearranged, thereby further greatly increasing the number of small holes and finally further improving the performance of the nano-cellulose sponge.
Drawings
FIG. 1 is a graph of a test of the strength properties of a cellulose sponge;
FIG. 2 is a microscopic image of a scanning electron microscope of the cellulose sponge of example 5;
FIG. 3 is a microscopic image of the scanning electron microscope of the cellulose sponge of example 4.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
Example 1: a preparation method of cellulose sponge for copper ion adsorption comprises the steps of putting 0.3g of cellulose sponge into 11ml of 600ppm quinizarine acetone solution, mixing and stirring for 55min, then drying at 58 ℃ for 35min, then putting into deionized water after drying, stirring for 20min, and finally air-drying to obtain quinizarine modified cellulose sponge.
Example 2: a preparation method of cellulose sponge for copper ion adsorption comprises the steps of putting 0.5g of cellulose sponge into 10ml of 500ppm quinizarine acetone solution, mixing and stirring for 45min, drying at 55 ℃ for 45min, putting into deionized water after drying, stirring for 15min, and finally air-drying to obtain quinizarine modified cellulose sponge.
Example 3: a preparation method of cellulose sponge for copper ion adsorption comprises the steps of putting 0.8 part of cellulose sponge into 8ml of quinizarine acetone solution with the concentration of 8ppm, mixing and stirring for 35min, then drying at 55 ℃ for 55min, then putting into deionized water after drying, stirring for 13min, and finally air-drying to obtain quinizarine-modified cellulose sponge.
Example 4: a preparation method of a nano-cellulose reinforced cellulose sponge comprises the following steps:
a. alkalization: selecting cotton linters within the range of 40-100 meshes as a cellulose raw material, mixing 1.2g of oven-dried cotton linters and 4g of NaOH solution with the concentration of 18.5% according to parts by mass, and reacting at room temperature (25 ℃) for 3.5 hours to obtain sodium cellulose;
b. yellowing: take 1.2gCS2Reacting with sodium cellulose at room temperature for 3h to obtain cellulose sulfonate;
c. dissolving and aging: adding 4g of water into cellulose sulfonate, and mixing for 52 hours to obtain a sodium cellulose sulfonate solution;
d. mixing the nano-cellulose with a sodium cellulose sulfonate solution: taking 3g of 0.7% nano cellulose solution and sodium cellulose sulfonate solution, and mixing for 1.5h in a rotating manner;
e. sponge forming: uniformly mixing the mixed solution obtained in the step d with sodium phosphate according to the mass ratio of 1:1, pouring the mixture into a mold, putting the mold into an oven, reacting for 12 hours at 85 ℃, and then fully rinsing with hot water at 40-60 ℃ to obtain cellulose sponge;
f. sponge modification: and (3) putting 0.5g of cellulose sponge into 10ml of acetone solution of quinizarine with the concentration of 500ppm, mixing and stirring for 45min, then drying for 45min at 55 ℃, putting into deionized water after drying, stirring for 15min, and finally air-drying to obtain the quinizarine modified cellulose sponge.
Example 5: a preparation method of a nano-cellulose reinforced cellulose sponge comprises the following steps:
a. alkalization: selecting cotton linters within the range of 40-100 meshes as a cellulose raw material, mixing 1g of oven-dried cotton linters with 5g of NaOH solution with the concentration of 20% in parts by mass, and reacting at room temperature for 4 hours to obtain sodium cellulose;
b. yellowing: fetch 1gCS2Reacting with sodium cellulose at room temperature for 2h to obtain cellulose sulfonate;
c. dissolving and aging: adding 4g of water into cellulose sulfonate, and mixing for 60 hours to obtain a sodium cellulose sulfonate solution;
d. mixing the nano-cellulose with a sodium cellulose sulfonate solution: taking 2g of nano cellulose solution with the concentration of 0.5 percent and sodium cellulose sulfonate solution to be mixed for 1 hour in a rotating way; the preparation method of the nano-cellulose solution comprises the steps of taking bleached bamboo pulp with the concentration of 10% as a raw material, grinding the bleached bamboo pulp by using a PFI mill to enable the beating degree to reach 85-95 DEG SR, diluting the pulp to 0.5-1%, circularly homogenizing the pulp for 30-60 times by using a high-pressure homogenizer with the homogenizing pressure of 80-120MPa, and obtaining the nano-cellulose solution after the completion.
e. Sponge forming: and d, uniformly mixing the mixed solution obtained in the step d and sodium phosphate according to the mass ratio of 1:1.5, pouring the mixture into a mold, putting the mold into an oven, reacting for 12 hours at the temperature of 80 ℃, and fully rinsing the mixture by using hot water at the temperature of 40-60 ℃ to obtain the cellulose sponge.
f. Sponge modification: 0.5g of cellulose sponge is put into 10ml of quinizarine acetone solution with the concentration of 500ppm to be mixed and stirred for 45min, then the mixture is dried for 45min at the temperature of 58 ℃, and then the mixture is put into deionized water to be stirred for 15min after being dried, and finally the quinizarine modified cellulose sponge is obtained after air drying.
Example 6: a preparation method of a nano-cellulose reinforced cellulose sponge comprises the following steps:
a. alkalization: selecting cotton linters within the range of 40-100 meshes as a cellulose raw material, mixing 1g of oven-dried cotton linters with 5g of NaOH solution with the concentration of 20% in parts by mass, and reacting at room temperature for 4 hours to obtain sodium cellulose;
b. yellowing: fetch 1gCS2Reacting with sodium cellulose at room temperature for 2h to obtain cellulose sulfonate;
c. dissolving and aging: adding 4g of water into cellulose sulfonate, and mixing for 60 hours to obtain a sodium cellulose sulfonate solution;
d. mixing the nano-cellulose with a sodium cellulose sulfonate solution: taking 2g of nano cellulose solution with the concentration of 0.5 percent and sodium cellulose sulfonate solution to be mixed for 1 hour in a rotating way; the nano cellulose solution is prepared by taking bleached bamboo pulp with the concentration of 10 percent as a raw material, grinding the bleached bamboo pulp by a PFI mill to make the beating degree reach 85-95 DEG SR, air-drying the pulp, mixing and defibering with NaOH solution with the mass ratio of 1:5 and the concentration of 5 percent, soaking at normal temperature for 12h, sending into an explosion device, heating to 120 ℃ by saturated steam, controlling the pressure to be 3MPa, preserving the heat for 70min, then carrying out explosion treatment, fully washing and air drying the slurry after the explosion treatment, mixing and defibering with HNO3 solution with the mass ratio of 1:5 and the concentration of 8 percent, soaking at normal temperature for 12 hr, feeding into blasting unit, heating to 120 deg.C with saturated steam, controlling pressure at 3MPa, maintaining for 60min, blasting again, diluting the slurry to 0.8%, and then circularly homogenizing for 45 times by using a high-pressure homogenizer at the homogenizing pressure of 100MPa to obtain the nano-cellulose solution.
e. Sponge forming: and d, uniformly mixing the mixed solution obtained in the step d and sodium phosphate according to the mass ratio of 1:1.5, pouring the mixture into a mold, putting the mold into an oven, reacting for 12 hours at the temperature of 80 ℃, and fully rinsing the mixture by using hot water at the temperature of 40-60 ℃ to obtain the cellulose sponge.
f. Sponge modification: 0.5g of cellulose sponge is put into 10ml of quinizarine acetone solution with the concentration of 500ppm to be mixed and stirred for 45min, then the mixture is dried for 45min at the temperature of 58 ℃, and then the mixture is put into deionized water to be stirred for 15min after being dried, and finally the quinizarine modified cellulose sponge is obtained after air drying.
Comparative example 1: the sewage treatment sponge is sold on the market conventionally.
Comparative example 2: cellulose sponge sold on the market
The applicant carried out the copper ion adsorption performance tests on the modified cellulose sponges prepared in example 1, example 2 and example 3 and the sewage treatment sponge sold on the market in the control example 2. Respectively taking 1L of water containing the same copper ion concentration, respectively putting the modified cellulose sponge with the length, width and height of 5cm multiplied by 5cm and the sewage treatment sponge into the soaking device, respectively taking out the cellulose sponge and the sewage treatment sponge after 30min, detecting the copper ion adsorption quantity, measuring the concentration by using an inductively coupled plasma emission spectrometer, comparing with the original concentration, calculating the reduction quantity, namely the adsorbed copper ion quantity, and detecting results are shown in the following table.
As can be seen from the table, the adsorption capacity of the modified cellulose sponge prepared by the invention on copper ions can reach more than 64.8mg/g, and in example 2, the adsorption capacity reaches more than 79.1mg/g, and is about 5-6 times of that of the existing sewage treatment sponge, so that the modified cellulose sponge has excellent copper ion adsorption capacity. Example 4 adopts the preparation process and flow of the preferred cellulose sponge, the adsorption of copper ions can be further improved, because the invention creatively combines the nano-cellulose and the sodium cellulose sulfonate solution for preparing the cellulose sponge, the strength performance of the cellulose sponge is greatly improved, and better adsorption effect can be obtained. In the embodiment 5, a preparation process of nano-cellulose is also optimized, after the nano-cellulose is prepared by taking bamboo pulp as a raw material physical method, the cellulose sponge can form small holes on the basis of conventional large holes, the improvement of the specific surface area is facilitated, the adsorption capacity of the cellulose sponge is greatly improved, and further the modified cellulose sponge prepared by the cellulose sponge has better copper ion adsorption capacity, compared with the embodiment 5, the embodiment 6 adopts the blasting treatment of the bamboo pulp, and is beneficial to the softening of the cellulose under the combined action of 2 mediums of vapor phase saturated steam and high temperature liquid water; then through the sudden pressure release, the softened cellulose generates water shearing force deformation movement under the impact of the expansion gas and is separated, in the process, steam water spoons which have penetrated into the inside of the cellulose among the microfibril crystal bundles and the air flow are released instantly at high speed, so that friction and collision are generated among microfibrils and unit cells of the cellulose, the crystal area is reduced, the surface of the accessible crystal area is increased, and hydrogen bonds in the amorphous area are broken and rearranged, thereby further greatly increasing the number of small holes, further forming more small holes on the basis of the large holes, and further having more excellent adsorption capacity. After the adsorption test, the modified cellulose sponge adsorbing copper ions is put into nitric acid solution with the pH value of 1-3 for 5-10min, so that the adsorption can be released, and then the modified cellulose sponge is used for adsorbing the copper ions again, and the secondary adsorption effect is the same as the primary adsorption effect, so that the invention has good recycling property.
Further, the applicant conducted strength property tests on the cellulose sponges obtained after step e in examples 5 and 6 and on the conventional commercially available cellulose sponge in comparative example 2, and the test results are shown in fig. 1 by measuring the pressure applied to the sample when the sample is compressed to the remaining thirty percent and the magnitude of the resilience after compression. Each detection sample in fig. 1 has two connected curves, the upper one is a compression curve, the lower one is a rebound curve, and it can be seen from fig. 1 that when the volume of the cellulose sponge is compressed to the remaining thirty percent, the pressure borne by the cellulose sponge in example 6 is close to 180KPa, the pressure borne by the cellulose sponge in example 5 is close to 140KPa, the pressure borne by the cellulose sponge in example 4 is close to 100140KPa, and the pressure borne by the comparative example 2 is only 40KPa, so that it can be seen that the strength of the cellulose sponge prepared by the present invention is far greater than that of the cellulose sponge sold in the comparative example, and the overall ratio is improved by about 5-8 times, thereby greatly enhancing the strength performance of the cellulose sponge; further, when the test sample is compressed to the remaining thirty percent, the recovery degree of the sample is detected again, and as can be seen from fig. 1, the cellulose sponges in examples 5 and 6 can be recovered to nearly 95% as a whole, and in example 4 to nearly 85% -90% as a whole, but the conventional cellulose sponge can be recovered to only about 60%, so that the strength and recovery performance of the cellulose sponge can be greatly enhanced, and the prepared cellulose sponge has better copper ion adsorption capacity after being used for modification. Comparing example 4, example 5 and example 6, it can be seen that example 5 employs a preferred preparation process to prepare nanocellulose, and the strength performance of the cellulose sponge can be improved by preparing the cellulose sponge with the nanocellulose. And in the embodiment 6, the bamboo pulp is further subjected to blasting treatment, so that the strength performance of the cellulose sponge achieves a better effect. The applicant makes microscopic observation on the cellulose sponges of examples 5 and 6 by using an electron scanning microscope, and the results are shown in fig. 2-3, fig. 2 is a microscopic image of the cellulose sponge electron scanning microscope of example 6, fig. 3 is a microscopic image of the cellulose sponge electron scanning microscope of example 5, and it can be seen from fig. 2 and 3 that the cellulose sponge of example 6 forms small holes on the basis of conventional large holes to form a porous structure, so that the specific surface area is larger, the specific surface area is improved, and the structure performance is better, while the cellulose sponge of example 5 forms a small number of small holes, so the effect is slightly less than that of the cellulose sponge of example 6, and thus, the adsorption capacity of the cellulose sponge can be greatly improved by adopting the preferred process and method, and the porous structure can be developed and applied to copper ion adsorbing materials, has better advantages and development and application potentials.
Claims (8)
1. A preparation method of cellulose sponge for copper ion adsorption is characterized by comprising the following steps: 0.1-1 part of cellulose sponge is put into 8-12 parts of acetone solution of quinizarine with the concentration of 200-1000ppm, mixed and stirred for 30-60min, then dried for 30-60min at 50-60 ℃, then put into deionized water to be stirred for 10-20min after being dried, and finally air-dried to obtain the quinizarine modified cellulose sponge.
2. The method for preparing cellulose sponge for copper ion adsorption according to claim 1, wherein: and (2) putting 0.5 part of cellulose sponge into 10 parts of quinizarine acetone solution with the concentration of 500ppm, mixing and stirring for 45min, then drying for 45min at 55 ℃, putting the dried cellulose sponge into deionized water, stirring for 15min, and finally air-drying to obtain quinizarine modified cellulose sponge.
3. The method for preparing a cellulose sponge for copper ion adsorption according to claim 1 or 2, characterized in that: the preparation method of the cellulose sponge comprises the following steps:
a. alkalization: mixing 0.5-2 parts of oven-dried cotton linters and 3-8 parts of NaOH solution with the concentration of 17.5-25% by mass, and reacting at room temperature for 3-6h to obtain sodium cellulose;
b. yellowing: 0.8-1.5 parts of CS2Reacting with sodium cellulose at room temperature for 1.5-4h to obtain cellulose sulfonate;
c. dissolving and aging: adding 4-6 parts of water into cellulose sulfonate, and mixing for 48-72 hours to obtain a sodium cellulose sulfonate solution;
d. mixing the nano-cellulose with a sodium cellulose sulfonate solution: taking 1-5 parts of 0.2-1% nano cellulose solution and sodium cellulose sulfonate solution, and mixing for 0.5-2h in a rotating manner;
e. sponge forming: and d, uniformly mixing the mixed solution obtained in the step d with sodium phosphate according to the mass ratio of 1:1-2, pouring the mixture into a mold, putting the mold into an oven, reacting for 6-24 hours at the temperature of 65-90 ℃, and fully rinsing to obtain the cellulose sponge.
4. The method for preparing cellulose sponge for copper ion adsorption according to claim 3, wherein: the method comprises the following steps:
a. alkalization: mixing 1 part of oven-dried cotton linter and 5 parts of NaOH solution with the concentration of 20% in parts by mass, and reacting at room temperature for 4 hours to obtain sodium cellulose;
b. yellowing: taking 1 part of CS2Reacting with sodium cellulose at room temperature for 2h to obtain cellulose sulfonate;
c. dissolving and aging: adding 4 parts of water into cellulose sulfonate, and mixing for 60 hours to obtain a sodium cellulose sulfonate solution;
d. mixing the nano-cellulose with a sodium cellulose sulfonate solution: taking 2 parts of nano cellulose solution with the concentration of 0.5 percent and sodium cellulose sulfonate solution, and rotationally mixing for 1 hour;
e. sponge forming: and d, uniformly mixing the mixed solution obtained in the step d and sodium phosphate according to the mass ratio of 1:1.5, pouring the mixture into a mold, putting the mold into an oven, reacting for 12 hours at the temperature of 80 ℃, and fully rinsing to obtain the cellulose sponge.
5. The method for preparing cellulose sponge for copper ion adsorption according to claim 3 or 4, characterized in that: the oven-dried cotton linters are crushed into particles with the particle size of 40-300 meshes.
6. The method for preparing cellulose sponge for copper ion adsorption according to claim 3 or 4, characterized in that: the preparation method of the nano-cellulose solution comprises the steps of taking bleached bamboo pulp with the concentration of 10% as a raw material, grinding the bleached bamboo pulp by using a PFI mill to obtain pulp, enabling the beating degree to reach 85-95 DEG SR, diluting the pulp to 0.5-1%, circularly homogenizing the pulp for 30-60 times by using a high-pressure homogenizer with the homogenizing pressure of 80-120MPa, and obtaining the nano-cellulose solution after the completion.
7. The method for preparing cellulose sponge for copper ion adsorption according to claim 6, wherein: air-drying the slurry obtained when the beating degree reaches 85-95 DEG SR, mixing and defibering the slurry with NaOH solution with the mass ratio of 1:4-6 and the concentration of 2-10% at normal temperature, soaking the mixture for 4-24h, then sending the soaked mixture into a reaction kettle, heating the soaked mixture to the temperature of 110-130 ℃ by using saturated steam, controlling the pressure to be 1-4MPa, preserving the heat for 30-120min, then instantly discharging the pressure to explode the slurry in the reaction kettle, fully washing and air-drying the slurry, and fully washing and air-drying the slurry with HNO with the mass ratio of 1:4-6 and the concentration of 5-10%3Mixing and defibering the solution, soaking for 4-24h at normal temperature, then sending into the reaction kettle again, heating to 110-130 ℃ with saturated steam, controlling the pressure to be 1-4MPa, keeping the temperature for 30-120min, then instantly discharging the pressure again to explode the slurry in the reaction kettle again, finally diluting the slurry to 0.5-1%, then circularly homogenizing for 30-60 times with a high-pressure homogenizer at 80-120MPa, and finally obtaining the nano-cellulose solution.
8. The method for preparing cellulose sponge for copper ion adsorption according to claim 3 or 4, characterized in that: and in the step e, fully rinsing with hot water at 40-60 ℃.
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