METHOD FOR PREPARING MODIFIED NATURAL WOOD MATERIAL AND APPLICATION THEREOF IN SEWAGE TREATMENT

Abstract

The present invention belongs to the field of sewage treatment, and relates to a method for preparing a modified natural wood material and an application thereof in sewage treatment. The method for preparing the modified natural wood material includes the following steps: S1. placing wood into a lignin removal solution, after a heating reaction, washing, impregnating, and lyophilizing the wood to obtain removed lignin wood; S2. blending TiO.sub.2 with NaBH.sub.4, performing low-heat reduction treatment, and then washing and drying to obtain reduced black titanium; S3. dispersing the reduced black titanium ultrasonically in a solvent, then coating dropwise on the removed lignin wood, and drying to obtain a modified natural wood material. The modified natural wood material prepared by the present invention has high disinfection and sterilization performance, and has the ability to remove bio-risk components.

Claims

1. A method for preparing a modified natural wood material, comprising the following steps: S1. placing wood into a lignin removal solution, after a heating reaction, washing, impregnating, and lyophilizing the wood to obtain removed lignin wood; blending TiO.sub.2 with NaBH.sub.4, performing low-heat reduction treatment, and then washing and drying to obtain reduced black titanium; S2. dispersing the reduced black titanium ultrasonically in a solvent, then coating on the removed lignin wood, and drying to obtain a modified natural wood material; wherein, the natural wood material is American lightwood; the reduced black titanium has a bandgap of 2.10-2.20 eV.

2. The method for preparing the modified natural wood material according to claim 1, wherein in step S1, the method for preparing the lignin removal solution comprises the following steps: dissolving acetate in water, adjusting pH, and then adding chlorate.

3. The method for preparing the modified natural wood material according to claim 2, wherein a molar ratio of acetate to chlorate is (2.5-3):1.

4. The method for preparing the modified natural wood material according to claim 2, wherein the pH is 4.4-4.8.

5. The method for preparing the modified natural wood material according to claim 1, wherein in step S1, the heating reaction has a temperature of 100-120° C. and time of 8-10 h.

6. The method for preparing the modified natural wood material according to claim 1, wherein in step S1, a molar ratio of TiO.sub.2 to NaBH.sub.4 is (1-1.5):1.

7. The method for preparing the modified natural wood material according to claim 1, wherein in step S1, the method for blending TiO.sub.2 with NaBH.sub.4 is ball-milling mixing.

8. The method for preparing the modified natural wood material according to claim 1, wherein in step S1, the low-heat reduction treatment is performed under an inert gas atmosphere at a temperature of 300-350° C. for 1-1.5 h.

9. The method for preparing the modified natural wood material according to claim 1, wherein in step S2, ultrasonic dispersion has time of 20-40 min.

10. An application of the modified natural wood material of claim 1 in sewage treatment.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0028] FIG. 1 shows a diagram of XRD results for detecting reduced black titanium prepared for P25 TiO.sub.2 and step S1 in Embodiment 1.

[0029] FIG. 2 shows an ultraviolet-visible diffuse reflection spectrum diagram of reduced black titanium prepared for P25 TiO.sub.2 and step S1 in Embodiment 1.

[0030] FIG. 3 shows a diagram of growth results of general microorganisms in Test Embodiment 1; wherein,

[0031] FIG. 3(a) shows a diagram of growth test results of general microorganisms in domestic sewage (Blank sample 1);

[0032] FIG. 3(b) is a diagram of performance test results of killing general microorganisms with a modified natural wood material prepared in Embodiment 1;

[0033] FIG. 3(c) is a diagram of performance test results of killing general microorganisms with a modified natural wood material prepared in Comparative Embodiment 1;

[0034] FIG. 3(d) is a diagram of performance test results of killing general microorganisms with a modified natural wood material prepared in Comparative Embodiment 2.

[0035] FIG. 4 shows a diagram of growth results of Escherichia coli in Test Embodiment 2; wherein,

[0036] FIG. 4(a) is a diagram of growth test results of Escherichia coli in domestic sewage (Blank sample 2);

[0037] FIG. 4(b) is a diagram of performance test results of killing Escherichia coli with a modified natural wood material prepared in Embodiment 1;

[0038] FIG. 4(c) is a diagram of performance test results of killing Escherichia coli with a modified natural wood material prepared in Comparative Embodiment 1;

[0039] FIG. 4(d) is a diagram of performance test results of killing of Escherichia coli with a modified natural wood material prepared in Comparative Embodiment 2.

[0040] FIG. 5 shows a diagram of detection results of oxygen-containing radical produced by a modified natural wood material in Test Embodiment 2; wherein,

[0041] FIG. 5(a) shows a magnetic field intensity-signal intensity curve of oxygen-containing radical produced by a modified natural wood material under irradiation of one natural light for 1 h;

[0042] FIG. 5(b) shows a magnetic field intensity-signal intensity curve of oxygen-containing radical produced by a modified natural wood material under unirradiated conditions.

[0043] FIG. 6 shows a diagram of test results of bio-risk components in ARGs in a sample in Test Embodiment 3; wherein,

[0044] FIG. 6(a) shows a diagram of test results of bio-risk component contents in domestic sewage (Blank sample 3);

[0045] FIG. 6(b) shows a diagram of test results of an enrichment separation effect of bio-risk components of ARGs by a modified natural wood material prepared in Embodiment 1;

[0046] FIG. 6(c) shows a diagram of test results of an enrichment separation effect of bio-risk components of ARGs by a modified natural wood material prepared in Comparative Embodiment 1;

[0047] FIG. 6(d) shows a diagram of test results of an enrichment separation effect of bio-risk components of ARGs by a modified natural wood material prepared in Comparative Embodiment 2.

DETAILED DESCRIPTION OF EMBODIMENTS

[0048] In order to more clearly describe technical solutions of the present invention, the following embodiments are given, but the present invention is not limited thereto.

[0049] Experimental methods used in the following embodiments are all conventional methods unless otherwise specified. Reagents, materials and the like used in the following embodiments can be obtained from commercial routes unless otherwise specified.

[0050] Wood in the embodiments of the present invention was American lightwood and purchased from a local wood retail market, and had a size of 30 mm×30 mm×5 mm (length×width×height).

[0051] TiO.sub.2 in the embodiments of the present invention was commercial P25 TiO.sub.2.

[0052] The method for preparing a lignin removal solution in the embodiments of the present invention had the following steps: dissolving 0.2 mol of sodium acetate in 150 mL of deionized water, adding glacial acetic acid dropwise to adjust pH to 4.6, then adding the deionized water of 300 mL, then adding 0.07 mol of sodium chlorite, stirring and dissolving to obtain the lignin removal solution.

[0053] The LB-agar solid culture medium in the test embodiment of the present invention had the following compositions: 10.0 g of peptone, 5.0 g of yeast paste powder, 5.0 g of sodium chloride, 1.0 g of glucose, and 15.0 g of agar per liter of a LB-agar culture medium. The pH was finally adjusted to be 7.0.

[0054] The EMB-agar solid culture medium in the test embodiment of the present invention had the following compositions: 10.0 g of peptone, 10.0 g of lactose, 2.0 g of potassium dihydrogen phosphate, 15.0 g of agar, 0.4 g of eosin, and 0.065 g of methylene blue per liter of an EMB-agar culture medium. The pH was finally adjusted to be 7.1.

[0055] The plate number of an electron-paramagnetic resonator in the test embodiment of the present invention was Bruker A300.

[0056] The method for testing a macrogenome-antibiotic resistance gene in the test embodiment of the present invention had the following steps: firstly, extracting a total DNA of microorganisms from an original sample, then testing a DNA sample, and performing subsequent experiments after a total amount and purity of the DNA sample meet requirements, otherwise, the DNA is re-extracted or an existing DNA is purified according to a specific reason; adding the DNA sample passing a quality test to a breakage buffer, randomly interrupting the DNA with an ultrasonic crusher, applying the interrupted short fragmented DNA to establish a library, quality-testing the library, PE150-sequencing the library passing the quality test by using an Illumina HiSeq 2500 high-throughput sequencing platform, and transforming a raw image data file obtained by the sequencing into an original sequencing sequence by a base recognition analysis. After obtaining macrogenome sequencing data of the original sample, performing quality control of original data, evaluating quality of the data to be sequenced and removing the low-quality data to ensure a confidence level of subsequent separation results. Performing macrogenome assembly on each of the samples after quality control treatment, individually assembling the samples, combining a mixed assembled open reading frame among the samples, performing gene clustering, removing redundancy, taking the longest sequence in each cluster as a representative sequence to obtain a non-redundant gene catalogue; annotating resistance genes on the samples with drug resistance, and labeling bacterial drug resistance genes from different environmental sources with a drug resistance gene database of CARD (The Complementary Antibiotic Resistance Database), to obtain gene annotations of various resistance mechanism roles and corresponding number of resistance mechanism genes.

Embodiment 1

[0057] A method for preparing a modified natural wood material includes the following steps:

[0058] S1. placing wood into a lignin removal solution, reacting in an oil bath at a temperature of 100° C. for 8 h, washing the wood 3 times with deionized water, then placing and impregnating the wood into the deionized water for 12 h, then pre-freezing the wood at a temperature of −20° C. for 24 h, lyophilizing the wood for 12 h to obtain a lignin removal wood; [0059] performing low-speed ball-milling mixing on TiO.sub.2 and NaBH.sub.4 with a molar ratio of TiO.sub.2 to NaBH.sub.4 of 1.25:1, placing TiO.sub.2 and NaBH.sub.4 into a corundum crucible, heating to 350° C. at a rate of 10° C./min under an argon atmosphere, cooling to a room temperature after reaction for 1 h, then washing 3 times with the deionized water and anhydrous ethanol, respectively, and drying in an oven at a temperature of 60° C. to obtain reduced black titanium;

[0060] S2. placing 0.5 g of the reduced black titanium in 5 mL of the anhydrous ethanol, ultrasonically dispersing for 30 min, then coating dropwise and modifying on the lignin removal wood for 3 times, and drying in the oven at the temperature of 60° C. to obtain the modified natural wood material.

[0061] FIG. 1 showed a diagram of XRD results for detecting the reduced black titanium prepared for P25 TiO.sub.2 and step S1. It could be seen that a main crystalline form of the reduced black titanium prepared by the present invention was completely converted from an anatase phase in P25 TiO.sub.2 to a rutile phase.

[0062] FIG. 2 showed an ultraviolet-visible diffuse reflection spectrum diagram of the reduced black titanium prepared for P25 TiO.sub.2 and step S1. According to an intercept of a curve on horizontal coordinates, it could be calculated that P25 TiO.sub.2 had a bandgap of about 3.21 eV, and the reduced black titanium prepared by the present invention had a bandgap of about 2.15 eV.

Embodiment 2

[0063] A method for preparing a modified natural wood material includes the following steps:

[0064] S1. placing wood into a lignin removal solution, reacting in an oil bath at a temperature of 110° C. for 9 h, washing the wood 3 times with deionized water, then placing and impregnating the wood into the deionized water for 12 h, then pre-freezing the wood at a temperature of −20° C. for 24 h, lyophilizing the wood for 12 h to obtain a lignin removal wood; [0065] performing low-speed ball-milling mixing on TiO.sub.2 and NaBH.sub.4 with a molar ratio of TiO.sub.2 to NaBH.sub.4 of 1.2:1, placing TiO.sub.2 and NaBH.sub.4 into a corundum crucible, heating to 340° C. at a rate of 10° C./min under an argon atmosphere, cooling to a room temperature after reaction for 1.2 h, then washing 3 times with the deionized water and anhydrous ethanol, respectively, and drying in an oven at a temperature of 60° C. to obtain reduced black titanium;

[0066] S2. placing 0.5 g of the reduced black titanium in 5 mL of the anhydrous ethanol, ultrasonically dispersing for 20 min, then coating dropwise and modifying on the lignin removal wood for 3 times, and drying in the oven at the temperature of 60° C. to obtain the modified natural wood material.

Embodiment 3

[0067] A method for preparing a modified natural wood material includes the following steps:

[0068] S1. placing wood into a lignin removal solution, reacting in an oil bath at a temperature of 120° C. for 10 h, washing the wood 3 times with deionized water, then placing and impregnating the wood into the deionized water for 12 h, then pre-freezing the wood at a temperature of −20° C. for 24 h, lyophilizing the wood for 12 h to obtain a lignin removal wood;

[0069] performing low-speed ball-milling mixing on TiO.sub.2 and NaBH.sub.4 with a molar ratio of TiO.sub.2 to NaBH.sub.4 of 1.5:1, placing TiO.sub.2 and NaBH.sub.4 into a corundum crucible, heating to 330° C. at a rate of 10° C./min under an argon atmosphere, cooling to a room temperature after reaction for 1.5 h, then washing 3 times with the deionized water and anhydrous ethanol, respectively, and drying in an oven at a temperature of 60° C. to obtain reduced black titanium;

[0070] S2. placing 0.5 g of the reduced black titanium in 5 mL of the anhydrous ethanol, ultrasonically dispersing for 40 min, then coating dropwise and modifying on the lignin removal wood for 3 times, and drying in the oven at the temperature of 60° C. to obtain the modified natural wood material.

Comparative Embodiment 1

[0071] Comparative Embodiment 1 was distinct from Embodiment 1 in that in step S1, reduced black titanium was prepared using a vacuum high heat method, which included the following specific steps: placing 1 g of TiO.sub.2 in 5 mL of anhydrous ethanol, ultrasonically dispersing for 30 min, extracting, filtering and washing a TiO.sub.2 dispersion liquid with the anhydrous ethanol and deionized water, drying a filter cake in an oven at a temperature of 60° C., then placing the resulting TiO.sub.2 in a corundum crucible, heating to 800° C. at a rate of 5° C./min under vacuum conditions, reacting for 5 h, cooling to a room temperature, restoring a pressure to a normal pressure when cooling to 200° C., washing with the deionized water and the anhydrous ethanol, and drying in the oven at the temperature of 60° C. to obtain the reduced black titanium. The remaining steps of the preparation method were the same as those in Embodiment 1.

Comparative Embodiment 2

[0072] Comparative Embodiment 2 was distinct from Embodiment 1 in that in step S1, reduced black titanium was prepared using a high heat reduction method, which included the following specific steps: ultrasonically washing and drying 1 g of TiO.sub.2, then placing the TiO.sub.2 in a corundum crucible, heating to 800° C. at a rate of 10° C./min under an argon atmosphere, reacting for 2 h, and cooling to room temperature to obtain the reduced black titanium. The remaining steps of the preparation methods were the same as those in Embodiment 1.

Test Embodiment 1

[0073] Growth test of general microorganisms in domestic sewage:

[0074] coating uniformly 10 μL of the domestic sewage on a LB-agar solid culture medium under aseptic conditions, then incubating in an incubator at a constant temperature of 37° C. for 48 h, and observing growth of the microorganisms on a surface of the culture medium.

[0075] Performance test of killing the general microorganisms with a modified natural wood material: [0076] placing 50 mL of the domestic sewage in an evaporation container, placing the modified natural wood materials prepared in Embodiment 1 and Comparative Embodiments 1-2 on an upper surface of the evaporation container, respectively, placing the above container in a condensing device constructed by a transparent spherical glass cover, performing simulation irradiation for 12 consecutive hours under one natural light, collecting a condensed water phase in the condensed glass cover under aseptic conditions, coating uniformly the water phase on a LB-agar solid culture medium, then placing in the incubator to be cultured at a constant temperature of 37° C. for 48 h, and observing the growth of the microorganisms on the surface of the culture medium.

[0077] Test Results:

[0078] FIG. 3(a) showed a diagram of growth test results of the general microorganisms in the domestic sewage (Blank sample 1). It could be seen that the number of colonies was extremely large and the growth of the microorganisms was rapid.

[0079] FIG. 3(b) was a diagram of performance test results of killing the general microorganisms with the modified natural wood material prepared in Embodiment 1. No macroscopic flora was provided, indicating that the modified natural wood material of the present invention had a good performance of killing the microorganisms;

[0080] FIG. 3(c) was a diagram of performance test results of killing the general microorganisms with the modified natural wood material prepared in Comparative Embodiment 1. It could be seen that the modified natural wood material prepared in Comparative Embodiment 1 did not effectively kill the microorganisms, and a certain amount of colonies still grew on a surface of a culture medium;

[0081] FIG. 3(d) was a diagram of performance test results of killing the general microorganisms with the modified natural wood material prepared in Comparative Embodiment 2. It could be seen that a certain amount of colonies still existed on the surface of the medium, indicating that reduced black titanium completely converted to a rutile phase had a stronger photothermal property than reduced black titanium in which an anatase phase was mixed with the rutile phase, and could promote a photocatalytic process, so as to produce a higher heat value, thereby having a stronger performance of killing the microorganisms.

Test Embodiment 2

[0082] Growth Test of Escherichia coli in Domestic Sewage:

[0083] coating uniformly 10 μL of the domestic sewage on a EMB-agar solid culture medium under aseptic conditions, then incubating in an incubator at a constant temperature of 37° C. for 48 h, and observing growth of the Escherichia coli on a surface of the culture medium.

[0084] Performance test of killing the Escherichia coli with a modified natural wood material: [0085] placing 50 mL of the domestic sewage in an evaporation container, placing the modified natural wood materials prepared in Embodiment 1 and Comparative Embodiments 1-2 on an upper surface of the evaporation container, respectively, placing the above container in a condensing device constructed by a transparent spherical glass cover, performing simulation irradiation for 12 consecutive hours under one natural light, collecting a condensed water phase in the condensed glass cover under aseptic conditions, coating uniformly the water phase on a EMB-agar solid culture medium, then placing in the incubator to be cultured at a constant temperature of 37° C. for 48 h, and observing the growth of the Escherichia coli on the surface of the culture medium. The number of oxygen-containing radical in the modified natural wood material prepared in Embodiment 1 was then detected using an electron-paramagnetic resonator under visible light simulated light source excitation and unirradiated conditions.

[0086] Test Results:

[0087] FIG. 4(a) was a diagram of growth test results of the Escherichia coli in the domestic sewage (Blank sample 2). It could be seen that a large number of metallic coliforms existed on the surface of the culture medium.

[0088] FIG. 4(b) was a diagram of performance test results of killing the Escherichia coli with the modified natural wood material prepared in Embodiment 1. No macroscopic coliforms was provided, indicating that the modified natural wood material of the present invention had a good performance of killing the Escherichia coli.

[0089] FIG. 4(c) was a diagram of performance test results of killing Escherichia coli with the modified natural wood material prepared in Comparative Embodiment 1. It could be seen that the modified natural wood material prepared in Comparative Embodiment 1 failed to effectively and selectively kill the coliforms.

[0090] FIG. 4(d) was a diagram of performance test results of killing the Escherichia coli with the modified natural wood material prepared in Comparative Embodiment 2. It could be seen that the modified natural wood material prepared in Comparative Embodiment 2 failed to effectively and selectively kill the coliforms.

[0091] Detection test results of the quantity of the oxygen-containing radical were shown in Table 1 and FIG. 5:

TABLE-US-00001 TABLE 1 Detection Test Results of Quantity of the Oxygen-containing Radical Signal Strength (a.u.) Magnetic Field Irradiation of One Natural Light for 1 h No Irradiation Strength (G) DMPO—.sup.1O.sub.2 DMPO—•OH DMPO—O.sub.2.sup.− DMPO—.sup.1O.sub.2 DMPO—•OH DMPO—O.sub.2.sup.− 3492.36 125656.73 / / / / / 3509.46 123723.74 / / / / / 3526.96 123912.97 / / / / / 3487.17 / 66153.50 / / / / 3502.13 / 81615.59 / / / / 3517.08 / 83045.52 / / / / 3531.94 / 67987.02 / / / / 3489.91 / / 14987.89 / / / 3499.88 / / 16126.63 / / / 3513.76 / / 16150.10 / / / 3527.74 / / 15062.60 / / /

[0092] FIG. 5 showed a diagram of detection results of the oxygen-containing radical produced by the modified natural wood material. FIG. 5(a) showed a magnetic field intensity-signal intensity curve of the oxygen-containing radical produced by the modified natural wood material under irradiation of one natural light for 1 h. It could be seen that the modified natural wood material utilized surface modification to reduce the black titanium components, which could produce the oxygen-containing radical such as monolinear oxygen, hydroxyl radical, and superoxide radical under visible light excitation, and could be used efficiently for sterilization of domestic sewage microorganisms. FIG. 5(b) showed a magnetic field intensity-signal intensity curve of the oxygen-containing radical produced by the modified natural wood material under unirradiated conditions. It could be seen that even with the modification of the reduced black titanium components, the modified natural wood material could not produce the oxygen-containing radical under the unirradiated conditions. It was indicated that light excitation was also critical for the production of the oxygen-containing radical.

Test Embodiment 3

[0093] Test of Bio-Risk Component Contents in Domestic Sewage:

[0094] Taking 50 mL of the domestic sewage as a sample and performing a macrogenome-antibiotic resistance gene test on the sample.

[0095] Test of an enrichment separation effect of bio-risk components by a modified natural wood material: [0096] treating 50 mL of the domestic sewage as the sample with the modified natural wood materials prepared in Embodiment 1 and Comparative Embodiments 1-2 under one natural light for 15 h, respectively, and then performing a macrogenome-antibiotic resistance gene test on the modified natural wood material.

[0097] Test results were shown in Table 2 and FIG. 6:

TABLE-US-00002 TABLE 2 Macrogenome-antibiotic Resistance Gene Test Results Quantity (Pcs) Comparative Comparative ARGs Blank Sample 3 Embodiment 1 Embodiment 1 Embodiment 2 Antibiotic efflux 36.67 31.33 16.84 20.29 Antibiotic inactivation 18.13 15.63 10.50 12.36 Antibiotic target 58.54 47.26 10.39 11.44 protection Antibiotic target 54.84 61.55 12.10 13.25 alteration Antibiotic target 15.56 35.78 24.73 19.79 replacement Reduced permeability 42.28 26.17 27.13 26.39 to antibiotic

[0098] It could be derived from Table 2 that the modified natural wood material prepared by the present invention has a highly efficient enriching separation capacity on ARG components in the sewage. The number of “antibiotic target alteration” genes in Embodiment 1 was more than that in the blank sample, because the number of resistance genes in the blank sample itself was less. Embodiment 1 was continuously enriched during a process, resulting in the number of enriched partial genes exceeded a corresponding value in the blank sample. The number of “reduced permeability to the antibiotic” genes in Embodiment 1 was lower than the comparative embodiment, which might be due to non-uniformity of a resistance gene-sequencing sample. An enrichment effect of Embodiment 1 on other resistance genes was significantly higher than that of the comparative embodiment. Therefore, it could still be concluded that the present invention had the ability to efficiently separate the bio-risk components.

[0099] FIG. 6(a) showed a diagram of test results of bio-risk component contents in the domestic sewage (Blank sample 3). It could be seen that the domestic sewage contained a large number of antibiotic resistance genes and other bio-risk components.

[0100] FIG. 6(b) showed a diagram of test results of an enrichment separation effect of the bio-risk components by the modified natural wood material prepared in Embodiment 1. It could be seen that the components and quantity of the modified natural wood material of the present invention was similar to those of the antibiotic resistance gene in untreated domestic sewage, indicating that the antibiotic resistance genes in the domestic sewage were enriched and transferred to the modified natural wood material. The modified natural wood material of the present invention had an efficient removal capacity on the bio-risk components such as the antibiotic resistance gene.

[0101] FIGS. 6(c) and 6(d) showed a diagram of the test results of the enrichment separation effect of the modified natural wood materials prepared at Comparative Embodiment 1 and Comparative Embodiment 2 on the bio-risk components. It could be seen that the bio-risk components in domestic sewage could also be enriched and separated by the modified natural wood material prepared in Comparative Embodiment 1 and Comparative Embodiment 2 with a photothermal effect, but an effect was reduced and significantly weaker than that of the modified natural wood material prepared in Embodiment 1.

[0102] It is obvious to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the present invention can be realized in other specific forms without departing from the spirit or basic features of the present invention. Therefore, the embodiments should be regarded as exemplary and non-limiting from any standpoint. The scope of the present invention is defined by the appended claims rather than the above description. It is therefore intended that all variations falling within the meaning and scope of equivalent elements of claims be encompassed by the present invention.

[0103] In addition, it should be understood that although this specification is described in terms of embodiments, not each embodiment only includes an independent technical solution. This description in the specification is only for the sake of clarity. A person skilled in the art should take the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementations that can be understood by a person skilled in the art.