CN108855031B

CN108855031B - Nanotube material suitable for kasugamycin wastewater treatment and preparation method thereof

Info

Publication number: CN108855031B
Application number: CN201810817368.5A
Authority: CN
Inventors: 潘忠成; 张宏远; 翁婧; 秦秋菊; 邓钊; 张楠; 李向荣; 郭秀艳; 周晶晶; 张心心; 王军; 李蒲民
Original assignee: Shaanxi Microbe Biotechnology Co ltd
Current assignee: Shaanxi Microbe Biotechnology Co ltd
Priority date: 2018-07-24
Filing date: 2018-07-24
Publication date: 2021-06-11
Anticipated expiration: 2038-07-24
Also published as: CN108855031A

Abstract

The invention relates to a nanotube material suitable for kasugamycin wastewater treatment and a preparation method thereof, wherein the nanotube material comprises Na₂O‑Al₂O₃‑SiO₂‑TiO₂. The novel nanotube material provided by the invention can well remove COD and ammonia nitrogen in kasugamycin wastewater, is efficient, safe and environment-friendly, and is beneficial to treatment of the kasugamycin wastewater. In addition, the novel nanotube material can well treat the kasugamycin wastewater treated by biological combined membranization, and the wastewater treated by the nanotube reaches the national relevant antibiotic wastewater discharge standard.

Description

Nanotube material suitable for kasugamycin wastewater treatment and preparation method thereof

Technical Field

The invention belongs to the technical field of biological wastewater treatment, and particularly relates to a nanotube material suitable for kasugamycin wastewater treatment and a preparation method thereof.

Background

Kasugamycin (Kasugamycin) and beggaramycin, and Jiashou rice, which are microbial agricultural pesticides for preventing and treating crop diseasesThe microbial inoculum has the chemical name of (5-amino-2-methyl-6- (2, 3, 4, 5, 6-hydroxycyclohexyl oxo) tetrahydropyran-3-yl) amino-alpha-imino acetic acid and the molecular formula C₁₄H₂₅N₃O₉Molecular weight 379.4. The kasugamycin pure product is white crystal; the hydrochloride is white needle-shaped or sheet-shaped crystal, and the melting point of a pure product is as follows: decomposing at 236-239 ℃, wherein the melting point of hydrochloride is as follows: 202-204 deg.C (decomposition), is easily soluble in water, can be dissolved in water of 25 deg.C by 12.5% (W/V), and is insoluble in organic solvent such as methanol, ethanol, acetone, benzene, etc. The structural formula is shown as the following formula:

kasugamycin has no toxicity, residue and pollution to people and livestock, meets the modern environmental protection requirement, and is listed as a recommended biopesticide for producing nuisanceless agricultural products by the Ministry of agriculture. Along with the improvement of the awareness of people on the safety of pesticides, the kasugamycin has more and more extensive market prospect due to high-efficiency, broad-spectrum and pollution-free biological characteristics.

Although kasugamycin has obvious drug effect in preventing and treating bacterial diseases such as rice blast and the like, a large amount of kasugamycin wastewater is generated in the process of producing the kasugamycin by fermenting streptomyces aureofaciens, and the wastewater has the following characteristics:

(1) the COD and ammonia nitrogen value are high, and the COD mean value of the waste water from the kasugamycin fermentation workshop reaches 6250 and 11000 mg/L; the ammonia nitrogen mean value is 350-450 mg/L;

(2) the kasugamycin wastewater treatment is generally biological combined membranization treatment, but the average value of COD and ammonia nitrogen of the membranization effluent is 600-;

(3) how to further and deeply treat the effluent of the kasugamycin through the biological combined membranization treatment is a great problem faced by enterprises.

In response to this problem, photocatalytic decomposition of organic pollutants from cleaning of pollutants is the first method of choice to address this problem. Metal oxides such as TiO₂Nanotubes are used as photoelectrodes in these systems due to their high redox activity. This successfully demonstrated the effectiveness of titanium nanotubes as contaminant decomposers in photocatalytic systems. Study of the use of TiO₂The result of the decomposition of the rhodamine B in water by using the nanotube as a catalyst shows that the organic pollutants show excellent performance in the decomposition process, which is formed by doping the titanium nanotube with Fe³⁺After 4 degradation cycles, the doped titanium nanotubes can still achieve high removal efficiency, but Fe³⁺Less loss of energy.

The study of the decomposition of rhodamine B pigment was performed using bismuth-doped titanium nanotubes, and the study was performed in direct sunlight. The superior performance is ensured by the superior result of the larger surface area provided by the titanium nanotubes due to the doping of Bi itself. The recent studies by massa et al are as follows, the titanium nanotube is a good material, the conversion rate of phenol is 26.8%, and the deterioration of the intermediate product of the manganese oxide composition titanium nanotube, and the calculation fact proves that the electric oxidation process of phenol is about 1-1.5V. As a result of the durability test, an electrode capable of withstanding for a long time at a high current density of up to 15 hours can be obtained. This is said to be due to the hollow structure of the titanium nanotubes, which promotes the movement of electrons in the process that takes place and contributes to good adhesion of MnOx to the titanium nanotube surface.

Chinese patent application CN108031308A discloses a membrane material suitable for kasugamycin wastewater treatment and a preparation method thereof, wherein the membrane casting solution comprises 2.0-16% of polyvinyl chloride PVC (polyvinyl chloride); the content of polyvinylpyrrolidone PVP is 2.0-4.0%; 2.0-10.0% of polyvinylidene fluoride (PVDF); 76-79% of N, N-dimethylacetamide DMAC; 0.3-1.0% of calcium-zinc heat stabilizer; 3.0-9.0% of modifier. The kasugamycin wastewater is treated by the membrane material, so that the removal efficiency of COD and ammonia nitrogen is improved, the cost for treating the kasugamycin wastewater is reduced, and the quality of the treated wastewater is improved.

Disclosure of Invention

In order to solve the problems in the prior art, the invention provides a nanotube material suitable for kasugamycin wastewater treatment and a preparation method thereof. The novel nanotube material obtained by the invention can well remove COD and ammonia nitrogen of kasugamycin wastewater, is efficient, safe and environment-friendly, and is beneficial to treatment of the kasugamycin wastewater. In addition, the novel nanotube material can well treat the kasugamycin wastewater treated by biological combined membranization, and the wastewater treated by the nanotube reaches the national relevant antibiotic wastewater discharge standard.

In order to realize the purpose of the invention, the invention adopts the following technical scheme:

a nanotube material suitable for kasugamycin wastewater treatment comprises Na₂O-Al₂O₃-SiO₂-TiO₂ 。

Further, to prepare Na₂O-Al₂O₃-SiO₂-TiO₂Preparing Na from the nanotube material₂O-Al₂O₃-SiO₂-TiO₂The powder of (4).

The invention also discloses a preparation method of the nanotube material, which comprises the steps of mixing a certain volume of 10mol/L sodium hydroxide solution with a certain amount of Na₂O-Al₂O₃-SiO₂-TiO₂Fully mixing the composite nano powder and CTAB powder, placing the mixture in a beaker, carrying out ultrasonic treatment for 24min, then pouring the mixture into a reactor, placing the mixture in a muffle furnace for reaction, taking out the mixture, naturally cooling the mixture, depositing solid matters at the bottom of the cup, repeatedly washing the mixture by using deionized water, cutting and filtering the mixture, standing the mixture for 3 h, then leaving the solid matters deposited at the bottom of the cup, then washing a sample by using the deionized water until the pH value is close to 7, pouring concentrated nitric acid into a clean reactor, placing the reactor in a steel sheath, taking out the reactor for cooling, recovering the concentrated nitric acid, washing a reaction kettle, placing the reactor in an ultrasonic device for ultrasonic treatment for 30 min, repeatedly washing the sample by using distilled water, filling the kettle with the distilled water, and.

Further, the reaction is carried out for 1 to 26 hours in a muffle furnace at the temperature of between 20 and 250 ℃.

Further, Na with different molar ratios of Al to Ti is prepared₂O-Al₂O₃-SiO₂-TiO₂Nanotube, structureTreating the obtained solution with 0.1mol/L nitric acid to wash the solid precipitate, heating and stirring for 1 hour, standing and centrifuging, adding a certain amount of anhydrous ethanol into the filtered solid precipitate, completely drying at 150 ℃, and calcining at 550 ℃ for 3 hours to obtain a white powdery product, namely Na₂O-Al₂O₃-SiO₂-TiO₂The molar ratio of Al to Ti in the nano-tubes is 1-1.5:1 respectively.

Further, said Na₂O-Al₂O₃-SiO₂-TiO₂The powder of (a) is carried out in a liquid a and a liquid B, wherein the ratio of liquid a: 100mL of absolute ethanol and 150mL of silica sol were placed in a 500mL beaker; and B, liquid B: adding a certain amount of butyl titanate into a mixture of 20mL of absolute ethyl alcohol and 10mL of glacial acetic acid, placing the mixture into a 250mL beaker, and standing for 10 minutes; weighing a certain amount of aluminum nitrate, placing the aluminum nitrate into 20mL of absolute ethyl alcohol, carrying out ultrasonic treatment in an ultrasonic generator, and standing for 10 minutes; the two solutions were mixed and mixed under magnetic stirring and left to stand.

Further, keeping the beaker filled with the liquid B in a magnetic stirring water bath, dropwise adding the liquid A into the liquid B for 30 minutes at room temperature by using a separating funnel, then setting the temperature of a water bath pot to be 75 ℃ to start stirring, when the stirring time is about 9 hours, the transparent sol starts to be converted into dry gel, and when the magnetic stirrer cannot rotate in the dry gel, taking out the beaker from the magnetic stirring water bath and putting the beaker into a drying box; after the xerogel is changed into light yellow transparent solid particles in a drying oven, taking the xerogel out of the drying oven, washing a mortar with absolute ethyl alcohol, drying the xerogel by a blower, putting a sample into the mortar for grinding, putting the sample into a crucible when the sample is ground into white fine powder, washing the sample with absolute ethyl alcohol, drying the sample, putting the sample into a muffle furnace, and calcining the sample at 500 ℃ for 3 hours to obtain Na₂O-Al₂O₃-SiO₂-TiO₂And (3) compounding the nano powder.

The invention also protects the application of the nanotube material in the treatment of kasugamycin wastewater, and the prepared Na₂O-Al₂O₃-SiO₂-TiO₂Nanotube material to kasugamycin wasteThe effluent of the water combined treatment of the biology and the MBR membrane is treated again, wherein the Na of the nano tube₂O-Al₂O₃-SiO₂-TiO₂The water retention time is 45min, and the illumination is 3000 Lx.

Wherein, the Na is₂O-Al₂O₃-SiO₂-TiO₂The powder and the nanotube material respectively carry out retreatment on the effluent of kasugamycin wastewater subjected to combined treatment of organisms and MBR membranes, under the conditions that the water retention time is 45min and the illumination is 3000Lx, the COD removal rate is 95 percent and the ammonia nitrogen removal rate is 92 percent, the treatment is obviously superior to that of powder type Na and that of powder type Na₂O-Al₂O₃-SiO₂-TiO₂The removal rate of COD in the wastewater is only 82.5, and the removal rate of ammonia nitrogen is only 75%.

Compared with the prior art, the invention has the beneficial effects that:

on the basis of optimizing the preparation process conditions, the novel nanotube material suitable for treating the kasugamycin wastewater is prepared, the novel carbon nanotube is used for treating the kasugamycin wastewater, the removal rate of COD (chemical oxygen demand) and ammonia nitrogen in the kasugamycin wastewater is effectively improved, the cost for treating the kasugamycin wastewater is reduced, and the effluent quality is completely up to the national relevant antibiotic wastewater discharge standard. In addition, the novel nanotube material has irreplaceable effects in the fields of chemical catalysts, ship tail gas purification, electric conduction, photocatalytic oxidation and the like.

Drawings

The following is further illustrated with reference to the accompanying drawings:

FIG. 1 is a TEM image of nanotubes at different reaction times;

FIG. 2 is a graph obtained by XRD test of a sample with a reaction time of 29 h;

FIG. 3 is a transmission image of different tube-forming regions of a sample with a reaction time of 29 h;

FIG. 4 is a TEM image of Al to Ti molar ratio of 1: 1;

FIG. 5 is a TEM image of Al to Ti molar ratio of 1.2: 1;

FIG. 6 is a TEM image of Al to Ti molar ratio of 1.5: 1;

FIG. 7 shows a molar ratio of Al/Ti of 1:1Na₂O-Al₂O₃-SiO₂-TiO₂Nanotube N₂Adsorption and desorption isotherms;

FIG. 8 shows Na having an Al/Ti molar ratio of 1.2:1₂O-Al₂O₃-SiO₂-TiO₂Nanotube N₂Adsorption and desorption isotherms;

FIG. 9 shows Na having an Al/Ti molar ratio of 1.5:1₂O-Al₂O₃-SiO₂-TiO₂Nanotube N₂Adsorption and desorption isotherms;

FIG. 10 shows adsorbed H at different molar ratios of Al to Ti₂Isotherms.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described with the following specific examples, but the present invention is by no means limited to these examples. The test method adopted by the invention is as follows:

first, specific surface area test (BET)

The Brunauer-Emmett-teller (bet) theory is intended to explain the physical adsorption of gas molecules on solid surfaces and serves as the basis of an important analytical technique for measuring the specific surface area of materials. The first article on the BET theory was published in 1938 by Stephen Brunauer, Paul Hugh Emmett, Edward Teller, in the journal of the American chemical society.

BET theory is applied to a multi-layer adsorption system, and generally utilizes a gas that does not chemically react with the surface of a material as an adsorption substance as a probe gas, thereby quantifying the specific surface area.

N₂Is the most commonly used gas adsorbate for BET surface detection. Standard BET analysis is usually at N₂At a boiling temperature of (77K). Argon, carbon dioxide and water are further utilized for the detection of the adsorbate, which, although less frequent, allows the detection to measure the surface area of the sample at different temperatures and measurement ranges. The specific surface area is a characteristic depending on the ratio of substances, and is not determined by a single true value. Thus, the amount of specific surface area determined by BET theory may depend on the adsorbent molecules used and their adsorptionA section is attached.

The BET equation is:

in the field of solid catalysis, the size of the surface area of the catalyst is an important factor in determining the strength of catalytic activity. In the case of inorganic materials, such as porous silica and layered clay minerals, high surface areas of several hundred square meters per gram, as calculated by the BET method, indicate the possible utility of the sample in the field of catalysis.

The instrument used herein for the specific surface area test (BET) is a Builder SSA-5000 type specific surface area analyzer. The basic operating environment is as follows;

(1) when in test, 0.6-1.0g of sample is weighed

(2) Helium as carrier gas and nitrogen as adsorption gas

(3) The temperature of liquid nitrogen was maintained at 77K, and the catalyst sample was measured at low temperature to adsorb nitrogen gas to obtain an adsorption-desorption isotherm.

(4) Pretreatment: during testing, 0.6-1.0g of sample is weighed, the sample is loaded (the powdery sample needs to be loaded by a funnel and a platinum wire to ensure that the tube wall has sample powder, the granular sample is directly loaded), the quartz tube is loaded into an experimental instrument (the pretreatment is carried out on the left side, attention is paid to one-to-one correspondence), a nitrogen bottle is opened, the numerical value is set, and the air pressure is reduced to about-0.1 by starting.

(5) After the pretreatment is finished, long-time pressing gas injection is carried out, the pointer is reset to zero, the gas pressure is increased to 120, and then cooling and weight measurement are carried out to calculate the difference value m. It is noted here that the powder sample should be filled with a glass rod to remove dead volume; granular samples were run directly to the next step), quartz tubes were installed, liquid nitrogen (about 2/3 in the container) was added, and surface area software was turned on to begin analyzing the data.

(6) Based on the above, the BET equation was performed to calculate the number of specific surface areas of the analyzed samples.

Second, phase analysis (XRD)

X-ray diffraction (XRD) is a common technique for studying crystal structure and atomic spacing. This technique is based on the principle of constructive interference between monochromatic X-rays and a crystalline sample, which is generated by a cathode ray tube and filtered to produce a monochromatic radiation concentration directed towards the sample. When the conditions satisfy bragg's law (n λ =2 dsin θ), the interaction of incident light with the sample produces constructive interference (and diffracted light), and these diffracted X-rays are then detected, processed and counted. By scanning the sample over 2 ranges, all possible diffraction directions of the crystal lattice should be covered due to the random orientation of the powder material. Since each mineral has a unique set of d-spacings, the different d-spacings allow for the identification of the minerals. All diffraction methods are based on the generation of X-rays in an X-ray tube. These X-rays are directed at the sample and the diffracted rays are collected. The critical part of all diffraction is the angle between the incident and diffracted rays. An X-ray diffractometer consists of three basic elements: an X-ray tube, a sample holder and an X-ray detector.

The geometry of the X-ray diffractometer is such that the sample is rotated at an angle θ in the path of the collimated X-ray beam. An X-ray detector is mounted on the arm to collect diffracted X-rays at an angle of 2 theta. The instrument used to hold the angle and rotate the sample is called a goniometer. For a typical powder pattern, data is collected from about 5 ° to 70 ° using 2 θ, the preset angle in the X-ray scan. X-ray powder diffraction is widely used to identify unknown crystalline substances (e.g. minerals, inorganic compounds). Although XRD possesses many advantages, it still inevitably possesses the following limitations;

1) homogeneous and single-phase materials are most suitable for identifying unknown substances;

2) standard reference documents (d-spacing, hkls) that must have access to inorganic compounds;

3) one tenth of a gram of material that must be ground to a powder;

4) -2% of the sample for the mixed material;

5) for single cell assays, the mode index of the anisometric crystal system is a high angle 'reflection' that complex peak superpositions can occur and deteriorate.

The XRD instrument used in this experiment is Rigaku D/Max-III type A X-ray diffractometer for analyzing Na₂O- Al₂O₃- SiO₂-TiO₂Phase structure of composite nanotubes.

The basic operating environment is as follows;

(1) the tube voltage is 40kV

(2) Step angle of 0.02 °

(3) The tube current is 150mA

(4) The scanning speed is 10 degrees/min

(5) The scanning range 2 theta is 10-90 degrees.

Thirdly, nitrogen absorption and desorption (N2-TPD)

Temperature Programmed Desorption (TPD) is a test method to observe desorption of surface molecules at high surface temperatures. When molecules or atoms come into contact with a surface, they adsorb on the surface, minimizing their energy by forming bonds with the surface. The binding energy varies with the adsorbate and the surface. If the surface is heated, at one of the points the energy transferred to the adsorbed species will cause it to desorb, and the temperature at which this occurs is referred to as the desorption temperature.

TDS can also show what molecules are adsorbed on the surface of the substance, since it can observe the mass of desorbed molecules. Furthermore, TDS recognizes different adsorption conditions for the same molecule by differences between desorption temperatures that desorb molecules at different sites on the surface. TDS also derives the molecular weight adsorbed on a surface from the intensity of the TDS spectral peaks, and the integral of the spectrum represents the total amount of adsorbed material.

Meanwhile, in order to measure TDS, it is required to use a mass spectrometer such as a quadrupole mass spectrometer or a time-of-flight mass spectrometer (TOF) under Ultra High Vacuum (UHV) conditions. The amount of adsorbed molecules is measured by increasing the temperature at a typical heating rate of 2K/s to 10K/s. Several masses can be measured simultaneously by a mass spectrometer and the intensity of each mass is obtained as a function of temperature as a TDS spectrum. The heating process is typically controlled by a PID control algorithm, which may be a computer or a dedicated device.

N₂Temperature Programmed (TPD) desorption is one of the means currently used to test the acidity of catalyst surfaces. In the process, N is increased to a certain temperature by raising the treatment temperature₂Adsorbed on the catalyst surface, and the relationship between the adsorbed amount of N2 and the temperature was measured. From the spectrum, information on the active sites, the strength of the acid, the number of acid sites, and the like of the catalyst can be obtained.

In this experiment, argon gas at high purity was used as a carrier gas at a flow rate of 80ml/min (measured at room temperature), and the apparatus was a self-assembled TPD tester.

(1) Sample loading: 0.1g of the catalyst was weighed in a quartz tube having an inner diameter of 6mm, and quartz wool was used to prevent dispersion of the catalyst.

(2) Pretreatment: to control the continuous purge rate through the catalyst at 80ml/min, the temperature was set to 300 ℃ and treated for 2 hours, then cooled to room temperature, a process supported on high purity argon.

(3) Sample injection: at room temperature, pure N is first introduced₂To adsorb the sample until it is saturated. This process typically lasts 10 minutes. After about 10 minutes, the ammonia was stopped and the temperature was increased to 50 ℃. The sample was then purged with high purity argon to remove pure N due to physical adsorption₂。

(4) Temperature rising desorption: after waiting for the curve to flatten, the temperature was raised to 600 ℃ at a rate of 10 ℃ per min. NH (NH)₃After the desorption was completed, the obtained curve was N of the corresponding sample₂-TPD spectrum. From the obtained TPD spectrum, the acidic surface type of the sample can be obtained by the number of desorption peaks, the peak area indicates the relative intensity of the acidic site on the sample surface, and the peak temperature indicates the position of the acidic site.

Fourth, reduction Performance test (H2-TPR)

The reducing property of the sample can be measured by H₂-a TPR technique. The reducing gas used in this experimental test was H₂The experimental setup is a self-assembling device. The reaction principle is to increase the process temperatureThe concentration of the gas entering the gas column corresponds to the reduction peak. Finally, there is a one-to-one reduction spectrum between temperature and temperature to obtain current information. From the peak temperature and area of the reduction peak in the spectrum we know the corresponding reduction process of the oxide. It is also possible to know the interaction between the oxide and the oxide or between the oxide and the support. By using appropriate software, the peak area size can also be calculated so that the total number of electron transfers during the reaction is known. H used in this experiment₂The TPR instrument is self-assembled with the SP-6801 gas chromatograph.

The basic operating environment is as follows;

(1) the reducing gas used in the experiment was 5% H as reducing gas₂And Ar was used as a diluent gas.

(2) At the start of the experiment, 0.1g of catalyst was weighed into a quartz tube and purged with high purity argon at 50 ℃ for 30 minutes.

(3) After the baseline has settled, the temperature ramp-up process begins.

(4) And obtaining a corresponding TPR map after the process is finished. Among them, hydrogen consumption of the TPR spectrum was calculated using CuO as a standard.

Fifth, Transmission Electron microscopy characterization (TEM)

Transmission Electron Microscopy (TEM) is a microscopic technique in which an electron beam is transmitted through a sample to form an image. The sample is typically an ultra-thin section or suspension on a grid with a thickness of less than 100 nm. As the beam of light passes through the specimen, an image is formed by the interaction of the electrons with the specimen, which is then magnified and focused onto an imaging device, such as a phosphor screen, a photographic film layer, or a sensor such as a charge-coupled device.

The principle is that transmission electron microscopes can image with higher resolution than optical microscopes due to the smaller wavelength of de broglie electrons. This enables the instrument to capture images that are thousands of times smaller than objects in optical microscopes. Transmission electron microscopy is the primary analytical method in physics, chemistry and bioscience. TEMs are mainly used in cancer research, virology and material science as well as in pollution, nanotechnology and semiconductor research.

At lower magnifications, TEM image contrast is formed by differential absorption of electrons by materials due to differences in material composition or thickness. At higher magnification, complex wave interactions can modulate the intensity of the image, requiring specialized analysis of the observed image.

The transmission electron microscope model used herein for the TEM test is an H-7650 transmission electron microscope manufactured by Hitachi, japan.

It should be noted that prior to TEM experiments, the samples needed to be dispersed with absolute ethanol, and then dropped onto a copper mesh and dried before testing.

The basic operating environment is as follows;

(1) filament voltage 3.7 kV

(2) Acceleration voltage of 120 kV

(3) The maximum magnification is 60 ten thousand times

(4) The resolution of this transmission electron microscope was 0.2 nm.

Determination of mass fraction of kasugamycin and kasugamycin

The reagents were as follows:

acetonitrile: carrying out chromatographic purification; water: newly distilling the secondary distilled water; kasugamycin hydrochloride hydrate standard: the mass fraction is known to be more than or equal to 80.0%.

The instrument is as follows:

high performance liquid chromatograph: a variable wavelength ultraviolet detector; a chromatographic data processor; a chromatographic column: 150mm × 3.9mm (id) stainless steel column, Waters symmetrishird RP18, particle size 5 μm; microsyringe: 50 μ L.

The operating conditions of the high performance liquid chromatography are as follows:

mobile phase: 0.5% aqueous sodium lauryl sulfate solution acetonitrile = 80: 20 (v/v) and pH adjusted to 2.5 with phosphoric acid.

Flow rate: 1.0 mL/min; detection wavelength: 210 nm; the temperature is 25 ℃; sample introduction volume: 10 mu L of the solution; retention time: kasugamycin is about 10.7 min.

(4) Computing

Respectively averaging the areas of the kasugamycin in the two-needle sample solution and the two-needle sample solution before and after the sample, wherein the mass fraction omega of the kasugamycin in the sample₁(%) calculated according to formula (1):

in the formula:A ₁-average value of kasugamycin peak area in the standard solution;

A ₂-average value of kasugamycin peak area in the sample solution;

m ₁the mass of the kasugamycin standard in grams (g);

m ₂-mass of sample in grams (g);

omega-mass fraction (%) of kasugamycin in the standards.

Determination of ammonia nitrogen content in heptakasugamycin and kasugamycin wastewater

The commonly used method for analyzing the ammonia nitrogen content comprises a nano reagent method and an electrode determination method, wherein the nano reagent method is adopted in the experiment for analyzing the ammonia nitrogen content in the kasugamycin wastewater after being treated by a conventional membrane and a modified membrane, and the principle is that ammonia in the wastewater reacts with KI and HgI in the nano reagent to generate a colloidal compound with a light red brown color, a spectrophotometer is used for detecting the ammonia nitrogen content at the wavelength of 410-425-plus-one, and the ammonia nitrogen content in the wastewater is obtained by comparing the ammonia nitrogen content with a standard curve. The nano reagent method has the advantages of simple operation, high sensitivity and the like. The specific operation method comprises the following steps:

(1) preparing 500g/ml potassium sodium tartrate solution: 500.0g of the weighed analytically pure potassium sodium tartrate is placed into a beaker and dissolved by using ammonia-free water, and then transferred into a volumetric flask of 1000ml to be fixed in volume by using ammonia-free water.

(2) Preparing a nano reagent: adding 20.0g of weighed analytically pure KI into a No. 1 beaker, and adding 25ml of ammonia-free water for dissolving;a weighed amount of 10.0g of analytically pure HgCl was added to a No. 2 beaker₂Dissolving in about 40ml of hot water; adding weighed 60.0g of analytically pure KOH into a No. 3 beaker, adding about 120ml of ammonia-free water for dissolving, and cooling at room temperature; slowly pouring the solution in the hot No. 2 beaker into the No. 1 beaker, stopping adding when red precipitate appears, and cooling at room temperature; the solution No. 3, which had all been cooled to room temperature, was poured into No. 1 and diluted to 400ml with anhydrous ammonia, to which 0.5ml of HgCl was added₂The solution was allowed to stand for 24 hours and the supernatant was stored in a brown reagent bottle.

(3) Preparation of ammonium Standard solution (1.000 mg/m L): 20.0g of analytically pure NH are weighed out₄Cl in a drying bottle, drying for 2 hours at 100 ℃, accurately weighing 3.1473 NH₄Adding Cl into a dry and clean beaker, adding ammonia-free water to dissolve, transferring to a 1000mL volumetric flask to fix the volume, and obtaining 1.000mg/mL ammonium standard solution.

(4) Drawing a standard curve: 0.00mL, 0.50mL, 1.00mL, 3.00mL, 5.00mL, 7.00mL and 10.00mL of ammonium standard solution are respectively added into 7 50mL colorimetric tubes, and ammonia-free water is added to fix the volume to the scale mark. Then, 1.0mL of the prepared potassium sodium tartrate solution of 500g/mL is added, and after fully mixing, 1.5mL of the prepared sodium reagent is added and shaken up. After 10 minutes, the wavelength of the spectrophotometer was adjusted to 420nm, the cell difference was first eliminated using a 2cm cuvette, and the absorbance values were measured separately and the results used to develop a standard curve.

(5) Calculating the ammonia nitrogen content: and (3) subtracting the absorbance value of a blank test from the absorbance value measured by the wastewater sample, and then finding out the ammonia nitrogen content (mg) from the standard curve, wherein the calculation formula is as follows:

in the formula:

m is the tested ammonia nitrogen amount in mg on a calibration curve;

v-water sample volume, m L.

Eighthly, determination of chemical oxygen demand (CODCr)

Chemical oxygen demand refers to various reducing substances (mainly organic substances) and strong oxidant (K) in 1L water under given conditions₂Cr₂O₇) The amount of oxidant consumed during the reaction corresponds to the amount of oxygen, expressed in mg/L. The COD value of each fermentation liquid is measured by a potassium dichromate method in the experiment.

(1) The test principle is as follows: organic substances are oxidized by potassium dichromate under acidic condition, Ag is used as catalyst for the reaction^[22]. The amount of potassium dichromate consumed by oxidizing organic matters can be known by titrating the residual potassium dichromate, so that the COD of the water sample can be calculated.

(2) Reagents and instrumentation: a potassium dichromate standard solution (C0: 0.2500 mol/L); a ferron indicator; standard solution of ferrous ammonium sulfate (C =0.1008 mol/L); concentrated sulfuric acid; sulfuric acid-silver sulfate solution; mercury sulfate; grinding a flask and a reflux condenser pipe; pipettes and burettes, etc.

(3) The method comprises the following operation steps:

firstly, sucking 20mL of uniformly mixed water sample (or diluting the water sample to 20mL by using a proper amount) and placing the water sample into a ground flask, accurately adding 10mL of potassium dichromate standard solution, slowly adding 30mL of silver sulfate monosulfate solution, slightly shaking the flask to uniformly mix the solution, and adding about 4 glass beads;

connecting a ground reflux condenser, heating and refluxing for 2 hours, and calculating the time when the solution begins to boil;

thirdly, after cooling, washing the wall of the condenser tube by using 90mL of distilled water;

fourthly, after the solution is cooled again, 3 drops of ferron indicator is added, the solution is titrated by ammonium ferrous sulfate standard solution, the titration end point is obtained when the color of the solution is changed from orange to reddish brown from blue green, and the dosage (V) of the ammonium ferrous sulfate standard solution is recorded₁)；

Fifthly, 20mL of distilled water is taken and a blank experiment is carried out according to the same operation steps. Recording the dosage (V) of the standard solution of ferrous ammonium sulfate when titrating blank₀)。

(4) Calculating the formula:

in the formula: v₀-amount of ferrous ammonium sulfate consumed (mL) by the blank;

V₁-the amount (mL) of ammonium ferrous sulfate consumed by a water sample;

V₂-water sample volume (mL);

c is the concentration (mol/L) of the ferrous ammonium sulfate solution;

。

the COD chemical analyzer used in the experiment is used for analyzing the COD of the rhodopseudomonas palustris by a potassium dichromate method. The COD of the solution was read by absorbance. The instrument operation method is as follows:

a plurality of reaction tubes are prepared, washed with deionized water and dried for later use. 0.05g of mercuric sulfate is added into each reaction tube to remove halogen ions in water, so that the interference on an instrument when the absorbance is read is avoided. Then, 2mL of the sample to be tested was added to each reaction tube, and one of the reaction tubes was added with deionized water as a blank solution.

Example 1

Mixing a certain volume of 10mol/L sodium hydroxide solution with a certain amount of Na₂O-Al₂O₃-SiO₂-TiO₂The composite nano powder and CTAB powder are fully mixed. The mixture was placed in a beaker and sonicated for 24min, then the mixture was poured into the reactor. Placing the mixture in a muffle furnace, reacting at a certain temperature of 250 ℃ for a period of time, taking out the mixture, naturally cooling the mixture, depositing the solid matter on the cup bottom, repeatedly washing the mixture by using deionized water, cutting and filtering the mixture, standing the mixture for 3 hours, leaving the solid matter deposited on the cup bottom, and then washing the sample by using the deionized water until the pH value is close to 7. Concentrated nitric acid was poured into a clean reactor and the reactor was placed in a steel sheath. Taking out and cooling, recovering concentrated nitric acid, cleaning the reaction kettle, putting the reaction kettle into an ultrasonic device for ultrasonic treatment for 30 minutes, repeatedly cleaning the reaction kettle with distilled water, and filling the kettle with distilled water and putting the kettle back. In which the reaction was carried out in a muffle furnace at 250 ℃ for 15, 22, 29 and 36h, see FIGS. 1, 2 and FIGSFIG. 1 shows that sample No. 1 was prepared at a reaction time of 29 hours, and TEM images show that sample No. 1 had some flaky crystal fragments but had a partially tubular crystal structure, and thus Na was presumed₂O-Al₂O₃-SiO₂-TiO₂The nanotubes have been substantially shaped, which is the experimental temperature for compounding the temperature required for titanium nanotube formation. Sample No. 4 was prepared at a reaction time of 15 hours and all products were in the form of platelets. Sample No. 5 was prepared at a reaction time of 22h and it can be seen that the product already possessed a tendency to curl. Sample No. 6 was prepared at a reaction time of 36h, and the resulting product was all in the form of a flocculent or powder. FIG. 2 is an XRD image obtained for the No. 1 sample as the tube region, showing diffraction peaks and Na at diffraction angles₂O-Al₂O₃-SiO₂-TiO₂The peaks were all identical. No hetero-peaks appeared, indicating that all samples were Na₂O-Al₂O₃-SiO₂-TiO₂

Na of sample No. 1₂O-Al₂O₃-SiO₂-TiO₂Transmission pattern of different points measured in the substance region, in the four images, it can be observed that the tubular crystalline material of sample No. 1 prepared by hydrothermal reaction was hollow for 29 hours. Can basically confirm that Na exists in the sample No. 1₂O-Al₂O₃-SiO₂-TiO₂Titanium nanotubes formed, and it was speculated that Na having a hollow tubular morphology but with inclusion of partially crystalline fragments could be produced at a hydrothermal reaction time of 29h₂O-Al₂O₃-SiO₂-TiO₂Composite titanium nanotubes.

Example 2

Preparation of Na having different molar ratios of Al to Ti₂O-Al₂O₃-SiO₂-TiO₂Nanotube and method of manufacturing the same

(1) Solution A: 20mL of absolute ethyl alcohol, a certain amount of silica sol and a certain amount of distilled water are measured, placed in a small beaker and mixed uniformly under magnetic stirring.

(2) And B, liquid B: a mixture of 17mL of butyl titanate to 20mL of absolute ethanol and 10mL of glacial acetic acid was measured and placed in a 250mL beaker. According to the Al/Ti ratio of 1: 1. aluminum nitrate is weighed according to the proportion of 1.2:1 and 1.5:1 and ultrasonically dissolved in 20mL of absolute ethyl alcohol, and the two solutions are mixed and uniformly mixed under magnetic stirring.

(3) The beaker containing solution B was kept in a magnetically stirred water bath, and solution A was added dropwise to solution B for 30 minutes at room temperature using a separatory funnel. The reaction was then started by setting the water bath temperature to 75 ℃. After the transparent sol became a xerogel, it was placed in a drying oven, dried at 110 ℃ for 10 hours, and the dried sample was ground. Calcining at 500 deg.C for 3 hr to obtain sol-gel prepared carrier.

(4) A10 mol/L sodium hydroxide solution was thoroughly mixed with the composite nanopowder and CTAB powder, and the mixture was placed in a beaker. Ultrasonic treatment is carried out for 0.4 hour, then the mixture is poured into a reactor and placed in a muffle furnace, the reaction temperature is 250 ℃, after reaction 29, naturally cooled solid matters are taken out and deposited on the bottom of a cup, after repeated washing with deionized water, the deposit is kept stand for 3 hours and then washed with the deionized water until the pH value reaches about 7. The resulting solution was treated with 0.1mol/L nitric acid to wash the solid precipitate. Heated and stirred for 1 hour, and left to centrifuge. A certain amount of absolute ethanol was added to the filtered solid precipitate, thoroughly dried at 150 c, and calcined at 550 c for 3 hours to obtain a white powdery product. Is Na₂O-Al₂O₃-SiO₂-TiO₂A nanotube. Wherein the molar ratio of Al to Ti is 1:1, 1.2:1 and 1.5:1 respectively. Specific results as shown in fig. 4, 5 and 6, it can be observed from fig. 4 that the product obtained at a molar ratio of Al to Ti of 1:1 is a part of nanotubes and plate-like crystal pieces. From FIG. 5, it can be observed that the product obtained at a molar ratio of Al to Ti of 1.2:1 possesses a portion of Na which is clearly visible₂O-Al₂O₃-SiO₂-TiO₂The nanotubes, but still with a small amount of plate-like crystalline debris, the plate-like debris area is reduced from that shown in fig. 3.1, however, a non-uniform distribution of nanotubes can be observed in the tube area. From FIG. 6 it can be observed that the molar ratio of Al to Ti is 1.5, in the first case obtaining a tube with hollownessOpen ended and very homogeneous form of Na₂O-Al₂O₃-SiO₂-TiO₂A nanotube. The tube formation rate is close to 100% and is about several hundred nanometers long.

Example 3

Al/Ti molar ratios of 1:1, 1.2:1, 1.5:1, respectively, were prepared according to example 2, and their specific surface areas are given in Table 1 below.

TABLE 1 specific surface area of samples prepared at different Al/Ti molar ratios

The hydrothermal reaction gave a sample having a specific surface area of 238.5m at an Al/Ti molar ratio of 1:1²(ii)/g; the hydrothermal reaction gave a specific surface area of 254.2m for the sample at an Al/Ti molar ratio of 1.2:1²(ii)/g; the hydrothermal reaction gave a sample having a specific surface area of 365.1m at an Al/Ti molar ratio of 1.5:1²(ii) in terms of/g. The molar ratio of Al to Ti is in a positive correlation trend with the specific surface area. The sample prepared with an Al/Ti molar ratio of 1.5:1 had the best morphology, the longest tube length, and the largest specific surface area. The specific surface area of the prepared sample is reduced when the molar ratio of Al to Ti is 1:1 or 1.2:1, which is probably because the morphology of the product is changed due to the molar ratio of Al to Ti, thereby affecting the size of the specific surface area.

Example 4

Mixing a certain volume of 10mol/L sodium hydroxide solution with a certain amount of Na₂O-Al₂O₃-SiO₂-TiO₂The composite nano powder and CTAB powder are fully mixed (wherein the molar ratio of Al to Ti is 1:1, 1.2:1 and 1.5:1 respectively). The mixture was placed in a beaker and sonicated for 24min, then the mixture was poured into the reactor. And placing the mixture in a muffle furnace to react for 29h at 150 ℃, taking out the mixture, naturally cooling the mixture, depositing the solid matter on the cup bottom, repeatedly washing the mixture by using deionized water, cutting and filtering the mixture, standing the mixture for 3 h, leaving the solid matter deposited on the cup bottom, and then washing the sample by using the deionized water until the pH value is close to 7. Concentrated nitric acid was poured into a clean reactor and the reactor was placed in a steel sheath. Taking out the coldHowever, the concentrated nitric acid is recovered, the reaction kettle is cleaned, the reaction kettle is placed into an ultrasonic device for ultrasonic treatment for 30 minutes, the reaction kettle is repeatedly cleaned by distilled water, and the kettle is filled with the distilled water and is placed back. Na (Na)₂O-Al₂O₃-SiO₂-TiO₂Nanotube N₂The adsorption and desorption isotherms are shown in FIGS. 7, 8 and 9. As can be seen from FIGS. 7, 8 and 9, the Na reacted for 29 hours at 150 ℃ was obtained from the composite powders with different Al/Ti molar ratios₂O-Al₂O₃-SiO₂-TiO₂Nanotube N₂Adsorption and desorption isotherms, it can be seen from FIG. 7 that all four samples begin at P/P₀At 0.43 a hysteresis loop occurs. The hysteresis phenomenon at this time is caused by the capillary condensation phenomenon of the porous adsorbent. Isotherms for Al/Ti molar ratios of 1:1, 1.2:1, 1.5:1, respectively, according to the IUPAC classification are similar to the IV adsorption isotherms in the IUPAC classification. The three products are typical mesoporous structures and belong to mesoporous materials which adsorb a single layer under lower relative pressure. As can be seen from FIG. 10, the molar ratio of Al/Ti was 1:1, and the amount of adsorbed hydrogen was larger than the molar ratio of Al/Ti, 1.2:1 and 1.5:1, respectively, in the initial stage. This is due to the Al/Ti molar ratio of sample 1 resulting in Na₂O-Al₂O₃-SiO₂-TiO₂The fact that the tube formation of the composite titanium nanotube is inefficient. The shape of the tube is not good, a part of crystal fragments which are not formed into the tube exist, and a large number of gaps exist, so that a large amount of hydrogen can be adsorbed in the early stage. When the relative pressure is more than or equal to 0.8, the molar ratio of Al to Ti is 1.2:1, and the molar ratio of Al to Ti is 1.5: the sample No. 1 has the highest tube forming efficiency and the best appearance due to the optimal Al/Ti molar ratio, and the storage capacity in the later period is 299 cc/g at most.

Example 5

The kasugamycin wastewater influent COD is 6000-plus 8000mg/L, ammonia nitrogen 275-plus 325mg/L, and is treated by an adjusting tank, a sedimentation tank, a UASB, a denitrification tank, a nitrification tank, a secondary sedimentation tank and an MBR, wherein the MBR effluent quality COD is 600-plus 625mg/L, the ammonia nitrogen is 100-plus 125mg/L, and the molar ratio of Al/Ti is 1: 1. 1.2:1 and 1.5:1 of Na₂O-Al₂O₃-SiO₂-TiO₂Treating MBR effluent in a nanotube apparatus while the MBR membrane effluent is charged with different Al/Ti molar ratios Na₂O-Al₂O₃-SiO₂-TiO₂The nanometer tube is used for further treating MBR effluent, an ultraviolet lamp is arranged in the device, in order to further determine the effect of the MBR effluent after being treated by the device, the light intensity of the ultraviolet lamp is 3000Lx, the retention time of the MBR effluent in the device is respectively 15 min, 25 min, 35 min, 45min, 55 min and 65min, and the COD removal rate of the MBR effluent is shown in Table 2.1

TABLE 2.1 COD removal Rate

TABLE 2.2 Ammonia nitrogen removal

As can be seen from table 2.1, Al/Ti = 1.5: the 1 nanotube has the highest COD removal rate on MBR effluent, and then Al/Ti = 1.2:1 nanotube, Al/Ti = 1:1 nanotube and Na₂O-Al₂O₃-SiO₂-TiO₂The powder of (4). Wherein Al/Ti = 1.5: the COD removal of the 1 nanotubes on the MBR effluent was 95%, from table 2.2 the ammonia nitrogen removal was also Al/Ti = 1.5:1 nanotube, Na₂O-Al₂O₃-SiO₂-TiO₂The removal rate of the powder to the ammonia nitrogen is 75 percent.

Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims

1. An application of a nanotube material in kasugamycin wastewater treatment is characterized in that,the nanotube material has a composition of Na₂O-Al₂O₃-SiO₂-TiO₂Wherein the molar ratio of Al/Ti is 1.5: 1.

2. Use according to claim 1, for the production of Na₂O-Al₂O₃-SiO₂-TiO₂Preparing Na from the nanotube material₂O-Al₂O₃-SiO₂-TiO₂The powder of (4).

3. Use according to any one of claims 1 to 2 to produce Na₂O-Al₂O₃-SiO₂-TiO₂The nano tube material is used for treating the effluent of the kasugamycin wastewater which is treated by combining a biological membrane and an MBR (membrane bioreactor) membrane again, wherein Na of the nano tube₂O-Al₂O₃-SiO₂-TiO₂The water retention time is 45min, and the illumination is 3000 Lx.