CN113818152B - Preparation method and application of biomass carbon nanofiber membrane loaded with microorganisms - Google Patents

Preparation method and application of biomass carbon nanofiber membrane loaded with microorganisms Download PDF

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CN113818152B
CN113818152B CN202111130611.4A CN202111130611A CN113818152B CN 113818152 B CN113818152 B CN 113818152B CN 202111130611 A CN202111130611 A CN 202111130611A CN 113818152 B CN113818152 B CN 113818152B
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nanofiber membrane
solution
biomass charcoal
microorganisms
biomass
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CN113818152A (en
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王远鹏
陈俊洁
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Xiamen University
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/34—Biological treatment of water, waste water, or sewage characterised by the microorganisms used
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
    • C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/16—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from products of vegetable origin or derivatives thereof, e.g. from cellulose acetate
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4282—Addition polymers
    • D04H1/43—Acrylonitrile series
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D06C7/04—Carbonising or oxidising
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic System
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Abstract

The invention discloses a preparation method and application of a biomass charcoal nanofiber membrane loaded with microorganisms, which comprises the steps of soaking a nanofiber membrane added with straw biomass charcoal and prepared by electrostatic spinning in a liquid culture medium inoculated with Hertzia arsenica (Aureoxidans), culturing at 27-29 ℃ until the logarithmic growth phase, and then carrying out heat preservation culture for 9-11h to ensure that the Hertzia arsenica (Aureoxidans) in the culture solution is fully adhered to the biomass charcoal nanofiber membrane, thus obtaining the biomass charcoal nanofiber membrane loaded with microorganisms. The biomass charcoal nanofiber membrane loaded with microorganisms prepared by the invention shows good As (III) biocatalysis effect and recycling performance in five circulating reaction periods, is a good microorganism carrier, and the oxidation catalysis efficiency of the microorganism composite membrane on As (III) is gradually improved along with the increase of the circulating times.

Description

Preparation method and application of biomass carbon nanofiber membrane loaded with microorganisms
Technical Field
The invention belongs to the technical field of microbial composite materials, and particularly relates to a preparation method and application of a biomass carbon nanofiber membrane loaded with microorganisms.
Background
With the increasing population of the world and the advancement of urban industrialization, water resources are increasingly polluted, and a large amount of arsenic-containing wastewater is discharged into the environment. Arsenic (As) is a primary carcinogen that is toxic to humans and other living organisms, enters the human body through the respiratory tract and skin, and is rapidly distributed throughout the body through the blood, and most of it binds to hemoglobin lipoproteins, causing skin, reproductive, cancer, neurological and cardiovascular diseases. Arsenic in the environment is predominantly AsO 2 - (trivalent) and AsO 4 3- Two soluble (pentavalent) forms exist, in which As (III) is 60-100 times more toxic than As (V) and is more mobile and water soluble.
The removal of arsenic from wastewater is a worldwide environmental problem and the existing arsenic removal techniques reported in the prior art can be categorized into the following main categories: oxidation, precipitation, coagulation, membrane separation, ion exchange, biological treatment systems and adsorption. In some cases, these arsenic removal techniques may be used in combination to maximize the removal of arsenic compounds from the environmental system. The composite materials such as natural minerals, metal oxide nanoparticles, graphene oxide and carbon base are widely applied to adsorption removal of arsenic in wastewater due to high specific surface area and good adsorption capacity. However, since As (III) is not easily removed by an adsorbent having a negatively charged surface, it is usually necessary to pre-oxidize As (III) to As (V). However, the rate of oxidation of As (III) to As (V) by oxygen is very slow, while chemical oxidants tend to be expensive and may also generate secondary contaminants. As (III) oxidation by arsenic oxidizing bacteria is therefore considered a cheaper and environmentally friendly option. It has been found that some bacteria such As Bacillus, proteus, pseudomonas, rhizobium and Micrococcus have a certain ability to oxidatively fix As (III).
However, in the practical application process, the microorganism is difficult to enrich and recycle, and the disadvantage of secondary biological pollution to the environment is limited to be used for the treatment of environmental problems. Therefore, it is a hot spot of current research to load microorganisms into a carrier medium in an immobilized form or form a biofilm with a certain thickness on a substrate material to achieve scientific recycling. CN 113248004A discloses a preparation method of a sewage treatment microbial carrier, which is characterized in that microbes are embedded into prepared polyvinyl alcohol resin pellets and are subjected to a series of modification treatments, and the carrier is applied to sewage treatment. CN 112897705A discloses a preparation method and application of multilayer graphene oxide modified microbial carrier, wherein a silane coupling agent is used for carrying out surface function modification on a polyurethane carrier, and multilayer graphene oxide is grafted on the surface of the carrier, so that the biological loading capacity of the carrier is improved.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a biomass charcoal nanofiber membrane loaded with microorganisms.
The invention also aims to provide application of the biomass charcoal nanofiber membrane loaded with the microorganisms.
The technical scheme of the invention is as follows:
a preparation method of a biomass charcoal nanofiber membrane loaded with microorganisms comprises the following steps:
(1) Cleaning and crushing waste biomass straws, sieving the straws with a 200-mesh sieve, and drying the straws;
(2) Slowly adding concentrated sulfuric acid into the material obtained in the step (1), fully stirring and mixing, then slowly adding hydrogen peroxide under an ice bath condition, stirring while adding to prevent liquid from splashing, fully carbonizing the material, cooling to room temperature, fully washing with deionized water to be nearly neutral, centrifuging to obtain a precipitate, and then drying to obtain straw biomass charcoal;
(3) Stirring and mixing polyacrylonitrile, the straw biomass charcoal and N, N-dimethylformamide at 55-65 ℃, and then carrying out ultrasonic treatment to obtain a spinning solution;
(4) Carrying out electrostatic spinning on the spinning solution to obtain a nanofiber membrane;
(5) Heating the nanofiber membrane to 260-280 ℃ under the condition of keeping proper tension, preserving heat and semi-carbonizing for 1.5-2.5h to obtain a precursor product;
(6) Cooling the precursor product to room temperature, cutting and molding, heating to 790-810 ℃ in a nitrogen atmosphere, preserving heat and carbonizing for 1.5-2.5h;
(7) Activating the material obtained in the step (6) with a KOH solution for 10-12h at room temperature, then washing the material to be neutral with deionized water, and drying the material to obtain a biomass carbon nanofiber membrane;
(8) And soaking the biomass carbon nanofiber membrane in a liquid culture medium inoculated with arsenic-oxidizing Hertzia Hertziae, culturing at 27-29 ℃ until the logarithmic growth phase, and then performing heat preservation culture for 9-11h to ensure that the arsenic-oxidizing Hertzia Hertziae in the culture solution is fully adhered to the biomass carbon nanofiber membrane, thus obtaining the biomass carbon nanofiber membrane loaded with the microorganisms.
In a preferred embodiment of the present invention, in the step (2), the ratio of the material obtained in the step (1), concentrated sulfuric acid and hydrogen peroxide is 28-31g:190-210mL:60-70mL.
Further preferably, in the step (2), the drying temperature is 77-81 ℃ and the drying time is 45-50h.
In a preferred embodiment of the present invention, in the step (3), the concentration of the N, N-dimethylformamide is 98%, and the Mr of the polyacrylonitrile is 150,000.
Further preferably, the ratio of polyacrylonitrile to the straw biomass charcoal to N, N-dimethylformamide is 0.2-0.6g:2.0g:20mL.
More preferably, the ratio of the polyacrylonitrile to the straw biomass charcoal to the N, N-dimethylformamide is 0.4g:2.0g:20mL.
In a preferred embodiment of the present invention, the specific process of the electrostatic spinning in the step (4) is: slowly sucking the spinning solution into a 20mL syringe, wherein the type of a metal needle is 20, and the inner diameter of the metal needle is 0.6mm; setting the distance between the injector and the receiving roller to be 16cm, the injection speed to be 0.1mm/min and the rotating speed of the receiving roller to be 100rpm; applying a positive voltage of 17kV to a needle point, and applying a negative voltage of 3kV to a receiving roller to carry out electrostatic spinning; setting the electrospinning time to be 12h, and keeping the temperature and the humidity in a box body of the electrostatic spinning equipment at 35 ℃ and 40% respectively; after spinning is finished, the membrane is gently peeled off and placed in a vacuum oven, and the membrane is dried for 12 hours at the temperature of 60 ℃ to remove residual solvent on the surface.
In a preferred embodiment of the present invention, the method for preparing the liquid medium in the step (8) comprises:
A. the following three solutions were prepared:
solution A:81.2mM MgSO 4 ·7H 2 O，187mM NH 4 Cl，70mM Na 2 SO 4 ，0.574mM K 2 HPO 4 ， 4.57mM CaCl 2 ·2H 2 O,446mM sodium lactate,
solution B:4.8mM FeSO 4 ·7H 2 O，
Solution C:950mM NaHCO 3 ；
B. Solution A was sterilized at 121 ℃ for 20min, and solutions B and C were sterile filtered through a 0.22 μm pore size filter.
C. Preparing a liquid culture medium according to the following proportion: mixing 100mL of the solution A,2.5mL of the solution B and 10mL of the solution C, supplementing the mixture to 1L with water, and adjusting the pH value to 7.2 to obtain the liquid culture medium.
The other technical scheme of the invention is as follows:
the biomass charcoal nanofiber membrane loaded with microorganisms prepared by the preparation method is applied to removal of As (III) in environmental water.
A method for removing As (III) in environmental water comprises the step of using the biomass charcoal nanofiber membrane loaded with microorganisms prepared by the preparation method.
The invention has the beneficial effects that:
1. the biomass carbon nanofiber membrane disclosed by the invention is good in comprehensive mechanical property, has certain flexibility, is suitable for being applied to a sewage treatment system, and due to the fact that waste biomass straws are selected as raw materials, the production cost is reduced, the use of chemicals is reduced, and the purposes of environmental friendliness and 'treatment of waste with waste' are achieved.
2. According to the invention, the biomass carbon is added into the electrospun carbon nanofiber, and the KOH is used for carrying out surface activation modification, so that the prepared composite membrane material has a very large specific surface area, high roughness and more micropores, and the added biomass carbon is prepared by chemical oxidation, so that the composite membrane is endowed with good hydrophilicity and biocompatibility, a sufficient space is provided for the enrichment and growth of microorganisms, and a large number of attached active sites are also provided.
3. The biomass carbon nanofiber membrane loaded with microorganisms prepared by the invention shows good As (III) biocatalysis effect and recycling performance in five cycle reaction periods, is a good microorganism carrier, and the oxidation catalysis efficiency of the microorganism composite membrane on As (III) is gradually improved along with the increase of cycle times.
Drawings
Fig. 1 is a schematic flow chart of a preparation process of a biomass charcoal nanofiber membrane loaded with microorganisms in example 1 of the present invention.
FIG. 2 is a comparison diagram of a scanning electron microscope and a transmission electron microscope of biomass charcoal nanofiber membranes with different amounts of straw biochar added in example 2 of the invention.
FIG. 3 is a comparison graph of stress-strain curves and Young's modulus curves of biomass charcoal nanofiber membranes with different amounts of straw biochar added in example 3 of the present invention.
FIG. 4 is a comparison graph of Fourier transform infrared spectra before and after the biomass charcoal nanofiber membrane loaded with microorganisms at different amounts of straw biochar in example 4 of the present invention.
FIG. 5 is a comparison graph of the microorganism attachment amounts of the microorganism-loaded biomass charcoal nanofiber membrane in example 5 of the present invention with different amounts of straw biochar added.
Fig. 6 is a comparison graph of the cycle performance test results of the biomass charcoal nanofiber membrane loaded with microorganisms at different additive amounts of straw biochar in example 6 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated and described by the following detailed description in conjunction with the accompanying drawings.
The straw used in the invention is purchased from Beijing Soilebao Tech & ltd. Other drugs for use in the present invention are available from sigma aldrich trade ltd. The microorganism Herminimonas anseniumoxidans (ULPAs 1, DSM 17148) used in the present invention is commercially available from German Collection of microorganisms and cell cultures DSMZ-German, germany.
Example 1
As shown in fig. 1, a preparation method of a biomass charcoal nanofiber membrane loaded with microorganisms comprises the following steps:
(1) Selecting waste biomass straws as a raw material, cleaning, crushing, sieving by a 200-mesh sieve, and drying at 80 ℃;
(2) And (2) slowly adding 200mL of concentrated sulfuric acid into 30g of the material obtained in the step (1), stirring for 20-30min, and then slowly adding 67mL of hydrogen peroxide into the material under an ice bath condition according to the volume ratio of the concentrated sulfuric acid to the hydrogen peroxide being 3. Cooling to room temperature, adding deionized water, washing for several times, centrifuging when the washing liquid is nearly neutral, separating precipitate, and drying at 80 deg.C for 48 hr to obtain straw biomass charcoal;
(3) Adding straw biochar (0 g, 0.2g, 0.4g, and 0.6 g), 2.0g polyacrylonitrile (Mr =150,000) to 20mL of N, N-dimethylformamide (98%), magnetically stirring for 10h in a water bath at 60 ℃, and finally sonicating for 2h to obtain a spinning solution;
(4) Performing electrostatic spinning on the spinning solution to obtain a nanofiber membrane, which specifically comprises the following steps: the spinning solution was slowly drawn into a 20mL syringe with a metal needle type of 20 gauge (inner diameter 0.6 mm). The distance between the injector and the receiving roller is set to be 16cm, the injection speed is 0.1mm/min, and the rotating speed of the receiving roller is 100rpm. A positive voltage of 17kV was applied to the needlepoint, and a negative voltage of 3kV was applied to the receiving roller to carry out electrospinning. To ensure similar nanofiber film thickness obtained on the receiving roll each time, the electrospinning time was set to 12h. In addition, the temperature and humidity in the box of the electrostatic spinning equipment (SS-1334H, yongkang Leye science and technology development Co., ltd., beijing) were kept at about 35 ℃ and 40%, respectively. After spinning is finished, the membrane is slightly removed and placed in a vacuum oven, and the membrane is dried for 12 hours at the temperature of 60 ℃ to remove residual solvent on the surface;
(5) Fixedly placing four corners of the nanofiber membrane into a muffle furnace to keep certain tension, heating the nanofiber membrane from room temperature to 260 ℃ at the heating rate of 1 ℃/min in the air atmosphere, and keeping the nanofiber membrane for 2 hours to perform semi-carbonization (pre-oxidation) to obtain a precursor product;
(6) Cooling the precursor product to room temperature, carefully cutting into 8cm × 1.5cm rectangles, and loading into porcelain boatPlacing into a tube furnace at N 2 Raising the temperature from room temperature to 800 ℃ at the temperature raising rate of 5 ℃/min under the atmosphere and keeping for 2h for carbonization;
(7) Cooling the material obtained in the step (6) to room temperature, immersing the material into 2M/L KOH solution for activation for 12h, taking out the material, washing the material to be neutral by using deionized water, and drying the material at 60 ℃ for 6h to obtain a biomass carbon nanofiber membrane (the amount of the added straw biochar is BACF-0, BACF-0.2, BACF-0.4 and BACF-0.6 in sequence);
(8) Soaking the biomass charcoal nanofiber membrane in a liquid culture medium inoculated with Hertzia arsenic oxide to prepare the biomass charcoal nanofiber membrane loaded with the microorganisms, wherein the steps are as follows:
I. herminimonas arsenica (Herminimunas arsenicoxydans) (ULPAs 1, DSM 17148) was purchased from DSMZ-Germany, microorganisms and cell culture, inc.
II. A chemically-defined liquid medium was prepared by mixing the following three solutions: solution A:81.2mM MgSO 4 ·7H 2 O(Sigma)，187mM NH 4 Cl(Merck，99.8％)，70mM Na 2 SO 4 (Prolabo，99％)， 0.574mM K 2 HPO 4 (Prolabo，97％)，4.57mM CaCl 2 ·2H 2 O (Merck, 99.5%), 446mM sodium lactate (Sigma, 98%). Solution B:4.8mM FeSO 4 ·7H 2 O (Prolabo, 99%). Solution C:950mM NaHCO 3 (Prolabo, 99.5%). Solution A was sterilized by high temperature and high pressure (121 ℃,20 min), and solutions B and C were sterilized by filtration through a filter having a pore size of 0.22. Mu.m. Then 100mL of solution A,2.5mL of solution B and 10mL of solution C were mixed, made up to 1L with water, and the pH was adjusted to 7.2 to obtain a liquid medium. All solutions were prepared with deionized water previously sterilized by autoclaving.
III, taking the bacterial liquid from a super clean bench, adding the bacterial liquid into 50mL of sterilized liquid culture medium, uniformly mixing, adding two sheets of prepared biomass activated carbon nanofiber membranes with the diameters of 8cm multiplied by 1.5cm, and putting the biomass activated carbon nanofiber membranes into a shaker at 28 ℃ and 100rpm for culture. When the strain reaches the logarithmic phase of growth, the strain is transferred into an incubator at 28 ℃ for continuous culture for 10 hours, so that the strain in the culture solution is deposited and adhered to the surface of the composite membrane as much as possible. And taking out to obtain the final biomass carbon nanofiber membrane loaded with the microorganisms.
Example 2
And (3) observing the biomass charcoal nanofiber membranes with different addition amounts of the straw biochar prepared in the example 1 by a scanning electron microscope and a transmission electron microscope.
Preparing a sample by a scanning electron microscope: adhering a sample on a sample observation platform of a scanning electron microscope by using conductive adhesive, then spraying platinum on the sample for pretreatment for 30s, vacuumizing under the voltage of 15kV, and observing the microscopic morphology of the sample.
Preparing a sample by a transmission electron microscope: dissolving a small amount of sample powder in alcohol, carrying out ultrasonic treatment on the sample solution for 2h, dripping a small amount of sample solution on the pretreated copper mesh by using a rubber head dropper, volatilizing and drying the alcohol, and storing the sample copper mesh in a dryer for later use.
As a result, as shown in fig. 2, many pores are generated on the surface and inside of the activated nanofiber, the specific surface area of the material is increased, and the material has certain flexibility; along with the increase of the adding amount of the straw biochar, the roughness of the nanofiber is improved. When the addition amount reaches 0.4g, the surface modification is most uniform and is in a bead string shape, and the continuous addition can cause fiber adhesion and thickening of the diameter.
Example 3
The biomass charcoal nanofiber membranes with different addition amounts of the straw biochar prepared by the method of example 1 are taken as experimental samples, the experimental samples are placed under a mold and pressed into a barbell shape with the diameter of 3 x 10mm by a model machine (as shown in figure 3 b), and a tensile strain machine is used for testing. Before testing, the thickness of a sample measured by a vernier caliper is input into a testing method of a system, the sample to be tested is fixed in a clamping groove of a tension strain machine, the position of a sensor is adjusted to enable stress and displacement to return to zero, and finally the sample is stretched at the speed of 0.1 mm/sec. As shown in fig. 3a, as the content of the straw biochar increases, the breaking tensile strain of the composite membrane increases, and the breaking tensile strength decreases; calculating the Young modulus of the material to be gradually reduced (as shown in FIG. 3 b) through a formula, wherein the Young modulus is represented by reduction of rigidity and enhancement of flexibility of the material; the rupture tensile strain and the strength of the material can obtain the BACF-0.2 and the BACF-0.4 which have better comprehensive mechanical properties and are suitable for a microorganism liquid culture system.
Example 4
Materials formed before and after the biomass charcoal nanofiber membrane loaded with microorganisms and prepared by the method of example 1 and with different addition amounts of the straw biochar are taken as experimental samples, and a Fourier transform infrared spectrometer is adopted for testing. The samples are all prepared by adopting a KBr tabletting method, and the specific operation is that the mass ratio of the sample to be detected to the spectral pure KBr is 1:100, grinding and mixing in an agate mortar, and tabletting to prepare a sample. The test is carried out at room temperature, and the wavelength range of the instrument is 4000-500cm -1 . As shown in fig. 4, compared with the biomass carbon nanofiber membrane before loading, the surface hydrophilicity and electropositive functional groups (amino and aldehyde groups) of each biomass carbon nanofiber membrane after loading appear, which is beneficial for further adhesion of bacteria; and the peak intensity of the oxygen-containing functional groups (hydroxyl, carboxyl and the like) after loading is obviously enhanced, which shows that the oxidability of the biomass carbon nanofiber membrane is enhanced.
Example 5
The biomass carbon nanofiber membranes loaded with microorganisms and prepared by the method of example 1 and with different amounts of straw biochar added are taken as experimental samples, and the biomass attached to the membranes is measured by using a BCA method. As shown in figure 5, the biomass loaded on the surface of the material shows a trend of increasing firstly and then decreasing with the increase of the adding amount of the straw biochar, and when the adding amount of the straw biochar is 0.4g, the highest biomass loaded on the surface of the material reaches 47.43 mu g/cm in an experimental group 2 。
Example 6
Taking biomass charcoal nanofiber membranes loaded with microorganisms with different amounts of straw biochar prepared by the method in example 1 As experimental samples, putting the last microbial composite membrane into a fresh culture medium containing 50mg/L of As (III) after 72h of circulation every time, repeating the circulation test in such a way, and detecting the concentration of As (III) in the culture medium by adopting an atomic fluorescence spectroscopy-liquid chromatography combined method every 12h or so. As shown in fig. 6, each microbial composite membrane shows better and better biocatalysis effect in a circulation experiment, and when the addition amount of the straw biochar is 0.4g, the catalytic effect on As (III) oxidation is best; in the performance test of five times of cycles, because the thickness of the surface biological film and the evolution effect of the microorganisms on the composite film tend to be stable, the composite film is kept stable after reaching the self optimal value.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.

Claims (7)

1. A preparation method of a biomass charcoal nanofiber membrane loaded with microorganisms is characterized by comprising the following steps: the method comprises the following steps:
(1) Cleaning and crushing waste biomass straws, sieving the straws with a 200-mesh sieve, and drying the straws;
(2) Slowly adding concentrated sulfuric acid into the material obtained in the step (1), fully stirring and mixing, then slowly adding hydrogen peroxide under an ice bath condition, stirring while adding to prevent liquid from splashing, fully carbonizing the material, cooling to room temperature, fully washing with deionized water to be nearly neutral, centrifuging to obtain a precipitate, and then drying to obtain straw biomass charcoal; the proportion of the material obtained in the step (1), concentrated sulfuric acid and hydrogen peroxide is 28-31g:190-210mL:60-70mL;
(3) Stirring and mixing polyacrylonitrile, the straw biomass charcoal and N, N-dimethylformamide at 55-65 ℃, and then carrying out ultrasonic treatment to obtain a spinning solution; the concentration of N, N-dimethylformamide is 98%, and the Mr of polyacrylonitrile is 150,000; the ratio of polyacrylonitrile to the straw biomass charcoal to N, N-dimethylformamide is 0.2-0.6g:2.0g:20mL;
(4) Performing electrostatic spinning on the spinning solution to obtain a nanofiber membrane;
(5) Heating the nanofiber membrane to 260-280 ℃ under the condition of keeping proper tension, preserving heat and semi-carbonizing for 1.5-2.5h to obtain a precursor product;
(6) Cooling the precursor product to room temperature, cutting and molding, heating to 790-810 ℃ in nitrogen atmosphere, preserving heat and carbonizing for 1.5-2.5h;
(7) Activating the material obtained in the step (6) by using a KOH solution at room temperature for 10-12h, washing the material to be neutral by using deionized water, and drying the material to obtain a biomass carbon nanofiber membrane;
(8) And soaking the biomass carbon nanofiber membrane in a liquid culture medium inoculated with arsenic-oxidizing Hertzia Hertziae, culturing at 27-29 ℃ until the logarithmic growth phase, and then performing heat preservation culture for 9-11h to ensure that the arsenic-oxidizing Hertzia Hertziae in the culture solution is fully adhered to the biomass carbon nanofiber membrane, thus obtaining the biomass carbon nanofiber membrane loaded with the microorganisms.
2. The method of claim 1, wherein: in the step (2), the drying temperature is 77-81 ℃ and the drying time is 45-50h.
3. The method of claim 1, wherein: the ratio of polyacrylonitrile to the straw biomass charcoal to N, N-dimethylformamide is 0.4g:2.0g:20mL.
4. The method of claim 1, wherein: the specific process of electrostatic spinning in the step (4) is as follows: slowly sucking the spinning solution into a 20mL syringe, wherein the type of a metal needle is 20, and the inner diameter of the metal needle is 0.6mm; setting the distance between the injector and the receiving roller to be 16cm, the injection speed to be 0.1mm/min and the rotating speed of the receiving roller to be 100rpm; applying a positive voltage of 17kV to a needle point, and applying a negative voltage of 3kV to a receiving roller to carry out electrostatic spinning; setting the electrospinning time to be 12h, and keeping the temperature and the humidity in a box body of the electrostatic spinning equipment at 35 ℃ and 40% respectively; and after spinning is finished, slightly removing the film, putting the film into a vacuum oven, and drying the film for 12 hours at the temperature of 60 ℃ to remove residual solvent on the surface.
5. The method of claim 1, wherein: the preparation method of the liquid medium in the step (8) comprises the following steps:
A. the following three solutions were prepared:
solution A:81.2mM MgSO 4 ·7H 2 O，187mM NH 4 Cl，70mM Na 2 SO 4 ，0.574mM K 2 HPO 4 ，4.57mM CaCl 2 ·2H 2 O,446mM sodium lactate,
solution B:4.8mM FeSO 4 ·7H 2 O，
Solution C:950mM NaHCO 3 ；
B. Sterilizing solution A at 121 deg.C for 20min, and filtering solution B and C through 0.22 μm pore size filter for sterilization; c. Preparing a liquid culture medium according to the following proportion: mixing 100mL of the solution A,2.5mL of the solution B and 10mL of the solution C, supplementing the mixture to 1L with water, and adjusting the pH value to 7.2 to obtain the liquid culture medium.
6. Use of the biomass charcoal nanofiber membrane loaded with microorganisms prepared by the preparation method of any one of claims 1 to 5 in removing As (III) in environmental water.
7. A method for removing As (III) from an environmental water body, comprising: comprises the biomass charcoal nanofiber membrane loaded with microorganisms prepared by the preparation method of any one of claims 1 to 5.
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