CN108384574B - Electrostatic spinning biological composite desulphurization membrane and preparation method thereof - Google Patents
Electrostatic spinning biological composite desulphurization membrane and preparation method thereof Download PDFInfo
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- CN108384574B CN108384574B CN201810181273.9A CN201810181273A CN108384574B CN 108384574 B CN108384574 B CN 108384574B CN 201810181273 A CN201810181273 A CN 201810181273A CN 108384574 B CN108384574 B CN 108384574B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G31/00—Refining of hydrocarbon oils, in the absence of hydrogen, by methods not otherwise provided for
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0069—Electro-spinning characterised by the electro-spinning apparatus characterised by the spinning section, e.g. capillary tube, protrusion or pin
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0092—Electro-spinning characterised by the electro-spinning apparatus characterised by the electrical field, e.g. combined with a magnetic fields, using biased or alternating fields
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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
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses an electrostatic spinning biological composite desulphurization membrane and a preparation method thereof. The desulfurization film is formed by stacking a plurality of disordered fibers, each fiber consists of a core layer and a shell layer, the shell layer comprises an inner shell layer and an outer shell layer wrapping the inner shell layer, the core layer is formed by dispersing glycerol containing desulfurization bacteria, the inner shell layer is a high polymer material layer, and the outer shell layer is formed by stacking a plurality of ZIF-8 particles. The preparation method comprises the following steps: dissolving a macromolecule in an organic solvent to obtain coaxial electrospinning shell liquid; 2) dispersing bacteria in glycerol to obtain coaxial electrospinning core liquid; 3) carrying out electrostatic spinning on the shell core solution by using an electrospinning needle head to obtain an electrostatic spinning membrane; 4) immersing the electrostatic spinning membrane into a dimethyl imidazole solution, adding a zinc acetate solution, slightly shaking, uniformly mixing and standing for a plurality of minutes; 5) washing the membrane obtained in the step 4) with deionized water for several times. The biological composite desulfurization membrane prepared by the invention has simple and convenient process, is easy for industrial mass production, and has equivalent desulfurization activity and superior cycle stability.
Description
Technical Field
The invention belongs to the field of biological composite materials, and particularly relates to an electrostatic spinning biological composite desulphurization membrane and a preparation method thereof.
Background
In the petroleum industry, sulfur-containing compounds pose a great hazard to human health and environmental protection. The biological desulfurization method is recognized as a green and effective desulfurization method at present, and the biological desulfurization method is promoted to industrial application by utilizing bacterial immobilization, so that the biological desulfurization method has great potential. Common bacterial immobilization has three disadvantages: firstly, the combination degree of bacteria and carrier materials is low, and the bacteria are easy to fall off; secondly, the strength of the immobilized material is low, and bacteria are easy to leak to the external environment; thirdly, the bacteria can not be dispersed evenly, which results in the reduction of active area and the low efficiency of material transfer. Therefore, it is desirable to provide a practical and effective method for desulfurizing immobilized bacteria.
Disclosure of Invention
The invention aims to solve the technical problem of providing an electrostatic spinning biological composite desulphurization membrane with good desulphurization effect and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the utility model provides an electrostatic spinning biological composite desulfurization membrane, electrostatic spinning biological composite desulfurization membrane is piled up by a plurality of unordered fibre and is formed, and every fibre comprises nuclear layer and shell, the shell includes inner shell and the outer shell of parcel inner shell, the nuclear layer comprises for the glycerine that has the desulfurization fungus that disperses, the inner shell is the macromolecular material layer, the outer shell is piled up for a plurality of ZIF-8 granules and forms.
In the above scheme, the polymer material layer is a polycaprolactone layer.
In the scheme, the desulfurization bacteria are Gordonia aminocalis WQ-01.
In the scheme, the technological parameters of electrostatic spinning in the step 3) are as follows: the receiving distance is 13-15 cm; the voltage of the receiving plate is set to be 0 to-0.2 kv; the voltage at the needle is set to 10-12 kv; the inner core advancing speed is 0.1-0.15 mm/min; the shell propelling speed is 7.0-8.0mm/min, and the spinning time is 30-60 min.
A preparation method of an electrostatic spinning biological composite desulphurization membrane comprises the following steps:
1) dissolving a high molecular material in an organic solvent, and stirring until the solution is clear and free of bubbles to obtain a coaxial electrospinning shell solution;
2) cleaning bacteria with buffer solution for several times, dispersing the bacteria in glycerol, and stirring at low speed to uniformly disperse the bacteria to obtain coaxial electrospinning core liquid;
3) carrying out electrostatic spinning on the shell core solution by using an electrospinning needle head to obtain an electrostatic spinning membrane;
4) immersing the electrostatic spinning membrane into a dimethyl imidazole solution, adding a zinc acetate solution, slightly shaking, mixing uniformly and standing;
5) washing the membrane obtained in the step 4) with deionized water.
In the above scheme, the organic solvent is chloroform.
In the above scheme, the organic solvent further comprises 0-15% by mass of dimethylformamide.
In the scheme, the high polymer material is polycaprolactone.
In the above scheme, the polymer material further comprises 0-10% by mass of polyethylene glycol.
In the scheme, the desulfurization bacteria are Gordonia aminocalis WQ-01.
In the scheme, the technological parameters of electrostatic spinning in the step 3) are as follows: the receiving distance is 13-15 cm; the voltage of the receiving plate is set to be 0 to-0.2 kv; the voltage at the needle is set to 10-12 kv; the inner core advancing speed is 0.1-0.15 mm/min; the shell propelling speed is 7.0-8.0mm/min, and the spinning time is 30-60 min.
The invention provides a method for preparing a biological composite desulfurization membrane by using a coaxial electrostatic spinning technology to carry desulfurization bacteria. Firstly, dissolving a macromolecule in an organic solvent, stirring until the macromolecule is clear and bubble-free to obtain a coaxial electrospinning shell solution, cleaning bacteria for a plurality of times by using a PBS solution, dispersing the bacteria in glycerol, and stirring at a low speed to uniformly disperse the bacteria to obtain a coaxial electrospinning core solution; and finally, growing a layer of continuous compact ZIF-8 shell on the surface of the coaxial electrostatic spinning fiber in situ.
The invention has the following beneficial effects: the biggest innovation of the invention is to synthesize a fiber hollow membrane structure by a coaxial electrostatic spinning technology, provide a certain living space for immobilized bacteria, ensure that the bacteria have higher bioactivity while being immobilized, form a ZIF-8 shell outside the fiber, increase the hydrophobicity of the material and improve the adsorption rate of sulfur-containing substances. The method has simple process and easy industrialized mass production, the bacteria are immobilized in the coaxial electrostatic spinning fiber membrane, the bacteria can be efficiently exchanged with external substances by utilizing the larger specific surface area of electrostatic spinning, the produced biological composite membrane has equivalent desulfurization activity due to relatively independent space, the adsorption desulfurization and the biological desulfurization are combined by the larger hydrophobicity, and meanwhile, the prepared membrane can effectively improve the circulation stability of the bacteria.
Drawings
FIG. 1 is a schematic view of the structure of the electrospun bio-composite desulfurization membrane obtained in example 1.
FIG. 2 is a photograph of the electrospun bio-composite desulfurization film obtained in example 1.
FIG. 3 is a scanning electron micrograph of the electrospun bio-composite desulfurization film obtained in example 1: a) unmodified low magnification, b) unmodified high magnification, c) an unmodified cross section, d) after modification of ZIF-8.
FIG. 4 is a fluorescent microscope photograph of the electrospun bio-composite desulfurization film obtained in example 1: a) visible light photograph, b) fluorescence photograph.
FIG. 5 shows the contact angle of the electrospun bio-composite desulfurization film obtained in example 1: a) unmodified, b) modified ZIF-8.
FIG. 6 shows the catalytic performance of the electrospun biological composite desulfurization membrane obtained in example 1 with naked bacteria.
FIG. 7 shows the cycle performance test of the electrospun biocomposite desulfurization membrane obtained in example 1 with naked bacteria.
Detailed Description
The invention is described in further detail below with reference to the figures and specific embodiments.
Example 1
As shown in fig. 1, the electrospun biological composite desulfurization film provided by this embodiment is formed by stacking a plurality of disordered fibers, each fiber is composed of a core layer and a shell layer, the shell layer includes an inner shell layer and an outer shell layer wrapping the inner shell layer, the core layer is composed of glycerol in which desulfurization bacteria are dispersed, the inner shell layer is a polymer material layer, and the outer shell layer is formed by stacking a plurality of ZIF-8 particles. In this embodiment, the polymer material is polycaprolactone. The desulfurization bacteria are Gordoniaamicalis WQ-01, are derived from China center for the culture collection of industrial microorganisms, and have the collection number of CICC 20663.
The embodiment also provides a method for preparing the biological composite desulphurization membrane by using coaxial electrostatic spinning, which comprises the following specific operation steps:
(1) dissolving 2g of polycaprolactone in 20g of a mixture with the mass ratio of 9: 1, stirring the mixed solution of chloroform and dimethylformamide until the mixed solution is clear, standing the mixed solution in a dark place until no bubbles exist, and taking the mixed solution as an electrospinning external liquid for later use;
(2) washing 5ml of Gordonia aminocalis WQ-01 with OD value of 1.0 with PBS solution for several times, concentrating, dispersing in 2ml of glycerol, and stirring at low speed until the dispersion is uniform to serve as electrospinning internal liquid for later use;
(3) assembling coaxial electrostatic spinning, and respectively installing the internal liquid and the external liquid on a propulsion pump by using a 5ml needle cylinder;
(4) setting the receiving distance to be 14cm, setting the voltage of a receiving plate to be-0.15 kv, setting the voltage at a needle head to be 10.5kv, setting the advancing speed of an inner core to be 0.1165mm/min, setting the advancing speed of a shell to be 0.7000mm/min, spinning for 30min, and obtaining an electrostatic spinning film on the receiving plate;
(5) the obtained electrostatic spinning membrane is cut into 5cm multiplied by 5cm, is washed by deionized water once, is immersed into 5ml of dimethyl imidazole solution (160mM), is added with 5ml of zinc acetate solution (40mM), is slightly shaken for 5min, and is washed by deionized water once again.
Example 2
The embodiment provides a method for preparing the biological composite desulphurization membrane by using coaxial electrostatic spinning, which comprises the following specific operation steps:
(1) dissolving 2g of polycaprolactone in chloroform, stirring until the polycaprolactone is clear, and standing in a dark place until no bubbles exist, wherein the polycaprolactone is used as an electrospinning external liquid for later use;
(2) washing 5ml of Gordonia aminocalis WQ-01 with OD value of 1.0 with PBS solution for several times, concentrating, dispersing in 2ml of glycerol, and stirring at low speed until the dispersion is uniform to serve as electrospinning internal liquid for later use;
(3) assembling coaxial electrostatic spinning, and respectively installing the internal liquid and the external liquid on a propulsion pump by using a 5ml needle cylinder;
(4) the receiving distance is set to be 14cm, the voltage of the receiving plate is set to be-0.15 kv, the voltage at the needle head is set to be 10.5kv, the advancing speed of the inner core is 0.1165mm/min, the advancing speed of the outer shell is 0.7000mm/min, spinning is carried out for 30min, and an electrostatic spinning film is obtained on the receiving plate.
(5) The obtained electrostatic spinning membrane is cut into 5cm multiplied by 5cm, is washed by deionized water once, is immersed into 5ml of dimethyl imidazole solution (160mM), is added with 5ml of zinc acetate solution (40mM), is slightly shaken for 5min, and is washed by deionized water once again.
Example 3
The embodiment provides a method for preparing the biological composite desulphurization membrane by using coaxial electrostatic spinning, which comprises the following specific operation steps:
(1) dissolving 1.8g of polycaprolactone and 0.2g of polyethylene glycol in 20g of a mixture with the mass ratio of 9: 1, stirring the mixed solution of chloroform and dimethylformamide until the mixed solution is clear, standing the mixed solution in a dark place until no bubbles exist, and taking the mixed solution as an electrospinning external liquid for later use;
(2) washing 5ml of Gordonia aminocalis WQ-01 with OD value of 1.0 with PBS solution for several times, concentrating, dispersing in 2ml of glycerol, and stirring at low speed until the dispersion is uniform to serve as electrospinning internal liquid for later use;
(3) assembling coaxial electrostatic spinning, and respectively installing the internal liquid and the external liquid on a propulsion pump by using a 5ml needle cylinder;
(4) the receiving distance is set to be 14cm, the voltage of the receiving plate is set to be-0.15 kv, the voltage at the needle head is set to be 10.5kv, the advancing speed of the inner core is 0.1165mm/min, the advancing speed of the outer shell is 0.7000mm/min, spinning is carried out for 30min, and an electrostatic spinning film is obtained on the receiving plate.
(5) The obtained electrostatic spinning membrane is cut into 5cm multiplied by 5cm, washed by deionized water once, immersed into 5ml of dimethyl imidazole solution (160mM), added with 5ml of zinc acetate solution (40mM), shaken slightly for 5min, and washed by deionized water once again.
As shown in FIG. 2, the prepared electrostatic spinning biological composite membrane has a complete membrane structure and has equivalent mechanical properties. As shown in FIG. 3, the prepared electrospun bio-composite membrane is formed by stacking fibers with a diameter of about 3 microns under a scanning electron microscope, which means a very high specific surface area, and as can be seen from the cross section, the fibers are in a core-shell structure, and as can be seen from FIG. 3d, the outer layer of the modified fibers is provided with a layer of dense and continuous ZIF-8 particles, and the particle diameter is about 100 nm. Fig. 4a shows that the electrospun fiber is of a core-shell structure, and fig. 4b shows that bacteria are dispersed in the inner core structure of the fiber, which verifies that cells are immobilized in relatively independent hollow fibers. Fig. 5 shows the contact angle of the spun film and the modified ZIF-8 spun film, and it can be observed that the unmodified contact angle is less than 90 degrees and has no hydrophobicity, while the contact angle of the modified film is 123 degrees, has higher hydrophobicity and has good adsorption effect on oil phase. FIG. 6 shows that the bacteria and the spinning membrane are subjected to desulfurization performance test, it can be observed that the catalysis rate of naked bacteria is highest within 40h, the unmodified biological composite membrane achieves higher catalysis efficiency within about 80h, and the biological composite membrane modified by ZIF-8 is higher than the catalysis efficiency of naked bacteria within about 50h, which indicates that the biological composite membrane modified by ZIF-8 shows higher catalysis efficiency at the early stage because the naked cells do not have the constraint effect and is always higher than the unmodified biological composite membrane, but shows higher catalysis efficiency because the modified biological composite membrane has better physical adsorption effect. From FIG. 7, it can be seen that in the cyclic test experiment, the relative activity of the naked cell after 5 cycles is reduced to 35%, while the relative activity of the unmodified and modified ZIF-8 biological composite membrane after 5 cycles is maintained at 73% and 82%, respectively, which shows that the stability of the unmodified and modified biological composite membrane is much higher than that of the naked cell, while the modified ZIF-8 biological membrane has higher structural stability due to the presence of the shell modification material, and has better stability compared with the unmodified biological membrane, and the cyclic stability of the biological composite membrane means the ultrahigh potential in industrial application.
It should be understood that the above-mentioned embodiments are only examples for clearly illustrating the present invention, and are not to be construed as limiting the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications are therefore intended to be included within the scope of the invention as claimed.
Claims (10)
1. The electrostatic spinning biological composite desulphurization membrane is characterized by being formed by stacking a plurality of unordered fibers, each fiber consists of a core layer and a shell layer, each shell layer comprises an inner shell layer and an outer shell layer wrapping the inner shell layer, the core layer is formed by glycerol dispersed with desulphurization bacteria, the inner shell layer is a high polymer material layer, and the outer shell layer is formed by stacking a plurality of ZIF-8 particles.
2. The electrospun bio-composite desulfurization membrane of claim 1, wherein the polymeric material layer is a polycaprolactone layer.
3. The electrospun bio-composite desulfurization membrane of claim 1, wherein said desulfurization bacteria is Gordoniaamicalis WQ-01.
4. The preparation method of the electrostatic spinning biological composite desulphurization membrane is characterized by comprising the following steps:
1) dissolving a high molecular material in an organic solvent, and stirring until the solution is clear and free of bubbles to obtain a coaxial electrospinning shell solution;
2) cleaning the desulfurization bacteria with buffer solution for several times, dispersing the desulfurization bacteria in glycerol, and stirring at low speed to uniformly disperse the desulfurization bacteria to obtain coaxial electrospinning core liquid;
3) carrying out electrostatic spinning on the coaxial electrospinning shell liquid and the coaxial electrospinning core liquid by using the electrospinning needle head to obtain an electrostatic spinning film;
4) immersing the electrostatic spinning membrane into a dimethyl imidazole solution, adding a zinc acetate solution, slightly shaking, mixing uniformly and standing;
5) washing the membrane obtained in the step 4) with deionized water.
5. The method according to claim 4, wherein the organic solvent is chloroform.
6. The method according to claim 5, wherein the organic solvent further comprises 0 to 15% by mass of dimethylformamide.
7. The method according to claim 4, wherein the polymer material is polycaprolactone.
8. The method according to claim 7, wherein the polymer material further comprises 0 to 10 mass% of polyethylene glycol.
9. The method according to claim 4, wherein the desulfurizing bacterium is Gordonia aminocalis WQ-01.
10. The preparation method according to claim 4, wherein the electrostatic spinning in step 3) has the following process parameters: the receiving distance is 13-15 cm; the voltage of the receiving plate is set to be 0 to-0.2 kv; the voltage at the needle is set to 10-12 kv; the inner core advancing speed is 0.1-0.15 mm/min; the shell propelling speed is 7.0-8.0mm/min, and the spinning time is 30-60 min.
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