CN104674365A - Biomass tar-PAN (polyacrylonitrile) fibrous material and preparation method thereof - Google Patents
Biomass tar-PAN (polyacrylonitrile) fibrous material and preparation method thereof Download PDFInfo
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- CN104674365A CN104674365A CN201510095819.5A CN201510095819A CN104674365A CN 104674365 A CN104674365 A CN 104674365A CN 201510095819 A CN201510095819 A CN 201510095819A CN 104674365 A CN104674365 A CN 104674365A
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Abstract
The invention belongs to the technical field of fibrous materials, and particularly relates to a fibrous material which takes biomass tar and PAN (polyacrylonitrile) as the raw materials, is prepared with an electrospinning process and has antibacterial performance. The fibrous material is prepared with the electrospinning process, and the mass of the biomass tar in the fibrous material accounts for 30%-100% of the mass of the PAN. The biomass tar is taken as the raw material, so that use of the PAN raw material is partially replaced. The diameter of the prepared fibrous material as well as the porosity and specific surface area of a prepared fibrous membrane can be better adjusted through change of the content of the biomass tar in a spinning solution, and the prepared fibrous material has smoother surface; meanwhile, the biomass tar contains phenol derivatives, so that the prepared fibrous material has certain antibacterial performance, overall utilization of the biomass tar is realized better, and a novel path is provided for comprehensive development and utilization of the biomass tar.
Description
Technical field
The invention belongs to fibrous material technical field, be specifically related to a kind of with biomass coke tar and polyacrylonitrile (PAN) for raw material, utilize the fibrous material with anti-microbial property prepared by electrostatic spinning process.
Background technology
Day by day reduce at reserves such as coal, oil, natural gases, today that environmental pollution goes from bad to worse, greatly develop utilization and the research of renewable natural resources, to substitute traditional petroleum base macromolecular material, there is important strategic importance.
Biomass energy, due to the character of its uniqueness, as advantages such as abundant raw material, recyclability and Carbon balance, is just causing increasing concern.By thermochemical study, if biomass conversion can be gas, liquid and solid by pyrolysis and gasification, can be used for producing heat, electricity and the basic chemical feedstock etc. required for industry.The thermochemical study process of living beings can produce the accessory substance of tar class, and be called biomass coke tar (tar), biomass char oil require removes from process gas, produces blockage problem to avoid downstream equipment and terminal applies.But because biomass coke tar is difficult to degraded, thus arbitrarily placement also can cause environmental pollution.
Conventional treatment method at present for biomass coke tar mainly utilizes steam and catalyst to carry out catalyzed conversion to biomass coke tar, but these method operating process are complicated, expensive, also will consume a large amount of chemicals, and recycling is worth lower.Therefore, the sustainable development of exploitation to living beings and bioenergy of biomass coke tar comprehensive utilization technique is significant.Consider the chemical composition of biomass coke tar and high carbon content feature, it should be made as far as possible to be processed into material as a kind of living resources, and need not dispose as refuse.
In prior art, electrostatic spinning has become the organic and inorganic material of simple and general employing to prepare the method for multifunctional fibrous material, can obtain diameter from tens nanometers to the fiber of several microns by this technology.Be there is by the fibrous material prepared by electrostatic spinning the characteristic of many excellences, such as the surface group of small size, bigger serface, multiple dimensioned porosity and high degree of flexibility is functionalized, is thus had a wide range of applications in sorbing material, filter, photoelectric device, sensor, organizational project and anti-biotic material etc. by the fibrous material prepared by electrostatic spinning process.
There are some researches show, after tar is dispersed in oxolane, electrospinning process can be adopted to prepare fibrous material, but due to the low molecular weight of tar and low solubility in a solvent, cause spinning fluid viscosity lower, the fibrous material surface obtained by the method is made to have more projection, not smoothly.Thus still need and improve further, thus for the comprehensive utilization exploitation of biomass coke tar provide new may.
Summary of the invention
Main purpose of the present invention is to provide the new way that a kind of biomass coke tar develops, specifically be to provide the fibrous material that one is raw material with biomass coke tar and polyacrylonitrile (PAN), this material has good anti-microbial property, adopts electrostatic spinning process to be prepared from.
The technical solution used in the present invention is as follows.
Utilize the biomass coke tar-PAN fibrous material prepared by electrostatic spinning process, this material adopts electrostatic spinning process to be prepared from, and in fibrous material, the quality of biomass coke tar is 30 ~ 100% of PAN quality.
Utilize the biomass coke tar-PAN fibrous material prepared by electrostatic spinning process, its preparation method comprises the following steps:
(1) PAN is dissolved in DMF(N, N-dimethyl formamide) in, obtain the DMF solution of PAN; The DMF concentration of polymer solution of preferred PAN is 10%;
(2) the biomass coke tar powder of drying is added DMF(N, N-dimethyl formamide) in, vigorous stirring, obtains the DMF suspension of biomass coke tar; Preferably by magnetic agitation mode vigorous stirring 24h;
(3) by composite in proportion for the DMF suspension of the biomass coke tar in the DMF solution of PAN in step (1) and step (2), obtained mixing suspension, preferred ultrasonic disperse 30min;
In described composite rear mixing suspension, the quality of biomass coke tar is 30 ~ 100% of PAN quality; The quality of preferred biomass coke tar is 30 ~ 50% of PAN quality;
(4) syringe get composite in step (3) after mixing suspension, electrostatic spinning, spinning parameter preferably arranges as follows:
Needle diameter is 0.413mm; Mixing suspension is 0.5 mL/h by syringe pump syringe needle flow;
Electrostatic potential is 15 ~ 20KV; Spinning distance is 15 ~ 25cm; Spinning temperature is 20 ~ 35 DEG C; Relative humidity is 50 ~ 65%; Baking temperature is 60 DEG C;
Preferred spinning parameter is set to: electrostatic potential is 20KV; Spinning distance is 20cm; Spinning temperature is 25 DEG C; Relative humidity is 60%; Baking temperature is 60 DEG C.
Electrospun fibers material prepared by the present invention is at gas and liquid filtration material, water pollutant and heavy metal ion adsorbed, and the aspects such as antibiotic property wound coating film have potential application foreground.
There are some researches show, the biomass coke tar obtained from gasification of biomass is formed primarily of phenols, aromatic compounds, furans, aliphatic compounds and ester class.Elementary analysis shows, biomass coke tar has higher H/C and O/C and lower aromatic species compound ratio, and compared with fossil fuel, more easily oxidized, this just means that biomass coke tar has more reactivity.In fibrous material preparation field, existing more tar about obtaining from coal and oil or pitch carry out the research of fiber manufacture, but there is not yet the biomass coke tar that produces in relevant use thermal conversion processes to prepare the report of fibrous material.
Polyacrylonitrile (PAN) is a kind of conventional raw material in electrostatic spinning process.The present invention by adopting biomass coke tar as raw material, the Some substitute use of PAN raw material.The fibrous material prepared by raw material employing electrostatic spinning process with biomass coke tar and PAN, by changing the content of biomass coke tar in spinning solution, porosity and the specific area of the diameter of prepared fibrous material and obtained tunica fibrosa can be regulated preferably, and prepared fibrous material has comparatively level and smooth surface, simultaneously due to the existence of the phenol analog derivative in biomass coke tar composition, prepared fibrous material is made to have certain anti-microbial property, achieve the whole utilization of biomass coke tar preferably, comprehensive development and utilization for biomass coke tar provides new approach.
Accompanying drawing explanation
The SEM figure of the fibrous material of Fig. 1 prepared by related embodiment, wherein scheming A is that in comparative example and composite mixing suspension, the quality of biomass coke tar is the SEM figure of 0% of PAN quality; The SEM of figure B to be the quality of biomass coke tar in embodiment 1 i.e. composite mixing suspension be 30% of PAN quality schemes; The SEM of figure C to be the quality of biomass coke tar in embodiment 2 i.e. composite mixing suspension be 50% of PAN quality schemes; The SEM of figure D to be the quality of biomass coke tar in embodiment 3 i.e. composite mixing suspension be 100% of PAN quality schemes;
Fig. 2 is anti-microbial property testing result, wherein schemes A ~ C and is respectively comparative example, example 2, fibrous material antibacterial ability schematic diagram in staphylococcus aureus culture medium prepared by example 3; Figure D ~ F is respectively comparative example, example 2, fibrous material antibacterial ability schematic diagram in Escherichia coli culture medium prepared by example 3.
Detailed description of the invention
Below in conjunction with embodiment the present invention will be further explained explanation.
It should be noted that before introducing specific embodiment, in embodiment, biomass coke tar used is purchased from Xigou ditch, Shanxi biological fuel gas factory, is obtained 500 ~ 600 DEG C of condition gasified by maize straw.
embodiment 1
Biomass coke tar-PAN fibrous material that what the present embodiment provided utilize prepared by electrostatic spinning process, its preparation method comprises the following steps:
(1) PAN is dissolved in DMF(N, N-dimethyl formamide) in, obtain the DMF solution that mass concentration is the PAN of 10%;
(2) the biomass coke tar powder of drying is added DMF(N, N-dimethyl formamide) in, magnetic agitation vigorous stirring 24h, obtain the DMF suspension of biomass coke tar, owing to being dissolved, being scattered in DMF solution mainly in order to prepare the suspension of biomass coke tar by biomass coke tar, be convenient to mixing and the spinning of subsequent material, thus theoretical, biomass coke tar is any concentration when being scattered in DMF, but typical concentrations is 6 ~ 20 wt%, and in the present embodiment, concentration used is 10 wt%;
(3) by composite in proportion for the DMF suspension of the biomass coke tar in the DMF solution of PAN in step (1) and step (2), obtained mixing suspension, and use ultrasonic disperse 30min;
In described composite rear mixing suspension, the quality of biomass coke tar is 30% of PAN quality;
(4) syringe get composite in step (3) after mixing suspension, electrostatic spinning, process is as follows:
With syringe get composite in step (3) after mixing suspension 5mL, be arranged on syringe pump, connect the syringe needle that diameter is 0.413mm, mixing suspension is 0.5 mL/h by syringe pump syringe needle flow; Adjustment electrostatic potential is 20KV, spinning distance for 20cm, spinning temperature be 25 DEG C, relative humidity is 60% carry out spinning, after spinning terminates, baking temperature is dry 12h under 60 DEG C of conditions.
After measured, specific area 12 m of gained fiber
2/ g, average pore size is 6.2 nm, and porosity is 61%.
embodiment 2
The preparation method of biomass coke tar in the present embodiment-PAN fibrous material and electrostatic spinning process optimum configurations are with embodiment 1, in mixing suspension after the DMF suspension of the biomass coke tar only in set-up procedure (1) in the DMF solution of PAN and step (2) is composite, the quality of biomass coke tar is 50% of PAN quality.After measured, specific area 12 m of gained fiber
2/ g, average pore size is 5.7 nm, and porosity is 58%.
embodiment 3
The preparation method of biomass coke tar in the present embodiment-PAN fibrous material and electrostatic spinning process optimum configurations are with embodiment 1, in mixing suspension after the DMF suspension of the biomass coke tar only in set-up procedure (1) in the DMF solution of PAN and step (2) is composite, the quality of biomass coke tar is 100% of PAN quality.After measured, the specific area of gained fiber is 10 m
2/ g, average pore size is 7.1 nm, and porosity is 51%.
comparative example
For the specific performance of comparative illustration biomass coke tar provided by the present invention-PAN fibrous material, inventors performed is only the routine intravenous Electrospun of raw material with PAN, correlation step is with embodiment 1, but do not add biomass coke tar as raw material, namely be equivalent to the DMF suspension of the biomass coke tar in the DMF solution of PAN in set-up procedure (1) and step (2) composite after mixing suspension in, the quality of biomass coke tar is 0% of PAN quality, and namely the spinning mass concentration spinning PAN in liquid used is 10%.
Electrospun fibers specific area prepared by this comparative example is 14 m
2/ g, average pore size is 5.6 nm, and voidage is 63%.
(field emission scanning electron microscope, FEI Co. of the U.S. produces, Quanta to carry out electron-microscope scanning to biomass coke tar-PAN fibrous material prepared by embodiment 1 ~ 3 and comparative example
tM3D SEM/FIB Double electron beam scanning, voltage is 10kv)), result is as shown in Figure 1.Can be seen by Fig. 1, along with the increase of biomass coke tar addition, the surface that electrostatic spinning obtains fiber is progressively transitioned into rough zone protruding condition (Fig. 1 .D) from smooth state (Fig. 1 .A).
antibacterial inspection
The anti-microbial property of the fibrous material prepared by inspection the present invention, the anti-microbial property of inventor to the fibrous material prepared by comparative example, embodiment 2,3 has carried out further inspection, and brief introduction is as follows.
Fibrous material prepared by comparative example, embodiment 2,3 is cut rear be immersed in respectively there is staphylococcus aureus and colibacillary nutrient solution agar plate on, under 37 DEG C of conditions cultivate 24 hours.
Statistics fibrous material adds the change of front and back clump count, and to characterize the antibacterial ability of fibrous material, result represents with antibiotic rate (Antimicrobial), and computing formula is as follows:
Antibiotic rate (%)=(A-B)/A × 100,
Wherein A and B represents the clump count added before and after fibrous material respectively.
Result shows, the fibrous material prepared by example 2 and 3, is respectively 19 ± 3% and 36 ± 7%, is respectively 17 ± 4% and 39 ± 6% to Escherichia coli to the anti-microbe ability calculated value of staphylococcus aureus.And comparative example gained fiber is zero to staphylococcus aureus and colibacillary anti-microbe ability calculated value
.
Result as shown in Figure 2.As can be seen from the figure, along with the raising of biomass char oil content, two kinds of bacterial colony count reduce all gradually, show good antibacterial effect.
Claims (5)
1. biomass coke tar-PAN fibrous material, is characterized in that, this fibrous material is with biomass coke tar and PAN for raw material, adopts electrostatic spinning process to be prepared from; Wherein the quality of biomass coke tar is 30 ~ 100% of PAN quality.
2. biomass coke tar-PAN fibrous material as claimed in claim 1, it is characterized in that, the quality of biomass coke tar is 50% of PAN quality.
3. the preparation method of the biomass coke tar described in claim 1 or 2-PAN fibrous material, it is characterized in that, the method comprises the following steps:
(1) PAN is dissolved in DMF, obtains the DMF solution of PAN;
(2) the biomass coke tar powder of drying is added in DMF, obtain the DMF suspension of biomass coke tar;
(3) by composite in proportion for the DMF suspension of the biomass coke tar in the DMF solution of PAN in step (1) and step (2), obtained mixing suspension;
In described composite rear mixing suspension, the quality of biomass coke tar is 30 ~ 100% of PAN quality;
(4) syringe get composite in step (3) after mixing suspension, electrostatic spinning, obtained fibrous material, wherein spinning parameter arranges as follows:
Needle diameter is 0.413mm; Mixing suspension is 0.5 mL/h by syringe pump syringe needle flow;
Electrostatic potential is 15 ~ 20KV; Spinning distance is 15 ~ 25cm; Spinning temperature is 20 ~ 35 DEG C; Relative humidity is 50 ~ 65%; Baking temperature is 60 DEG C.
4. the preparation method of biomass coke tar-PAN fibrous material as claimed in claim 3, is characterized in that, in step (1), the mass concentration of the DMF solution of PAN is 10%.
5. the preparation method of biomass coke tar-PAN fibrous material as claimed in claim 3, is characterized in that, in step (4): electrostatic potential is 20KV; Spinning distance is 20cm; Spinning temperature is 25 DEG C; Relative humidity is 60%; Baking temperature is 60 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105040165A (en) * | 2015-07-01 | 2015-11-11 | 河南省科学院能源研究所有限公司 | Biomass tar/nano-silver/PAN compound carbon-fiber material and preparation method |
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| JPS53119322A (en) * | 1977-03-28 | 1978-10-18 | Asahi Chem Ind Co Ltd | Production of acrylic fibers |
| CN102239106A (en) * | 2008-11-06 | 2011-11-09 | 全南大学校产学协力团 | Carbon nano fiber having skin-core structure, method of preparing same, and product containing said carbon nano fiber |
| CN102877151A (en) * | 2012-11-05 | 2013-01-16 | 福建师范大学 | Preparation method of CdS/carbon nano tube/polyacrylonitrile hybrid nano-fiber |
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2015
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53119322A (en) * | 1977-03-28 | 1978-10-18 | Asahi Chem Ind Co Ltd | Production of acrylic fibers |
| CN102239106A (en) * | 2008-11-06 | 2011-11-09 | 全南大学校产学协力团 | Carbon nano fiber having skin-core structure, method of preparing same, and product containing said carbon nano fiber |
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Non-Patent Citations (1)
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| KUNLIN SONG等: "Fabricating electrospun nanofibers with antimicrobial capability: A facile route to recycle biomass tar", 《FUEL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105040165A (en) * | 2015-07-01 | 2015-11-11 | 河南省科学院能源研究所有限公司 | Biomass tar/nano-silver/PAN compound carbon-fiber material and preparation method |
| CN105040165B (en) * | 2015-07-01 | 2017-07-07 | 河南省科学院能源研究所有限公司 | Biomass coke tar/Nano Silver/PAN is combined carbon fibre material and preparation method |
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Application publication date: 20150603 |