CN108588882A - A kind of industrial residue based composite fibre and preparation method thereof - Google Patents
A kind of industrial residue based composite fibre and preparation method thereof Download PDFInfo
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- CN108588882A CN108588882A CN201810436544.0A CN201810436544A CN108588882A CN 108588882 A CN108588882 A CN 108588882A CN 201810436544 A CN201810436544 A CN 201810436544A CN 108588882 A CN108588882 A CN 108588882A
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- composite fibre
- moulding material
- industrial residue
- based composite
- residue based
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- 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
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
- D01F2/28—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives from organic cellulose esters or ethers, e.g. cellulose acetate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/50—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyalcohols, polyacetals or polyketals
-
- 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
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/105—Phosphorus compounds
Abstract
The present invention is a kind of industrial residue based composite fibre dephosphorization material and preparation method thereof, which includes flyash, slag, zeolite, basalt fibre, moulding material, and the mass ratio group that a variety of materials account for the gross mass of complex fiber material is divided into：
Description
Technical field
The present invention is a kind of industrial residue based composite fibre dephosphorization material for dirty (useless) water process, belongs to water prevention and cure of pollution
Technical field.
Background technology
Phosphorus is the principal element for leading to body eutrophication.Meanwhile phosphorus is also the indispensable nutrient of life entity, is
It is a kind of be difficult to regenerate, the resource of increasingly depleted.
The minimizing technology of phosphor in sewage mainly has bioanalysis and chemical method at present.Bioanalysis dephosphorization process is complicated, and is discharged
Stability is poor；Though dephosphorization (medicament) material of chemical method dephosphorization high treating effect, application is mostly lime, aluminium salt, molysite, Asia
The industrial products such as molysite and magnesium salts cause the method in production application since Dephosphorization reagent is costly, sludge quantity is larger
In bottleneck.Phosphorus adsorption capacity is hindered by force, with some strength and chemical stability, flow existing research shows that developing
Small, the good in economic efficiency efficient dephosphorization material of power, and be applied in the chemical dephosphorization technique of various dirty (useless) water, it will be in sewage
Phosphorus is enriched with and separates, and is the important means for ensureing sewage dephosphorization effect, realizing phosphor resource recycling, and in recent years
One of hot subject of research.
The waste residues such as slag, cinder, flyash are the solid waste of the industries such as metallurgy, electric power discharge.These wastes
A large amount of bank up not only wastes land resource, and be easy to cause environmental pollution.The annual emissions of China's slag are up to 16,000,000 tons at present
More than, the annual emissions of flyash are about 11,000,000 tons, but its cyclic utilization rate is only 10% or so.These waste residues mainly by with
Make the low value-added utilization pattern such as road-making material, backfilling material, brick producing material.
Natural zeolite is a kind of porous silicoaluminate mineral in rack-like structure, rich reserves, internal complicated lattice
Structure determines it with unique physicochemical characteristic, research find zeolite have preferable absorption property, ion-exchange performance and
Catalytic performance.
Traditional adsorbent is mostly graininess, there are problems that solid-liquid is difficult to detach applied to actual waste water processing, therefore
Develop the great realistic meaning of adsorbent of other forms.In recent years, the research about functional fiber sorbing material is increasingly becoming
Adsorbent research hot spot, study at present more functional fiber sorbing material mainly active Carbon fibe, cellulose fibre,
Chitin fiber and surface modified fibre etc..
Basalt fibre is the wire drawing after 1500 DEG C or so high-temperature fusions and the company that is formed using natural basalt as raw material
Continuous fiber.It has the excellent properties such as high-strength light, high temperature resistant, corrosion-resistant, anti-oxidant, radiation protection, wide in numerous areas purposes
It is general.In materialogy field, basalt fibre is usually as a kind of reinforcing material, in enhancing concrete, asphalt, You Jigao
Superior effect is shown in the application of the materials such as molecule.
Using the functional fibers such as cellulose acetate, PVA, polyacrylonitrile, chitosan sorbing material as moulding material, the Black Warrior
Rock fiber is as reinforcing material, and by industrial residue, zeolite etc., composite fibre material is prepared into using certain technological means and method
Material can either make industrial residue obtain the recycling of high added value for dirty (useless) water dephosphorization, while can greatly improve dephosphorization effect
Fruit.
Suitable sewage disposal is successfully compounded out currently with industrial residue, zeolite, basalt fibre and the moulding material
The high efficiency composition threadiness dephosphorization material that technique uses, and dirty (useless) water process and regulating water environment are used for this and realize that phosphorus provides
The recycling in source, domestic there is not been reported.
Invention content
Technical problem：The object of the present invention is to provide one kind by various industrial waste residues, zeolite, basalt fibre and forming material
Expect that the fibrous dephosphorization material and preparation method thereof being combined can make dirt by the use of the composite fibre dephosphorization material
The phosphorus concentration of (useless) water discharge reaches country《Urban wastewater treatment firm pollutant emission standard》(GB18918-2002) one in
Grade (A) standard, mitigates Eutrophication Status, so as to improve region environment.
Technical solution：A kind of each component mass ratio of industrial residue based composite fibre of the present invention is：
Wherein, each component mass ratio of the optimum value of the composite fibre is：
The moulding material is cellulose acetate, PVA, polyacrylonitrile or chitosan.
The flyash, slag, zeolite granularity be the mesh of 400 mesh~500.
The length of the basalt fibre is 0.5~1mm.
The preparation method of industrial residue based composite fibre of the present invention is：
Flyash, slag, zeolite, basalt fibre, moulding material are pressed to the mass component and coordinative solvent of composite fibre
It puts into and carries out uniform stirring in container, until be completely dissolved, and standing and defoaming；Then mixed liquor is added to wet-spinning frame
In, mixed liquor enters coagulation forming in coagulating bath through spinning head, then composite fibre is put into air dry oven, is dried at 60 DEG C
Dry 4h, until fiber is molded completely.
Wherein, when the moulding material uses cellulose acetate, solvent is acetone soln, and the volumetric concentration of acetone soln is
85%~90%, it is dissolved with 6.8~7.3L acetone solns per 1kg cellulose acetates；
When moulding material uses PVA, solvent is distilled water, distills water dissolution with 5.8~6.5L per 1kgPVA；
When moulding material uses polyacrylonitrile, solvent is sodium thiocyanate solution, and the mass concentration of sodium thiocyanate solution is
45%~50%, per 1kg polyacrylonitrile 7.3~8.5L sodium thiocyanate solutions dissolvings；
When moulding material uses chitosan, solvent is acetic acid solution, and the volumetric concentration of acetic acid solution is 2~2.3%, often
1kg chitosans 22.5~27.5L acetic acid solutions dissolve.
When moulding material uses cellulose acetate, it is 20~30 DEG C that the coagulating bath, which uses water-bath, water temperature,；
When moulding material uses PVA, it is 40~45 DEG C that the coagulating bath, which uses oversaturated aqueous sodium persulfate solution, temperature,；
When moulding material uses polyacrylonitrile, the coagulating bath uses mass concentration water-soluble for 9~12% sodium sulfocyanate
Liquid, temperature are 0~2 DEG C；
When moulding material uses chitosan, the coagulating bath uses mass concentration water-soluble for 4.8~5.3% sodium hydroxide
Liquid, temperature are 20~30 DEG C.
Advantageous effect：By the use of the composite fibre dephosphorization material, the phosphorus concentration of dirty (useless) water discharge can be made to reach
Country《Urban wastewater treatment firm pollutant emission standard》(GB18918-2002) level-one (A) standard in mitigates water body richness battalion
Fosterization situation improves region environment.
By to the exploitation of the New-type composite fibre dephosphorization material, production, application and final disposal, it can be achieved that industrial waste
The recycling of object, and the added value of waste utilization has been added, reduce the cost recovery of phosphor resource.
Innovation of the present invention is：Utilize several industrial residue, zeolite, basalt fibre, molding to adaptation to local conditions
Developing material goes out the composite fibre dephosphorization material of suitable sewage treatment process or eutrophic lake.Compound fibre after adsorption saturation
Dephosphorization material is tieed up because having higher phosphorus content, can realize phosphor resource again with this directly as fertilizer or soil improvement material
It recycles.
The present invention can not only environmental protection, realize waste recycling, moreover it is possible to obtain good social benefit and warp
Ji benefit.
Specific implementation mode
Slag, cinder, flyash equal industrial residue particle not only have huge specific surface area, but also containing a large amount of
The metal oxides such as Ca, Al, Fe have stronger absorption and respond to the phosphorus in water body.It is in frame that natural zeolite, which is a kind of,
The porous silicoaluminate mineral of shape structure, rich reserves, internal complicated lattice structure determine it with unique materialization
Characteristic, research find that zeolite has preferable absorption property, ion-exchange performance and catalytic performance.Cellulose acetate, gathers PVA
The functional fibers sorbing material such as acrylonitrile, chitosan has the advantages that source is wide, renewable, yield is high, price is low etc., and adsorbs
Rate is fast, is suitable for quickly processing high-concentration waste water.Basalt fibre is using natural basalt as raw material, at 1500 DEG C or so
Wire drawing after high-temperature fusion and the continuous fiber formed.It has high-strength light, high temperature resistant, corrosion-resistant, anti-oxidant, radiation protection etc. excellent
Anisotropic energy, it is widely used in numerous areas.In materialogy field, basalt fibre is enhancing usually as a kind of reinforcing material
Superior effect is shown in the application of the materials such as concrete, asphalt, organic polymer.
Required according to dephosphorization characteristics, adaptation to local conditions of the present invention using several industrial residue, zeolite, basalt fibre and
Moulding material is primary raw material, exploitation compounded out convenient for application, with the compound of some strength, porosity and suitable ph
Fibrous dephosphorization material can make the phosphorus concentration of dirty (useless) water discharge reach state by the use of the composite fibre dephosphorization material
Family《Urban wastewater treatment firm pollutant emission standard》
(GB18918-2002) level-one (A) standard in mitigates Eutrophication Status, improves region environment.
The present invention a kind of industrial residue based composite fibre dephosphorization material include flyash, slag, zeolite, moulding material,
Basalt fibre, the mass ratio group that a variety of materials account for the gross mass of composite fibre dephosphorization material are divided into：
Wherein,
Foaming agent can also be added in the material component.The foaming agent is：Vegetalitas cement blowing agent, concrete hair
Infusion, cement foaming agent, bagasse, soluble starch.
The moulding material is cellulose acetate, PVA, polyacrylonitrile, chitosan etc..
The zeolite, slag, flyash are 400~500 mesh.
The forming method of the industrial residue based composite fibre of the present invention is wet spinning, i.e.,：By flyash, slag, zeolite,
Basalt fibre, moulding material are put by the mass component and coordinative solvent of composite fibre carries out uniform stirring in container, until
It is completely dissolved, and standing and defoaming.Then mixed liquor is added in wet-spinning frame, mixed liquor enters through spinning head in coagulating bath
Coagulation forming, then composite fibre is put into air dry oven, 4h is dried at 60 DEG C, until fiber is molded completely.
A certain proportion of foaming agent can be also added in above-mentioned material component, such as vegetalitas cement blowing agent, concrete (cement)
Foaming agent, cement foaming agent, bagasse, soluble starch etc..
Wet spinning is used when above-mentioned material is molded：
Wet spinning technology
Flyash, slag, zeolite, basalt fibre, moulding material are pressed to the mass component and coordinative solvent of composite fibre
It puts into and carries out uniform stirring in container, until be completely dissolved, and standing and defoaming.Then mixed liquor is added to wet-spinning frame
In, mixed liquor enters coagulation forming in coagulating bath through spinning head, then composite fibre is put into air dry oven, is dried at 60 DEG C
Dry 4h, until fiber is molded completely.
The mass ratio group that a variety of materials account for the gross mass of composite fibre dephosphorization material is divided into：
(1) flyash (mass ratio)：
The ratio upper limit：23%
Ratio lower limit：4%
Ratio Best Point：7.7%
(2) slag (mass ratio)：
The ratio upper limit：26%
Ratio lower limit：6%
Ratio Best Point：11.5%
(3) zeolite (mass ratio)：
The ratio upper limit：16%
Ratio lower limit：2%
Ratio Best Point：3.8%.
(4) moulding material (mass ratio)：
The ratio upper limit：84%
Ratio lower limit：66%
Ratio Best Point：76.4%.
(5) basalt fibre (mass ratio)：
The ratio upper limit：10‰
Ratio lower limit：2‰
Ratio Best Point：6‰
By to the exploitation of material of the present invention, production, application and final disposal, it can be achieved that the recycling of trade waste and
Recycling, and the added value of waste utilization has been added, the cost recovery of phosphor resource is reduced, ring can not only be protected and improve
Border, the recycling for realizing waste, moreover it is possible to obtain good Social benefit and economic benefit.
Claims (8)
1. a kind of industrial residue based composite fibre, it is characterised in that each component mass ratio of the composite fibre is：
2. industrial residue based composite fibre according to claim 1, it is characterised in that the optimum value of the composite fibre
Each component mass ratio is：
3. industrial residue based composite fibre according to claim 1 or 2, it is characterised in that the moulding material is acetic acid
Cellulose, PVA, polyacrylonitrile or chitosan.
4. industrial residue based composite fibre according to claim 1 or 2, it is characterised in that the flyash, slag, boiling
The granularity of stone is the mesh of 400 mesh~500.
5. industrial residue based composite fibre according to claim 1 or 2, it is characterised in that the length of the basalt fibre
Degree is 0.5~1mm.
6. a kind of preparation method of industrial residue based composite fibre as described in claim 1, it is characterised in that the preparation method
For：
Flyash, slag, zeolite, basalt fibre, moulding material are put by the mass component and coordinative solvent of composite fibre
Uniform stirring is carried out in container, until be completely dissolved, and standing and defoaming；Then mixed liquor is added in wet-spinning frame, is mixed
It closes liquid and enters coagulation forming in coagulating bath through spinning head, then composite fibre is put into air dry oven, 4h is dried at 60 DEG C,
Until fiber is molded completely.
7. the preparation method of industrial residue based composite fibre according to claim 6, it is characterised in that the moulding material
When using cellulose acetate, solvent is acetone soln, and the volumetric concentration of acetone soln is 85%~90%, per 1kg acetate fibers
Element 6.8~7.3L acetone solns dissolve；
When moulding material uses PVA, solvent is distilled water, distills water dissolution with 5.8~6.5L per 1kgPVA；
When moulding material uses polyacrylonitrile, solvent is sodium thiocyanate solution, the mass concentration of sodium thiocyanate solution is 45%~
50%, per 1kg polyacrylonitrile 7.3~8.5L sodium thiocyanate solutions dissolvings；
When moulding material uses chitosan, solvent is acetic acid solution, and the volumetric concentration of acetic acid solution is 2~2.3%, per 1kg shells
Glycan 22.5~27.5L acetic acid solutions dissolve.
8. the preparation method of industrial residue based composite fibre according to claim 6, it is characterised in that moulding material uses
When cellulose acetate, it is 20~30 DEG C that the coagulating bath, which uses water-bath, water temperature,；
When moulding material uses PVA, it is 40~45 DEG C that the coagulating bath, which uses oversaturated aqueous sodium persulfate solution, temperature,；
When moulding material uses polyacrylonitrile, the coagulating bath uses mass concentration for 9~12% sodium thiocyanate water solution, temperature
Degree is 0~2 DEG C；
Moulding material use chitosan when, the coagulating bath use mass concentration for 4.8~5.3% sodium hydrate aqueous solution,
Temperature is 20~30 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810436544.0A CN108588882A (en) | 2018-05-09 | 2018-05-09 | A kind of industrial residue based composite fibre and preparation method thereof |
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| CN201810436544.0A CN108588882A (en) | 2018-05-09 | 2018-05-09 | A kind of industrial residue based composite fibre and preparation method thereof |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320017A (en) * | 2018-11-02 | 2019-02-12 | 浙江海洋大学 | A kind of processing method of landfill leachate |
| CN113511865A (en) * | 2021-07-28 | 2021-10-19 | 河北宏京新型建材有限公司 | Preparation method of fiber concrete prefabricated truss |
| CN115872689A (en) * | 2022-12-02 | 2023-03-31 | 盐城市福奇混凝土有限公司 | Composite fiber high-strength pervious concrete and preparation method thereof |
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| CN100528768C (en) * | 2007-10-30 | 2009-08-19 | 东南大学 | Industrial residue based compound dephosphorization material |
| CN101623619A (en) * | 2009-07-29 | 2010-01-13 | 东南大学 | Foaming-type industrial waste residue base compound dephosphorization material |
| CN101693186A (en) * | 2009-10-16 | 2010-04-14 | 东南大学 | Dephosphorization and denitrification integrated material prepared based on battering method and preparation method thereof |
| CN101982580A (en) * | 2010-11-02 | 2011-03-02 | 大连工业大学 | Polyacrylonitrile/hydroxyapatite composite adsorbent fiber and preparation method thereof |
| US20130244871A1 (en) * | 2010-02-18 | 2013-09-19 | Helfenberger Immobilien Llc & Co | Mixture and method for producing a fiber |
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2018
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Patent Citations (5)
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|---|---|---|---|---|
| CN100528768C (en) * | 2007-10-30 | 2009-08-19 | 东南大学 | Industrial residue based compound dephosphorization material |
| CN101623619A (en) * | 2009-07-29 | 2010-01-13 | 东南大学 | Foaming-type industrial waste residue base compound dephosphorization material |
| CN101693186A (en) * | 2009-10-16 | 2010-04-14 | 东南大学 | Dephosphorization and denitrification integrated material prepared based on battering method and preparation method thereof |
| US20130244871A1 (en) * | 2010-02-18 | 2013-09-19 | Helfenberger Immobilien Llc & Co | Mixture and method for producing a fiber |
| CN101982580A (en) * | 2010-11-02 | 2011-03-02 | 大连工业大学 | Polyacrylonitrile/hydroxyapatite composite adsorbent fiber and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109320017A (en) * | 2018-11-02 | 2019-02-12 | 浙江海洋大学 | A kind of processing method of landfill leachate |
| CN109320017B (en) * | 2018-11-02 | 2021-09-17 | 浙江海洋大学 | Method for treating landfill leachate |
| CN113511865A (en) * | 2021-07-28 | 2021-10-19 | 河北宏京新型建材有限公司 | Preparation method of fiber concrete prefabricated truss |
| CN115872689A (en) * | 2022-12-02 | 2023-03-31 | 盐城市福奇混凝土有限公司 | Composite fiber high-strength pervious concrete and preparation method thereof |
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Application publication date: 20180928 |