CN107737584A - A kind of porous material with micro-nano structure and preparation method thereof - Google Patents
A kind of porous material with micro-nano structure and preparation method thereof Download PDFInfo
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- CN107737584A CN107737584A CN201710853250.3A CN201710853250A CN107737584A CN 107737584 A CN107737584 A CN 107737584A CN 201710853250 A CN201710853250 A CN 201710853250A CN 107737584 A CN107737584 A CN 107737584A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28085—Pore diameter being more than 50 nm, i.e. macropores
-
- 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
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
- C02F2101/30—Organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention discloses a kind of porous material with micro-nano structure and preparation method thereof.Present invention seek to address that the problems such as existing porous material preparation process is complicated, energy consumption is big, cost is high, is become more meticulous using quick forming fabri-cation FDM technology and prepares the porous material with micro-nano structure.Technical scheme is as follows：1st, it is PLA 55 85 according to percentage of weight formula, pore creating material 10 30, toughener 2 12, plasticizer 1 10, stabilizer 15.2nd, preparation method is to extrude PLA and various auxiliary agents by mixed melting 3D printing wire rod is made, then is printed as specific structure by FDM technology, most obtains the porous material with micro-nano structure through water process afterwards.Porosity of porous material prepared by the present invention is high, structure-controllable, and preparation method is simple efficiently, non-secondary pollution, can be applied to sewage disposal.
Description
Technical field
The present invention relates to a kind of porous material with micro-nano structure and preparation method thereof.
Background technology
With global industry progress faster, water pollution situation is on the rise.Wastewater treatment level how is improved, is alleviated useless
The situation such as water pollution and water resource anxiety has turned into the focus of current water treatment field.The main reason for water pollution is organic matter dirt
The discharge of thing and heavy metal ion is contaminated, on the one hand the direct polluted source of meeting causes the generation of a large amount of waste water so that water resource is tight
, it on the other hand can pass through the health of the biological chain building-up effect threat mankind.Therefore, water pollution control and improvement are turned into weight
Weight.At present, many technologies are applied to water pollution purified treatment, such as adsorb, precipitate, are electrolysed, flocculate, membrane technology.With it
Its method is compared, and absorption method has the advantages that low stain, processing efficient, economical and practical enjoy people to favor.
At present, conventional porous adsorbent is mainly based on inorganic material, including activated carbon, diatomite, bentonite and two
Silica etc., this kind of adsorbent has preferable adsorption activity, but preparation process is complicated, energy consumption is big, cost is high, is unfavorable for realizing
Device and practical application.
Polymer absorbant is due to having the advantages that adsorption efficiency is higher, prepare simplicity, cost is cheap and is widely studied.
But polymer absorbant internal pore creating material in processing procedure is difficult to, through loose structure of the over etching without easily forming homogeneous, cause
Relatively low specific surface area, then influences adsorption effect.3D printing is a kind of new intelligent Manufacturing Technology, compared to traditional shaping side
For formula, it is quickly prepared, the manufacture that becomes more meticulous, the advantages that stock utilization is high and receive much concern.Fused glass pellet（FDM）Make
For 3D printing technique important component, polymer can be stacked to form the device with labyrinth by it by fuse, into
To prepare the effective way of polymer absorbant.
PLA（PLA）It is a kind of environmentally friendly material, there is good mechanical strength and biocompatibility.It is main
Obtained by lactide ring-opening polymerisation, ester group therein makes it have certain polarity, simultaneously because it has good melting
Deposition modeling performance, it can be used to prepare the skeleton of polymer absorbant.Polyvinyl alcohol（PVA）, will not with good water solubility
The secondary pollution of solvent is caused, can be used to the pore creating material as polymer absorbant.In addition, in order to better adapt to be molded
Journey, thermoplastic polyurethane is also selected herein（TPU）Or polycaprolactone（PCL）As toughener toughness reinforcing compound system.
The content of the invention
For above-mentioned background and problem, the purpose of the present invention aims to solve the problem that existing porous material preparation process complexity, energy consumption
Greatly, the problems such as cost is high, and a kind of porous material with micro-nano structure and preparation method thereof is provided.It is produced by the present invention porous
Material porosity is high, structure-controllable, and preparation method is simple efficiently, non-secondary pollution, can be applied to sewage disposal.
The purpose of the present invention is achieved by the following technical solution：
1st, a kind of porous material with micro-nano structure, it is characterised in that be according to percentage by weight proportioning：
PLA 55-85
Pore creating material 10-30
Toughener 2-12
Plasticizer 1-10
Stabilizer 1-5.
Described pore creating material is polyvinyl alcohol（PVA）.
Described toughener is at least a kind of to be selected from thermoplastic polyurethane（TPU）, polycaprolactone（PCL）.
Described plasticizer is at least a kind of selected from glycerine, ethylene glycol, polyethylene glycol.
Described stabilizer is at least a kind of selected from talcum powder, calcium hydroxide, calcium oxide, magnesium hydroxide.
The preparation method of a kind of porous material with micro-nano structure of the present invention, it is characterised in that including following
Step：
A. it is granulated after mixing PLA, pore creating material, toughener, plasticizer and stabilizer by screw rod melting extrusion；
B. by gained pellet by wire rod machine travel into 3D printing wire rod；
C. 3D printing wire rod is printed as specific structure by FDM technology；
D. specific structure is put into water and dissolved, obtain the porous material with micro-nano structure.
The a diameter of 0.01-0.5mm of printer nozzle of described FDM technology.
The water temperature dissolved in the water of the step D is 0 DEG C -80 DEG C.
The dissolution time dissolved in the water of the step D is 5-300min
The aperture that the step D obtains the porous material with micro-nano structure is 0.005-10 μm；The step D obtains having micro-
It is cylindrical shape that the pore morphology of the porous material of micro-nano structure is at least a kind of, plate shaped or wedge-shaped.
Beneficial effects of the present invention are：1）Porous material produced by the present invention, it is a kind of high score based on FDM technology shaping
Sub- material, there is excellent printing shaping performance, and printed product stability is high, structure-controllable；2）It is produced by the present invention porous
Material, using water-soluble polymer as pore creating material, poration process is green, and pore size is controllable；3）The present invention is made
Porous material, have that porosity is high, adsorbent is extensive, and preparation method is simply efficient, can be applied to sewage disposal.
Brief description of the drawings
Fig. 1 is a kind of porous material scanning electron microscope (SEM) photograph with micro-nano structure.
Embodiment
The present invention is described in further details with reference to specific embodiment, but this should not be interpreted as to the present invention's
Scope is only limitted to following examples.
Embodiment 1
1st, a kind of porous material with micro-nano structure, it is characterised in that according to percentage of weight formula：
PLA 65
PVA 20
TPU 6
Ethylene glycol 7
Talcum powder 2.
2nd, the preparation method of the above-mentioned porous material with micro-nano structure, comprises the following steps：
A. it is granulated after mixing PLA, PVA, TPU, ethylene glycol and talcum powder by screw rod melting extrusion；
B. by gained pellet by wire rod machine travel into 3D printing wire rod；
C. 3D printing wire rod is printed as specific structure by the 3D printer that nozzle diameter is 0.1mm；
D. specific structure is put into the water that temperature is 40 DEG C and carries out dissolving 60min, obtained based on cylinder-shaped hole, pore-size distribution
For 0.2-5 μm of porous material（As shown in Figure 1）.
Embodiment 2
1st, a kind of porous material with micro-nano structure, it is characterised in that according to percentage of weight formula：
PLA 70
PVA 15
PCL 8
Polyethylene glycol 5.8
Calcium oxide 1.2.
2nd, the preparation method of the above-mentioned porous material with micro-nano structure, comprises the following steps：
A. it is granulated after mixing PLA, PVA, PCL, polyethylene glycol and calcium oxide by screw rod melting extrusion；
B. by gained pellet by wire rod machine travel into 3D printing wire rod；
C. 3D printing wire rod is printed as specific structure by the 3D printer that nozzle diameter is 0.2mm；
D. specific structure is put into the water that temperature is 50 DEG C and carries out dissolving 30min, obtained based on cylinder-shaped hole, pore-size distribution
For 0.1-4 μm of porous material.
Embodiment 3
1st, a kind of porous material with micro-nano structure, it is characterised in that according to percentage of weight formula：
PLA 58
PVA 26
PCL 5
Glycerine 7.5
Magnesium hydroxide 3.5.
2nd, the preparation method of the above-mentioned porous material with micro-nano structure, comprises the following steps：
A. it is granulated after mixing PLA, PVA, PCL, glycerine and magnesium hydroxide by screw rod melting extrusion；
B. by gained pellet by wire rod machine travel into 3D printing wire rod；
C. 3D printing wire rod is printed as specific structure by the 3D printer that nozzle diameter is 0.2mm；
D. specific structure is put into the water that temperature is 50 DEG C and carries out dissolving 55min, obtained based on plate shaped hole, pore-size distribution
For 0.3-6 μm of porous material.
Embodiment 4
1st, a kind of porous material with micro-nano structure, it is characterised in that according to percentage of weight formula：
PLA 75
PVA 12
TPU 8
Ethylene glycol 4
Calcium hydroxide 1.
2nd, the preparation method of the above-mentioned porous material with micro-nano structure, comprises the following steps：
A. it is granulated after mixing PLA, PVA, TPU, ethylene glycol and calcium hydroxide by screw rod melting extrusion；
B. by gained pellet by wire rod machine travel into 3D printing wire rod；
C. 3D printing wire rod is printed as specific structure by the 3D printer that nozzle diameter is 0.3mm；
D. specific structure is put into the water that temperature is 25 DEG C and carries out dissolving 30min, obtained based on wedged hole, pore-size distribution is
0.05-4 μm of porous material.
Embodiment 5
1st, a kind of porous material with micro-nano structure, it is characterised in that according to percentage of weight formula：
PLA 64
PVA 23
TPU 6
Glycerine 6
Calcium oxide 1.
2nd, the preparation method of the above-mentioned porous material with micro-nano structure, comprises the following steps：
A. it is granulated after mixing PLA, PVA, TPU, glycerine and calcium oxide by screw rod melting extrusion；
B. by gained pellet by wire rod machine travel into 3D printing wire rod；
C. 3D printing wire rod is printed as specific structure by the 3D printer that nozzle diameter is 0.4mm；
D. specific structure is put into the water that temperature is 20 DEG C and carries out dissolving 150min, obtained based on plate shaped hole, aperture point
Cloth is 0.2-8 μm of porous material.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (10)
1. a kind of porous material with micro-nano structure, it is characterised in that be made up of the component of following percentage by weight：
PLA 55-85
Pore creating material 10-30
Toughener 2-12
Plasticizer 1-10
Stabilizer 1-5.
A kind of 2. porous material with micro-nano structure according to claim 1, it is characterised in that：Described pore creating material is
Polyvinyl alcohol（PVA）.
A kind of 3. porous material with micro-nano structure according to claim 1, it is characterised in that：Described toughener is extremely
Rare one kind is selected from thermoplastic polyurethane（TPU）, polycaprolactone（PCL）.
A kind of 4. porous material with micro-nano structure according to claim 1, it is characterised in that：Described plasticizer is extremely
It is rare a kind of selected from glycerine, ethylene glycol, polyethylene glycol.
A kind of 5. porous material with micro-nano structure according to claim 1, it is characterised in that：Described stabilizer is extremely
It is rare a kind of selected from talcum powder, calcium hydroxide, calcium oxide, magnesium hydroxide.
6. a kind of preparation method of porous material with micro-nano structure described in claim 1-5 any one, its feature exist
In comprising the following steps：
A. it is granulated after mixing PLA, pore creating material, toughener, plasticizer and stabilizer by screw rod melting extrusion；
B. by gained pellet by wire rod machine travel into 3D printing wire rod；
C. 3D printing wire rod is printed as specific structure by FDM technology；
D. the step C specific structures obtained are put into water and dissolved, obtain the porous material with micro-nano structure.
A kind of 7. preparation method of porous material with micro-nano structure according to claim 6, it is characterised in that：It is described
FDM technology a diameter of 0.01-0.5mm of printer nozzle.
A kind of 8. preparation method of porous material with micro-nano structure according to claim 6, it is characterised in that：It is described
The water temperature dissolved in step D water is 0 DEG C -80 DEG C.
A kind of 9. preparation method of porous material with micro-nano structure according to claim 6, it is characterised in that：It is described
The dissolution time dissolved in step D water is 5-300min.
A kind of 10. preparation method of porous material with micro-nano structure according to claim 6, it is characterised in that：Institute
The aperture for stating the porous material that step D obtains having micro-nano structure is 0.005-10 μm；The step D is obtained with micro-nano structure
Porous material pore morphology it is at least a kind of for cylindrical shape, it is plate shaped or wedge-shaped.
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Cited By (8)
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| CN109569543A (en) * | 2019-01-08 | 2019-04-05 | 福建师范大学 | A kind of compressible adsorbent material of 3D printing and preparation method thereof |
| CN109748351A (en) * | 2019-02-11 | 2019-05-14 | 福建师范大学 | A kind of preparation method of 3D printing photocatalytic device |
| CN109878069A (en) * | 2019-02-11 | 2019-06-14 | 福建师范大学 | A kind of dendritic phthalocyanine@SiO2The preparation method of photocatalytic device |
| WO2019199482A1 (en) * | 2018-04-10 | 2019-10-17 | The Procter & Gamble Company | Polymeric materials and articles manufactured there from |
| CN110615979A (en) * | 2019-10-31 | 2019-12-27 | 孝感市易生新材料有限公司 | 3D printing material capable of being cooled and solidified quickly and preparation method thereof |
| US10543639B2 (en) | 2016-08-19 | 2020-01-28 | The Procter & Gamble Company | Method for manufacturing a three-dimensional object |
| CN110756171A (en) * | 2019-11-06 | 2020-02-07 | 福建师范大学 | Method for preparing oyster shell powder-based sewage treatment device |
| CN112044397A (en) * | 2020-09-07 | 2020-12-08 | 福州职业技术学院 | Modified biochar-based adsorbent with core-shell structure and preparation method thereof |
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Cited By (14)
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| CN109748351A (en) * | 2019-02-11 | 2019-05-14 | 福建师范大学 | A kind of preparation method of 3D printing photocatalytic device |
| CN109878069A (en) * | 2019-02-11 | 2019-06-14 | 福建师范大学 | A kind of dendritic phthalocyanine@SiO2The preparation method of photocatalytic device |
| CN109878069B (en) * | 2019-02-11 | 2020-11-24 | 福建师范大学 | Dendritic phthalocyanine @ SiO2Preparation method of photocatalytic device |
| CN109748351B (en) * | 2019-02-11 | 2021-11-02 | 福建师范大学 | Preparation method of 3D printing photocatalytic device |
| CN110615979A (en) * | 2019-10-31 | 2019-12-27 | 孝感市易生新材料有限公司 | 3D printing material capable of being cooled and solidified quickly and preparation method thereof |
| CN110615979B (en) * | 2019-10-31 | 2022-02-08 | 孝感市易生新材料有限公司 | 3D printing material capable of being cooled and solidified quickly and preparation method thereof |
| CN110756171A (en) * | 2019-11-06 | 2020-02-07 | 福建师范大学 | Method for preparing oyster shell powder-based sewage treatment device |
| CN112044397A (en) * | 2020-09-07 | 2020-12-08 | 福州职业技术学院 | Modified biochar-based adsorbent with core-shell structure and preparation method thereof |
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Application publication date: 20180227 |