CN109158090A - One kind wire rod of 3D printing containing spirulina and preparation method thereof - Google Patents

One kind wire rod of 3D printing containing spirulina and preparation method thereof Download PDF

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Publication number
CN109158090A
CN109158090A CN201810741405.9A CN201810741405A CN109158090A CN 109158090 A CN109158090 A CN 109158090A CN 201810741405 A CN201810741405 A CN 201810741405A CN 109158090 A CN109158090 A CN 109158090A
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China
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wire rod
spirulina
printing
preparation
printing containing
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Inventor
陈庆华
徐晓榕
肖荔人
黄宝铨
钱庆荣
杨松伟
夏新曙
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Fujian Normal University
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Fujian Normal University
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Priority to CN201810741405.9A priority Critical patent/CN109158090A/en
Publication of CN109158090A publication Critical patent/CN109158090A/en
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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
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • 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
    • B01J20/264—Synthetic macromolecular compounds derived from different types of monomers, e.g. linear or branched copolymers, block copolymers, graft copolymers
    • 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
    • B01J20/28014—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 form
    • 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
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/286—Treatment of water, waste water, or sewage by sorption using natural organic sorbents or derivatives thereof
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/44—Materials comprising a mixture of organic materials
    • B01J2220/445—Materials comprising a mixture of organic materials comprising a mixture of polymers
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
    • B01J2220/4843—Algae, aquatic plants or sea vegetals, e.g. seeweeds, eelgrass
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)

Abstract

The present invention discloses one kind wire rod of 3D printing containing spirulina and preparation method thereof.The 3D printing wire rod is matrix resin 59-91, spirulina 8-40, white oil 0.05-2 according to weight percent composition.The preparation method comprises the following steps: (1) is dry；(2) weighing；(3) high-speed kneading；(4) melt pelletization；(5) melting extrusion；(6) cooling traction；(7) volume bundle；(8) specific structure is printed as by FDM technology.Present invention introduces a kind of prokaryotes, can combine with dye molecule or heavy metal ion rich in functional functional group and cheap, using efficiently accurately FDM technology prepares the open support skeleton of fine particle.Preparation process is simple, low energy consumption overcomes polysaccharide with more difficult after solution, powder, microballoon and gel form processing dyestuff and adsorbent and solution separation is caused secondary pollution as adsorbent, with certain recycling performance, realizes the green circulatory of material and efficiently utilize.

Description

One kind wire rod of 3D printing containing spirulina and preparation method thereof
Technical field
The invention belongs to Material Fields, and in particular to one kind wire rod of 3D printing containing spirulina and preparation method thereof.
Background technique
Water pollution caused by heavy metal and dyestuff is always the global environmental problem got worse.Heavy metal from Son and synthetic dyestuffs are to common are poison, carcinogen, they are not easy to be biodegradable, and are enriched in organism by food chain It is interior, cause various diseases and disorder to generate.It is extremely important that excessive heavy metal is removed from natural water.Such as chemical precipitation, Ion exchange, absorption and the conventional methods such as reverse osmosis are the common methods of heavy metals removal, but due to technology or economic restriction, this The use of a little methods is restricted.Therefore, explore is using the potential material to heavy metal with strong tolerance and adsorption capacity It is vital.Dye wastewater treatment also includes absorption method, membrane separation process, extraction, Coagulation Method and electrochemical process etc..At these A possibility that method of reason heavy metal and waste water from dyestuff requires greatly secondary treatment, and input cost is high, causes secondary pollution is big.One The kind micro-nano device of 3D printing containing spirulina has just agreed with this social demand, realizes the device of adsorbent, can be easy Apply to chemical production process, can also largely put into wastewater from chemical industry subsequent processing.
Currently, common adsorbent is mainly clay mineral adsorbent (such as montmorillonite, diatomite, galapectite and rectorite Deng), carbon material adsorbent (such as active carbon, graphene, carbon nanotube), synthesis polymeric sorbent (such as polyaniline), clipped wire Sub- adsorbent (such as Mg, Zn), this kind of adsorbent plays obvious action in sewage treatment, but its preparation process is cumbersome, Energy is consumed, it is at high cost, and wherein most sorbent circulation is big using difficulty, it is difficult to secondary use, and hold in regenerative process Be also easy to produce toxic and harmful gas, need to put into a large amount of cost this make its in the treatment of waste water application be restricted.
Spirulina is a kind of photoautotrophy type cyanobacteria, the Primary Production being responsible in major part aquatic environment, in aquatic ecological It is played an important role in the food web of system.Because its protein rich in, multivitamin, carbohydrate, algae are more The substances such as sugar, unsaturated fatty acid and microelement.Because alga cells wall is by fibrous structure and unbodied various polysaccharide Embedding matrix, several functional chemical groups (functional groups such as amino, hydroxyl, carboxyl, phosphate radical) on frustule surface It can attract and be isolated heavy metal ion, dye molecule can be made to be integrated to spirulina surface, can be used as decoloring dye waste water biology Material.Compared with other biological adsorbent material, spirulina adsorbent has many advantages, such as that large specific surface area, adsorption capacity are big.But because The limitation that powder granule is tiny, is difficult to realize be separated by solid-liquid separation is restricted its application.
What matrix resin selection had good mechanical strength and a biocompatibility can be used for the poly- of fused glass pellet (FDM) Object is closed, spirulina is combined with high molecular material, is produced by newest fused glass pellet (FDM) mode containing spirulina 3D printing micro-nano device realizes the device of adsorbent.
Summary of the invention
Aiming at the problem that above-mentioned background technique, the purpose of the present invention aims to solve the problem that existing porous adsorbing material preparation process is numerous It is trivial, energy consumption is high, subsequent processing difficulty is big, be easy to cause secondary pollution problems, provide a kind of wire rod of 3D printing containing spirulina and Preparation method.The micro-nano device of 3D printing containing spirulina made from this method is easy, and energy consumption is small, at low cost, exemplar controlled shape, And it is high to the treatment effeciency containing heavy metal or toxic dye, recycling is simple, can efficient circulation utilization.
The purpose of the present invention is what is be achieved through the following technical solutions:
1. a kind of wire rod of 3D printing containing spirulina, is made of the component of following weight percent:
Matrix resin 59-91
Spirulina 8-40
White oil 0.05-2.
2. matrix resin described in is at least a kind of selected from polylactic acid (PLA), polyethylene terephthalate -1,4- ring Hexane diformazan alcohol ester (PETG), polyamide (PA), thermoplastic polyurethane (TPU), is gathered acrylonitrile-butadiene-styrene (ABS) (ABS) Succinic acid-butanediol ester (PBS) or polycaprolactone (PCL).
3. spirulina described in is at least a kind of selected from blunt top spirulina, spirulina maxim or India's spirulina.
The preparation method of wire rod of 3D printing containing spirulina described in 4. a kind of the following steps are included:
A. matrix resin and spirulina are dried in vacuo 12h respectively；
B. according to percentage of weight formula, matrix resin, spirulina and white oil after weighing drying；
C. each group after weighing is placed in high-speed kneading machine, keeps revolving speed 1000-6000rpm/min, high-speed stirred 3- 20min；
D. it is sufficiently mixed uniform raw material by above-mentioned and puts into screw extruder, heated by 60-255 DEG C of temperature, in screw rod It melts intracavitary fusion plastification and is that 10-280rpm squeezes out raw material with revolving speed；It is sent into pelleter from the raw material of Screw Extrusion through cooling It is cut into particle；
E. the pellet after cutting is put into screw extruder, is heated by 60-255 DEG C of temperature, melts intracavitary melting in screw rod It is plasticized and is that 10-280rpm squeezes out lines from stainless steel mouth mold with revolving speed；
F. lines are fully cooled molding through three-stage cooling sink, and the wire rod of fixed size diameter is then distracted into through dragger；
G. the wire rod after being formed enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected The frequency of dragger is 5-40HZ.
H. wire rod made from step G is applied into 3D printing, prints corresponding 3D printing micro-nano device.
5. screw extruder described in is one of single screw extrusion machine, double screw extruder, three-screw extruder.
6. the first cooling trough water temperature described in is 25 DEG C -40 DEG C；Second cooling trough water temperature is 5 DEG C -20 DEG C；Third is cold But sink is 0 DEG C of mixture of ice and water.
7. 3D printing micro-nano device print temperature described in is 60-200 DEG C, baseplate temp is 25-80 DEG C, print speed is 15-100mm/s, printing thickness are 0.1-0.2mm.
8. 3D printing micro-nano device shape described in is square, cuboid, sphere and conveyor screw.
A kind of biodegradable plastic with adsorption function/spirulina 3D printing line made from preparation method described in 9. The micro-nano device of material preparation is used for the wastewater treatment of heavy metal and toxic dye.
The preferred methylene blue of the toxic dye, rhodamine B, methyl orange, sunset yellow or Congo red;The heavy metal The preferred Cd of ion2+、Pb2+、Cu2+、Cr6+Or Zn+。
The invention has the benefit that 1) micro-nano device of the wire rod of 3D printing containing spirulina preparation produced by the present invention is adopted Adsorbent skeleton is made with FDM forming technique, printing precision is high, and structure-controllable provides skeletal support for small absorption particle, Solve the problems, such as subsequent recovery；2) micro-nano device of 3D printing containing spirulina preparation process produced by the present invention is easy, less energy-consuming；3) The micro-nano device of 3D printing containing spirulina produced by the present invention efficiently applies to the wastewater treatment of heavy metal and toxic dye；4) originally Invention is obtained, and there is adsorption function 3D printing containing spirulina micro-nano device can be recycled, and realize the ancestor of resource green circulatory Purport.
Detailed description of the invention
Fig. 1 is a kind of micro-nano device exterior appearance figure of wire rod of 3D printing containing spirulina preparation.
Fig. 2 is that a kind of micro-nano device of wire rod of 3D printing containing spirulina preparation adsorbs the exterior appearance of Congo red preceding solution.
Fig. 3 is the exterior appearance that a kind of micro-nano device of wire rod of 3D printing containing spirulina preparation adsorbs Congo red rear solution.
Fig. 4 is a kind of removal rate of the micro-nano device to the Congo red solution of various concentration of wire rod of 3D printing containing spirulina preparation Figure.
Specific embodiment
Son is described in further details the present invention combined with specific embodiments below, but this should not be interpreted as of the invention Range is only limitted to following embodiment.
Embodiment 1
A kind of wire rod of 3D printing containing spirulina, which is characterized in that be made of the component of following weight percent:
Polylactic acid (PLA) 70
Blunt top spirulina 29.95
White oil 0.05
A kind of preparation method of the wire rod of 3D printing containing spirulina the following steps are included:
A. PLA(700g) and blunt top spirulina (299.5g) are dried in vacuo 12h respectively；
B. according to percentage of weight formula, weigh it is dry after PLA(700g), blunt top spirulina (299.5g) and white oil (0.5g)；
C. each group after weighing is placed in high-speed kneading machine, keeps revolving speed 1000rpm/min, high-speed stirred 5min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into double screw extruder, extrusion temperature be set as 110 DEG C, 120 DEG C, 135 DEG C, 160 DEG C, 175 DEG C, 175 DEG C, 170 DEG C, 165 DEG C, 160 DEG C, 155 DEG C, melt intracavitary fusion plastification in twin-screw And with revolving speed be 150rpm/min, squeeze out raw material；Particle is cut into through cooling be sent into pelleter from the raw material of twin-screw extrusion；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter are as follows: 110 DEG C of an area, two areas 160 DEG C, three 170 DEG C of areas, four 175 DEG C of areas, five 175 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with revolving speed 80rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and cooling trough water temperature is respectively as follows: 26 DEG C, 20 DEG C and 0 DEG C, then passes through Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after being formed enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected The frequency of dragger is 30HZ.
H., 3D printing wire rod that step G is obtained is printed as to the square of hollow out, print temperature 180 by FDM technology DEG C, baseplate temp be 60 DEG C, print speed 50mm/s, printing thickness be 0.1mm, see Fig. 1.
I., the 3D printing hollow out square that step H is obtained is used for the absorption of congo red, Fig. 2 and Fig. 3 are seen, by Fig. 3 It knows lighter color, shows that adsorption effect is good, Fig. 4 experimental data further demonstrates the absorption property of material.
Embodiment 2
A kind of wire rod of 3D printing containing spirulina, which is characterized in that be made of the component of following weight percent:
Poly butylene succinate (PBS) 78
India's spirulina 21.8
White oil 0.2
A kind of preparation method of the wire rod of 3D printing containing spirulina the following steps are included:
A. PBS(780g) and India's spirulina (218g) are dried in vacuo 12h respectively；
B. according to percentage of weight formula, weigh it is dry after PBS(780g), India's spirulina (218g) and white oil (2g)；
C. each group after weighing is placed in high-speed kneading machine, keeps revolving speed 2000rpm/min, high-speed stirred 6min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into double screw extruder, extrusion temperature be set as 98 DEG C, 105 DEG C, 110 DEG C, 120 DEG C, 130 DEG C, 132 DEG C, 125 DEG C, 125 DEG C, 120 DEG C, 110 DEG C melt intracavitary fusion plastification in twin-screw and to turn Speed is 130rpm/min, squeezes out raw material；Particle is cut into through cooling be sent into pelleter from the raw material of twin-screw extrusion；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter are as follows: 90 DEG C of an area, two areas 100 DEG C, three 120 DEG C of areas, four 125 DEG C of areas, five 125 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with revolving speed 60rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and cooling trough water temperature is respectively as follows: 23 DEG C, 20 DEG C and 0 DEG C, then passes through Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after being formed enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected The frequency of dragger is 25HZ.
H., 3D printing wire rod that step G is obtained is printed as to the cuboid of hollow out, print temperature 130 by FDM technology DEG C, baseplate temp be 30 DEG C, print speed 30mm/s, printing thickness be 0.1mm.
I. the 3D printing hollow out cuboid that step H is obtained is used for Cd2+Absorption.
Embodiment 3
A kind of wire rod of 3D printing containing spirulina, which is characterized in that be made of the component of following weight percent:
Polycaprolactone (PCL) 65
Spirulina maxim 34.7
White oil 0.3
A kind of preparation method of the wire rod of 3D printing containing spirulina the following steps are included:
A. PCL(650g) and spirulina maxim (347g) are dried in vacuo 12h respectively；
B. according to percentage of weight formula, weigh it is dry after PC(650g), spirulina maxim (347g) and white oil (3g)；
C. each group after weighing is placed in high-speed kneading machine, keeps revolving speed 2000rpm/min, high-speed stirred 6min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into double screw extruder, extrusion temperature be set as 60,65 DEG C, 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 100 DEG C, 95 DEG C, 80 DEG C, 65 DEG C, melt intracavitary fusion plastification and with revolving speed in twin-screw for 120rpm/ Min squeezes out raw material；Particle is cut into through cooling be sent into pelleter from the raw material of twin-screw extrusion；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter are as follows: 60 DEG C of an area, two areas 80 DEG C, three 95 DEG C of areas, four 100 DEG C of areas, five 100 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with revolving speed 60rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and cooling trough water temperature is respectively as follows: 25 DEG C, 20 DEG C and 0 DEG C, then passes through Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after being formed enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected The frequency of dragger is 25HZ.
H., 3D printing wire rod that step G is obtained is printed as to the square of hollow out, print temperature 130 by FDM technology DEG C, baseplate temp be 30 DEG C, print speed 30mm/s, printing thickness be 0.1mm.
Embodiment 4
A kind of wire rod of 3D printing containing spirulina, which is characterized in that be made of the component of following weight percent:
Polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PETG) 67
Blunt top spirulina 32.8
White oil 0.2
A kind of preparation method of the wire rod of 3D printing containing spirulina the following steps are included:
A. PETG(670g) and blunt top spirulina (328g) are dried in vacuo 12h respectively；
B. according to percentage of weight formula, weigh it is dry after PETG(670g), blunt top spirulina (328g) and white oil (2g)；
C. each group after weighing is placed in high-speed kneading machine, keeps revolving speed 2500rpm/min, high-speed stirred 10min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into double screw extruder, extrusion temperature be set as 150 DEG C, 160 DEG C, 180 DEG C, 195 DEG C, 210 DEG C, 220 DEG C, 225 DEG C, 225 DEG C, 200 DEG C, 190 DEG C melt intracavitary fusion plastification in twin-screw and to turn Speed is 200rpm/min, squeezes out raw material；Particle is cut into through cooling be sent into pelleter from the raw material of twin-screw extrusion；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter are as follows: 170 DEG C of an area, two areas 180 DEG C, three 200 DEG C of areas, four 215 DEG C of areas, five 220 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with revolving speed 65rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and cooling trough water temperature is respectively as follows: 25 DEG C, 22 DEG C and 0 DEG C, then passes through Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after being formed enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected The frequency of dragger is 35HZ.
H., 3D printing wire rod that step G is obtained is printed as to the sphere of hollow out by FDM technology, print temperature is 215 DEG C, Baseplate temp is 80 DEG C, print speed 80mm/s, printing thickness are 0.2mm.
Embodiment 5
A kind of wire rod of 3D printing containing spirulina, which is characterized in that be made of the component of following weight percent:
Acrylonitrile-butadiene-styrene (ABS) (ABS) 74
Spirulina maxim 25.94
White oil 0.06
A kind of preparation method of the wire rod of 3D printing containing spirulina the following steps are included:
A. ABS(740g) and spirulina maxim (259.4g) are dried in vacuo 12h respectively；
B. according to percentage of weight formula, weigh it is dry after ABS(740g), spirulina maxim (259.4g) and white oil (0.6g)；
C. each group after weighing is placed in high-speed kneading machine, keeps revolving speed 1550rpm/min, high-speed stirred 10min；
D. be sufficiently mixed uniform raw material by above-mentioned and put into double screw extruder, extrusion temperature be set as 195 DEG C, 200 DEG C, 205 DEG C, 215 DEG C, 220 DEG C, 230 DEG C, 235 DEG C, 235 DEG C, 230 DEG C, melt intracavitary fusion plastification in twin-screw and are with revolving speed 180rpm/min squeezes out raw material；Particle is cut into through cooling be sent into pelleter from the raw material of twin-screw extrusion；
E. the pellet after cutting is put into single screw rod wire rod extruder, wire rod extruder parameter are as follows: 190 DEG C of an area, two areas 200 DEG C, three 230 DEG C of areas, four 230 DEG C of areas, five 215 DEG C of areas melt intracavitary fusion plastification in single screw rod wire rod extruder and are with revolving speed 65rpm/min squeezes out lines from stainless steel mouth mold；
F. lines are fully cooled molding through three-stage cooling sink, and cooling trough water temperature is respectively as follows: 25 DEG C, 21 DEG C and 0 DEG C, then passes through Dragger is distracted into the wire rod of fixed size diameter；
G. the wire rod after being formed enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected The frequency of dragger is 31HZ.
H., 3D printing wire rod that step G is obtained is printed as to 24 face bodies of hollow out, print temperature 215 by FDM technology DEG C, baseplate temp be 65 DEG C, print speed 40mm/s, printing thickness be 0.1mm.

Claims (10)

1. a kind of wire rod of 3D printing containing spirulina, which is characterized in that be made of the component of following weight percent:
Matrix resin 59-91
Spirulina 8-40
White oil 0.05-2.
2. one kind wire rod of 3D printing containing spirulina according to claim 1, which is characterized in that the matrix resin is extremely It is rare a kind of selected from polylactic acid (PLA), polyethylene terephthalate -1,4 cyclohexane dimethanol ester (PETG), acrylonitrile - Butadiene-styrene (ABS), polyamide (PA), thermoplastic polyurethane (TPU), poly butylene succinate (PBS) gather in oneself Ester (PCL).
3. one kind wire rod of 3D printing containing spirulina according to claim 1, which is characterized in that the spirulina is at least One kind being selected from blunt top spirulina, spirulina maxim or India's spirulina.
4. a kind of preparation method of any wire rod of 3D printing containing spirulina of claims 1 to 3, which is characterized in that including Following steps:
A. matrix resin and spirulina are dried in vacuo 12h respectively；
B. according to percentage of weight formula, matrix resin, spirulina and white oil after weighing drying；
C. each group after weighing is placed in high-speed kneading machine, keeps revolving speed 1000-6000rpm/min, high-speed stirred 3- 20min；
D. the uniform raw material that is sufficiently mixed step C obtained puts into screw extruder, heats by 60-255 DEG C of temperature, Intracavitary fusion plastification is melted in screw rod and is that 10-280rpm squeezes out raw material with revolving speed；It is cut from the raw material of Screw Extrusion through cooling feeding Particle is cut into grain machine；
E. the pellet after cutting is put into screw extruder, is heated by 60-255 DEG C of temperature, melts intracavitary melting in screw rod It is plasticized and is that 10-280rpm squeezes out lines from stainless steel mouth mold with revolving speed；
F. the lines that step E is obtained are fully cooled molding through three-stage cooling sink, and it is straight to be then distracted into fixed size through dragger The wire rod of diameter；
G. the wire rod after being formed enters two-wheel storage rack and pulls out wire rod and be wound into finished product in coil winder, what coil winder was connected The frequency of dragger is 5-40HZ；
H. wire rod made from step G is applied into 3D printing, prints corresponding 3D printing micro-nano device.
5. a kind of preparation method of wire rod of 3D printing containing spirulina according to claim 4, which is characterized in that described Screw extruder is one of single screw extrusion machine, double screw extruder, three-screw extruder.
6. a kind of preparation method of wire rod of 3D printing containing spirulina according to claim 4, which is characterized in that described First cooling trough water temperature is 25 DEG C -40 DEG C；Second cooling trough water temperature is 5 DEG C -20 DEG C；Third cooling trough is 0 DEG C of ice water Mixture.
7. a kind of preparation method of wire rod of 3D printing containing spirulina according to claim 4, which is characterized in that described 3D printing micro-nano device print temperature is 60-200 DEG C, baseplate temp is 25-80 DEG C, print speed 15-100mm/s, printing Thickness is 0.1-0.2mm.
8. one kind wire rod of 3D printing containing spirulina according to claim 4 and preparation method thereof, which is characterized in that described 3D printing micro-nano device shape be square, cuboid, sphere or conveyor screw.
9. a kind of micro-nano of the preparation of the wire rod of 3D printing containing spirulina made from any preparation method of claim 4-8 Device is for heavy metal or the wastewater treatment of toxic dye.
10. application according to claim 9, which is characterized in that the toxic dye is methylene blue, rhodamine B, first Base orange, day malachite green or Congo red；The heavy metal ion is Cd2+、Pb2+、Cu2+、Cr6+Or Zn+。
CN201810741405.9A 2018-07-09 2018-07-09 One kind wire rod of 3D printing containing spirulina and preparation method thereof Pending CN109158090A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110343283A (en) * 2019-07-20 2019-10-18 福建师范大学 A kind of light of 3D printing skeleton@stannic oxide/wolframic acid tin urges the preparation method of device
CN110394192A (en) * 2019-07-20 2019-11-01 福建师范大学 A kind of light of 3D printing skeleton@zinc oxide urges the preparation method of device
CN110433770A (en) * 2019-07-17 2019-11-12 天津大学 Photocatalysis honeycomb C-base composte material and preparation method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110433770A (en) * 2019-07-17 2019-11-12 天津大学 Photocatalysis honeycomb C-base composte material and preparation method
CN110433770B (en) * 2019-07-17 2022-03-18 天津大学 Photocatalytic honeycomb carbon-based composite material and preparation method thereof
CN110343283A (en) * 2019-07-20 2019-10-18 福建师范大学 A kind of light of 3D printing skeleton@stannic oxide/wolframic acid tin urges the preparation method of device
CN110394192A (en) * 2019-07-20 2019-11-01 福建师范大学 A kind of light of 3D printing skeleton@zinc oxide urges the preparation method of device
CN110343283B (en) * 2019-07-20 2021-12-31 福建师范大学 Preparation method of photocatalyst device with skeleton of tin dioxide/tin tungstate printed in 3D mode

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