CN107213812B - Method for manufacturing stirrer for sewage treatment through 3D printing - Google Patents

Method for manufacturing stirrer for sewage treatment through 3D printing Download PDF

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Publication number
CN107213812B
CN107213812B CN201710518883.9A CN201710518883A CN107213812B CN 107213812 B CN107213812 B CN 107213812B CN 201710518883 A CN201710518883 A CN 201710518883A CN 107213812 B CN107213812 B CN 107213812B
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China
Prior art keywords
stirrer
stirring paddle
treating
sewage
printing
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CN201710518883.9A
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Chinese (zh)
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CN107213812A (en
Inventor
陶胜洋
孙雪艳
闫英
于永鲜
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Dalian University of Technology
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Dalian University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F33/00—Other mixers; Mixing plants; Combinations of mixers
    • B01F33/86—Mixing heads comprising a driven stirrer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05—Stirrers
    • B01F27/051—Stirrers characterised by their elements, materials or mechanical properties
    • B01F27/053—Stirrers characterised by their elements, materials or mechanical properties characterised by their materials
    • B01F27/0531—Stirrers characterised by their elements, materials or mechanical properties characterised by their materials with particular surface characteristics, e.g. coated or rough
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • 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
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • 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
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/305—Treatment of water, waste water or sewage
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Abstract

A method for manufacturing a stirrer for sewage treatment through 3D printing belongs to the technical field of environmental remediation. Printing a stirrer made of iron-containing polylactic acid by using a fused deposition type 3D printer; under the condition that the water bath temperature is 50-60 ℃, the printed stirrer is placed in NaOH solution for processing for 10-20 minutes, so that PLA coated outside the iron particles on the stirrer is dissolved in the NaOH solution, and the Fe particles are exposed; the stirring paddle is used for directly replacing and treating sewage containing metal ions due to the existence of iron particles on the surface; placing the stirrer treated by the NaOH solution in H saturated with NaCl2O2Treating in the solution for 1.8-2.3 hours to obtain an etched stirrer, wherein Fe particles on the surface of the stirrer are coated with H2O2Is oxidized into Fe2O3The catalyst is used for catalytically treating organic dye molecules in sewage. The method can be used for treating the sewage containing the organic dye repeatedly, and the removal rate of the organic dye is basically unchanged.

Description

Method for manufacturing stirrer for sewage treatment through 3D printing
Technical Field
The invention belongs to the technical field of environmental remediation, relates to a 3D printing stirrer, and particularly relates to a method for manufacturing a stirrer capable of removing organic dye molecules and partial heavy metal ions in sewage by 3D printing of iron-containing polylactic acid.
Background
Water, as an essential resource on which humans live, has apparently tended to be in short supply in many arid water-deficient areas. Water pollution causes a large amount of waste of water resources, and pollutants in water cause various human health problems. Therefore, a large number of sewage treatment methods have been developed. Organic dyes and heavy metal ions are two common pollutants in water and can be removed through the steps of adsorption, flocculation, oxidative degradation and the like. For example, the Fenton reaction, one of the advanced oxidation processes, is commonly used to treat organic dyes in water. In the process of removing heavy metal ions such as copper, mercury and the like, different metal ions can be removed through intermetallic reduction and replacement. For example, scrap iron can react with copper sulfate to extract copper and produce ferric sulfate. At present, the fenton reaction for removing dye molecules and the common replacement process for removing metal ions in sewage use different equipment and chemical reagents, and the process of the method is different. This brings about much invariance to the treatment of sewage containing complex components of both metal ions and organic dyes. It is therefore of great importance to develop an inexpensive and versatile process which can be used to treat different types of waste water.
In sewage treatment, the core process is the catalyst of oxidation reaction or the heterogeneous reaction process between various adsorbents and displacing agents and pollutants, which all occur on the interface, and the pollutants are subjected to substance migration and catalytic reaction between the interfaces. In these heterogeneous reactions, the diffusion process influenced by stirring is often one of the important steps in determining the reaction efficiency. Meanwhile, the traditional method of simply spreading and adding the catalyst, the flocculating agent or the displacing agent can cause a large amount of foreign substances to be introduced into the sewage, and the subsequent separation treatment work is time-consuming and labor-consuming. Therefore, it is important to develop a new sewage treatment method that can rapidly remove pollutants from water and remove water treatment chemicals from sewage.
3D printing is a new additive manufacturing technology that has been developed in recent years to produce a variety of materials into desired shapes through a layer-by-layer additive process. For example, plastics, metals, ceramics and various physically and chemically active composite materials can be processed into pre-designed shapes by 3D printing. Therefore, the chemical substance with the sewage treatment function can be processed and molded in a 3D printing mode to form a stirring device with mechanical stirring capacity.
Disclosure of Invention
The invention aims to provide a method for combining a 3D printing technology with surface treatment, and a 3D printing stirrer device capable of treating organic sewage is constructed.
The technical scheme of the invention is as follows:
a method for manufacturing a stirrer for treating sewage through 3D printing comprises the following steps:
printing a stirrer by using a fused deposition type 3D printer, wherein the stirrer is made of iron-containing polylactic acid;
under the condition that the water bath temperature is 50-60 ℃, the printed stirrer is placed in NaOH solution for processing for 10-20 minutes, so that PLA coated outside the iron particles on the stirrer is dissolved in the NaOH solution, and the Fe particles are exposed; the stirring paddle can be used for directly replacing and treating sewage containing metal ions due to the existence of iron particles on the surface;
preparation of saturated NaCl H2O2An aqueous solution; placing the stirrer treated by the NaOH solution in H saturated with NaCl2O2Treating in the solution for 1.8-2.3 hours to obtain an etched stirrer, wherein Fe particles on the surface of the stirrer are coated with H2O2Is oxidized into Fe2O3Therefore, the stirring paddle can be used for catalytically treating organic dye molecules in sewage.
The invention has the beneficial effects that: firstly, the invention adopts an additive manufacturing method, and the 3D printing technology is utilized for processing and forming, so that the shape designed by people in advance can be processed; secondly, the printed stirring device has two functions of stirring and catalyzing after surface treatment, so that the diffusion process in the reaction process is eliminated, and the reaction efficiency is improved; thirdly, after the organic dye or heavy metal ions in the sewage are treated, the stirring paddle can be directly taken out, and compared with the traditional method for spreading the catalyst, the method is simple and easy to implement and is easy for effective separation of the catalyst; fourthly, the sewage containing the organic dye can be circularly treated for many times, and the removal rate of the organic dye is basically unchanged.
Drawings
FIG. 1 is a schematic view of a designed 3D paddle model.
In the figure: 1 stirring paddle blade; 2 sets of shafts.
Detailed Description
The invention will be further described in detail by taking preferred examples as examples with reference to the drawings and technical schemes.
Example 1
A method for treating sewage containing metal ions by a 3D printing stirrer comprises the following specific steps:
(1) the stirring paddle model is designed by using 123D Design modeling software, the stirring paddle is printed by using a fused deposition type 3D printer, the stirring paddle has 6 blades, the thickness of each blade is 0.8mm, the length of each blade is 15mm, the height of each blade is 10mm, the height of each sleeve is 30mm, and the adopted printing line is a commercial iron-doped PLA printing line.
(2) 10g of sodium hydroxide is weighed and placed into a 500mL beaker, 250mL of deionized water is added, and the mixture is stirred and dissolved to obtain a NaOH aqueous solution with the concentration of 1 mol/L.
(3) And (3) heating the NaOH aqueous solution obtained in the step (2) to 54 ℃ in a water bath, and placing the stirring paddle printed in the step (1) in the NaOH for treating for 15 minutes, so that PLA on the outer surface of the stirring paddle is dissolved in the NaOH to expose Fe particles.
(4) And (4) taking out the stirring paddle obtained in the step (3), repeatedly washing the stirring paddle by using deionized water, and naturally drying the stirring paddle to obtain the stirring paddle capable of treating the heavy metal ions in the water.
(5) Sleeving the stirring paddle sleeve obtained by airing in the step (4) on a rotating shaft of a mechanical stirring device, treating 80mL of sewage with the mercury concentration of 100mg/L or the copper concentration of 20mg/L, adjusting the stirring speed of mechanical stirring to 300rad/min, and stirring for 8 hours to realize deep treatment of the sewage containing mercury or copper, wherein through an atomic absorption spectrophotometer (ICP) test, the mercury content in a treated water sample is almost zero, namely the removal rate is as high as 100%, and the removal rate of the copper content is as high as 97%.
Example 2
A method for treating organic sewage by a 3D printing stirrer comprises the following specific steps:
(1) the stirring paddle model is designed by using 123D Design modeling software, the stirring paddle is printed by using a fused deposition type 3D printer, the stirring paddle has 6 blades, the thickness of each blade is 0.8mm, the length of each blade is 15mm, the height of each blade is 10mm, the height of each sleeve is 30mm, and the adopted printing line is a commercial iron-doped PLA printing line.
(2) 10g of sodium hydroxide is weighed and placed into a 500mL beaker, 250mL of deionized water is added, and the mixture is stirred and dissolved to obtain a NaOH aqueous solution with the concentration of 1 mol/L.
(3) And (3) heating the NaOH aqueous solution obtained in the step (2) to 54 ℃ in a water bath, placing the stirring paddle printed in the step (1) in the NaOH for processing for 15 minutes to enable PLA on the outer surface of the stirring paddle to be dissolved in the NaOH to expose Fe particles, repeatedly washing the stirring paddle with deionized water, and naturally drying the stirring paddle.
(4) And (4) carrying out further etching treatment on the dried stirring paddle obtained in the step (3). Measuring 36mL of hydrogen peroxide with the mass fraction of 30%, adding 80mL of deionized water, and preparing to obtain H with the mass fraction of 10%2O2A solution; adding excessive sodium chloride until saturation, stirring thoroughly to dissolve to obtain saturated NaCl H2O2And (3) solution. And (4) placing the stirring paddle obtained in the step (3) in the NaCl saturated solution for etching treatment for 2 hours, then washing the stirring paddle by using deionized water, and naturally drying the stirring paddle to obtain the stirring paddle capable of catalytically treating the degradation of the methylene blue in the sewage.
(5) 80mL of wastewater containing methylene blue at a concentration of 100ppm was poured into a 100mL beaker, and 1mL of 30% by mass H was added thereto2O2Solution, and 44mg of hydroxylamine hydrochloride was added; sleeving the stirring paddle sleeve obtained in the step (4) on a rotating shaft of a mechanical stirring device, setting the stirring speed to be 300rad/min, testing the concentration of methylene blue before and after reaction by using an ultraviolet spectrophotometer after stirring for 30 minutes, and calculating to obtain the removal rate of the processed methylene blue to be 88%.
(6) And (5) repeating the step (5), repeatedly catalyzing the degradation of the methylene blue light by using the stirring paddle used in the step (5), repeatedly circulating for 10 times, and reacting for 30 minutes until the removal rate of the methylene blue can still reach 87%.

Claims (1)

1. A method for manufacturing a stirrer for treating sewage through 3D printing is characterized by comprising the following steps:
printing a stirring paddle by using a fused deposition type 3D printer, wherein the stirring paddle is made of iron-containing polylactic acid;
under the condition that the water bath temperature is 50-60 ℃, the printed stirring paddle is placed in NaOH solution for processing for 10-20 minutes, so that PLA coated outside the iron particles on the stirring paddle is dissolved in the NaOH solution, and the Fe particles are exposed; the stirring paddle can be used for directly replacing and treating sewage containing metal ions due to the existence of iron particles on the surface;
placing the stirring paddle treated by the NaOH solution in H saturated with NaCl2O2Treating the mixture in the solution for 1.8 to 2.3 hours to obtain an etched stirring paddle, wherein Fe particles on the surface of the stirring paddle are coated with H2O2Is oxidized into Fe2O3The stirring paddle can be used for catalytically treating organic dye molecules in sewage.
CN201710518883.9A 2017-06-30 2017-06-30 Method for manufacturing stirrer for sewage treatment through 3D printing Active CN107213812B (en)

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CN109603746A (en) * 2018-12-11 2019-04-12 中国科学院生态环境研究中心 Support structures and the preparation method and application thereof for heavy metal contaminants absorption
CN113373026A (en) * 2021-06-15 2021-09-10 东北电力大学 Adjustable static magnetic field and nickel-based additive composite strengthening device for improving biogas yield

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014209994A2 (en) * 2013-06-24 2014-12-31 President And Fellows Of Harvard College Printed three-dimensional (3d) functional part and method of making
CN105189826A (en) * 2013-03-15 2015-12-23 莫杜美拓有限公司 Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes
CN106317811A (en) * 2016-08-16 2017-01-11 西安建筑科技大学 Method for making stainless steel texture component in building landscape model by 3D printing

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US20040228705A1 (en) * 2003-05-16 2004-11-18 Abbott-Interfast Corporation. Fasteners for composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105189826A (en) * 2013-03-15 2015-12-23 莫杜美拓有限公司 Electrodeposited compositions and nanolaminated alloys for articles prepared by additive manufacturing processes
WO2014209994A2 (en) * 2013-06-24 2014-12-31 President And Fellows Of Harvard College Printed three-dimensional (3d) functional part and method of making
CN106317811A (en) * 2016-08-16 2017-01-11 西安建筑科技大学 Method for making stainless steel texture component in building landscape model by 3D printing

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