阅读说明：本技术 基于3d打印纸基的便携式废水cod检测装置及制作、测量方法 (Portable wastewater COD detection device based on 3D printing paper base and manufacturing and measuring method ) 是由 沈文浩 李嘉庆 于 2019-07-16 设计创作，主要内容包括：本发明公开了一种基于3D打印纸基的便携式废水COD检测装置及制作、测量方法,涉及废水COD检测技术领域。本发明利用碱性高锰酸钾溶液室温下氧化废水,使其颜色发生变化的特点,设计可自然降解的纸基检测装置,达到快速检测废水COD的目的。通过三维打印技术构建纸基检测基底,利用移动终端拍照以及计算机软件Image J处理获得废水RGB的色度值,建立基于废水色度(R-G)值的废水COD表征数学模型,用于废水COD值的检测。本装置操作便捷,检测速度较快,以绿色环保的纸为基底,使用后可自然分解,具有广泛的工业废水检测应用前景。(The invention discloses a portable wastewater COD detection device based on a 3D printing paper base and manufacturing and measuring methods thereof, and relates to the technical field of wastewater COD detection. The invention designs a paper-based detection device capable of being naturally degraded by utilizing the characteristic that alkaline potassium permanganate solution oxidizes wastewater at room temperature to change the color of the wastewater, thereby achieving the purpose of quickly detecting COD in the wastewater. A paper-based detection substrate is constructed through a three-dimensional printing technology, the mobile terminal is used for photographing and the computer software Image J is used for processing to obtain the colorimetric values of RGB of the wastewater, and a wastewater COD characterization mathematical model based on the wastewater colorimetric (R-G) value is established and used for detecting the COD value of the wastewater. This device simple operation detects fastly to green's paper is the basement, can decompose naturally after using, has extensive industrial waste water detection application prospect.)

1. a portable waste water COD detection device based on a 3D printing paper base is characterized in that the detection device comprises a paper base substrate (1), a reaction tank (2), a hydrophobic layer (3), a color developing agent (4), a transparent sealing film layer (5) and a black glue film layer (6), wherein,

The paper-based substrate (1) is used as a carrier for accommodating wastewater COD detection; the reaction tank (2) is arranged on the upper side of the paper-based substrate (1); the hydrophobic layer (3) forms a solid film on the surface of the reaction tank (2); the color developing agent (4) is stored in the reaction tank (2); the transparent sealing film layer (5) is fixed on the upper surface of the paper-based substrate (1); the black glue film layer (6) is fixed on the transparent sealing film layer (5) and forms a sealing lightproof layer together with the transparent sealing film layer (5); the reaction tank (2) is injected with wastewater, a mobile terminal is used for shooting, the color of the wastewater is input into computer software Image J, and color change characteristics of organic matters in the wastewater oxidized by color developing agents are utilized to detect color value change caused by reaction of the wastewater with different COD values and the color developing agents.

2. the portable waste water COD detection device based on 3D printing paper base is characterized in that the paper base substrate (1) is a cylinder with the diameter of 3.0-10.0cm and the height of 1.0-5.0cm, and comprises four reaction tanks and two photographing positioning areas; the photographing positioning area consists of an equilateral triangle positioning area (7) and a circular positioning area (8), the centers of the equilateral triangle positioning area (7) and the circular positioning area (8) are symmetrically distributed on the diameter of the upper surface of the paper base substrate (1), the side length of the equilateral triangle positioning area (7) is 0.05-2.0cm, the diameter of the circular positioning area (8) is 0.05-2.0cm, and the centers of the equilateral triangle positioning area (7) and the circular positioning area (8) are 1.0-3.0cm away from the center of the circle of the upper surface of the paper base.

3. The portable waste water COD detection device based on 3D printing paper base of claim 1, characterized in that the reaction tank (2) is hemispherical, the diameter is 0.5-3.5cm, the sphere center of the reaction tank (2) is located on the upper surface of the paper base substrate and is 1.0-4.5cm away from the circle center of the upper surface of the paper base substrate (1).

4. The portable waste water COD detection device based on 3D printing paper base of claim 1 is characterized in that the transparent sealing film layer (5) is fixed on the upper surface of the paper base substrate (1) through gluing; the black glue film layer (6) is fixed on the transparent sealing film layer (5) through gluing.

5. The manufacturing method of the portable wastewater COD detection device based on the 3D printing paper base is characterized by comprising the following steps:

S1, guiding the designed paper-based model into a full-color paper-based 3D printer, and printing a paper-based substrate (1) as a detection substrate;

S2, heating the paraffin particles in water bath at 65-95 ℃, uniformly coating the paraffin particles in the reaction tank (2), drying the paraffin particles in an oven at 100-150 ℃ for 30-200S, and constructing a hydrophobic layer (3) in the reaction tank (2);

S3, weighing 0.1-0.5g of potassium permanganate and 0.1-1.0g of sodium hydroxide, adding into 10-100mL of distilled water, stirring uniformly, adding 0.001-0.1g of fatty alcohol-polyoxyethylene ether, and placing the prepared color developing agent in a brown reagent bottle to be sealed and stored in a dark place;

s4, sequentially dripping 0.1-1.5ml of color developing agent into four reaction tanks by using a pipette, and sequentially adhering a transparent sealing film layer (5) and a black adhesive film layer (6) which are cut to be 3.0-10.0cm in diameter to the upper surface of the paper-based substrate after the dripping is finished, wherein the black adhesive film layer (6) is positioned on the transparent sealing film layer (5) and is used for sealing the color developing agent and storing in a dark place;

S5, tearing off a black adhesive film layer (6) on the surface of the manufactured wastewater COD detection device, injecting a water sample to be detected into a reaction tank (2) by using an injector, oxidizing the organic matters by utilizing alkaline potassium permanganate at room temperature, changing manganese ions from a high valence state to a low valence state, changing the color value caused by the change, and representing the COD value of the wastewater.

6. A measuring method of a portable wastewater COD detection device based on a 3D printing paper base is characterized by comprising the following steps:

T1, digesting waste water: firstly, tearing off a black glue film layer (6) on the surface of a paper base, reserving a transparent sealing film layer (5), then extracting 0.1-2.0ml of wastewater to be detected by adopting an injector, penetrating a needle through the transparent film layer (5), and injecting the needle into a reaction tank (2) of a detection device, wherein the reaction time is 1-5 min;

t2, acquiring image: utilizing a mobile terminal camera to shoot a reaction pool of the detection device;

t3, process data: extracting the color value data of the wastewater to be detected in the reaction tank by using computer software, and converting according to a constructed COD representation mathematical model to obtain a COD value of the wastewater, wherein the COD representation mathematical model adopts an RGB color mode colorimetric method to obtain the changes of two color channels of red R and green G, and the COD value of the wastewater is represented by using a chromaticity R-G value of the wastewater.

7. The measuring method of the portable waste water COD detection device based on the 3D printing paper base is characterized in that the procedure of the step T2 is as follows:

The image that adopts the nine palace check of mobile terminal camera to treat the collection is fixed a position, and wherein horizontal line passes the centre of sphere of reaction tank (2), and vertical line is tangent with reaction tank (2), and two location areas of shooing are located the center of its place palace respectively, and the whole and vertical block diagram line of paper base are tangent, and wherein, the parameter of shooing of mobile terminal camera sets for: the sensitivity parameter is in the range of 100 to 800, the distance between the lens of the camera of the mobile terminal and the upper surface of the paper-based detection device is less than 8cm, the focusing mode is set to be a micro-distance, an automatic focusing option is adopted, and all photographed pictures are stored in a joint image expert group format.

8. The measuring method of the portable waste water COD detecting device based on the 3D printing paper base is characterized in that the COD characteristic mathematical model is that the color value data are the changes of two color channels of red R and green G, and the relation between the waste water COD value and the waste water chroma R-G value is as follows:

y＝0.1732x-6.1054

Wherein y is the R-G value, and x is the COD value of the wastewater.

Technical Field

The invention relates to the technical field of wastewater COD detection, in particular to a portable wastewater COD detection device based on a 3D printing paper base and a manufacturing and measuring method thereof.

background

chemical Oxygen Demand (COD) is an important index for reflecting organic pollution of water, and the amount of reducing substances to be oxidized in a water sample is measured by a Chemical method. At present, the method for offline detecting COD in wastewater mainly bases on the national standard potassium dichromate method for determining chemical oxygen demand of water (GB 11914-89), and has the problems of long reaction time (more than 3h), high medicine consumption, secondary pollution easily caused by heavy metal salts such as silver sulfate, mercury sulfate and the like used in the reaction process and the like; by adopting COD on-line detection equipment, the continuous monitoring of the COD in the wastewater can be realized, but the equipment is high in cost, large in size (the height of the equipment exceeds 1m), and inconvenient to carry out portable detection, and the weight of the equipment exceeds 50 kg; the Chinese invention patent (CN201020141968.3, COD monitor by ultraviolet absorption method) provides a spectrum detection device, which has simple structure and convenient measurement, but has the problems of poor correlation, low measurement precision and the like aiming at different types of water samples; the Chinese invention patent (CN201310259871.0, COD rapid detection liquid, test box and determination method) does not need to use a precise detection instrument, has low cost, realizes the measurement of the COD range of the detected water sample according to the color change of the detected water sample under the action of the color developing agent, but realizes the subjective judgment of the color of the water sample only by naked eyes and the measurement of the COD range of the detected water sample only, and has lower precision.

The alkaline potassium permanganate is used as an oxidant, is relatively stable and easy to store, and can oxidize organic matters in the wastewater at normal temperature. The permanganate ion is purple in color and is first reduced to manganate ion (green) and further to manganese dioxide (brown) under alkaline conditions. The reaction process provides an important theoretical basis for rapidly and conveniently detecting the COD of the wastewater.

disclosure of Invention

The invention aims to solve the defects in the prior art and provides a portable wastewater COD detection device based on a 3D printing paper base and a manufacturing and measuring method thereof. The device coats solid wax on the surface of a 3D printing paper base substrate to form a hydrophobic layer as a reaction tank, a special color developing agent is dripped into the reaction tank to be used as the representation of the COD detection of the wastewater, the color of the wastewater in the reaction tank and the change of the RGB color mode are recorded by adopting a mobile terminal photographing method through color developing reaction, and the rapid detection of the COD of the wastewater is realized by constructing a COD representation mathematical model. The device reduces the usage amount of the color developing agent and shortens the digestion reaction time, adopts paper as a substrate to replace high molecular substances such as glass, plastic and the like, is safe, low in consumption and environment-friendly, and can realize cyclic utilization and self-decomposition so as to solve the problems in the background technology.

the first purpose of the invention can be achieved by adopting the following technical scheme:

a portable waste water COD detection device based on 3D printing paper base comprises a paper base substrate 1, a reaction tank 2, a hydrophobic layer 3, a color developing agent 4, a transparent sealing film layer 5 and a black glue film layer 6; the paper-based substrate 1 is used as a carrier for containing wastewater COD detection; the reaction tank 2 is arranged on the upper side of the paper-based substrate 1; the hydrophobic layer 3 forms a solid film on the surface of the reaction tank 2; the color developing agent 4 is stored in the reaction tank 2; the transparent sealing film layer 5 is fixed on the upper surface of the paper-based substrate 1 through gluing; the black glue film layer 6 is fixed on the transparent sealing film layer 5 through gluing and forms a sealing light-shading layer together with the transparent sealing film layer 5; the reaction tank 2 is used for injecting wastewater, photographing is carried out through a mobile terminal, the color of the color developing agent is input into computer software Image J, and color value change caused by reaction of wastewater with different COD values and the color developing agent is detected by utilizing the color change characteristic of organic matters in the wastewater oxidized by the color developing agent.

Wherein, the paper base substrate 1 is a cylinder with the diameter of 3.0-10.0cm and the height of 1.0-5.0cm, and comprises four reaction tanks and two photographing positioning areas; the reaction tank 2 is hemispherical, the diameter is 0.5-3.5cm, the sphere center of the reaction tank 2 is positioned on the upper surface of the paper-based substrate and is 1.0-4.5cm away from the circle center of the upper surface of the paper-based substrate; the photographing positioning area consists of an equilateral triangle positioning area 7 and a circular positioning area 8, the centers of the equilateral triangle positioning area 7 and the circular positioning area 8 are symmetrically distributed on the diameter of the upper surface of the paper base substrate, the side length of the equilateral triangle positioning area 7 is 0.05-2.0cm, the diameter of the circular positioning area 8 is 0.05-2.0cm, and the distance between the centers of the equilateral triangle positioning area 7 and the circular positioning area 8 and the center of the upper surface circle of the paper base is 1.0-3.0 cm.

the second purpose of the invention can be achieved by adopting the following technical scheme:

A method for manufacturing a portable wastewater COD detection device based on a 3D printing paper base comprises the steps of leading a designed paper base model into a Mcor IRIS 3D color printer full-color paper base 3D printer, and printing a paper base substrate 1 as a detection substrate; smearing paraffin in the paper-based reaction tank 2 to form a hydrophobic layer 3; adding potassium permanganate and sodium hydroxide into distilled water, uniformly stirring, adding fatty alcohol-polyoxyethylene ether (MOA-9), and preparing a color developing agent; injecting the color developing agent into the reaction tank 2 through a liquid transfer gun; assembling the transparent sealing film layer 5 on the upper surface of the paper-based substrate 1 through gluing, and gluing the black glue film layer 6 on the transparent sealing film layer 5; when the black glue film layer 6 is torn off, the waste water is injected into the reaction tank 2, the mobile terminal is used for photographing, the color of the waste water is input into the computer software Image J, and the color value change caused by the reaction of different waste water and the color developing agent is detected by utilizing the color change characteristic of the color developing agent for oxidizing the organic matters in the waste water, so that the COD value of the waste water is detected.

The manufacturing method specifically comprises the following steps:

S1, guiding the designed paper base model into a Mcor IRIS 3D color printer full-color paper base 3D printer, and printing a paper base substrate 1 as a detection substrate;

Wherein the paper base substrate is a cylinder with the diameter of 3.0-10.0cm and the height of 1.0-5.0cm, and comprises four reaction tanks and two photographing positioning areas; the reaction tank 2 is hemispherical, the diameter is 0.5-3.5cm, the sphere center of the reaction tank 2 is positioned on the upper surface of the paper-based substrate and is 1.0-4.5cm away from the circle center of the upper surface of the paper-based substrate; the photographing positioning area consists of an equilateral triangle positioning area 7 and a circular positioning area 8, the centers of the equilateral triangle positioning area 7 and the circular positioning area 8 are symmetrically distributed on the diameter of the upper surface of the paper base substrate, the side length of the equilateral triangle positioning area 7 is 0.05-2.0cm, the diameter of the circular positioning area 8 is 0.05-2.0cm, and the distance between the centers of the equilateral triangle positioning area 7 and the circular positioning area 8 and the center of the upper surface circle of the paper base is 1.0-3.0 cm.

S2, heating the paraffin particles in water bath at 65-95 ℃, uniformly coating the paraffin particles in the reaction tank 2, drying the paraffin particles in an oven at 100-150 ℃ for 30-200S, and constructing the hydrophobic layer 3 in the reaction tank 2.

S3, weighing 0.1-0.5g of potassium permanganate and 0.1-1.0g of sodium hydroxide, adding into 10-100mL of distilled water, stirring uniformly, adding 0.001-0.1g of fatty alcohol-polyoxyethylene ether (MOA-9), and placing the prepared color developing agent in a brown reagent bottle to be sealed and stored in a dark place.

S4, using a pipette to sequentially add 0.1-1.5ml of color developing agent into the four reaction tanks, after the addition is finished, sequentially adhering a transparent sealing film layer 5 and a black glue film layer 6 which are cut to be 3.0-10.0cm in diameter to the upper surface of the paper-based substrate, wherein the black glue film layer 6 is positioned on the transparent sealing film layer 5 and is used for sealing the color developing agent and storing in a dark place, so that the service life is prolonged.

S5, tearing off the black adhesive film layer 6 on the surface of the manufactured wastewater COD detection device, injecting a water sample to be detected into the reaction tank 2 by using an injector, oxidizing the organic matters by utilizing alkaline potassium permanganate at room temperature, changing manganese ions from a high valence state to a low valence state, changing the caused color value, and representing the COD value of the wastewater.

the third purpose of the invention can be achieved by adopting the following technical scheme:

A measuring method of a portable wastewater COD detection device based on a 3D printing paper base comprises the following steps:

T1, digesting waste water: firstly, tearing off a black glue film layer 6 on the surface of a paper base, reserving a transparent sealing film layer 5, then extracting 0.1-2.0ml of wastewater to be detected by adopting an injector, penetrating a needle through the transparent film layer (5), and injecting the needle into a reaction tank of a detection device, wherein the reaction time is 1-5 min;

T2, acquiring image: utilizing a mobile terminal camera to shoot a reaction pool of the detection device;

t3, process data: and extracting the obtained color value data of the wastewater to be detected in the reaction tank by using computer software (Image J software), and converting according to the constructed COD characterization mathematical model to obtain the COD value of the wastewater.

further, in the step T2, the image is collected and positioned by using a nine-square grid of the mobile terminal camera, wherein the transverse line passes through the center of the reaction cell, the longitudinal line is tangent to the reaction cell, the two photographing positioning areas are respectively located at the center of the grid where the two photographing positioning areas are located, and the whole paper base is tangent to the longitudinal frame. Setting photographing parameters: the light sensitivity (ISO) parameter is in the range of 100 to 800, the distance between the lens of the camera of the mobile terminal and the upper surface of the paper-based detection device is less than 8cm, the focusing mode is set to be a micro-distance, an automatic focusing option is adopted, and all photographed pictures are stored in a Joint Photographic Experts Group (JPEG) format.

Further, in the step T3, the color value data is the change of two color channels of red (R) and green (G), and the COD of the wastewater in the mathematical model is represented as follows:

y＝0.1732x-6.1054

wherein y is the value of (R-G) and x is the COD value of the wastewater.

compared with the prior art, the invention has the following advantages and effects:

1. According to the method, the color value change of the organic matters in the wastewater oxidized by the alkaline potassium permanganate solution is utilized, the mobile terminal is used for photographing to obtain the color value of the wastewater, the Image J software is used for extracting the color value, and the (R-B) value of the wastewater is used for representing the COD value, so that the problems that a colorimetric card method is interfered by the environment and subjective judgment of naked eyes are solved, and the accuracy and the stability of detection are improved;

2. The paper-based reaction model is adopted as the substrate of the detection device, the preparation is simple, the cyclic utilization and the self-decomposition can be realized, and the green and rapid detection is realized.

3. the detection device adopts trace detection, reduces the usage amount of digestion solution and shortens digestion time.

Drawings

FIG. 1 is a schematic diagram of a three-dimensional structure of a waste water COD detection device disclosed by the invention;

FIG. 2 is a schematic view of the present invention illustrating the positioning of a photograph;

FIG. 3 is a fitting graph of the mathematical model for COD characterization of wastewater according to the present invention;

The device comprises a paper-based substrate 1, a hydrophobic layer 2, a color developing agent 3, a reaction tank 4, a transparent sealing film layer 5, a black glue film layer 6, an equilateral triangle positioning area 7 and a circular positioning area 8.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.