Dechlorination method for constructing copper-containing dechlorinating agent block material through 3D printing technology

Abstract

The invention relates to a dechlorination method for constructing a copper-containing dechlorination agent block by a 3D printing technology in the technical field of chlorine-containing wastewater treatment, and the dechlorination method comprises the following steps: calcining a copper source, cooling, grinding, uniformly mixing with photosensitive resin according to a certain proportion, carrying out 3D printing, cleaning a model by absolute ethyl alcohol, and drying to obtain a preliminarily prepared 3D printing copper-containing dechlorination agent block; carrying out organic solvent treatment and high-temperature carbonization treatment on the copper-containing dechlorinating agent block to obtain a calcined 3D printing copper-containing dechlorinating agent block; and after dechlorination of the calcined copper-containing dechlorination agent block is completed, chloride ions are measured by using an ion chromatograph. According to the method, 3D printing and a traditional precipitation dechlorination method are combined for the first time, a cuprous dechlorination method serves as a research object, the copper-containing dechlorination agent is loaded on a 3D printing model with a filter element structure, Cu2O is prepared through a high-temperature carbon reduction reaction, the reaction specific surface area is increased, recovery of the copper-containing dechlorination agent is achieved, and the dechlorination cost is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of chlorine-containing wastewater treatment, and particularly to a chlorine removal method for constructing a copper-containing chlorine remover block by 3D printing technology. Background Art

[0002] With the development of human society and the progress of industrial technology, environmental problems such as air, soil, and water pollution have become increasingly prominent. In recent years, the awareness of environmental protection has taken root in people's hearts, and the country has actively implemented a series of policies to supervise production enterprises. However, with the rapid economic development and the expansion of industrial manufacturing scale, the amount of pollutants is still huge and highly polluting. Chlorine-containing wastewater is one of the typical wastewater pollutants. The sources of chloride ions in water bodies are extensive, and the high-salt and high-chlorine sewage caused by human life and industrial production is the main anthropogenic reason for the enrichment of chloride ions in environmental water bodies. Chloride ions are not easy to remove, and high-concentration chlorine-containing wastewater will cause serious harm to industrial production, the environment, and crop growth.

[0003] The existing methods for treating chlorine-containing wastewater mainly include electrolysis method, evaporation concentration method, ion exchange method, electroadsorption method, precipitation method, etc. The electrolysis method has a complex device and consumes a large amount of electric energy; the evaporation concentration method has high energy consumption and high treatment costs for a large amount of chlorine-containing wastewater; the ion exchange method is suitable for low-concentration chlorine-containing wastewater, but the chlorine removal is not thorough enough, and the resin is easy to reach saturation and needs to be regenerated. During its regeneration process, acids are consumed and a large amount of waste acids and alkalis are generated; the electroadsorption method does not involve chemical reactions during the removal of chloride ions, and has the advantages of low energy consumption, no secondary pollution, good tolerance, and low operating costs. However, the electroadsorption method is generally used for the treatment of low-concentration wastewater, and its current application range is small and has not been popularized. In contrast, the precipitation method is easy to operate, has quick results, a simple process, and a variety of types. However, due to the low recovery rate of the chlorine remover powder, the cost is high, and there are still limitations in practical applications.

[0004] In recent years, as an advanced manufacturing technology, 3D printing has developed rapidly in China. Its advantages of personalized and rapid manufacturing have attracted much attention, and there have been many reports in the fields of aerospace, engineering construction, archaeology, biomedicine, etc. Compared with traditional manufacturing technologies, 3D printing has high material utilization rate and less waste materials; it can independently design three-dimensional models, providing new solutions for personalized manufacturing; the production time is reduced, the product supply chain is simplified, and the time for products to enter the market is shortened; the accuracy is high, and it can complete parts or production processes that are not easy to process by traditional machines or manually. The present invention takes the lead in combining 3D printing with the traditional precipitation chlorine removal method, taking the cuprous chloride removal method as the research object, loading the copper-containing chlorine remover on a 3D printing model with a filter element structure, using a high-temperature carbon reduction reaction to prepare Cu2O, and increasing the reaction specific surface area to realize the recovery of the copper-containing chlorine remover and reduce the chlorine removal cost. Summary of the Invention

[0005] In order to solve the problems such as the easy agglomeration and low recovery rate of dechlorination agent powder in the precipitation process, the high price of high-purity copper powder and cuprous oxide powder, and the high residual amount of copper ions in the wastewater after dechlorination, the present invention provides a 3D printing technology to construct a dechlorination method for a copper-containing dechlorination agent block. The inventive method combines LCD 3D printing technology with cuprous dechlorination method, utilizes 3D printing technology to construct a copper-containing dechlorination agent block, and reduces the Cu (II) loaded by the block to Cu (I) by a high-temperature carbon reduction reaction, thereby obtaining a 3D printing technology to construct a dechlorination method for a copper-containing dechlorination agent block. The inventive method is simple to operate, has a fast preparation speed, can realize the preparation of multiple models at a time, uses low-cost CuSO4 at the same time, and the skeleton after the carbonization of the block can adsorb chloride ions in the wastewater, can react quickly without stirring, also avoids the waste of copper and the cost of post-processing, and is easy to recycle.

[0006] In order to achieve the above objectives, the present invention is implemented through the following technical solutions:

[0007] A chlorine removal method for constructing a copper-containing chlorine removal agent block using 3D printing technology comprises the following steps:

[0008] (1) After calcining the copper source, cool it under dry conditions, grind it with an agate mortar, and evenly mix it with a photosensitive resin in a certain ratio (g / mL). Then, pour it into a material tank, and perform 3D printing using a model file with set printing parameters. After printing, the model is cleaned with anhydrous ethanol and placed in an electric oven for drying to obtain a preliminarily prepared 3D printed copper-containing chlorine removal agent block;

[0009] Wherein, the photosensitive resin is prepared from oligomer, photoinitiator, reactive diluent and ultraviolet blocker;

[0010] (2) subjecting the preliminarily prepared 3D printed copper-containing chlorine removal agent block to an organic solvent treatment and a high-temperature carbonization treatment to obtain a calcined 3D printed copper-containing chlorine removal agent block;

[0011] (3) adding the calcined 3D printed copper-containing chlorine removal agent block to the chlorine-containing wastewater, and after the chlorine removal is completed, using an ion chromatograph to measure the chloride ions;

[0012] (4) In order to analyze the stability of the copper-containing dechlorination agent block, the iodine titration method was used to titrate the residual copper ions in the remaining chlorine-containing wastewater.

[0013] Furthermore, the copper source in step (1) is one or more of copper oxide, copper sulfide, copper sulfate, copper nitrate, cuprous thiocyanate, and copper bismuthate;

[0014] The calcination temperature is 300-500° C. and the calcination time is 10-60 minutes, so as to achieve the purpose of removing crystal water.

[0015] Further, the oligomer described in step (1) is one or more of epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy resin, and vinyl ether resin;

[0016] The photoinitiator is one or more of benzoin dimethyl ether, benzophenone, thio - propoxy thioxanthone, acylphosphine oxide, phenyl diazonium fluoroborate, and cumene ferrocene hexafluorophosphate;

[0017] The active diluent is one or more of hydroxyethyl acrylate, triethylene glycol divinyl ether, n - butyl glycidyl ether, hydroxypropyl acrylate, and tripropylene glycol diacrylate;

[0018] The UV blocker is one or more of benzophenones, benzotriazoles, salicylates, carbon black, inorganic pigments, and fillers.

[0019] Further, the ratio of the copper source to the photosensitive resin in step (1) is (0.5 - 3.0 g) / 10 mL;

[0020] The setting of the printing parameters is as follows: the layer thickness is 0.05 - 0.2 mm, the exposure time for the first layer is 5 - 10 s, and the exposure time is 5 - 10 s.

[0021] Further, the organic solvent described in step (2) is acetone, and the treatment time is 10 - 60 min. Since 3D printing prepares three - dimensional models by layer - by - layer accumulation, the surface of the mixed - material printed model is smooth, and its internal rich pore structure cannot be fully utilized to improve the chlorine - removal effect of the block after high - temperature calcination. If strong acids or bases are used for treatment, other ions will be introduced and the chlorine - remover will be lost. The organic - solvent treatment method, based on the principle of similar - phase solubility, does not react between the solvent itself and the copper - containing chlorine - remover, and only partially dissolves the surface of the resin model and the bonding part between layers. In addition, acetone is an organic solvent that can dissolve a variety of organic substances, so acetone is used as the treatment solvent to perform surface treatment on the preliminarily prepared copper - containing chlorine - remover block.

[0022] Further, the calcination temperature for the high - temperature carbonization treatment is 100 - 450 °C, and the calcination time is 10 - 120 min. The printing material used in the present invention is a polyurethane - acrylate - type photosensitive resin, which can withstand a calcination temperature below 500 °C. Since the component of the photosensitive resin contains O element, during the high - temperature calcination process, the O element may combine with the C and H elements therein and escape from the block, forming a rich pore structure inside the block, significantly increasing the reaction specific surface area of the block, and exposing more CuSO4 to undergo a high - temperature reduction reaction with the carbonization skeleton, thereby increasing the content of Cu2O in the copper - containing chlorine - remover block.

[0023] Further, in step (3), the initial concentration of the chlorine-containing wastewater is 500 - 1000 mg / L, and the pH of the chlorine-containing wastewater needs to be adjusted to 0.5 - 6 with sulfuric acid, and the reaction time is 2 - 30 min.

[0024] Further, the chromatographic system of the ion chromatograph in step (3) is an OIC-600 type ion chromatograph (Hebei Ourun Scientific Instruments Co., Ltd.).

[0025] Further, the specific operation steps for titration analysis of the residual copper ion content in the remaining chlorine-containing wastewater by the iodometric method in step (4) are as follows: Take three test solutions in a conical flask, add NaAc-HAc buffer solution and KI and shake well. Titrate with Na2S2O3 solution until it turns light yellow, add KSCN solution, then titrate until the yellow color almost disappears, add starch solution, and continue titrating until the blue color of the solution just disappears, which is the end point. Calculate the copper content in the test solution according to the volume of the consumed Na2S2O3 solution.

[0026] The beneficial effects of the present invention are as follows:

[0027] The present invention combines 3D printing technology to prepare a copper-containing chlorine remover block with a carbon skeleton structure. The resin skeleton is carbonized through a high-temperature carbonization reduction reaction, reacts with Cu(II) to generate Cu2O and is used to treat chloride ions in wastewater. The process is simple, the operation is convenient, the preparation speed is fast, and multiple printing models can be prepared at one time; before printing, it is necessary to prepare the model file and the mixture. The file only needs to be set once and then imported into the 3D printer through a USB flash drive. For the mixture, the photosensitive resin and the copper-containing powder need to be evenly mixed and then imported into the material tank for printing; due to the personalized design feature of 3D printing technology, the copper-containing chlorine remover block is not limited to small chlorine removal devices, can be used in combination with related treatment equipment, and can also be tried to design and produce a chlorine removal reactor; moreover, the copper-containing chlorine remover can use relatively low-cost CuSO4, and Cu2O is prepared through high-temperature carbonization reduction, successfully solving the problem of the high price of high-purity copper powder and cuprous oxide powder; under the condition of cooperating with a small amount of bismuth copper raw material, copper-bismuth bimetallic nanoparticles can also be formed, which can not only improve the chlorine removal efficiency but also reduce the loss of copper; the process is simple, and the skeleton after carbonization of the block can directly adsorb chloride ions in wastewater without stirring, and the reaction is rapid; using 3D printing technology to prepare the copper-containing chlorine remover block avoids copper waste and post-treatment costs, and is convenient for recycling, successfully solving the problems of high residual copper ion content in the wastewater after chlorine removal and easy agglomeration and low recovery rate of the chlorine remover powder in the precipitation process. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a process flow chart of the chlorine removal method for constructing a copper-containing chlorine remover block by 3D printing technology of the present invention;

[0029] Figure 2XRD patterns of copper-containing dechlorination agent blocks treated with acetone for different times in Examples 1-6, (a) 10 min, (b) 20 min, (c) 30 min, (d) 40 min, (e) 50 min, (f) 60 min;

[0030] Figure 3 SEM images of the interior and ground copper-containing dechlorination agent blocks. Detailed implementation manners

[0031] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments and drawings of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. The description of at least one exemplary embodiment below is actually only illustrative and in no way limits the present invention and its application or use. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0032] Unless otherwise specifically stated, the numerical values set forth in these embodiments do not limit the scope of the present invention. Technologies and methods known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, the said technologies and methods should be regarded as part of the specification. In all examples shown and discussed here, any specific value should be construed as merely exemplary and not as a limitation. Therefore, other examples of the exemplary embodiments may have different values.

[0033] The experimental methods without specific conditions noted in the following examples are generally determined according to national standards; if there are no corresponding national standards, they are carried out according to general international standards or the standard requirements proposed by relevant enterprises. Unless otherwise specified, all parts are by weight and all percentages are by weight percentage.

[0034] As Figure 1 shown, a dechlorination method for constructing a copper-containing dechlorination agent block by 3D printing technology includes the following steps:

[0035] Obtain a copper source from chlorine-containing wastewater through a precipitation method and a cuprous dechlorination method;

[0036] After calcining the copper source and cooling it under dry conditions, grind it with an agate mortar, uniformly mix it with a photosensitive resin in a certain ratio (g / mL), pour it into a material tank, perform LCD 3D printing with a model file with set printing parameters, wash the model with absolute ethanol after printing, and place it in an electric heating oven to dry to obtain a preliminarily prepared 3D printed copper-containing dechlorination agent block;

[0037] The above-prepared 3D-printed copper-containing dechlorination agent blocks are subjected to surface treatment with organic solvents and high-temperature carbonization treatment to obtain the calcined 3D-printed copper-containing dechlorination agent blocks;

[0038] The above-calcined 3D-printed copper-containing dechlorination agent blocks are added to the chlorine-containing wastewater. After dechlorination is completed, an ion chromatograph is used to measure the chloride ions;

[0039] The residual amount of copper ions in the remaining chlorine-containing wastewater is titrimetrically analyzed by the iodometric method.

[0040] The present invention will be specifically described below through examples.

[0041] Example 1

[0042] A dechlorination method for constructing a copper-containing dechlorination agent block by 3D printing technology includes the following steps:

[0043] (1) The copper source copper sulfate is calcined at 500 °C for 10 min and then cooled under dry conditions. After grinding, it is uniformly mixed with the photosensitive resin at a ratio of 3.0 g / 10 mL and poured into the material tank. The layer thickness is set to 0.2 mm, the exposure time for the first layer is 5 s, and a model file with an exposure time of 10 s is used for 3D printing. After printing is completed, the model is cleaned with absolute ethanol and dried in an electric heating oven to obtain the preliminarily prepared block.

[0044] (2) The above-prepared block is soaked in the organic solvent acetone for 60 min, and then subjected to high-temperature carbonization treatment at 100 °C for 120 min to obtain the calcined block. The XRD pattern of this copper-containing dechlorination agent block is as shown in Figure 2 (f) in.

[0045] (3) The above-calcined block is added to the chlorine-containing wastewater with an initial concentration of 500 mg / L under room temperature natural light conditions. The pH is adjusted to 6 by using sulfuric acid, and the reaction is carried out for 30 min. After dechlorination is completed, an ion chromatograph is used to measure the chloride ions. The chloride ion concentration in the system drops to 487 mg / L, and the dechlorination efficiency is 2.6%.

[0046] (4) The residual amount of copper ions in the remaining chlorine-containing wastewater is titrimetrically analyzed by the iodometric method. The specific titration steps are as follows: Accurately pipette three portions of 25.00 mL of the test solution into a conical flask, add 5 mL of the NaAc-HAc buffer solution and 1 g of KI and shake well. Immediately titrate with the Na2S2O3 solution until it turns light yellow. Add 3 mL of 20% KSCN solution, and then titrate until the yellow color almost disappears. Then add 3 mL of 0.5% starch solution and continue titrating until the blue color of the solution just disappears, which is regarded as the end point. According to the volume of the Na2S2O3 solution consumed, the copper content in the test solution is calculated to be 62.4 mg / L.

[0047] Example 2

[0048] A chlorine removal method for constructing a copper-containing chlorine removal agent block by 3D printing technology, comprising the following steps:

[0049] (1) Calcinate copper sulfate as the copper source at 450 °C for 20 min, then cool it under dry conditions, grind it, and uniformly mix it with photosensitive resin at a ratio of 2.5 g / 10 mL, pour it into the material tank, set the layer thickness to 0.2 mm, use a model file with an initial exposure time of 5 s and an exposure time of 10 s for 3D printing. After printing is completed, wash the model with absolute ethanol and place it in an electric heating oven for drying to obtain a preliminarily prepared block.

[0050] (2) Soak the above preliminarily prepared block in organic solvent acetone for 50 min, and then perform high-temperature carbonization treatment at 200 °C for 90 min to obtain a calcined block. The XRD pattern of this copper-containing chlorine removal agent block is as shown in Figure 2 (e) in the figure.

[0051] (3) Add the above calcined block to the chlorine-containing wastewater with an initial concentration of 500 mg / L under dark conditions, adjust the pH to 5 with sulfuric acid, react for 25 min. After chlorine removal is completed, use an ion chromatograph to measure the chloride ions. The chloride ion concentration in the system drops to 481 mg / L, and the chlorine removal efficiency is 3.8%.

[0052] (4) Use the iodometric method to titrate and analyze the residual amount of copper ions in the remaining chlorine-containing wastewater. The specific titration steps are as follows: Accurately pipette three portions of 25.00 mL of the test solution into a conical flask, add 5 mL of NaAc-HAc buffer solution and 1 g of KI, and shake well. Immediately titrate with Na2S2O3 solution until it turns light yellow, add 3 mL of 20% KSCN solution, then titrate until the yellow color almost disappears, add 3 mL of 0.5% starch solution, and continue titrating until the blue color of the solution just disappears as the end point. According to the volume of the consumed Na2S2O3 solution, the content of copper in the test solution is calculated to be 59.6 mg / L.

[0053] Example 3

[0054] A chlorine removal method for constructing a copper-containing chlorine removal agent block by 3D printing technology, comprising the following steps:

[0055] (1) Calcinate copper sulfate as the copper source at 300 °C for 60 min, then cool it under dry conditions, grind it, and uniformly mix it with photosensitive resin at a ratio of 0.5 g / 10 mL, pour it into the material tank, set the layer thickness to 0.15 mm, use a model file with an initial exposure time of 5 s and an exposure time of 10 s for 3D printing. After printing is completed, wash the model with absolute ethanol and place it in an electric heating oven for drying to obtain a preliminarily prepared block.

[0056] (2) The above-prepared bulk material was soaked in the organic solvent acetone for 40 min, and then subjected to high-temperature carbonization treatment at 400 °C for 30 min to obtain the calcined bulk material. The XRD pattern of the copper-containing chlorine remover bulk material is as shown in Figure 2 Figure (d) below, where the diffraction peak of Cu2O is relatively strong; the SEM morphology is as shown in Figure 3 Figure (a) below, with a large number of pore structures, and many Cu2O / Cu nanoparticles are embedded on the pore surface of the porous carbon (as shown in Figure 3 Figure (b) below).

[0057] (3) The above-calcined bulk material was added to the chlorine-containing wastewater with an initial concentration of 550 mg / L under dark conditions. The pH was adjusted to 4 using sulfuric acid, and the reaction was carried out for 20 min. After the chlorine removal was completed, an ion chromatograph was used to measure the chloride ions. The chloride ion concentration in the system decreased to 521.4 mg / L, and the chlorine removal efficiency was 5.2%.

[0058] (4) The iodine titration method was used to analyze the residual amount of copper ions in the remaining chlorine-containing wastewater. The specific titration steps are as follows: Accurately pipette three portions of 25.00 mL of the test solution into a conical flask, add 5 mL of NaAc-HAc buffer solution and 1 g of KI, and shake well. Immediately titrate with the Na2S2O3 solution until it turns light yellow. Add 3 mL of 20% KSCN solution, and then titrate until the yellow color almost disappears. Then add 3 mL of 0.5% starch solution and continue titrating until the blue color of the solution just disappears, which is regarded as the end point. According to the volume of the Na2S2O3 solution consumed, the copper content in the test solution was calculated to be 54.9 mg / L.

[0059] Example 4

[0060] A method for removing chlorine from a copper-containing chlorine remover bulk material constructed by 3D printing technology, comprising the following steps:

[0061] (1) The copper source copper sulfate was calcined at 350 °C for 40 min, cooled under dry conditions, ground, and then uniformly mixed with the photosensitive resin at a ratio of 1.5 g / 10 mL and poured into the material tank. The layer thickness was set to 0.10 mm, the exposure time for the first layer was 10 s, and 3D printing was carried out using a model file with an exposure time of 5 s. After printing, the model was cleaned with anhydrous ethanol and dried in an electric heating oven to obtain the preliminarily prepared bulk material.

[0062] (2) The above-prepared bulk material was soaked in the organic solvent acetone for 30 min, and then subjected to high-temperature carbonization treatment at 400 °C for 60 min to obtain the calcined bulk material. The XRD pattern of the copper-containing chlorine remover bulk material is as shown in Figure 2 Figure (c) below.

[0063] (3) Add the above-mentioned calcined block materials into the chlorine-containing wastewater with an initial concentration of 750 mg / L under room temperature natural light conditions. Adjust the pH to 3 using sulfuric acid, react for 15 min. After chlorine removal is completed, use an ion chromatograph to measure the chloride ions. The chloride ion concentration in the system drops to 694.5 mg / L, and the chlorine removal efficiency is 7.4%.

[0064] (4) Use the iodometric method to titrate and analyze the residual amount of copper ions in the remaining chlorine-containing wastewater. The specific titration steps are as follows: Accurately pipette three portions of 25.00 mL of the test solution into a conical flask, add 5 mL of NaAc-HAc buffer solution and 1 g of KI and shake well. Immediately titrate with Na2S2O3 solution until it turns light yellow. Add 3 mL of 20% KSCN solution, then titrate until the yellow color almost disappears. Add 3 mL of 0.5% starch solution, and continue titrating until the blue color of the solution just disappears, which is regarded as the end point. According to the volume of the Na2S2O3 solution consumed, the copper content in the test solution is calculated to be 49.6 mg / L.

[0065] Example 5

[0066] A chlorine removal method for constructing a copper-containing chlorine removal agent block by 3D printing technology, including the following steps:

[0067] (1) Calcinate copper sulfate as the copper source at 300 °C for 50 min, then cool it under dry conditions, grind it, and uniformly mix it with photosensitive resin at a ratio of 1.0 g / 10 mL, pour it into the material tank, set the layer thickness to 0.05 mm, the exposure time for the first layer is 10 s, and perform 3D printing with a model file with an exposure time of 5 s. After printing is completed, wash the model with absolute ethanol and place it in an electric heating oven to dry, obtaining a preliminarily prepared block material.

[0068] (2) Immerse the above-mentioned preliminarily prepared block materials in organic solvent acetone for 20 min, and then perform high-temperature carbonization treatment at 450 °C for 30 min to obtain the calcined block materials. The XRD pattern of this copper-containing chlorine removal agent block is as shown in Figure 2 (b) in the figure.

[0069] (3) Add the above-mentioned calcined block materials into the chlorine-containing wastewater with an initial concentration of 500 mg / L under light conditions. Adjust the pH to 1 using sulfuric acid, react for 10 min. After chlorine removal is completed, use an ion chromatograph to measure the chloride ions. The chloride ion concentration in the system drops to 454 mg / L, and the chlorine removal efficiency is 9.2%.

[0070] (4) The residual amount of copper ions in the remaining chlorine-containing wastewater was titrimetrically analyzed by the iodometric method. The specific titration steps are as follows: Exactly pipette three 25.00 mL test solutions into a conical flask, add 5 mL of NaAc-HAc buffer solution and 1 g of KI, and shake well. Immediately titrate with the Na2S2O3 solution until it turns light yellow. Add 3 mL of 20% KSCN solution, and then titrate until the yellow color almost disappears. Then add 3 mL of 0.5% starch solution and continue titrating until the blue color of the solution just disappears, which is regarded as the end point. According to the volume of the Na2S2O3 solution consumed, the copper content in the test solution was calculated to be 48.2 mg / L.

[0071] Example 6

[0072] The chlorine removal method for constructing a copper-containing chlorine remover block by 3D printing technology includes the following steps:

[0073] (1) Calcinate copper sulfate as the copper source at 300 °C for 60 min, then cool it under dry conditions, grind it, and uniformly mix it with the photosensitive resin at a ratio of 0.5 g / 10 mL, and pour it into the material tank. Set the layer thickness to 0.05 mm, the exposure time for the first layer to 10 s, and perform 3D printing with a model file with an exposure time of 5 s. After printing is completed, wash the model with absolute ethanol and place it in an electric heating oven to dry, obtaining a preliminarily prepared block.

[0074] (2) Immerse the above preliminarily prepared block in the organic solvent acetone for 10 min, and then perform high-temperature carbonization treatment at 400 °C for 30 min to obtain a calcined block. The XRD pattern of this copper-containing chlorine remover block is as shown in Figure 2 (a) in the figure.

[0075] (3) Add the above calcined block to the chlorine-containing wastewater with an initial concentration of 500 mg / L under light conditions, adjust the pH to 0.5 with sulfuric acid, react for 2 min. After chlorine removal is completed, use an ion chromatograph to measure the chloride ions. The chloride ion concentration in the system drops to 443.7 mg / L, and the chlorine removal efficiency is 11.3%.

[0076] (4) The residual amount of copper ions in the remaining chlorine-containing wastewater was titrimetrically analyzed by the iodometric method. The specific titration steps are as follows: Exactly pipette three 25.00 mL test solutions into a conical flask, add 5 mL of NaAc-HAc buffer solution and 1 g of KI, and shake well. Immediately titrate with the Na2S2O3 solution until it turns light yellow. Add 3 mL of 20% KSCN solution, and then titrate until the yellow color almost disappears. Then add 3 mL of 0.5% starch solution and continue titrating until the blue color of the solution just disappears, which is regarded as the end point. According to the volume of the Na2S2O3 solution consumed, the copper content in the test solution was calculated to be 45.8 mg / L.

[0077] The above are only the preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, making equivalent substitutions or changes, shall be covered by the protection scope of the present invention.

Claims

1. A chlorine removal method for constructing a copper-containing chlorine remover block by 3D printing technology, characterized in that, It includes the following steps: (1) After calcining the copper source, it is cooled under dry conditions, ground with an agate mortar, uniformly mixed with photosensitive resin in a certain proportion, poured into a material tank, and 3D printed with a model file with set printing parameters. After printing, the model is washed with absolute ethanol and dried in an electric heating oven to obtain a preliminarily prepared 3D printed copper-containing chlorine remover block; Among them, the photosensitive resin is prepared from an oligomer, a photoinitiator, an active diluent, and an ultraviolet blocker; (2) The above-mentioned preliminarily prepared 3D printed copper-containing chlorine remover block is treated with an organic solvent and subjected to high-temperature carbonization treatment to obtain a calcined 3D printed copper-containing chlorine remover block; (3) The above-mentioned calcined 3D printed copper-containing chlorine remover block is added to the chlorine-containing wastewater. After chlorine removal is completed, an ion chromatograph is used to measure chloride ions; (4) The residual amount of copper ions in the remaining chlorine-containing wastewater is titrimetrically analyzed by the iodometric method.

2. The chlorine removal method for constructing a copper-containing chlorine remover block by the 3D printing technology according to claim 1, characterized in that, In step (1), the copper source is one or more of copper oxide, copper sulfide, copper sulfate, copper nitrate, cuprous thiocyanate, and copper bismuthate; The temperature of the calcination is 300 - 500 °C, and the calcination time is 10 - 60 min.

3. The chlorine removal method for constructing a copper-containing chlorine remover block by using the 3D printing technology according to claim 1, characterized in that, In step (1), the oligomer is one or more of epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate, epoxy resin, and vinyl ether resin; The photoinitiator is one or more of benzoin dimethyl ether, benzophenone, thio propoxy thioxanthone, acylphosphine oxide, phenyl diazonium fluoroborate, and cumene ferrocene hexafluorophosphate; The active diluent is one or more of hydroxyethyl acrylate, triethylene glycol divinyl ether, n-butyl glycidyl ether, hydroxypropyl acrylate, and tripropylene glycol diacrylate; The ultraviolet blocker is one or more of benzophenones, benzotriazoles, salicylate esters, carbon black, inorganic pigments, and fillers; 4. The chlorine removal method for constructing a copper-containing chlorine remover block by the 3D printing technology according to claim 1, characterized in that, In step (1), the ratio of the copper source to the photosensitive resin is (0.5 - 3.0 g) / 10 mL; The setting of the printing parameters, where the layer thickness is 0.05 - 0.2 mm, the exposure time of the first layer is 5 - 10 s, and the exposure time is 5 - 10 s.

5. The chlorine removal method for constructing a copper-containing chlorine removal agent block by the 3D printing technology according to claim 1, characterized in that, In step (2), the organic solvent is acetone, the treatment time is 10 - 60 min, the calcination temperature of the high-temperature carbonization treatment is 100 - 450 °C, and the calcination time is 10 - 120 min.

6. The chlorine removal method for constructing a copper-containing chlorine remover block by the 3D printing technology according to claim 1, characterized in that, In step (3), the initial concentration of the chlorine-containing wastewater is 500 - 1000 mg / L, the chlorine-containing wastewater needs to be adjusted to pH 0.5 - 6 with sulfuric acid, and the reaction time is 2 - 30 min.

7. The chlorine removal method for constructing a copper-containing chlorine remover block by the 3D printing technology according to claim 1, characterized in that, In step (3), the chromatographic system of the ion chromatograph is an OIC-600 type ion chromatograph.

8. The chlorine removal method for constructing a copper-containing chlorine remover block by the 3D printing technology according to claim 1, characterized in that, In step (4), the specific operation steps for titrimetric analysis of the residual amount of copper ions in the remaining chlorine-containing wastewater by the iodometric method are as follows: Take three test solutions in a conical flask, add a NaAc-HAc buffer solution and KI and shake well. Titrate with a Na2S2O3 solution until it turns light yellow, add a KSCN solution, then titrate until the yellow color almost disappears, add a starch solution, and continue titrating until the blue color of the solution just disappears, which is the end point. Calculate the content of copper in the test solution according to the volume of the consumed Na2S2O3 solution.

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