White phosphorus non-hazardous chemical treatment method

Abstract

The invention discloses a non-hazardous chemical treatment method for white phosphorus, which comprises the following steps: firstly, preparing a copper sulfate solution by using copper sulfate and water, adding white phosphorus to be treated into the copper sulfate solution for chemical reaction, and converting the white phosphorus into cuprous phosphide; then, potassium permanganate is added into the reaction liquid of the white phosphorus and the copper sulfate step by step for multiple times, cuprous phosphide is removed through a chemical reaction, and the white phosphorus wrapped by the cuprous phosphide continues to react with the copper sulfate until the white phosphorus and the cuprous phosphide in the reaction liquid are completely removed through the reaction. The non-hazardous chemical treatment method for the white phosphorus is simple and safe to operate; the treatment cost is low and the efficiency is high; the environment is protected.

Description

Technical Field

[0001] The present application relates to the technical field of white phosphorus treatment, and in particular to a method for non-hazardous treatment of white phosphorus. Background Art

[0002] With the progress of science and technology and the diversified development of industrial production, white phosphorus, as a highly active and strategically significant chemical substance, plays an indispensable role in the military, medicine, agriculture, chemical industry and other fields. However, due to its low ignition point, spontaneous combustion, toxicity and other characteristics, white phosphorus is very likely to cause fires, explosions and other safety accidents during production, storage, transportation and waste treatment, and also poses a serious threat to the environment and human health. Therefore, at present, white phosphorus is usually converted into a stable existence form for storage, transportation and utilization. The existing technologies for treating white phosphorus include (1) sealed storage in water, which has high long-term storage costs, serious waste of water resources, and does not fundamentally solve the safety hazards brought by white phosphorus; (2) cement solidification and deep burial treatment, which is expensive and wastes phosphorus resources; (3) combustion treatment, which seriously wastes phosphorus resources, pollutes the environment and has safety hazards; (4) converting white phosphorus into red phosphorus, which is expensive and requires special equipment, harsh conversion conditions and safety risks.

[0003] Faced with increasingly stringent environmental regulations and high social requirements for safe production, there is an urgent need to develop a safe, economical, environmentally friendly, efficient and easy-to-operate white phosphorus treatment method. This technology should be able to reduce the hazard of white phosphorus at the source, while achieving efficient conversion and harmless treatment of white phosphorus, thereby minimizing environmental pollution. Summary of the invention

[0004] In view of the above problems in the prior art, the purpose of the present application is to provide a method for non-hazardous treatment of white phosphorus to solve the safety risks caused by spontaneous combustion, toxicity, etc. of white phosphorus.

[0005] To achieve the above objectives, the present application proposes a method for non-hazardous treatment of white phosphorus, comprising:

[0006] Step 1: Prepare a copper sulfate solution using copper sulfate and water, add the white phosphorus to be treated into the copper sulfate solution to carry out the following chemical reaction, and convert the white phosphorus into cuprous phosphide;

[0007] 33P+45CuSO4+72H2O=15Cu3P↓+18H3PO4+45H2SO4 (1)

[0008] Step 2: Add potassium permanganate to the reaction solution of white phosphorus and copper sulfate in multiple steps to remove cuprous phosphide through the following chemical reaction, and allow the white phosphorus wrapped by cuprous phosphide to continue to react with copper sulfate until all the white phosphorus and cuprous phosphide in the reaction solution are removed by the reaction:

[0009] 15Cu3P+55KMnO4+50H2SO4=55MnO2↓+45CuSO4+15K3PO4+50H2O+5K2SO4 (2).

[0010] According to some embodiments of the present application, when the color of the copper sulfate solution in step 1 changes from the initial dark blue to light blue-black and the color of the reaction solution basically no longer changes significantly, potassium permanganate is added to the white phosphorus and copper sulfate reaction solution for the first time; after the potassium permanganate and cuprous phosphide are reacted for a period of time, potassium permanganate is added to the mixed reaction solution again; potassium permanganate is added to the reaction solution repeatedly until all the white phosphorus and cuprous phosphide in the reaction solution are removed by the reaction;

[0011] According to some embodiments of the present application, after the potassium permanganate added each time is consumed, potassium permanganate is added again after a period of pause.

[0012] According to some embodiments of the present application, the reactants are stirred during the reaction process of step one and step two.

[0013] According to some embodiments of the present application, in step 1 and step 2, the temperature of the copper sulfate solution is maintained at 45-100°C.

[0014] According to some embodiments of the present application, in step one, the molar ratio of copper sulfate to white phosphorus is in the range of 0.494-1.358.

[0015] According to some embodiments of the present application, the reaction residence time of step one is 5 min-50 min.

[0016] According to some embodiments of the present application, the molar ratio of potassium permanganate added for the first time in step 2 to white phosphorus added in step 1 is in the range of 0-0.781, and the reaction residence time is 5 min-50 min.

[0017] According to some embodiments of the present application, the molar ratio of potassium permanganate added each time after the first time in step 2 to the white phosphorus added in step 1 is in the range of 0-0.390, and the reaction residence time is 5 min-50 min.

[0018] According to some embodiments of the present application, the number of times potassium permanganate is added in step 2 is 4 times or more, preferably 4-6 times.

[0019] The principle and advantages of this application: The non-hazardous treatment method of white phosphorus in this application first generates Cu3P and H3PO4 by reacting white phosphorus with copper sulfate. Considering that the generated cuprous phosphide will wrap on the surface of white phosphorus, preventing the further reaction, and the generated Cu3P may be decomposed into white phosphorus and copper again at a higher temperature, there is still a certain risk in storing the white phosphorus without complete treatment. Therefore, this application introduces potassium permanganate into the reaction solution several times after the white phosphorus reacts with copper sulfate for a period of time to solve the problem of Cu3P wrapping; the introduced potassium permanganate can react with Cu3P together with the H2SO4 generated in the first step, and the reaction product CuSO4 can participate in the reaction of converting white phosphorus into Cu3P, and the reaction is cyclically carried out until the white phosphorus and cuprous phosphide in the reaction solution are completely removed by the reaction. Compared with several existing white phosphorus treatment processes, the white phosphorus treatment method of this application is simple and safe to operate; the treatment cost is low and efficient; it is green and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The figure is a schematic diagram of a process for non-hazardous treatment of white phosphorus according to an embodiment of the present invention. DETAILED DESCRIPTION

[0021] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following is a brief introduction to the drawings required for the description of the embodiments. In the drawings, components with the same or similar functions are indicated by the same or similar reference numerals. In addition, for some components that are not directly related to the concept of the present invention, their illustrations may be omitted. The description of the drawings and specific embodiments is only for a better understanding of the present invention, and the present invention is not limited to the embodiments illustrated in the drawings and described in the specification.

[0022] The technical terms or scientific terms used in the present invention should be the common meanings understood by people with ordinary skills in the field to which the present invention belongs. The use of "including" or "comprising" and similar words in the present invention indicates an open meaning, and does not exclude other elements, components, parts or items except for the elements, parts, parts or items clearly listed. "Connect" or "connected" and similar words are not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. "Up", "down", "left", "right" and the like are only used to indicate relative positional relationships. When the absolute position of the described object changes, the relative positional relationship may also change accordingly. "First", "second" and the like are used to distinguish different components and do not indicate a specific order.

[0023] The technical solution of the present application is further explained below with reference to the accompanying drawings and through specific implementation methods.

[0024] The core of this application is to convert white phosphorus into safe and harmless phosphorus-containing compounds, completely solving the potential safety hazards caused by white phosphorus during storage and transportation. Aiming at the limitations of current white phosphorus treatment technology, this application proposes a new white phosphorus non-hazardous treatment method, which aims to completely solve the safety problems of white phosphorus through a carefully designed chemical reaction process and process route, and promote white phosphorus waste treatment technology to a new stage of green, safe, efficient and economical.

[0025] Figure 1 FIG. 1 is a schematic diagram of a process for de-hazardous treatment of white phosphorus according to an embodiment of the present invention. Figure 1 In general, the novel white phosphorus non-hazardous treatment method of the present application comprises the following steps:

[0026] Step 1: Prepare a copper sulfate solution using copper sulfate and water, add the white phosphorus to be treated into the copper sulfate solution to carry out the following chemical reaction, and convert the white phosphorus into cuprous phosphide;

[0027] 33P+45CuSO4+72H2O=15Cu3P↓+18H3PO4+45H2SO4 (1)

[0028] Step 2: Add potassium permanganate to the reaction solution of white phosphorus and copper sulfate in multiple steps to remove cuprous phosphide through the following chemical reaction, and allow the white phosphorus wrapped by cuprous phosphide to continue to react with copper sulfate until all the white phosphorus and cuprous phosphide in the reaction solution are removed by the reaction:

[0029] 15Cu3P+55KMnO4+50H2SO4=55MnO2↓+45CuSO4+15K3PO4+50H2O+5K2SO4 (2).

[0030] Specifically, in step 1, copper sulfate pentahydrate may be used to prepare a copper sulfate solution, and then white phosphorus may be added, and white phosphorus and copper sulfate may be reacted to generate Cu3P and H3PO4. The reactants may be stirred during the reaction, and stirring may be used to break up the added white phosphorus into small particles, thereby increasing the contact area between the white phosphorus and copper sulfate, and at the same time, the Cu3P wrapped on the surface of the white phosphorus may be broken up, so that the wrapped white phosphorus is exposed to continue to react with the copper sulfate, thereby accelerating the reaction process.

[0031] In addition, since the melting point of P is about 44 degrees, during the reaction, the temperature of the copper sulfate solution is maintained above 44 degrees, preferably maintained at 45-100 degrees, which is also conducive to rapid reaction and to accelerate the conversion of white phosphorus into Cu3P. Specifically, the temperature of the copper sulfate solution can be heated to above 44 degrees before adding white phosphorus, and then white phosphorus is added; or the temperature of the copper sulfate solution can be heated to above 44 degrees after adding white phosphorus, so as to facilitate rapid reaction.

[0032] In step 1, the molar ratio of copper sulfate to white phosphorus is in the range of about 0.494-1.358. Within this range, the ratio of copper sulfate to white phosphorus is appropriate, and the white phosphorus can be fully reacted and removed; copper sulfate will not be wasted, and the amount of copper sulfate that converts white phosphorus into cuprous phosphide in the first time will not be too small due to the small amount of copper sulfate, resulting in a small amount of potassium permanganate added each time and a large number of times, and at the same time causing the reaction time to be too long. The reaction residence time of white phosphorus in the copper sulfate aqueous solution can be 5min-50min, depending on factors such as temperature and stirring intensity.

[0033] According to some embodiments of the present application, when the color of the copper sulfate solution in step one changes from the original blue to light blue-black, and the color of the reaction solution basically no longer changes significantly, it means that the white phosphorus may be wrapped by the cuprous phosphide generated by the preliminary reaction, and the chemical reaction stops; at this time, step two is performed, and potassium permanganate is added to the white phosphorus and copper sulfate reaction solution in steps and multiple times. Usually, the number of times potassium permanganate is added is 4 times or more, preferably 4-6 times, so that white phosphorus and cuprous phosphide can be completely converted into safe, non-toxic and pollution-free substances. As in step one, stirring can be performed during each step of the reaction in step two to speed up the reaction process.

[0034] The purpose of introducing potassium permanganate is to react chemically with cuprous phosphide, a reaction product of step one, to remove the cuprous phosphide encapsulating white phosphorus through the reaction, and to allow the white phosphorus to continue to react chemically with copper sulfate to be converted into cuprous phosphide; by repeatedly adding potassium permanganate for cyclic reaction, the white phosphorus is finally removed by the reaction, and the cuprous phosphide is completely converted into phosphoric acid, thereby solving the problem of Cu3P encapsulation and the potential safety risk of Cu3P residue storage, and also completely solving the problem of safe conversion of white phosphorus.

[0035] Specifically, when the color of the copper sulfate solution changes from the initial dark blue to light blue-black and the color of the reaction solution basically no longer changes significantly, potassium permanganate is added to the white phosphorus and copper sulfate reaction solution for the first time; the molar ratio of the potassium permanganate added for the first time to the white phosphorus added in step 1 can be controlled within a range of about 0-0.781, so that the potassium permanganate cannot be completely consumed due to the small amount of cuprous phosphide generated, resulting in residual potassium permanganate in the solution to inhibit the continued reaction of copper sulfate and white phosphorus; the reaction residence time after the potassium permanganate is added for the first time can be 5 min-50 min, depending on the reaction temperature and stirring conditions.

[0036] Furthermore, the molar ratio of the potassium permanganate added each time in step 2 to the white phosphorus added in step 1 can be controlled within a range of about 0-0.390, so that the potassium permanganate cannot be completely consumed due to the small amount of cuprous phosphide generated, resulting in residual potassium permanganate in the solution to inhibit the continued reaction of copper sulfate and white phosphorus; the reaction residence time after each addition of potassium permanganate is 5 min-50 min, depending on the reaction temperature and stirring conditions.

[0037] According to some embodiments of the present application, after each addition of potassium permanganate is consumed, potassium permanganate is added again after a period of pause to facilitate the white phosphorus released from the cuprous phosphide package to continue to react for a period of time to generate new cuprous phosphide. This will not result in the potassium permanganate not being completely consumed or the subsequent reaction time being too long due to the small amount of cuprous phosphide generated.

[0038] After the white phosphorus and cuprous phosphide are completely converted into safe, non-toxic and non-polluting substances by repeatedly adding potassium permanganate to the reaction solution of white phosphorus and copper sulfate, specifically, when the purple-red color of potassium permanganate does not completely fade after the last addition of potassium permanganate and the reaction, it can be judged that the white phosphorus and cuprous phosphide have been completely converted and removed, and the residue generated after the reaction is completed can be filtered and separated. The separated residue can be subjected to combustion analysis to confirm again whether the white phosphorus has been completely processed.

[0039] The following is a specific experimental example to illustrate the implementation process of the method for non-hazardous treatment of white phosphorus of the present invention and the technical effects produced.

[0040] Experimental Example 1

[0041] First, weigh 275g (1.1mol) of copper sulfate pentahydrate and place it in a reaction container, then pour 2L of water into the container, then heat the solution to 50°C, and then add 25g (0.81mol) of white phosphorus to be treated into the solution. The molar ratio of copper sulfate to white phosphorus is about 1.358. After reacting for 2h, the reaction liquid changes from the original dark blue to light blue with black, and it is determined that the reaction has basically stopped. Subsequently, the reaction residue is analyzed, and a large amount of white phosphorus is still not converted into Cu3P. The residue analysis method can be selected to heat the residue. The more white phosphorus, the more intense the combustion, so as to judge the conversion of white phosphorus.

[0042] Experimental Example 2:

[0043] A stirring process is added on the basis of Experimental Example 1 to illustrate the effect of stirring on the reaction progress of white phosphorus and copper sulfate in step one.

[0044] First, weigh 275g (1.1mol) of copper sulfate pentahydrate and place it in a reaction container, then pour 2L of water into the container, then heat the solution to 50°C, and then add 25g (0.81mol) of white phosphorus to be treated into the solution, that is, the molar ratio of copper sulfate to white phosphorus is about 1.358, and start the agitator at the same time, stir the reaction system, react for 25min, the reaction liquid changes from the original dark blue to light blue with black, and the subsequent color no longer changes significantly, and it is determined that the reaction has basically stopped. The reaction residue is then analyzed, and a small amount of white phosphorus is not converted into Cu3P.

[0045] Experimental Example 2 is compared with Experimental Example 1, which proves that stirring has a significant effect on the conversion rate and reaction rate of white phosphorus. After the introduction of stirring, the reaction rate is greatly shortened and the conversion rate of white phosphorus is significantly improved.

[0046] Experimental Example 3

[0047] Experimental Example 3 is based on Experimental Example 2, in which potassium permanganate is added to the reaction solution of white phosphorus and copper sulfate to illustrate the effect of adding potassium permanganate on the conversion rate of white phosphorus.

[0048] First, 275 g (1.1 mol) of copper sulfate pentahydrate was weighed and placed in a reaction container, and then 2 L of water was poured into the container, and then the solution was heated to 50° C., and then 25 g (0.81 mol) of white phosphorus to be treated was added to the solution, and the stirrer was started at the same time to stir the reaction system. After reacting for 25 minutes, the reaction solution changed from the original dark blue to light blue with black, and there was no obvious change in the subsequent color. It was determined that the reaction was basically stopped. At this time, 200 g (1.27 mol) of potassium permanganate was added to the reaction solution, that is, the molar ratio of potassium permanganate to the initial white phosphorus was about 1.568. It was allowed to react for 2 hours, and it was found that the purple-red color of potassium permanganate did not fade, and it was determined that the reaction was basically completed. Subsequently, the reaction residue was analyzed, and a small amount of white phosphorus was still untreated.

[0049] Comparison between Experimental Example 3 and Experimental Example 2 shows that the conversion rate of white phosphorus is improved after adding potassium permanganate.

[0050] Experimental Example 4

[0051] Experimental Example 4 is based on Experimental Example 3, except that the addition of a relatively large amount of potassium permanganate at one time is replaced by adding a small amount of potassium permanganate in multiple steps.

[0052] First, weigh 275g (1.1mol) of copper sulfate pentahydrate and place it in a reaction container, then pour 2L of water into the container, then heat the solution to 50°C, and then add 25g (0.81mol) of white phosphorus to be treated to the solution, and start the agitator at the same time to stir the reaction system. After reacting for 25 minutes, the reaction solution changes from the original dark blue to light blue with black, and there is no obvious change in subsequent color. It is determined that the reaction is basically stopped. At this time, 100g (0.633mol) of potassium permanganate is added to the reaction solution, that is, the molar ratio of the potassium permanganate added for the first time to the initial white phosphorus is about 0.781. After reacting for 10 minutes, it is found that the color of potassium permanganate has completely faded. At this time, the reaction is allowed to continue for 5 minutes, and 50g (0.316mol) of potassium permanganate is added to the solution again, that is, the potassium permanganate added for the second time. The molar ratio of potassium permanganate to the initial white phosphorus is about 0.390. After the reaction is carried out for 17 minutes, it is found that the purple-red color of potassium permanganate is completely faded. At this time, the reaction is allowed to continue for 5 minutes, and 25g (0.158mol) of potassium permanganate is added to the reaction system, that is, the molar ratio of the potassium permanganate added for the third time to the initial white phosphorus is about 0.195. After 13 minutes of reaction, the color of potassium permanganate is completely faded. At this time, the reaction is allowed to continue for 5 minutes, and 25g (0.158mol) of potassium permanganate is added to the reaction system, that is, the molar ratio of the potassium permanganate added for the fourth time to the initial white phosphorus is about 0.195. After 20 minutes of reaction, it is found that the color of potassium permanganate in the reaction solution has not completely faded, and it is determined that the reaction is basically completed. Subsequently, the reaction residue is analyzed, and it is found that the white phosphorus is basically completely processed.

[0053] By comparing Experimental Example 4 with Experimental Example 3, the necessity of adding potassium permanganate in multiple times was studied. It was found that the concentration of potassium permanganate introduced at one time was too high, which was not conducive to the full reaction of copper sulfate and white phosphorus; adding potassium permanganate in steps could speed up the reaction process, improve the conversion rate of white phosphorus, and consume white phosphorus more thoroughly.

[0054] Experiments have shown that the molar ratio of the potassium permanganate added for the first time to the white phosphorus added initially is in the range of 0-0.781, the molar ratio of the potassium permanganate added each time after the first time to the white phosphorus added initially is in the range of 0-0.390, the number of times potassium permanganate is added is 4 times or more, preferably 4-6 times, and the white phosphorus is basically completely consumed.

[0055] Experimental Example 5

[0056] The melting point of white phosphorus is about 44.1 degrees Celsius, and it is solid below the melting point. Compared with Experimental Example 2, Experimental Example 5 changes the temperature of the copper sulfate solution in step 1, and sets the reaction temperature to 40°C, which is lower than the melting point of white phosphorus.

[0057] First, 275 g (1.1 mol) of copper sulfate pentahydrate was weighed and placed in a reaction container, and then 2 L of water was poured into the container. The solution was then heated to 40°C, and 25 g (0.81 mol) of white phosphorus to be treated was added to the solution. At the same time, the agitator was started to stir the reaction system. After reacting for 20 minutes, there was basically no obvious color change. The reaction residue was analyzed and it was found that only the surface of the white phosphorus reacted, and the internal white phosphorus did not react.

[0058] Compared with Experimental Examples 2 and 4, Experimental Example 5 found that too low a temperature would cause the white phosphorus to remain in a blocky state, and only the white phosphorus on the surface would react, while the white phosphorus inside would basically not participate in the reaction, resulting in an excessively long subsequent reaction time; this proves that the amount of reaction below the melting point of white phosphorus is very small, and the conversion rate of white phosphorus is low.

[0059] Compared with Experimental Example 5, the reaction temperature of Experimental Example 2 is above the melting point of white phosphorus, the reaction amount is large, and the white phosphorus conversion rate is high.

[0060] Experimental Example 6:

[0061] Experimental Example 6 is based on Experimental Example 4, and the temperature of the copper sulfate solution is increased.

[0062] First, weigh 275g (1.1mol) of copper sulfate pentahydrate and place it in a reaction container, then pour 2L of water into the container, then heat the solution to 85°C, and then add 25g (0.81mol) of white phosphorus to be treated to the solution, and start the agitator at the same time to stir the reaction system. After reacting for 15 minutes, the reaction solution changes from the original dark blue to light blue with black, and there is no obvious change in subsequent color. It is determined that the reaction has basically stopped. At this time, 100g (0.633mol) of potassium permanganate is added to the reaction solution. After reacting for 8 minutes, it is found that the color of potassium permanganate has completely faded. At this time, the reaction is allowed to continue for 5 minutes and then restarted. 50 g (0.316 mol) of potassium permanganate was added to the solution. After the reaction was carried out for 5 minutes, it was found that the purple-red color of potassium permanganate completely faded. At this time, the reaction was allowed to continue for 5 minutes. Then 25 g (0.158 mol) of potassium permanganate was added to the reaction system. After the reaction was carried out for 10 minutes, the color of potassium permanganate completely faded. At this time, the reaction was allowed to continue for 5 minutes. Then 25 g (0.158 mol) of potassium permanganate was added to the reaction system. After the reaction was carried out for 20 minutes, it was found that the color of potassium permanganate in the reaction solution was not completely faded, and it was determined that the reaction was basically completed. Subsequently, the reaction residue was analyzed, and it was found that the white phosphorus was basically completely processed.

[0063] Comparing Experimental Example 4 with Experimental Example 6, we can illustrate the effect of temperature on the reaction rate;

[0064] Experimental Example 6: The temperature is very high, the reaction rate is large, and the conversion rate of white phosphorus is higher. Experiments have shown that keeping the temperature of the copper sulfate solution at 45-100°C is more conducive to the conversion reaction of white phosphorus.

[0065] Experimental Example 7

[0066] Experimental Example 7 is mainly based on Experimental Example 4, but the grams of copper sulfate (concentration of the solution) are changed, that is, the molar ratio of white phosphorus to copper sulfate is changed.

[0067] First, 137.5 g (0.55 mol) of copper sulfate pentahydrate was weighed and placed in a reaction container, and then 2 L of water was poured into the container, and then the solution was heated to 50°C, and then 25 g (0.81 mol) of white phosphorus to be treated was added to the solution, that is, the molar ratio of copper sulfate to white phosphorus was about 0.679, and the agitator was started at the same time to stir the reaction system. After reacting for 15 minutes, the reaction solution changed from the original dark blue to light blue with black, and there was no obvious change in the subsequent color, and it was determined that the reaction was basically stopped. At this time, 100 g (0.633 mol) of potassium permanganate was added to the reaction solution. After reacting for 20 minutes, it was found that the color of potassium permanganate completely faded. The reaction was allowed to continue for 5 minutes, and 50g (0.316mol) of potassium permanganate was added to the solution again. After the reaction was carried out for 25 minutes, it was found that the purple-red color of potassium permanganate had completely faded. The reaction was allowed to continue for 5 minutes, and 25g (0.158mol) of potassium permanganate was added to the reaction system. After the reaction was carried out for 20 minutes, the color of potassium permanganate had completely faded. The reaction was allowed to continue for 5 minutes, and 25g (0.158mol) of potassium permanganate was added to the reaction system. After the reaction was carried out for 20 minutes, it was found that the color of potassium permanganate in the reaction solution had not completely faded, and it was determined that the reaction was basically completed. Subsequently, the reaction residue was analyzed, and it was found that the white phosphorus was basically completely processed.

[0068] Experimental Example 8

[0069] Experimental Example 8 is mainly based on Experimental Example 4, except that the amount of copper sulfate in grams (concentration of the solution) is changed, that is, the molar ratio of white phosphorus to copper sulfate is changed.

[0070] First, 100 g (0.4 mol) of copper sulfate pentahydrate was weighed and placed in a reaction container, and then 2 L of water was poured into the container, and then the solution was heated to 50 ° C. Then, 25 g (0.81 mol) of white phosphorus to be treated was added to the solution, that is, the molar ratio of copper sulfate to white phosphorus was about 0.494, and the agitator was started at the same time to stir the reaction system. After reacting for 12 minutes, the reaction solution changed from the original dark blue to light blue with black, and there was no obvious change in the subsequent color. It was determined that the reaction was basically stopped. At this time, 100 g (0.633 mol) of potassium permanganate was added to the reaction solution. After reacting for 10 minutes, it was found that the color of potassium permanganate did not fade. At this time, The reaction was continued for 5 minutes, and 50 g (0.316 mol) of potassium permanganate was added to the solution again. After the reaction was carried out for 30 minutes, it was found that the purple-red color of potassium permanganate completely faded. The reaction was allowed to continue for 5 minutes, and 25 g (0.158 mol) of potassium permanganate was added to the reaction system. After 25 minutes of reaction, the color of potassium permanganate completely faded. The reaction was allowed to continue for 5 minutes, and 25 g (0.158 mol) of potassium permanganate was added to the reaction system. After 20 minutes of reaction, it was found that the color of potassium permanganate in the reaction solution was not completely faded, and it was determined that the reaction was basically completed. Subsequently, the reaction residue was analyzed, and it was found that the white phosphorus was basically completely processed.

[0071] Comparing Experimental Examples 4, 7 and 8, the effects of different molar ratios of white phosphorus to copper sulfate on the reaction were reflected. It was found that if the amount of copper sulfate added in the initial stage was too small, it would lead to too many processing steps, prolonged reaction time and slow reaction progress.

[0072] Through experiments, it can be determined that the molar ratio of copper sulfate to white phosphorus is 0.494-1.358, which can control the overall reaction time within a reasonable range.

[0073] Experimental Example 9

[0074] Compared with Experimental Example 3, Experimental Example 9 changed the amount of potassium permanganate added at one time.

[0075] First, 275 g (1.1 mol) of copper sulfate pentahydrate was weighed and placed in a reaction container, and then 2 L of water was poured into the container, and then the solution was heated to 50° C., and then 25 g (0.81 mol) of white phosphorus to be treated was added to the solution, and the agitator was started at the same time to stir the reaction system. After reacting for 25 minutes, the reaction solution changed from the original dark blue to light blue with black, and the subsequent color no longer had obvious changes, and it was determined that the reaction was basically stopped. At this time, 120 g (0.76 mol) of potassium permanganate was added to the reaction solution, that is, the molar ratio of potassium permanganate to the initial white phosphorus was about 0.938. After reacting for 60 minutes, it was found that the color of potassium permanganate did not fade. It was found that the excessively high concentration of potassium permanganate inhibited the reaction of copper sulfate and white phosphorus, and the white phosphorus was not completely treated.

[0076] Experimental Example 9 is similar to Experimental Example 3, demonstrating that the conversion rate of white phosphorus is improved after adding potassium permanganate.

[0077] Compared with Experimental Example 4, Experimental Example 9 proves that when an excess of potassium permanganate is added at one time in step 2, the reaction is incomplete.

[0078] Experimental Example 10 (Potassium permanganate was added twice)

[0079] Compared with Experimental Example 4, Experimental Example 10 changed the number of times potassium permanganate was added.

[0080] First, weigh 275g (1.1mol) of copper sulfate pentahydrate and place it in a reaction container. Then pour 2L of water into the container, and then heat the solution to 50°C. Then add 25g (0.81mol) of white phosphorus to be treated to the solution. At the same time, start the agitator and stir the reaction system. After reacting for 25 minutes, the reaction solution changes from the original dark blue to light blue with black, and there is no obvious change in the subsequent color. It is determined that the reaction has basically stopped. At this time, 100g (0.633mol) of potassium permanganate is added to the reaction solution. , that is, the molar ratio of the potassium permanganate added for the first time to the initial white phosphorus is about 0.781. After reacting for 12 minutes, it is found that the color of the potassium permanganate has completely faded. At this time, the reaction is allowed to continue for 5 minutes, and 60g (0.38mol) of potassium permanganate is added to the solution again, that is, the molar ratio of the potassium permanganate added for the second time to the initial white phosphorus is about 0.469. After reacting for 30 minutes, the color of the potassium permanganate has not faded, and it is determined that the reaction is basically completed. Subsequently, the reaction residue is analyzed, and it is found that the white phosphorus has not been completely processed.

[0081] Experimental Example 11 (Potassium permanganate was added three times)

[0082] First, 275g (1.1mol) of copper sulfate pentahydrate was weighed and placed in a reaction container, and then 2L of water was poured into the container, and then the solution was heated to 50°C, and then 25g (0.81mol) of white phosphorus to be treated was added to the solution, and the stirrer was started at the same time to stir the reaction system. After reacting for 25min, the reaction solution changed from the original dark blue to light blue with black, and there was no obvious change in the subsequent color. It was determined that the reaction was basically stopped. At this time, 100g (0.633mol) of potassium permanganate was added to the reaction solution, that is, the molar ratio of the potassium permanganate added for the first time to the initial white phosphorus was about 0.781. After reacting for 10min, it was found that the color of potassium permanganate completely faded. The reaction was allowed to continue for 5 minutes, and 50g (0.316mol) of potassium permanganate was added to the solution again, that is, the molar ratio of the potassium permanganate added for the second time to the initial white phosphorus was about 0.390. After the reaction was carried out for 17 minutes, it was found that the purple-red color of the potassium permanganate had completely faded. At this time, the reaction was allowed to continue for 5 minutes, and 50g (0.316mol) of potassium permanganate was added to the reaction system again, that is, the molar ratio of the potassium permanganate added for the third time to the initial white phosphorus was about 0.390. After the reaction was carried out for 25 minutes, it was found that the color of the potassium permanganate in the reaction solution had not completely faded, and it was determined that the reaction was basically completed. Subsequently, the reaction residue was analyzed, and it was found that there was still a small amount of white phosphorus that had not been processed.

[0083] Compared with Experimental Example 4, Experimental Examples 10 and 11 show that the number of times potassium permanganate is added is too small, and the conversion rate of white phosphorus is reduced. Experiments have shown that the number of times potassium permanganate is usually added needs to reach 4 times or more, and white phosphorus will be completely converted.

[0084] Compared with several existing white phosphorus treatment processes, the white phosphorus non-hazardous treatment method of the present application is simple and safe to operate; has low treatment cost and high efficiency; and is green and environmentally friendly. The technology should be able to reduce the hazard of white phosphorus at the source, while achieving efficient conversion and harmless treatment of white phosphorus, minimizing environmental pollution.

[0085] The above experimental examples are only illustrative of the principles and structures of the present invention, and are not intended to limit the present invention. Those skilled in the art should understand that any changes and improvements made to the present invention without departing from the overall concept of the present invention are within the scope of the present invention. The scope of protection of the present invention shall be based on the scope defined by the claims of this application.

Claims

1. A method for non-hazardous treatment of white phosphorus, comprising: Step 1: Prepare a copper sulfate solution using copper sulfate and water, add the white phosphorus to be treated into the copper sulfate solution to carry out the following chemical reaction, and convert the white phosphorus into cuprous phosphide; 33P+45CuSO4+72H2O=15Cu3P↓+18H3PO4+45H2SO4 (1) Step 2: Add potassium permanganate to the reaction solution of white phosphorus and copper sulfate in multiple steps to remove cuprous phosphide through the following chemical reaction, and allow the white phosphorus wrapped by cuprous phosphide to continue to react with copper sulfate until all the white phosphorus and cuprous phosphide in the reaction solution are removed by the reaction: 15Cu3P+55KMnO4+50H2SO4=55MnO2↓+45CuSO4+15K3PO4+50H2O+5K2SO4 (2).

2. The method for non-hazardous treatment of white phosphorus according to claim 1, wherein: When the color of the copper sulfate solution in step 1 changes from the initial dark blue to light blue-black and the color of the reaction solution basically no longer changes significantly, potassium permanganate is added to the white phosphorus and copper sulfate reaction solution for the first time; after the potassium permanganate and cuprous phosphide are reacted for a period of time, potassium permanganate is added to the mixed reaction solution again; potassium permanganate is added to the reaction solution repeatedly until all the white phosphorus and cuprous phosphide in the reaction solution are reacted and removed.

3. The method for non-hazardous treatment of white phosphorus according to claim 1, wherein: After each added potassium permanganate is consumed, potassium permanganate is added again after a period of pause.

4. The method for non-hazardous treatment of white phosphorus according to claim 1, wherein: The reactants are stirred during the reaction of step one and step two.

5. The method for non-hazardous treatment of white phosphorus according to claim 1, wherein: In step 1 and step 2, the temperature of the copper sulfate solution is maintained at 45-100°C.

6. The method for non-hazardous treatment of white phosphorus according to claim 1, wherein: In step 1, the molar ratio of copper sulfate to white phosphorus is in the range of 0.494-1.

358.

7. The method for non-hazardous treatment of white phosphorus according to claim 1, wherein: The reaction residence time of step 1 is 5 min-50 min.

8. The method for non-hazardous treatment of white phosphorus according to claim 1, wherein: The molar ratio of the potassium permanganate added for the first time in step 2 to the white phosphorus added in step 1 is in the range of 0-0.781, and the reaction residence time is 5 min-50 min.

9. The method for non-hazardous treatment of white phosphorus according to claim 1, wherein: The molar ratio of potassium permanganate added each time after the first time in step 2 to the white phosphorus added in step 1 is in the range of 0-0.390, and the reaction residence time is 5 min-50 min.

10. The method for non-hazardous treatment of white phosphorus according to claim 1, wherein: The number of times potassium permanganate is added in step 2 is 4 times or more, preferably 4-6 times.

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