Process for the treatment and recovery of spent materials from adamantane production

Abstract

The present application relates to the processing and recycling method of adamantane production waste bottom material, through the reaction of sulfuric acid liquid and anhydrous aluminum chloride in the waste bottom material to convert it into aluminum sulfate, then using clean water to dissolve and extract the aluminum sulfate from the oil phase of the waste bottom material, and separating and recycling the oil-water two phases after processing. The present application is relatively simple to operate, can obtain oil phase liquid with small consistency and light color, and is convenient for large-scale production implementation.

Description

TECHNICAL FIELD

[0001] The present invention relates to a method for treating and recycling waste materials generated in the production of adamantane products. BACKGROUND

[0002] The process for large-scale production of adamantane products at home and abroad is to isomerize tetrahydrodicyclopentadiene into adamantane under the catalysis of a catalyst. Except for the process of Japan Idemitsu which uses a solid metal catalyst and adopts high-temperature and high-pressure gas-phase reaction, most of the processes use anhydrous aluminum chloride as a catalyst and adopt normal-pressure liquid-solid two-phase reaction. In the case of using anhydrous aluminum chloride as a catalyst, the catalyst anhydrous aluminum chloride is transformed from a larger solid particle in the initial stage into a fine suspended particle and is wrapped and dispersed in the reaction materials during the catalytic reaction process. The traditional adamantane isomerization synthesis process generates a large amount of polymerized tar. After the target product adamantane is extracted by an organic solvent after the isomerization reaction is completed, a large amount of sticky waste materials is left, which is composed of polymerized tar, residual oil (tetrahydrodicyclopentadiene oligomers and decomposition products, etc.) and suspended anhydrous aluminum chloride, and is difficult to treat. This production waste material is strongly acidic, can absorb moisture and release hydrogen chloride gas in the air, and can violently boil and release a large amount of heat and a large amount of hydrogen chloride smoke when it meets water. Even if the "two-step one-cycle method" process is used to isomerize and synthesize adamantane, the production process no longer generates difficult-to-treat polymerized tar, but a large amount of waste materials containing suspended anhydrous aluminum chloride catalyst is generated during the production process. This waste material is composed of tetrahydrodicyclopentadiene decomposition products and oligomerization products, and the suspended anhydrous aluminum chloride is wrapped and dispersed therein. Due to the presence of anhydrous aluminum chloride, hydrogen chloride can still be released when it is in the air, and it can also react to release heat and hydrogen chloride smoke when it meets water, but the reaction is much less violent than that of the waste material of the traditional process.

[0003] At present, the method for treating the waste materials of adamantane production in the field of adamantane production is hydrolysis. The key of the technical route of the hydrolysis method is to make the anhydrous aluminum chloride wrapped in the waste materials lose activity. Specifically, the hydrolysis treatment method is to slowly add the waste materials into clear water or brine under strong stirring, make the anhydrous aluminum chloride in the waste materials react with water to lose activity, dissolve in the water, and then separate the oil phase from the water phase for separate recovery and treatment.

[0004] Once anhydrous aluminum chloride is contacted with water, it will react violently to form aluminum hydroxide and hydrogen chloride, and the aluminum hydroxide and hydrogen chloride in the water liquid will again be converted into inactive aluminum chloride combined with water (dissolved in water). When anhydrous aluminum chloride reacts with water, a large amount of heat will be released, causing the local material to rapidly heat up. Therefore, water or brine cannot be added to the waste material during hydrolysis treatment, which will cause the water to boil and splash out. Only the waste material can be slowly added to the water, and strong stirring is required to disperse the waste material into small oil phase particles in the water liquid as much as possible, so that the anhydrous aluminum chloride in the waste material reacts with water on the surface of the oil phase particles and dissolves into the water phase liquid.

[0005] However, in large-scale waste material hydrolysis treatment operations, the following problems exist:

[0006] 1. The waste material has high consistency and low flowability, and inevitably contacts with water vapor in the air during material transfer and storage, forming aluminum hydroxide solid blocks that are insoluble in the oil phase of the waste material, thus making it difficult to control the feeding speed of the waste material into the hydrolysis liquid. The feeding pipe is often blocked by the solid material contained therein or the reaction of the waste material with the water vapor volatilized in the treatment equipment at the feeding pipe opening, which is very troublesome in actual operation.

[0007] 2. Due to the above reasons, the waste material added to the water liquid is uneven, and the oil phase of the waste material is not fully dispersed in the water liquid, especially in the later stage of the treatment, where the amount of oil phase material in the water liquid is already relatively large, making the dispersion effect poor, causing the reaction of the hydrolysis material system to be violent locally, the reaction heat cannot be transferred in time, and the temperature of the local oil phase particles rises quickly, causing the oil phase material to further polymerize. The result of the polymerization of the oil phase material is that the consistency of the oil phase increases, making it difficult for the anhydrous aluminum chloride wrapped therein to hydrolyze, and the treatment effect becomes poor. The oil phase material after treatment is also difficult to recycle due to its viscous and polymerized tar-like state.

[0008] In order to solve the above problems, some people have tried to introduce water vapor into the waste material under strong stirring to make the hydrolysis reaction not too violent, and also to avoid the feeding problem of the waste material. However, the actual phenomenon is that as the hydrolysis reaction proceeds, the waste material gradually changes into a mixture of aluminum hydroxide solid and oil phase material, making it difficult to stir the mixture, the water vapor introduced is difficult to fully and effectively contact with the waste material, and the hydrolysis reaction cannot continue, so this method has no practical value in large-scale production and treatment. SUMMARY

[0009] The purpose of the present application is to provide a method for treating and recycling waste material containing anhydrous aluminum chloride generated in adamantane production, which adopts the following solutions:

[0010] 1. Add sulfuric acid solution reaction, the waste base material in anhydrous aluminum chloride is converted into aluminum sulfate.

[0011] The waste base material is placed in an acid-resistant container, and anhydrous aluminum chloride is converted into aluminum sulfate by slowly adding sulfuric acid solution under stirring. During the reaction, the temperature of the material is controlled below 60°C by passing cooling water through the reactor jacket layer.

[0012] The concentration of the sulfuric acid solution used is controlled in the range of 82% to 88%, and the amount of sulfuric acid solution added is based on the complete conversion of anhydrous aluminum chloride in the waste base material to aluminum sulfate. Theoretically, the molar consumption of sulfuric acid (net material) is 1.5 times the molar amount of anhydrous aluminum chloride in the waste base material, and it is preferred to control it in the range of 1.5 to 1.6 times.

[0013] 2. Add clean water to dissolve and extract, separate oil and water phases.

[0014] Clean water is added to the waste base material after the reaction to eliminate anhydrous aluminum chloride, and the aluminum sulfate in it is dissolved into the water solution under stirring. After standing and layering, the material is divided into oil and water phases. The upper layer is the oil phase material, and the lower layer is the water phase containing aluminum sulfate and hydrogen chloride.

[0015] The amount of water added is 0.5 to 2 times the weight of the waste base material, and the specific amount of water added is determined by the desired concentration of aluminum sulfate in the water phase. The operating temperature is room temperature (20°C to 40°C).

[0016] The method of the present application is to convert anhydrous aluminum chloride into aluminum sulfate by a mild displacement reaction, which is different from the current process method of eliminating the activity of anhydrous aluminum chloride by a strong exothermic hydrolysis reaction. According to the present operation, the waste base material containing anhydrous aluminum chloride produced by the "two-step one-cycle process" for producing adamantane is treated, and the upper oil phase material obtained is in good flow state and has light color, which can be separated and recovered as fuel or carbon black raw material. The lower water phase liquid containing aluminum sulfate is light yellow and nearly transparent, which can be directly used as raw water liquid for preparing wastewater flocculation treatment agent after separation and recovery, or it can be evaporated and concentrated, cooled and crystallized, and the aluminum sulfate crystal particles are further purified and treated for other purposes.

[0017] Using the present operation process to treat the waste base material containing anhydrous aluminum chloride produced by the traditional adamantane production process with a large amount of polymerized tar, the upper oil phase material with small consistency and the lower light yellow and nearly transparent water phase liquid can also be obtained, which are convenient for separation and recovery.

[0018] The researchers of the present application observed through multiple experiments that when the concentrated sulfuric acid solution with a concentration in the range of 82% to 88% is slowly added to the stirring waste material, the replacement reaction of aluminum trichloride and sulfuric acid mainly occurs instead of the hydrolysis reaction of aluminum trichloride, the reaction process is relatively mild, the heat release of the reaction is small, and the temperature is easy to control. The material is in good flow state during the whole reaction process. The oil phase separated after subsequent water extraction and dissolution treatment has good flowability.

[0019] Through the investigation experiment of the concentration of the sulfuric acid solution, it is shown that if the concentration of the sulfuric acid is lower than 82%, the reaction degree becomes violent, the lower the concentration of the sulfuric acid, the more violent the reaction, the heat release of the reaction is also increased, and the aluminum hydroxide solid begins to be obviously produced in the material, indicating that the hydrolysis reaction of aluminum trichloride occurs, and the liquid consistency of the oil phase separated after subsequent water dissolution and extraction is also increased. If the concentration of the sulfuric acid solution is higher than 88%, the color of the reaction material becomes dark, and the flowability of the oil phase obtained after the subsequent water dissolution and extraction is good, but the color of the oil phase becomes dark, which is judged to be caused by the oxidation of the organic matter in the oil phase in the waste material due to the increase of the oxidation of the sulfuric acid with a concentration higher than 88%. Therefore, it is specified that the concentration of the sulfuric acid solution needs to be controlled in the range of 82% to 88%.

[0020] Compared with the prior art, the present application has the following beneficial effects:

[0021] The technical scheme of the present application can achieve the following effects:

[0022] 1. The waste material containing anhydrous aluminum trichloride can be treated relatively simply and effectively, and the reaction temperature and the reaction degree are easy to control during the treatment process.

[0023] 2. The treated waste material is layered into the oil phase material with good flowability and light color, and the light and nearly transparent aluminum sulfate aqueous solution, which can be conveniently separated and recycled. DETAILED DESCRIPTION

[0024] Example:

[0025] The example data is obtained from the production example of treating the waste material containing anhydrous aluminum trichloride catalyst generated in the production of adamantane, and the amount of anhydrous aluminum trichloride in the waste material to be treated is about 17% to 17.5%.

[0026] The operation is as follows:

[0027] About 600 Kg of waste material to be treated was put into the glass lined reactor (with attached hydrogen chloride gas absorption facilities) and stirring was started. Then about 140 Kg of 85% sulfuric acid was slowly added from the overhead tank, and the addition was completed in 40-50 minutes. During the operation, cooling water was passed through the jacket of the reactor to maintain the temperature of the material in the reactor at 45-55°C. After the addition of sulfuric acid was completed, stirring was continued for 10 minutes, and a sample of the material in the reactor was taken for testing. The results showed that there was no residual active aluminum trichloride.

[0028] About 600 Kg of water was added to the reactor, and stirring was continued for 0.5 hours. During this period, the temperature of the material in the reactor was naturally maintained at 27-34°C. The stirring was stopped, and the material was allowed to stand for about 1 hour. It was observed that the material was well separated into two layers, and the aqueous and oil phases were collected separately.

[0029] About 765 Kg of aqueous phase was collected. The aqueous phase was light yellow and transparent, and it was strongly acidic. The aqueous phase contained mainly aluminum sulfate and some hydrogen chloride, and the content of aluminum sulfate was about 17.3%. The aqueous phase was directly used as raw material by a water treatment agent manufacturer.

[0030] About 483 Kg of oil phase was collected. The oil phase was light yellow and had good flowability. The oil phase was directly used as fuel or as raw material for carbon black.

Claims

1. A method for treating and recovering a waste material from adamantane production, characterized in that, Comprise: The following steps (1) Add sulfuric acid solution reaction, the waste base material into anhydrous aluminum chloride into aluminum sulfate; Slowly add sulfuric acid solution to the stirring waste base material, let the sulfuric acid and the waste base material wrapped in anhydrous aluminum chloride replacement reaction, let the active anhydrous aluminum chloride into inactive aluminum sulfate; (2) Add clean water to dissolve extraction, separate oil and water two phases: The clean water is added to the waste base material after the reaction to eliminate anhydrous aluminum chloride, and the aluminum sulfate in it is dissolved into the water. After standing and separating, the upper oil phase material and the lower water phase material are recovered; The reaction operation temperature in step (1) is 40-55°C; The concentration of sulfuric acid solution used in step (1) is controlled in the range of 82%-88%, the adding amount of sulfuric acid solution is equal to or greater than 1.5 times the molar amount of anhydrous aluminum chloride in the waste base material.

2. The method for treating and recovering the discarded raw material of adamantane production according to claim 1, characterized by, The reaction operation temperature in step (2) is 20-40°C.

3. The method for treating and recycling the discarded raw material for adamantane production according to claim 1, characterized by, The adding amount of clean water in step (2) is 0.5-2 times the weight of the waste base material.

4. The method for treating and recycling the discarded raw material for adamantane production according to claim 1, characterized by, The upper oil phase material in step (2) is recovered as a combustion material or a carbon black raw material, and the lower water phase material is recovered as a raw material for waste water flocculation treatment.