CN-117819490-B - Treatment recovery method for waste sulfuric acid liquid in adamantanone production

Abstract

The invention relates to a treatment recovery method of waste sulfuric acid liquid in 2-adamantanone production, which comprises the steps of preparing pasty slurry composed of inorganic mineral bentonite, alkane organic solvent and dilute sulfuric acid liquid, mixing the pasty slurry into the waste sulfuric acid liquid, agglomerating the pasty slurry to remove suspension polymerization colloid in the waste sulfuric acid liquid, evaporating and concentrating the pasty slurry, and removing sulfur dioxide in the waste sulfuric acid liquid by adopting hydrogen peroxide oxidation treatment to obtain purer dilute sulfuric acid liquid capable of being directly utilized. The invention has simple operation and low treatment cost, and the recovered dilute sulfuric acid solution can be directly used as other materials.

Inventors

• WANG NAN
• KONG LIN
• YANG LANG
• ZHOU JIANFENG
• HUANG FENG
• Yan Shangjie

Assignees

• 四川众邦新材料股份有限公司

Dates

Publication Date

20260512

Application Date

20231218

Claims (4)

1. 1. The method for treating and recycling the waste sulfuric acid liquid in the production of the 2-adamantanone is characterized by comprising the following steps of: (1) Preparing special adsorption coagulant paste: firstly, bentonite is mixed and infiltrated with an organic solvent, and after the bentonite swells, the bentonite is strongly mixed with dilute sulfuric acid solution to prepare pasty material; (2) Adding the pasty material prepared in the step (1) into waste sulfuric acid liquid to be treated, stirring strongly at 40-50 ℃ to ensure that the pasty material is fully mixed and dispersed, standing and naturally cooling to normal temperature, and fully floating the solid material in the waste sulfuric acid liquid to the surface layer and agglomerating into coarse particles; (3) Coarse solid particles on the surface layer of the material are separated and removed, and then the fine agglomerated particles remained in the dilute sulfuric acid solution are removed by stirring and adsorbing with activated carbon powder at 50-60 ℃; (4) Evaporating the dilute sulfuric acid solution with the solid materials of the active carbon filtered out under reduced pressure, concentrating until the sulfuric acid content reaches 60%, then adding hydrogen peroxide into the dilute sulfuric acid solution, reacting at 40-50 ℃, and oxidizing to remove residual sulfur dioxide to obtain purer dilute sulfuric acid solution; (1) The bentonite is inorganic mineral bentonite, the organic solvent is petroleum ether with the distillation range of 60-120 ℃, solvent oil with the distillation range of 60-120 ℃, n-hexane, n-heptane or n-octane, and the concentration of the dilute sulfuric acid solution is 55-65%; (1) Wherein, the bentonite is organic solvent, dilute sulfuric acid=2 (1-2) and 15 mass ratio, and the operation temperature is normal temperature.
2. 2. The method for treating and recycling waste sulfuric acid liquid in 2-adamantanone production according to claim 1, wherein in (2), the mass ratio of waste sulfuric acid liquid to pasty material=100:2-8, the specific addition amount of the pasty material depends on the content of suspended polymerized colloid in the waste sulfuric acid liquid, so that the suspended polymerized colloid in the waste sulfuric acid liquid can be fully adsorbed and aggregated.
3. 3. The method for treating and recovering waste sulfuric acid liquid produced by 2-adamantanone as claimed in claim 1, wherein in (3), the mass ratio of waste sulfuric acid liquid to active carbon powder is 100:0.2-0.5.
4. 4. The method for treating and recovering a waste sulfuric acid liquid from 2-adamantanone production as claimed in claim 1, wherein in (4), hydrogen peroxide is added in an amount sufficient to oxidize residual sulfur dioxide completely.

Description

Treatment recovery method for waste sulfuric acid liquid in adamantanone production Technical Field The invention relates to the technical field of chemical engineering, in particular to a method for treating and recycling waste sulfuric acid liquid generated in the production process of a 2-adamantanone product. Background 2-Adamantanone is used as a raw material for preparing various other 2-substituted adamantane derivative products, is an important intermediate for producing various medicines, and is prepared by taking adamantane or 1-adamantanol as a starting raw material and adopting a concentrated sulfuric acid direct oxidation method for reaction in the industrial production at home and abroad at present. And (3) carrying out an oxidation reaction on adamantane or 1-adamantanol and sulfuric acid to generate an intermediate product 2-adamantanol sulfate, and carrying out a hydrolysis reaction when meeting water after the reaction is ended to release a target product 2-adamantanone. Since polymerization side reaction of the reaction intermediate 2-adamantanol sulfate is inevitably generated under the condition of concentrated sulfuric acid and heating, polymerized colloid is generated. In the conventional oxidation production process, only 40% -50% of the initial raw materials are converted into target products, and the rest 50% -60% of the raw materials are changed into polymer colloid due to side reactions. Even with the improved oxidation process, not less than 20% -30% of the raw materials are usually converted into polymeric colloid due to side reactions. The oxidation reaction process of 2-adamantanone needs to dilute the reaction materials with water when the reaction is terminated, so as to eliminate the oxidability of concentrated sulfuric acid, and simultaneously hydrolyze 2-adamantanol sulfate which is an intermediate substance in the reaction, so as to release the target product 2-adamantanone. The reaction mixture after water dilution mainly comprises dilute sulfuric acid solution, the sulfuric acid content is generally 30% -40%, the target product 2-adamantanone floats on the surface layer of the dilute sulfuric acid solution in a precipitated crystal state, a large amount of polymerized colloid generated by side reaction is dispersed in the dilute sulfuric acid solution in a stable suspended matter state, and more sulfur dioxide serving as an oxidation reaction product is mixed in the dilute sulfuric acid solution. The concentrated sulfuric acid used in the production and preparation of 2-adamantanone is usually large in quantity, and after the target product 2-adamantanone is hydrolyzed, diluted, separated and extracted, more waste dilute sulfuric acid liquid is left, and 30-50 tons of waste dilute sulfuric acid liquid is generated in each production of 1 ton of 2-adamantanone. The waste sulfuric acid liquid contains a large amount of suspended polymeric colloid and a large amount of sulfur dioxide, so that the waste sulfuric acid liquid is in a dark gray thin paste state, and the environment is polluted by the odor of the sulfur dioxide which emits malodor. In order to treat these waste sulfuric acid solutions, the common method is to neutralize them with an inorganic strong base (sodium hydroxide, etc.), in neutral or weakly alkaline aqueous solution, the polymeric colloid is easily agglomerated and separated, and the sulfate and sulfite aqueous solutions after removal of the polymeric colloid are subjected to re-evaporation and concentration treatment. It is also recognized that if the waste sulfuric acid solution is directly treated and recycled in an optimal way, a great amount of suspension polymerized colloid exists in the waste sulfuric acid solution, and the polymerized colloid is in a fine suspension particle state in the dilute sulfuric acid solution, so that the suspension stability is good, the polymer colloid cannot be removed through filtration, and is difficult to effectively adsorb and agglomerate by using a flocculating agent, activated carbon and the like, and the difficulty of preparing pure dilute sulfuric acid by treating the waste sulfuric acid solution is high, so that the technology is also an urgent technical problem to be solved. Disclosure of Invention The invention aims to provide a treatment and recovery method for waste sulfuric acid liquid in adamantanone production, which aims to effectively remove suspension polymerization colloid and sulfur dioxide in the waste sulfuric acid liquid in 2-adamantanone production, and prepare pure dilute sulfuric acid for recycling. The invention adopts the following solution for treating and recycling the waste sulfuric acid liquid containing suspension polymerization colloid and sulfur dioxide generated in the production of 2-adamantanone: 1. preparing special adsorption coagulant paste: firstly, bentonite is mixed and infiltrated with an organic solvent, and after the bentonite swells, the bentonite is strongly mixed