Oxidative regeneration method of poisoned impregnated carbon
Through the oxidative detoxification, ammonia water treatment and calcination steps, the drug leakage and high cost problems caused by improper treatment of poison-impregnated impregnation charcoal is solved, the oxidative regeneration and performance recovery of impregnated charcoal is achieved, and the protection of HCN and CNC1 is significantly improved. Effect.
Patent Information
- Application Number
- CN202210512612.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-05-12
- Publication Date
- 2024-12-27
- Estimated Expiration
- 2042-05-12
AI Technical Summary
The prior art cannot effectively deal with and recycle the toxic impregnated charcoal, resulting in leakage of poisonous agents or heavy metals and high cost problems.
The oxidative detoxification, ammonia water treatment and calcination steps are adopted to remove the poison by reacting an oxidant with a toxic impregnated charcoal, forming a non-toxic substance, and redistribute the metal components into an active state, realizing the oxidative regeneration of the impregnated charcoal.
It effectively reduces the agglomeration phenomenon of metal components, restores the protective performance of impregnated charcoal, and can achieve the protective effect of HCN and CNC1 to a certain extent, reducing the manufacturing cost of impregnated charcoal.
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of adsorption material regeneration, in particular to an oxidation regeneration method for poisoned impregnated carbon. Background Art
[0002] Protective impregnated carbon generally uses oxidized copper-chromium-silver or copper-molybdenum-zinc-silver as metal active components to chemically react with poisons such as HCN and CNCl to achieve a protective effect. These impregnated carbons will be retired after one use. The retired impregnated carbons may contain a large amount of HCN, CNCl poisons and a large amount of heavy metals. These substances need to be specially treated. If they are not handled properly, it is very likely to cause the leakage of poisons or heavy metals, endangering the environment and even human safety. After being contaminated, the impregnated carbon may be toxic and have adverse effects on humans and the natural environment, and it contains a large amount of heavy metal components, which have a destructive effect on the natural environment. At the same time, the cost of manufacturing these impregnated carbons is very high. If the recycling and reuse of these contaminated impregnated carbons can be achieved economically and reasonably, it will be possible to achieve mixed use to a certain extent, thereby reducing the cost of impregnated carbons.
[0003] At present, the recycling technology is mainly aimed at the physical adsorption of activated carbon materials, and there are no reports on the patent technology related to the regeneration treatment of impregnated carbon by chemical adsorption. The biggest difficulty in the regeneration of poisoned impregnated carbon is, on the one hand, the toxicity elimination of the residues of the poisoning agent or the chemical reaction products that occurred during the adsorption process, and on the other hand, restoring the metal components that have chemically reacted with the poisoning agent to the active state in the original impregnated carbon. Existing physical desorption technologies for the regeneration of carbon-based materials, especially activated carbon, include reduced pressure (vacuum) desorption and temperature desorption. These two technologies are effective for the physical adsorption of activated carbon, but have little effect on impregnated carbon whose main mechanism of action is chemical reaction. There is no effective method for the regeneration of poisoned impregnated carbon, and the regeneration of poisoned impregnated carbon cannot be achieved. It is necessary to find a method for the chemical adsorption regeneration of used protective impregnated carbon and an oxidative regeneration method for poisoned impregnated carbon. Summary of the invention
[0004] In order to solve the problems that improper treatment of impregnated carbon after use is likely to cause leakage of toxic agents or heavy metals, the cost of manufacturing these impregnated carbons is very high, the current recycling technology is ineffective, and the recycling of contaminated impregnated carbon cannot be achieved, the present invention provides an oxidative regeneration method for contaminated impregnated carbon.
[0005] The present invention is implemented by the following technologies:
[0006] The specific preparation process of the oxidation regeneration method of poisoned impregnated carbon provided by the present invention is as follows:
[0007] a. Oxidative detoxification
[0008] Take the poison impregnated carbon, measure the water capacity of the corresponding uncontaminated impregnated carbon, take the oxidant according to the water capacity and the poison impregnated carbon to be regenerated, mix and stir the oxidant with the poison impregnated carbon, use the oxidant to react with the poison in the impregnated carbon to convert the poison into non-toxic substances, dry after standing, or remove the substances generated by the redox reaction by heating, vacuum desorption and other methods to achieve the purpose of oxidation detoxification;
[0009] b. Ammonia treatment
[0010] Adding ammonia water to the detoxified impregnated carbon treated in step a, stirring while injecting, and then stirring intermittently; using ammonia water and the metal components on the impregnated carbon after oxidation detoxification to form a metal ammonia complex, the formed metal ammonia complex redistributes the metal components in the pores of the activated carbon, which is beneficial to the uniform loading of the metal components and reduces the agglomeration of the metal components that may be caused;
[0011] c. Calcination
[0012] The product treated with ammonia water in step b is calcined, and the calcination temperature and time are consistent with the process of preparing impregnated carbon, so that the metal ammine complex formed in step b, that is, the precursor in the process of preparing impregnated carbon, will decompose after calcination to produce the same metal active component in the newly prepared impregnated carbon, and the metal ammine complex will be completely decomposed to obtain active regenerated impregnated carbon, thereby obtaining a regenerated impregnated carbon product.
[0013] Compared with the prior art, the present invention has the following beneficial effects:
[0014] The impregnated carbon oxidized and regenerated by the present invention passed the inspection, and the inspection standards refer to GJB6239.18-2008 "Military impregnated activated carbon performance test method Part 18: Hydrogen cyanide vapor protection time" and GJB6239.19-2008 "Military impregnated activated carbon performance test method Part 19: Cyanogen chloride vapor protection time", and the protection time for hydrocyanic acid is 35min and 36min, and the protection time for hydrogen chloride is 41min and 39min. Under the same other conditions, the protection time of uncontaminated impregnated carbon for hydrocyanic acid is 42min, and the protection time for hydrogen chloride is 44min. It can be proved that the impregnated carbon oxidized and regenerated by the present invention can be restored to a large extent, and has a certain protection effect on HCN and CNCl. According to GJB6239.18-2008, the performance of the regenerated carbon can meet the use requirements. The present invention utilizes an oxidant to treat the contaminated impregnated carbon, oxidizes and eliminates the detoxifier, realizes oxidative detoxification, and the coordination effect of ammonia water causes the metal components to be redistributed and restored to an active state, and restored to the state of a precursor (metal ammonia complex) in the process of preparing the impregnated carbon, thereby realizing regeneration without chemically extracting the metal components. At the same time, the metal components are redistributed in the pores of the activated carbon to reduce the agglomeration of the metal components caused during the treatment process, thereby providing a practical method for the regeneration of the contaminated impregnated carbon and restoring the performance of the contaminated impregnated carbon to a large extent. DETAILED DESCRIPTION
[0015] The present invention is further described below in conjunction with specific embodiments.
[0016] Example 1
[0017] The oxidation regeneration method of the poisoned impregnated carbon has the following specific steps:
[0018] a. Oxidative detoxification
[0019] The water capacity of the same uncontaminated impregnated carbon is determined to be 70%. For every 100g of HCN-contaminated impregnated carbon, 70ml of a 10% aqueous hydrogen peroxide solution is taken according to the determined water capacity. The aqueous hydrogen peroxide solution and the impregnated carbon with the HCN-contaminated agent are mixed and stirred, left to stand for 60min, and dried at 100°C.
[0020] b. Ammonia treatment
[0021] Add 70 ml of 25% ammonia water to the detoxified impregnated carbon treated in step a, the amount added is the same as that of the hydrogen peroxide solution, stir while injecting, then leave it for 60 minutes, and stir every 20 minutes;
[0022] c. Calcination
[0023] The product treated with ammonia water in step b was calcined at 150° C. for 1.5 h to obtain a regenerated impregnated carbon product.
[0024] Test various parameters of the samples obtained in the above steps
[0025] 1. Hydrocyanic acid vapor protection time
[0026] The inspection standard refers to GJB6239.18-2008 "Military Impregnated Activated Carbon Performance Test Method Part 18: Hydrogen Cyanide Vapor Protection Time". After experimental calculation, the protection time of impregnated columnar coal-based activated carbon against hydrocyanic acid is 35 minutes. The protection time of uncontaminated impregnated carbon against hydrocyanic acid is 42 minutes, which can prove that the impregnated carbon oxidized and regenerated by the present invention can be restored to a large extent, has a certain protection effect against HCN, and the protection time is not much different from that of uncontaminated impregnated carbon.
[0027] 2. Cyanogen chloride vapor protection time
[0028] The inspection standard refers to GJB6239.19-2008 "Military Impregnated Activated Carbon Performance Test Method Part 19: Cyanogen Chloride Vapor Protection Time". After experimental calculation, the protection time of the impregnated columnar coal-based activated carbon against cyanogen chloride vapor is 41 minutes. The protection time of the uncontaminated impregnated carbon against hydrogen chloride is 44 minutes, which can prove that the impregnated carbon oxidized and regenerated by the present invention can be restored to a large extent, has a certain protection effect against CNCl, and the protection time is not much different from that of the uncontaminated impregnated carbon.
[0029] Example 2
[0030] The oxidation regeneration method of the poisoned impregnated carbon has the following specific steps:
[0031] a. Oxidative detoxification
[0032] The water capacity of the same uncontaminated impregnated carbon was determined to be 70%. For every 100g of the CNCl-contaminated impregnated carbon, 70ml of a 25% aqueous hydrogen peroxide solution was taken according to the determined water capacity. The aqueous hydrogen peroxide solution and the contaminated impregnated carbon were mixed and stirred, left to stand for 80min, and dried at 110°C.
[0033] b. Ammonia treatment
[0034] Add 70 ml of 25% ammonia water to the detoxified impregnated carbon treated in step a, the amount added is the same as that of the hydrogen peroxide solution, stir while injecting, then leave it for 100 minutes, and stir every 20 minutes;
[0035] c. Calcination
[0036] The product treated with ammonia water in step b was calcined at 145° C. for 2 h to obtain a regenerated impregnated carbon product.
[0037] Test various parameters of the samples obtained in the above steps
[0038] 1. Hydrocyanic acid vapor protection time
[0039] The inspection standard refers to GJB6239.18-2008 "Military Impregnated Activated Carbon Performance Test Method Part 18: Hydrogen Cyanide Vapor Protection Time". After experimental calculation, the protection time of impregnated crushed coconut shell activated carbon against hydrocyanic acid is 36 minutes. The protection time of uncontaminated impregnated carbon against hydrocyanic acid is 42 minutes, which can prove that the impregnated carbon oxidized and regenerated by the present invention can be restored to a large extent, has a certain protection effect against HCN, and the protection time is not much different from that of uncontaminated impregnated carbon.
[0040] 2. Cyanogen chloride vapor protection time
[0041] The inspection standard refers to GJB6239.19-2008 "Military Impregnated Activated Carbon Performance Test Method Part 19: Cyanogen Chloride Vapor Protection Time". After experimental calculation, the protection time of impregnated crushed coconut shell activated carbon against cyanogen chloride vapor is 39 minutes. The protection time of uncontaminated impregnated carbon against hydrogen chloride is 44 minutes, which can prove that the impregnated carbon oxidized and regenerated by the present invention can be restored to a large extent, has a certain protection effect against CNCl, and the protection time is not much different from that of uncontaminated impregnated carbon.
[0042] Example 3
[0043] The oxidation regeneration method of the poisoned impregnated carbon has the following specific steps:
[0044] a. Oxidative detoxification
[0045] Determine the water capacity of the same uncontaminated impregnated carbon. For every 100g of the contaminated impregnated carbon, take 70ml of a 15% aqueous hydrogen peroxide solution according to the measured water capacity. Mix the aqueous hydrogen peroxide solution and the contaminated impregnated carbon, let it stand for 75min, and dry it at 107℃.
[0046] b. Ammonia treatment
[0047] Add 70 ml of 25% ammonia water to the detoxified impregnated carbon treated in step a, the amount added is the same as that of the hydrogen peroxide solution, stir while injecting, then place for 850 minutes, and stir every 20 minutes;
[0048] c. Calcination
[0049] The product treated with ammonia water in step b was calcined at 148° C. for 2 h to obtain a regenerated impregnated carbon product.
[0050] The scope of protection claimed by the present invention is not limited to the above specific embodiments. For those skilled in the art, the present invention may have various deformations and changes. Any modifications, improvements and equivalent substitutions made within the concept and principle of the present invention should be included in the protection scope of the present invention.
Claims
1. A method for the oxidative regeneration of contaminated impregnated carbon for CNCl and HCN protection, characterized in that: The following steps are involved: a. Oxidative detoxification Determine the water capacity of the corresponding uncontaminated impregnated carbon, take an oxidant according to the water capacity for every 100g of the contaminated impregnated carbon, wherein the oxidant is a hydrogen peroxide aqueous solution with a volume concentration of 10% to 25%, mix the oxidant with the contaminated impregnated carbon, let it stand and then dry to obtain the detoxified impregnated carbon; b. Ammonia treatment Adding ammonia water with a mass concentration of 25% to the detoxified impregnated carbon after treatment in step a, leaving it for 60 to 100 minutes, stirring it every 20 minutes, stirring it while injecting, and then stirring it intermittently; using ammonia water and the metal components on the impregnated carbon after oxidation detoxification to form a metal ammonia complex, the formed metal ammonia complex redistributes the metal components in the pores of the activated carbon, which is beneficial to the uniform loading of the metal components and reduces the phenomenon of agglomeration of the metal components that may be caused; c. Calcination The product treated with ammonia water in step b is calcined, and the calcination temperature and time are consistent with the process of preparing impregnated carbon, the calcination temperature is 145-150°C, and the time is 1.5-2h to obtain a regenerated impregnated carbon product.
2. The oxidative regeneration method of contaminated impregnated carbon for CNCl and HCN protection according to claim 1, characterized in that: The following steps are involved: a. Oxidative detoxification Determine the water capacity of the corresponding uncontaminated impregnated carbon. For every 100g of HCN-contaminated impregnated carbon, add a 10% volume concentration of hydrogen peroxide solution according to the measured water capacity. Mix the hydrogen peroxide solution and the contaminated impregnated carbon, let it stand for 60 minutes, and dry it at 100°C. b. Ammonia treatment Add 25% ammonia water to the detoxified impregnated carbon treated in step a, the amount added is the same as that of the hydrogen peroxide solution, stir while injecting, then leave it for 60 minutes, and stir every 20 minutes; c. Calcination The product treated with ammonia water in step b was calcined at 150° C. for 1.5 h to obtain a regenerated impregnated carbon product.
3. The oxidative regeneration method of contaminated impregnated carbon for CNCl and HCN protection according to claim 1, characterized in that: The following steps are involved: a. Oxidative detoxification Determine the water capacity of the corresponding uncontaminated impregnated carbon. For every 100g of CNCl-contaminated impregnated carbon, take a 25% volume concentration of hydrogen peroxide solution according to the measured water capacity. Mix the hydrogen peroxide solution and the contaminated impregnated carbon, let it stand for 80 minutes, and dry it at 110°C. b. Ammonia treatment Add 25% ammonia water to the detoxified impregnated carbon after treatment in step a, the amount added is the same as that of the hydrogen peroxide solution, stir while injecting, then leave it for 100 minutes, and stir it every 20 minutes; c. Calcination The product treated with ammonia water in step b was calcined at 145° C. for 2 h to obtain a regenerated impregnated carbon product.