Special columnar activated carbon catalyst for removing methyl sulfide and preparation method thereof

Abstract

The invention discloses a special columnar activated carbon catalyst for removing methyl sulfide and a preparation method thereof, and relates to the technical field of adsorption material preparation, and the preparation method comprises the following steps: taking columnar activated carbon as a raw material; soaking with hydrochloric acid, filtering, drying at 150 DEG C, mixing the dried sample with water, carrying out hydrothermal reaction at 80 DEG C for 180 minutes, filtering, and drying to obtain modified activated carbon; cuprous chloride and ammonia water are stirred and mixed to prepare a cuprous diamminechloride solution; and immersing the modified active carbon in a cuprous diamminechloride solution, stirring until the solution is completely absorbed by the active carbon, standing, drying through hot air at 170 DEG C, and adjusting the temperature to 140-160 DEG C when the active carbon is in a boiling state to prepare the impregnated active carbon after calcination and drying.

Description

Technical Field

[0001] The invention relates to the technical field of adsorption materials, and in particular to an activated carbon catalyst, specifically a columnar activated carbon catalyst specially used for removing methyl sulfide and a preparation method thereof. Background Art

[0002] With the rapid development of my country's economy, the emission of volatile organic sulfides (VOCs) has affected the quality of my country's ambient air. Methyl sulfide (methyl sulfide, dimethyl disulfide) is used as a pre-sulfurizing agent and anti-carbon deposition additive for catalysts in the petroleum industry. It is also an intermediate in the production of pesticides, but it is also a typical volatile organic pollutant with a bad smell. Methyl sulfide is one of the eight odor pollutants that are restricted in the emission of odor pollutants in my country's current standard "Emission Standard of Odor Pollutants" (GB14554-1993). High concentrations of methyl sulfide can cause strong irritation to human skin, eyes and respiratory tract. Long-term inhalation can cause serious damage to the human digestive system, endocrine system, blood circulation system and nervous system. As an odor pollutant, methyl sulfide has a wide range of sources. In addition to emission sources in the pharmaceutical chemical industry, petroleum refining and other industries, urban sewage treatment plants, black and smelly rivers, landfills and wet garbage anaerobic treatment stations are also common and important emission sources. As the hazards of volatile organic sulfides are gradually gaining attention, the development of effective removal materials for methyl sulfide removal has become an urgent issue to be addressed.

[0003] At the same time, with the sharp increase in the processing volume of high-sulfur crude oil, the removal of sulfides in oil products has attracted great attention. The adsorption method is favored in the field of sulfide removal because of its advantages such as clean and environmental protection, low energy consumption, high efficiency and the ability to realize waste resource utilization. Among many adsorbents, activated carbon is used because of its large specific surface area, strong corrosion resistance, stable chemical properties and wide sources. However, ordinary activated carbon cannot meet the needs of the project. It only relies on physical adsorption, but has poor selective adsorption and low adsorption capacity. At the same time, it is restricted by factors such as surface pH, ambient temperature, and humidity. It is more suitable for the removal of small amounts and low concentrations of methyl sulfide. Therefore, the activated carbon is modified by loading metal ions to improve its removal performance for methyl sulfide.

[0004] In the prior art, Jiang Chuandong et al. grind coconut shell activated carbon to 60-80 mesh, wash it to neutrality, dry it, immerse it in a cupric chloride solution for a certain period of time, dry it, heat it to 350℃ and roast it for 1h to prepare copper-loaded activated carbon with a copper mass fraction of 11%. The main active substance of the copper-loaded activated carbon prepared by this method is Cu 2+ The particle size of activated carbon is 60~80 mesh, the particle size is small, suitable for liquid phase adsorption, not suitable for gas phase adsorption.

[0005] Wang Jincheng et al. used different metal chlorides to modify the surface of activated carbon materials and determined that copper-loaded activated carbon prepared with cuprous chloride as the active component had the best removal effect on dimethyl sulfide. The specific method was to weigh a certain amount of activated carbon and add a certain amount of cuprous chloride solution, which was mainly used to remove dimethyl sulfide from gasoline. Cuprous chloride is poorly soluble in water. The loaded cuprous chloride catalyst prepared by this method has a low loading amount and a low content of active components. The removal efficiency of methyl sulfide is limited and it is only suitable for liquid phase removal.

[0006] Therefore, there is currently a technical gap in the special activated carbon catalyst and method for removing methyl sulfide in the gas phase. It is necessary to provide a special activated carbon catalyst for gas-phase removal of methyl sulfide, which can serve as an environmentally friendly adsorption material and provide efficient removal materials for the environmental protection management of methyl sulfide. Summary of the invention

[0007] In order to solve the problem that there is currently a technical gap in a special activated carbon catalyst and method for removing methyl sulfide in a gas phase, the present invention provides a special columnar activated carbon catalyst for removing methyl sulfide and a preparation method thereof.

[0008] The present invention is implemented by the following technologies: The present invention provides a method for preparing a columnar activated carbon catalyst for removing methyl sulfide, comprising the following steps: a. Select activated carbon adsorption material Columnar activated carbon with moisture ≤5%, strength ≥90%, water capacity ≥75%, and carbon tetrachloride adsorption rate ≥65% is used as raw material. The technical indicators are selected according to GB / T7701.3-2008 "Coal-based granular activated carbon for carrier", and the specifications of the raw materials are 1.5mm / 2.0mm / 3.0mm / 4.0mm.

[0009] b. Activated carbon modification Weigh the raw materials, soak them in 9% hydrochloric acid for 360 minutes, filter, and dry them at 150°C for 180 minutes. Mix the dried sample with water in a volume ratio of 1:2, perform hydrothermal reaction at 80°C for 180 minutes, filter, and dry them at 150°C for 240 minutes to obtain modified activated carbon for later use.

[0010] c. Preparation of diammine cuprous chloride solution The content of cuprous chloride in the prepared solution is calculated according to the content of copper in the prepared activated carbon catalyst for removing dimethyl sulfide, and ammonia water is selected as the solvent. According to the test, the removal effect of dimethyl sulfide is best when 10% of the copper component is impregnated in each portion of activated carbon. According to the molecular weight of cuprous chloride, the cuprous chloride content is 15.55%.

[0011] For every 100 parts of modified activated carbon, take 15.55 parts of cuprous chloride, and calculate the mass of diammine cuprous chloride solution according to the water capacity of activated carbon. Specifically, according to the equal amount impregnation method, determine the volume of the prepared solution according to the water capacity of activated carbon, weigh the modified activated carbon, calculate and weigh the diammine cuprous chloride solution according to the water capacity of activated carbon, and weigh the mass m of diammine cuprous chloride solution. 溶液 Calculated by the following formula: m 溶液 = V·m 活性炭 In the formula, m 溶液 - the mass of cuprous chloride diammine solution, in grams; V – water capacity of activated carbon, expressed as a percentage; m 活性炭 ——Mass of modified activated carbon, in grams.

[0012] Dissolve cuprous chloride in (m 溶液 -15.55) g ammonia water, and stir until the cuprous chloride is completely dissolved to prepare diammine cuprous chloride solution, which is packaged for later use.

[0013] d. Impregnation Immerse the modified activated carbon in diammine cuprous chloride solution and stir until the solution is completely absorbed by the activated carbon and the surface of the activated carbon is dry. Let it stand for 300 minutes.

[0014] e. Calcination and drying The calcination and drying is carried out in a boiling furnace, and the impregnated activated carbon is dried by hot air at 170°C. Specifically, a 170°C hot air flow passes through the mesh plate below the impregnated activated carbon to contact the impregnated activated carbon. When the activated carbon is in a boiling state, the temperature is adjusted to 140-160°C and maintained for 60 minutes to obtain the calcined and dried impregnated activated carbon. During the calcination and drying process, diammine cuprous chloride decomposes to generate cuprous chloride loaded in the pores of the activated carbon, so that the copper component is effectively loaded inside the pores of the activated carbon.

[0015] The invention also discloses a columnar activated carbon catalyst specially used for removing methyl sulfide, which is prepared by the method.

[0016] Compared with the prior art, the present invention has the following beneficial effects: The present invention discloses a columnar activated carbon catalyst for removing methyl sulfide and a preparation method thereof, which innovatively uses coal-based columnar activated carbon as a carrier material, prepares a diammine cuprous chloride solution, impregnates a monovalent copper compound in the columnar activated carbon by an equal amount impregnation method, and prepares a gas-phase methyl sulfide removal special activated carbon catalyst by calcination and drying. At present, this field in China is still in the process of technical control. The invention provides a highly efficient environmentally friendly adsorption material and preparation method for gas-phase methyl sulfide removal, and the method is simple, easy to implement, and operable. Example 1

[0018] A method for preparing a columnar activated carbon catalyst for removing methyl sulfide comprises the following steps: a. Select activated carbon adsorption material A 4.0 mm columnar activated carbon with a water content of 2.1%, a strength of 95%, a water capacity of 75%, and a carbon tetrachloride adsorption rate of 65% was used as a carrier.

[0019] b. Activated carbon modification Weigh 100g of the prepared activated carbon, soak it in 150ml of 9% hydrochloric acid for 360min to remove the easily soluble ash in the activated carbon, filter it, dry it at 150℃ for 180min, mix the dried sample with water in a volume ratio of 1:2, add it to a hydrothermal reactor, hydrothermally react at 80℃ for 180min, filter it, and bake it in an oven at 150℃ for 240min to obtain modified activated carbon for later use.

[0020] c. Preparation of diammine cuprous chloride solution For every 100g of modified activated carbon, take 15.55g of cuprous chloride, calculate the diammine cuprous chloride solution according to the water capacity of the activated carbon. Specifically, the water capacity of the activated carbon is 75%. Dissolve 15.55g of cuprous chloride in 59.45g of ammonia water, stir and mix until the cuprous chloride is completely dissolved, and prepare 75g of diammine cuprous chloride solution, which is packaged for later use.

[0021] d. Impregnation Immerse 100g of modified activated carbon in 75g of diammine cuprous chloride solution and stir until the solution is completely absorbed by the activated carbon and the surface of the activated carbon is dry. Let it stand for 300min.

[0022] e. Calcination and drying The impregnated activated carbon was dried by hot air at 170°C, and when the activated carbon was in a boiling state, the temperature was adjusted to 140-160°C and maintained for 60 minutes to obtain the calcined and dried impregnated activated carbon.

[0023] The adsorption capacity of the activated carbon catalyst for dimethyl sulfide was measured to be 0.62g / g, and the adsorption capacity of dimethyl disulfide was 0.61g / g, which are 30% higher than the adsorption capacity in the current literature. The measuring device referred to the saturated sulfur capacity measuring device in GB / T7702.14 "Test method for sulfur capacity of coal-based granular activated carbon", and the hydrogen sulfide gas was replaced with dimethyl sulfide or dimethyl disulfide, and the nitrogen gas was replaced with air.

[0024] 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 preparing a columnar activated carbon catalyst for removing methyl sulfide, characterized in that: The following steps are involved: a. Select activated carbon adsorption material Take columnar activated carbon with moisture ≤5%, strength ≥90%, water capacity ≥75%, and carbon tetrachloride adsorption rate ≥65% as raw material; b. Activated carbon modification Weigh the raw materials, soak them in 9% hydrochloric acid for 360 minutes, filter them, dry them at 150°C for 180 minutes, mix the dried samples with water in a volume ratio of 1:2, perform hydrothermal reaction at 80°C for 180 minutes, filter them, dry them at 150°C for 240 minutes to obtain modified activated carbon, and set them aside; c. Preparation of diammine cuprous chloride solution For every 100 parts of modified activated carbon, take 15.55 parts of cuprous chloride, calculate the mass of diammine cuprous chloride solution according to the water capacity of activated carbon, dissolve cuprous chloride in ammonia water and stir until all cuprous chloride is dissolved to prepare diammine cuprous chloride solution, which is packaged for later use; d. Impregnation Weigh the modified activated carbon, immerse the modified activated carbon in the diammine cuprous chloride solution, stir until the solution is completely absorbed by the activated carbon and the surface of the activated carbon is dry, and let it stand for 300 minutes; e. Calcination and drying The impregnated activated carbon was dried by hot air at 170°C, and when the activated carbon was in a boiling state, the temperature was adjusted to 140-160°C and maintained for 60 minutes to obtain the calcined and dried impregnated activated carbon.

2. The method for preparing a columnar activated carbon catalyst for removing methyl sulfide according to claim 1, characterized in that: In step a, the specifications of the raw materials are 1.5mm / 2.0mm / 3.0mm / 4.0mm.

3. The method for preparing a columnar activated carbon catalyst for removing methyl sulfide according to claim 1, characterized in that: In step c, weigh the mass m of diammine cuprous chloride solution 溶液 Calculated by the following formula: m 溶液 = V m 活性炭 In the formula, m 溶液 - the mass of cuprous chloride diammine solution, in grams; V – water capacity of activated carbon, expressed as a percentage; m 活性炭 ——Mass of modified activated carbon, in grams.

4. The method for preparing a columnar activated carbon catalyst for removing methyl sulfide according to claim 1, characterized in that: In step e, the impregnated activated carbon is placed on a mesh plate, and a hot air flow of 170° C. passes through the mesh plate below the mesh plate to contact the impregnated activated carbon.

5. The method for preparing a columnar activated carbon catalyst for removing methyl sulfide according to claim 4, characterized in that: In step e, calcination and drying are carried out in a fluidized bed furnace.

6. The method for preparing a columnar activated carbon catalyst for removing methyl sulfide according to claim 1, characterized in that: a. Select activated carbon adsorption material Take columnar activated carbon with moisture ≤5%, strength ≥90%, water capacity ≥75%, and carbon tetrachloride adsorption rate ≥65% as raw material, and the specification of the raw material is 4.0mm; b. Activated carbon modification Weigh 100g of the prepared activated carbon, soak it in 150ml of 9% hydrochloric acid for 360min, filter it, dry it at 150℃ for 180min, mix the dried sample with water in a volume ratio of 1:2, add it to a hydrothermal reactor, hydrothermally react it at 80℃ for 180min, filter it, and dry it in an oven at 150℃ for 240min to obtain modified activated carbon for later use; c. Preparation of diammine cuprous chloride solution For every 100g of modified activated carbon, take 15.55g of cuprous chloride, calculate the diammine cuprous chloride solution according to the water capacity of the activated carbon, dissolve 15.55g of cuprous chloride in (m solution - 15.55)g of ammonia water, stir and mix until the cuprous chloride is completely dissolved, to make the diammine cuprous chloride solution, and package it for later use; d. Impregnation Weigh the modified activated carbon, immerse the modified activated carbon in the diammine cuprous chloride solution, stir until the solution is completely absorbed by the activated carbon and the surface of the activated carbon is dry, and let it stand for 300 minutes; e. Calcination and drying The impregnated activated carbon was dried by hot air at 170°C, and when the activated carbon was in a boiling state, the temperature was adjusted to 140-160°C and maintained for 60 minutes to obtain the calcined and dried impregnated activated carbon.

7. A columnar activated carbon catalyst specially used for removing methyl sulfide prepared according to claim 1.