CN115007105B - Scale-like copper-based adsorbent and preparation method and application thereof - Google Patents

Scale-like copper-based adsorbent and preparation method and application thereof Download PDF

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CN115007105B
CN115007105B CN202210063303.2A CN202210063303A CN115007105B CN 115007105 B CN115007105 B CN 115007105B CN 202210063303 A CN202210063303 A CN 202210063303A CN 115007105 B CN115007105 B CN 115007105B
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copper
based adsorbent
scaly
activated carbon
adsorbent
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CN115007105A (en
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李凯
冯嘉予
王飞
宁平
孙鑫
王驰
马懿星
杨薪玉
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Jiangxi Blue Environmental Engineering Technology Co ltd
Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
    • B01D2253/1124—Metal oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic
    • B01D2257/553—Compounds comprising hydrogen, e.g. silanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character

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Abstract

The invention provides a scaly copper-based adsorbent, and a preparation method and application thereof, and relates to the technical field of air pollution control. The scale-shaped copper-based adsorbent provided by the invention comprises an active carbon carrier and scale-shaped copper oxide nano-sheets loaded on the surface of the active carbon carrier. The invention utilizes the abundant pore structure of the active carbon and the special scaly copper oxide nano-sheet structure, and can realize PH under the condition of low temperature and low oxygen 3 Is efficiently and stably removed, and PH 3 The penetration capacity is high. The scaly copper-based adsorbent provided by the invention has excellent adsorption activity, adsorption selectivity and stability, and can be used for PH in various systems 3 Is stable and efficient in removing and purifying.

Description

Scale-like copper-based adsorbent and preparation method and application thereof
Technical Field
The invention relates to the technical field of air pollution control, in particular to a scaly copper-based adsorbent and a preparation method and application thereof.
Background
PH 3 Is a poisonous and harmful gas which is inflammable and explosive and has comprehensive biological toxicity, and is often used as rodenticide and pesticide. And due to pH 3 Also severely threatens human health and the ecological environment. Human contact PH 3 Can lead to a series of different non-specific symptoms, which are characterized by high mortality rates. However, pH 3 The general mechanism of poisoning remains unclear and no effective antidote or therapeutic approach is currently found. The tail gas discharged from yellow phosphorus production is PH 3 Is one of the primary sources of emissions. Methane, landfill gas, semiconductor photoelectric industry tail gas and airtight calcium carbide furnace tail gas are also PH 3 Is a direct source of (a). However, in the past two decades, pH 3 Emission problems have not been considered sufficiently important in some areas, and the PH of the exhaust must be kept low in order to ensure human health and to protect the environment 3 And (5) effectively removing.
Catalytic decomposition although pH can be decomposed 3 Obtaining H 2 And yellow phosphorus, but the method has some limiting factors, such as higher working temperature>420 ℃ and lower space velocity, and has the problems of high catalyst cost, easy catalyst poisoning caused by impurities and the like.
Disclosure of Invention
The invention aims to provide a scaly copper-based adsorbent, a preparation method and application thereof, and the scaly copper-based adsorbent provided by the invention has excellent adsorption activity, adsorption selectivity and stability and can be used for realizing PH in various systems under the condition of low temperature and low oxygen 3 Is stable and efficient in removing and purifying.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a scaly copper-based adsorbent, which comprises an active carbon carrier and scaly copper oxide nano-sheets loaded on the surface of the active carbon carrier.
Preferably, the activated carbon carrier comprises coal activated carbon or biomass activated carbon.
Preferably, the loading of the scaly copper oxide nano-sheets is 1-60%.
Preferably, the scale-like copper oxide nano-sheet has a width of 0.2-2 μm and a thickness of 20-200 nm.
The invention provides a preparation method of the scaly copper-based adsorbent, which comprises the following steps:
mixing active carbon, copper nitrate solution and nitric acid solution, and performing hydrothermal reaction to obtain an adsorbent precursor;
and roasting the adsorbent precursor in a protective atmosphere to obtain the scaly copper-based adsorbent.
Preferably, the mass of the copper nitrate in the copper nitrate solution is 1 to 5 times of the mass of the activated carbon.
Preferably, the temperature of the hydrothermal reaction is 120-200 ℃; the hydrothermal reaction time is 8-16 h.
Preferably, the roasting temperature is 300-500 ℃; the roasting time is 1-4 h.
Preferably, the activated carbon is crushed and activated prior to mixing.
The invention provides the scaly copper-based adsorbent prepared by the technical scheme or the scaly copper-based adsorbent prepared by the preparation method of the technical scheme, which is used for removing PH by adsorption-oxidation under the condition of low temperature and low oxygen 3 Is applied to the application of the system; the adsorption-oxidation removal of PH 3 The temperature of the catalyst is less than or equal to 100 ℃, and the oxygen content is 0-50000 ppm.
The invention provides a scaly copper-based adsorbent, which comprises an active carbon carrier and scaly copper oxide nano-sheets loaded on the surface of the active carbon carrier. The invention utilizes the active carbon to enrichThe pore structure and the special scaly copper oxide nano-sheet structure can realize PH under the condition of low temperature and low oxygen 3 Is efficiently and stably removed, and PH 3 The penetration capacity is high. The experimental results of the examples show that at an oxygen content of 10000ppm, a space velocity of 20000h -1 Under the condition that the reaction temperature is 90 ℃, the scaly copper-based adsorbent provided by the invention has the pH value of 3 The removal efficiency is maintained above 97% for 360min, and the phosphorus content is 181mg (PH) 3 ) Per g (adsorbent), illustrating the pH of the scaly copper-based adsorbent provided by the present invention under low temperature and low oxygen conditions 3 High removal efficiency, long penetration time and large phosphorus capacity.
The invention also provides a preparation method of the scaly copper-based adsorbent, which takes activated carbon as a carrier, and adds a copper nitrate solution and a nitric acid solution in a hydrothermal process to enable basic copper carbonate to regularly grow on the surface of the activated carbon carrier in a scaly nano-sheet form, and the basic copper carbonate nano-sheet is converted into a copper oxide nano-sheet through roasting, so that the scaly copper-based adsorbent is finally obtained. The preparation method provided by the invention is simple to operate, rich in raw materials, wide in sources, low in cost, easy to realize industrial application and good in application prospect. Compared with the adsorbent prepared by the traditional impregnation method, the active component CuO regularly grows on the surface of the active carbon carrier in the form of scaly nano-sheets, and has a three-dimensional structure, so that the active component CuO can be more fully exposed, and the pH is more favorably realized 3 Is adsorbed by the adsorbent.
Drawings
FIG. 1 is a graph showing the microscopic morphology of the scaly copper-based adsorbent prepared in example 1 and the copper-based adsorbent prepared in comparative example 1;
FIG. 2 is an XRD contrast pattern of the scaly copper-based adsorbent prepared in example 1 and the copper-based adsorbent prepared in comparative example 1;
FIG. 3 shows the pH of the scaly copper-based adsorbent prepared in example 1 and the copper-based adsorbent prepared in comparative example 1 3 Is a graph of the removal effect of (c).
Detailed Description
The invention provides a scaly copper-based adsorbent, which comprises an active carbon carrier and scaly copper oxide nano-sheets loaded on the surface of the active carbon carrier.
The scaly copper-based adsorbent provided by the invention comprises an activated carbon carrier. In the present invention, the activated carbon support preferably includes coal activated carbon or biomass activated carbon. In the present invention, the source of the biomass activated carbon preferably includes one or more of wood, straw, walnut shell, coconut shell, and sludge. In the present invention, the specific surface area of the activated carbon support is preferably 200 to 1000m 2 /g; the pore volume is preferably 0.2-0.8 cm 3 /g; the average pore diameter is preferably 1 to 6nm.
The scaly copper-based adsorbent provided by the invention comprises scaly copper oxide nano-sheets loaded on the surface of the active carbon carrier. In the present invention, the loading amount of the scaly copper oxide nano-sheets is preferably 1 to 60wt%, more preferably 35 to 45wt%. In the present invention, the loading amount of the scaly copper oxide nano-sheets refers to the mass fraction of the scaly copper oxide nano-sheets relative to the active carbon carrier. In the implementation of the invention, the scaly copper oxide nano-sheet has a width of 0.2-2 μm and a thickness of 20-200 nm. In the present invention, the sheets of the scaly copper oxide nano-sheets are closely arranged.
The scale-shaped copper-based adsorbent provided by the invention has larger specific surface area, higher high oxygen hole abundance and stronger oxidizing property, thus having super-strong PH 3 Adsorption performance. The scale-shaped copper-based adsorbent provided by the invention has the pH value of 3 The removal efficiency was maintained at 97% for 360min, and the phosphorus content was 181mg (pH 3 ) /g (adsorbent).
The invention also provides a preparation method of the scaly copper-based adsorbent, which comprises the following steps:
mixing active carbon, copper nitrate solution and nitric acid solution, and performing hydrothermal reaction to obtain an adsorbent precursor;
and roasting the adsorbent precursor in a protective atmosphere to obtain the scaly copper-based adsorbent.
The invention mixes active carbon, copper nitrate solution and nitric acid solution, and carries out hydrothermal reaction to obtain the adsorbent precursor. In the present invention, the activated carbon is preferably subjected to a crushing and activating treatment before mixing.
The invention has no special requirements on the specific crushing method, and the conventional crushing method in the field can be adopted. The invention preferably performs sieving after the crushing. In the present invention, the particle size of the activated carbon is preferably 20 to 40 mesh.
In the present invention, the activation treatment preferably includes acid leaching, water washing and drying which are sequentially performed. In the invention, the acid solution used for acid leaching is preferably a nitric acid solution; the concentration of the nitric acid solution is preferably 40vol%; the acid leaching method preferably comprises the following steps: the original active carbon is placed in acid solution for soaking, and is firstly placed still and then treated by ultrasonic treatment. In the present invention, the time of the standing is preferably 12 hours; the time of the ultrasonic treatment is preferably 30 minutes. The invention carries out activation treatment on the activated carbon by acid leaching. In the invention, the washing liquid used for the water washing is preferably deionized water; the number of times of the water washing is preferably 4 to 6. The invention removes the impurity and ash content of the activated carbon by water washing. In the present invention, the temperature of the drying is preferably 100 ℃; the drying time is preferably 12 hours.
In the present invention, the concentration of the copper nitrate solution is preferably 0.1 to 3mol/L, more preferably 1 to 2mol/L. In the present invention, the copper nitrate in the copper nitrate solution is preferably 1 to 5 times, more preferably 2 to 3 times the mass of the activated carbon. In the present invention, the concentration of the nitric acid solution is preferably 40 to 70wt%, more preferably 68wt%. In the present invention, the amount of the nitric acid solution to be added is preferably 0.1 to 5%, more preferably 2 to 3% of the total volume of the activated carbon, the copper nitrate solution and the nitric acid solution.
In the present invention, the mixing of the activated carbon and the copper nitrate solution and the nitric acid solution preferably includes: premixing active carbon and a copper nitrate solution, and then adding the nitric acid solution.
In the present invention, the temperature of the hydrothermal reaction is preferably 120 to 200 ℃, more preferably 150 to 170 ℃; the time of the hydrothermal reaction is preferably 8 to 16 hours, more preferably 11 to 13 hours. In the present invention, the hydrothermal reaction is preferably performed in a hydrothermal reaction vessel.
In the hydrothermal reaction process, trace carbon elements, nitric acid and copper nitrate undergo a series of reactions to generate basic copper carbonate, and the basic copper carbonate grows directionally to form nano sheets.
In the invention, the solid matters obtained after the hydrothermal reaction are washed and dried in sequence to obtain the adsorbent precursor. In the present invention, the water washing is preferably ultrapure water washing; the drying temperature is preferably 100 ℃ and the drying time is preferably 12 hours.
After the adsorbent precursor is obtained, the invention calcines the adsorbent precursor in a protective atmosphere to obtain the scaly copper-based adsorbent. In the present invention, the protective atmosphere is preferably a nitrogen atmosphere. In the present invention, the temperature of the calcination is preferably 300 to 500 ℃, more preferably 350 to 400 ℃; the calcination time is preferably 1 to 4 hours, more preferably 2 to 3 hours. In the present invention, the firing is preferably performed in a tube furnace. In the present invention, the temperature rising rate from room temperature to the baking temperature is preferably 2 to 4 ℃/min.
In the roasting process, basic copper carbonate is decomposed into scaly copper oxide nano-sheets and is loaded on the surface of an active carbon carrier.
The invention also provides the scaly copper-based adsorbent prepared by the technical scheme or the preparation method of the technical scheme, and the scaly copper-based adsorbent is used for removing PH by adsorption-oxidation 3 Preferably for PH in plant tail gas 3 Purifying. In particular, the scaly copper-based adsorbent is preferably used for PH in yellow phosphorus tail gas, semiconductor factory tail gas or nonferrous metal smelting flue gas system 3 And (5) performing adsorption-oxidation removal. In the present invention, the non-ferrous metal smelting flue gas preferably comprises copper smelting flue gas.
In the present invention, the adsorption-oxidation removal of PH 3 Preferably at a temperature of 100℃or less, more preferably at 90 ℃; the oxygen content is preferably 0 to 50000ppm, more preferably 10000 to 20000ppm.
The scale-shaped copper-based adsorbent provided by the invention is at low temperatureCan better adsorb-oxidize and remove PH under the condition of low oxygen 3 。PH 3 Is captured by the scaly copper oxide nano-sheet and reacts to generate Cu 3 P、H 2 O and H 3 PO 4 The method comprises the steps of carrying out a first treatment on the surface of the At the same time pH 3 And O 2 Can react to generate H after the activation of the scaly copper oxide nano-sheet 3 PO 4 。
The scaly copper-based adsorbent provided by the invention has higher mechanical strength and good heat resistance, can be well adapted to complex environments, and is beneficial to realizing better PH in the actual tail gas purification process of factories 3 Purifying effect.
The technical solutions of the present invention will be clearly and completely described in the following in connection with the embodiments of the present invention. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
Immersing 20-40 mesh coal activated carbon in 40vol% nitric acid solution for 12h, ultrasonic oscillating for 0.5h, and finally washing with ultrapure water for 5-6 times. Subsequently transferred to a forced air drying oven and dried at 100 ℃ for 12 hours to obtain a coal-based activated carbon support, labeled CBAC. The specific surface area of the coal activated carbon carrier is 1017m 2 Per g, pore volume of 0.42cm 3 And/g, average pore diameter of 2nm.
1mol/L copper nitrate solution is prepared, 20mL of copper nitrate solution and 2g of coal active carbon carrier are measured, a polytetrafluoroethylene liner is added, 0.5mL of concentrated nitric acid (the concentration is 68 wt%) is added dropwise, the mixture is transferred into a hydrothermal reaction kettle for sealing, and the hydrothermal reaction is carried out for 9 hours at 160 ℃. And taking out the solid obtained by the hydrothermal reaction, cleaning the solid with ultrapure water for three times, and drying the solid in a blast drying oven at 100 ℃ for 12 hours to obtain the adsorbent precursor.
And roasting the adsorbent precursor for 2 hours at 350 ℃ by using a tube furnace under the protection of nitrogen atmosphere to obtain the scaly copper-based adsorbent, wherein the scaly copper-based adsorbent is marked as 3DCu/CBAC.
Comparative example 1 preparation of copper-based adsorbent by conventional impregnation
20mL of copper nitrate solution with the concentration of 1mol/L and 2g of coal active carbon carrier are mixed and treated by ultrasonic for 30min. The resulting mixture was dried in a forced air drying oven at 100℃for 12 hours to obtain a precursor. And roasting the precursor for 2 hours at 350 ℃ by using a tube furnace under the protection of nitrogen atmosphere to obtain the copper-based adsorbent, which is marked as Cu/CBAC.
Test example 1
Physicochemical characterization analysis was performed on the 3DCu/CBAC prepared in example 1 and the Cu/AC adsorbent prepared in comparative example 1, wherein microscopic morphology and element distribution information of the different copper-based adsorbents were obtained by scanning electron microscopy (Gemini 300, zeiss, germany) and energy spectroscopy (Oxford X-MAX, UK). 5-10 mg of adsorbent particles to be measured are weighed each time and stuck on the conductive adhesive for sample preparation, and before the test, all samples are subjected to Pt metal spraying treatment so as to enhance the surface conductivity of the samples, wherein the operation voltage is 3.00kV. The structure of the relevant crystalline material was determined by means of a D/MAX-2200X-ray diffractometer. CuKa radiation (λ= 0.15406 nm), voltage 36kV, current 30mA, scan range 20 ° to 80 °, scan speed 5 °/min.
FIG. 1 is a graph showing the microscopic morphology of the scale-like copper-based adsorbent prepared in example 1 versus that of the copper-based adsorbent prepared by the conventional impregnation method; the upper part of fig. 1 is a scale-shaped copper-based adsorbent prepared in example 1, and the lower part is a copper-based adsorbent prepared by a general impregnation method. As can be seen from FIG. 1, the 3DCu/CBAC has a plurality of ordered scale-like nano-sheets on the surface, the CuO nano-sheets are regularly arranged, and the surface has a plurality of mesoporous channels, and the special 3D structure is beneficial to PH 3 Capture and transport of molecules; and more active sites can be exposed and the specific surface area of the adsorbent can be increased, so that the performance of the adsorbent is improved. Compared with 3DCu/CBAC, cuO in Cu/CBAC exists on the surface of Cu/CBAC in the form of large particle spheres, and has no scale-shaped structure, the exposed specific surface area of the spherical CuO particles is relatively smaller, and the exposed active sites are also smaller; the product tends to accumulate on the surface of the spheres, preventing pH 3 The molecules further contact with the CuO component inside the sphere, thereby reducing the utilization efficiency of the active component.
Fig. 2 is an XRD comparison pattern of the scaly copper-based adsorbent prepared in example 1 and the copper-based adsorbent prepared by the general impregnation method. As can be seen from FIG. 2, the major phases of the active components of 3DCu/CBAC and Cu/CBAC are CuO with high crystallinity, but Cu is observed on the XRD pattern of Cu/CBAC 2 Characteristic peak of O, and Cu 2 O is less oxidizing than CuO, thus resulting in Cu/CBAC having less adsorption activity than 3DCu/CBAC.
Test example 2
Performance tests were performed on the scale-like copper-based adsorbent prepared in example 1 and the copper-based adsorbent prepared by the ordinary impregnation method, wherein the test conditions were: PH value 3 The concentration was 1000ppm, nitrogen was used as carrier gas, and O was contained in the gas at a concentration of 10000ppm 2 The prepared adsorbent is placed in a fixed bed reactor, and the space velocity is 20000h -1 The reaction temperature is 90 ℃; the reactor inlet and outlet concentrations were measured by gas chromatography.
FIG. 3 is a graph showing adsorption-oxidation removal of PH from 3DCu/CBAC and Cu/CBAC 3 Is a removal efficiency map of (2). As can be seen from FIG. 3, 3DCu/CBAC and Cu/CBAC vs PH 3 The removal efficiency of (C) was maintained at 97% or more for 360min and 180min, respectively, and the penetration phosphorus content was 181mg (pH 3 )·gsorbent -1 ，90mg(PH 3 )·gsorbent -1 . Wherein the 3DCu/CBAC performance with the scaly microstructure is much higher than that of Cu/CBAC.
As shown by the test results, the scaly copper-based adsorbent provided by the invention has good adsorption activity and can realize PH under the condition of low temperature and low oxygen 3 High-efficiency stable removal is beneficial to solving the problem of PH in tail gas of various factories 3 Is a problem of emissions. Meanwhile, the preparation method provided by the invention is simple to operate, the preparation time of the adsorbent is relatively short, the raw materials are cheap and easy to obtain, the method is not limited by time and region, and side reactions are not generated; moreover, the scaly copper-based adsorbent provided by the invention has mild application conditions, the working temperature is less than or equal to 100 ℃, and the industrial application is easy to realize.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (5)

1. Scale-like copper-based adsorbent for adsorbing-oxidizing to remove PH under low-temperature and low-oxygen conditions 3 Is applied to the application of the system; the adsorption-oxidation removal of PH 3 The temperature of the catalyst is 90-100 ℃, and the oxygen content is 10000-50000 ppm; airspeed of 20000h -1 ；
The scaly copper-based adsorbent comprises an activated carbon carrier and scaly copper oxide nano-sheets loaded on the surface of the activated carbon carrier;
the preparation method of the scaly copper-based adsorbent comprises the following steps:
mixing active carbon, copper nitrate solution and nitric acid solution, and performing hydrothermal reaction to obtain an adsorbent precursor; the temperature of the hydrothermal reaction is 120-200 ℃; the hydrothermal reaction time is 8-16 h;
roasting the adsorbent precursor in a protective atmosphere to obtain a scaly copper-based adsorbent; the roasting temperature is 300-500 ℃; and the roasting time is 1-4 hours.
2. The use according to claim 1, wherein the activated carbon support comprises coal activated carbon or biomass activated carbon.
3. The use according to claim 1, wherein the scaly copper oxide nanoplatelets have a width of 0.2 to 2 μm and a thickness of 20 to 200nm.
4. The use according to claim 1, characterized in that the copper nitrate in the copper nitrate solution has a mass of 1 to 5 times the mass of the activated carbon.
5. Use according to claim 1, characterized in that the activated carbon is subjected to a crushing and activation treatment before mixing.
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