CN113828276A - Activated carbon adsorbent for reducing sulfur content in pollutant gas - Google Patents
Activated carbon adsorbent for reducing sulfur content in pollutant gas Download PDFInfo
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Abstract
The invention discloses an activated carbon adsorbent for reducing the sulfur content in pollutant gas, which is obtained by preheating and drying raw material particles, primarily carbonizing the dried raw material particles, then carrying out alkali washing and impregnation combined high-temperature roasting on a carbonized material, adding an alkaline activator to load a metal compound on the surface of the carbonized material, and finally removing redundant water molecules through vacuum drying. The invention utilizes the unique structure and performance of the activated carbon as a desulfurization adsorbent, and the specific surface area and the pore size of the activated carbon pore are better increased by a method of combining alkaline washing and impregnation of the carbonized material with high-temperature roasting; meanwhile, alkaline impregnation can better promote the loading of metal ions, the loaded metal compounds can be better uniform in the ultrasonic vibration state, the adsorption performance of the activated carbon adsorbent is enhanced through the change of the specific surface area of the activated carbon and the effective modification of the metal compounds, and the sulfur content in the polluted gas can be better reduced.
Description
Technical Field
The invention relates to the technical field of activated carbon preparation, in particular to an activated carbon adsorbent capable of reducing sulfur content in pollutant gas.
Background
With the development of chemical technology, the utilization depth of natural energy substances is increased. The raw materials of coal, petroleum, natural gas, etc. contain a certain quantity of sulfur compounds, and the sulfur compounds are processedThe post-sulfur compounds may be present in the product in different forms, e.g. SO from the combustion of fossil fuels2A gaseous pollutant; the gas containing a plurality of sulfur impurities generated in the production process of a rayon factory and an oil refinery; there are also polluting gases formed by oxidation of hydrogen sulphide produced by biological decay in the atmosphere.
At present, the desulfurization technology in the prior art is mature, but acid liquid and sludge generated in the desulfurization process are difficult to treat, corrosion to equipment is difficult to avoid, and the energy consumption is too high and the cost is high in the desulfurization process. The active carbon is a mature carbon material, has unique surface physical and chemical properties, is used as an important adsorption material in the industries of chemical industry, food industry and the like, and currently, a desulfurization technology adopting the active carbon is also provided.
Disclosure of Invention
The invention aims to solve the problems that the desulfurization efficiency of an activated carbon adsorbent is poor, the porosity of the modified activated carbon adsorbent is reduced, and particularly the volume of micropores and the loading amount and distribution are uneven in the prior art, so that the desulfurization effect is not high enough. And provides an activated carbon adsorbent capable of reducing the sulfur content in the pollutant gas. In order to realize the optimization of the technology, the sulfur content in the air can be more efficiently reduced in the desulfurization process, the pollution is reduced, the energy consumption is reduced, and the cost is saved. The invention adopts the following production process:
the invention relates to an activated carbon adsorbent capable of reducing the sulfur content in pollutant gas, which is a preparation method of loading a metal compound on the surface of a carbonized material by in-situ synthesis by using a primary activated carbon adsorbent obtained by combining alkaline washing and impregnation with high-temperature roasting, and comprises the following steps:
1) and (3) a drying stage: preheating and drying the raw material particles at the temperature of 100-200 ℃ for 1-3 h, and releasing the moisture and the internal water in the raw material particles.
2) Primary carbonization: and carrying out primary carbonization on the dried raw material particles, wherein the temperature of the primary carbonization is set to be 300-600 ℃, and the time is set to be 2-4 hours for carbonization.
3) Alkali washing and dipping: and (3) putting the processed primary carbonized material into a rotary evaporator containing an alkaline activating agent and a water vapor activating aid for dipping, wherein the alkali-carbon ratio of alkaline washing dipping is 2-3: 1.
4) and (3) high-temperature roasting: and roasting the carbonized material subjected to alkaline washing and impregnation in an environment with the temperature of 600-900 ℃ and the time of 2-3 hours to obtain the primary activated carbon adsorbent.
5) Further activation: loading metal ions on the surfaces of active carbon pore channels by dipping with a metal salt solution, namely dipping the primary active carbon in 10-30% of alkaline solution for 4-8 hours; simultaneously adding metal salt into deionized water, heating and stirring for 1-2 hours at the temperature of 60-90 ℃ to obtain a metal ion solution; adding the obtained metal ion solution into a primary activated carbon adsorbent containing an alkaline solution, setting the temperature of a water bath at 40-60 ℃, mixing in ultrasonic waves for 2-6 hours, spreading out the carrier impregnated with the metal compound, and drying in the shade for 2-4 hours;
6) and drying the carrier dried in the shade at 100-200 ℃ for 2-5 hours, and then activating at 200-500 ℃ under nitrogen atmosphere for 2-5 hours to obtain the active carbon adsorbent uniformly loaded with the metal compound.
6) And (3) drying: the active carbon adsorbent loaded with the metal compound is dried at the temperature of 90-120 ℃ for 12-24 h to obtain the dry active carbon adsorbent capable of reducing the sulfur content in the polluted gas.
Further, the alkaline activator and the alkaline solution include at least one of a sodium hydroxide aqueous solution, a potassium hydroxide aqueous solution, and an ammonia aqueous solution.
Further, in the steam assisted activation, the amount of the steam is 1-2 times of that of the carbonized material, the temperature is 300-600 ℃, the activation time is 2-6 hours,
furthermore, the rotating speed of the rotary evaporator is 50-160 rpm.
Further, the metal salt comprises at least one of ferric chloride, copper chloride, calcium chloride and zinc chloride; the active carbon is impregnated by deionized metal salt solution, and metal ions are loaded in the pore channels of the active carbon adsorbent through in-situ synthesis.
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the invention utilizes the unique structure and performance of the active carbon as a deep desulfurization adsorbent, and the active carbon adsorbent is used for adsorbing sulfide in pollutant gas, so that the active carbon has the advantages of high activity, high mechanical strength, strong chemical stability, easy regeneration, recyclability and the like; meanwhile, the active carbon prepared by dipping in alkaline solution can increase the surface area and the aperture size of active carbon pores, increase the metal loading capacity, better enable metal compounds to be uniformly loaded under ultrasonic vibration, enhance the desulfurization effect of the active carbon by changing the specific surface area of the active carbon and effectively modifying surface functional groups and the metal compounds, and better reduce the sulfur content in gas.
Detailed Description
The present invention will be described in more detail below, and it should be understood that the described embodiments are only some of the described embodiments of the present invention, and not all of them.
An activated carbon adsorbent for reducing the content of sulfur in a polluted gas is a primary activated carbon adsorbent obtained by using alkaline washing and impregnation combined with high-temperature roasting, and a metal compound is loaded on the surface of the primary activated carbon adsorbent through in-situ synthesis to obtain the activated carbon adsorbent, wherein specific embodiments comprise the following steps:
example 1
1) And (3) a drying stage: crushing and extruding a coal raw material to form raw material particles with required shapes, setting the temperature of the raw material particles at 100 ℃ for 3 hours, preheating and drying under the condition, and releasing moisture and internal water in the raw material particles;
2) primary carbonization: carrying out primary carbonization on the dried raw material particles, setting the temperature of the primary carbonization at 300 ℃ for 4h, and obtaining a carbonized material after the primary carbonization, wherein a primary pore structure is formed at the moment, so that the subsequent operation is better carried out;
3) alkali washing and dipping: and (3) putting the processed primary carbonized material into an alkaline activator of 10% sodium hydroxide, wherein the ratio of alkaline washing and impregnating alkali to carbon is 2: simultaneously dipping in a rotary evaporator of a water vapor activating assistant agent, setting the rotary evaporator to be 100 r/min, setting the water vapor amount to be 2 times of that of the carbonized material, setting the temperature to be 300 ℃, and setting the activation time to be 4h to obtain the activated carbonized material, wherein the carbonized material can form a rich pore structure in the pyrolysis process of sodium hydroxide, so that the carbon yield is reduced, and the dipping is more sufficient through the rotary evaporator;
4) and (3) high-temperature roasting: calcining the carbonized material after alkaline washing and impregnation in an environment with the temperature of 600 ℃ and the time of 3 hours to obtain a primary activated carbon adsorbent, wherein the specific surface area of the pore channel of the carbonized material is further increased by the high-temperature calcination at the time because the carbonized material is activated by the alkaline;
5) further activation: loading metal compounds on the surfaces of active carbon pore channels by dipping with a metal salt solution, namely dipping the primary active carbon in a 10% sodium hydroxide solution for 4 hours; adding ferric chloride into deionized water, heating and stirring for 1h at the temperature of 60 ℃ to obtain a solution containing iron ions; adding the obtained iron ion solution into the primary activated carbon adsorbent impregnated with sodium hydroxide, and mixing for 3 hours in ultrasonic waves at the water bath temperature of 40 ℃ to obtain the activated carbon adsorbent uniformly loaded with the iron hydroxide; the alkaline solution is used for dipping to increase the attachment of metal ions, and the vibration of ultrasonic waves is used to make the distribution of iron ions more uniform, so that the ferric hydroxide precipitates are more uniformly loaded in the pore channel of the activated carbon adsorbent, and the sulfur substances in the polluted gas can be combined more efficiently.
6) And (3) drying: heating and drying the activated carbon adsorbent loaded with the metal compound at the temperature of 100 ℃ for 4h to obtain the dried activated carbon adsorbent capable of reducing the sulfur content in the polluted gas; through the drying process, the original loaded metal precipitate further generates stable compounds, so that the metal compounds can exist in the pore channels of the activated carbon more stably.
Example 2
1) And (3) a drying stage: crushing and extruding a coal raw material to form raw material particles with a required shape, setting the temperature of the raw material particles at 200 ℃ for 2 hours, preheating and drying under the condition, and releasing moisture and internal water in the raw material particles;
2) primary carbonization: carrying out primary carbonization on the dried raw material particles, setting the temperature of the primary carbonization at 600 ℃ for 3h, obtaining a carbonized material after the primary carbonization, and forming a primary pore channel structure so as to be convenient for better subsequent operation;
3) alkali washing and dipping: putting the processed primary carbonized material into an alkaline activator of 10 percent potassium hydroxide, wherein the ratio of alkaline washing and impregnating alkali to carbon is 2: simultaneously dipping in a rotary evaporator of a water vapor activating assistant agent, setting the rotary evaporator to be 100 r/min, setting the water vapor amount to be 2 times of that of the carbonized material, setting the temperature to be 300 ℃, and setting the activation time to be 4h to obtain the activated carbonized material, wherein the carbonized material can form a rich pore structure in the pyrolysis process of potassium hydroxide, so that the carbon yield is reduced, and the dipping is more sufficient through the rotary evaporator;
4) and (3) high-temperature roasting: calcining the carbonized material after alkaline washing and impregnation in an environment with the temperature of 900 ℃ and the time of 2 hours to obtain a primary activated carbon adsorbent, wherein the specific surface area of the pore channel of the carbonized material is further increased by the high-temperature calcination at the time because the carbonized material is activated by the alkaline;
5) further activation: loading metal compounds on the surfaces of active carbon pore channels by dipping with a metal salt solution, namely dipping the primary active carbon in 25% ammonia water for 4 hours; simultaneously adding aluminum chloride into deionized water, heating and stirring for 1h at the temperature of 90 ℃ to obtain a solution containing aluminum ions; adding the obtained aluminum ion solution into the primary activated carbon adsorbent soaked with ammonia water, and mixing for 2 hours in ultrasonic waves at the water bath temperature of 60 ℃ to obtain the activated carbon adsorbent uniformly loaded with aluminum hydroxide; the alkaline solution is used for dipping to increase the attachment of metal ions, and the vibration of ultrasonic waves is used to make the distribution of iron ions more uniform, so that the aluminum hydroxide precipitates are more uniformly loaded in the pore channel of the activated carbon adsorbent, and the sulfur substances in the polluted gas can be more efficiently combined.
6) And (3) drying: heating and drying the activated carbon adsorbent loaded with the metal compound at the temperature of 100 ℃ for 6 hours to obtain the dried activated carbon adsorbent capable of reducing the sulfur content in the polluted gas; through the drying process, the original loaded metal precipitate further generates stable compounds, so that the metal compounds can exist in the pore channels of the activated carbon more stably.
Example 3
By comparing the improved activated carbon adsorbent of the invention with other activated carbon in the market, the experiments for reducing the sulfur content in the polluted gas by different adsorbents are compared: the instrument comprises the following steps: dryers, water baths, gas flow meters, electronic balances, scanning electron microscopes, and the like.
1) Determination of specific surface area and pore size
The specific surface area and the pore size of different types of activated carbon are measured by a BET measuring method through a full-automatic specific surface area and porosity analyzer, and the detection materials are respectively 20g of common activated carbon adsorbent, NaOH alkali-washed activated carbon adsorbent, Fe metal compound-loaded activated carbon adsorbent and NaOH alkali-washed metal compound-loaded activated carbon adsorbent.
The specific surface area and pore size are determined, the specific surface area is the total surface area per unit mass of solid, the BET adsorption isotherm equation is now recognized as a standard method for measuring the specific surface area of a solid, and the formula: p/[ V (P o-P) ] + 1/(Vm × C [ (C-1)/(Vm × C) x (P/P o)
In the formula, P is nitrogen partial pressure
P0 saturated vapor pressure of nitrogen at adsorption temperature
V actual adsorption amount of nitrogen gas on sample surface
Vm is the single-layer saturated adsorption capacity of nitrogen
C constant related to sample adsorption Capacity
2) Determination of desulfurization efficiency
To examine the effectiveness of the modified activated carbon sorbent, the control was set to compare, and the same sulfur concentration was tested on different activated carbon sorbents by first converting both the inlet and outlet sulfur dioxide of the desulfurization to 6% oxygen, subtracting the outlet sulfur dioxide concentration from the inlet sulfur dioxide concentration, and multiplying the inlet sulfur dioxide concentration by 100%. The desulfurization efficiency is the percentage of the amount of sulfur dioxide removed by the desulfurization system in unit time to the amount of sulfur dioxide in the flue gas entering the desulfurization system. The formula: desulfurization efficiency (original sulfur dioxide concentration-sulfur dioxide concentration after desulfurization)/original sulfur dioxide concentration 100%
3) The saturated sulfur capacity determination method comprises the following steps:
cleaning with pure water, drying in a 120 ℃ drying oven, adjusting a gas preheating device to 20 ℃, simultaneously setting the temperature of water introduced to the outer layer of an adsorbent column to 20 ℃, placing dried activated carbon into the adsorption column, connecting an experimental device, opening a gas cylinder knob and a pressure reducing valve, adjusting the flow rate of gas to ensure that the flow rate of gas passing through a flowmeter is 500ml/min, and measuring the saturated sulfur capacity of the four activated carbons under normal pressure.
When the ratio of the hydrogen sulfide content in the gas outlet to the hydrogen sulfide content in the gas inlet is less than 0.05, the desulfurizer penetrates, the adsorbent column is weighed once every hour at this moment until the mass difference of the two times of weighing is not more than 0.0005g, the saturated activated carbon is taken out after the experiment is finished, the activated carbon is put into a drying oven at 100 ℃ for drying for 2 hours, the activated carbon is accurately weighed to 0.0002g after being cooled, the mass of the desulfurizer after desulfurization saturation is obtained, the adsorption capacity is calculated according to the mass, and the saturated sulfur capacity is calculated: the saturated sulfur capacity, w, is expressed in units of milligrams per gram (mg/g):
W＝(m-m0)/m(m0: represents the mass (g) of the dried desulfurizing agent before the experiment, and M represents the mass (g) of the dried desulfurizing agent after the experiment)
The experiment of sulfur content in different adsorbent reduction polluted gas, through comparing the activated carbon adsorbent after will improving with other different grade type activated carbon adsorbents, compare different grade type activated carbon's specific surface area, aperture size, desulfurization rate, saturated sulfur capacity and judge the adsorption effect of activated carbon, specific measured data is as follows:
as can be seen from the above table, compared with other types of activated carbon adsorbents, the activated carbon adsorbent loaded with metal compounds after alkaline cleaning has larger specific surface area and pore size, higher desulfurization rate and higher saturated sulfur capacity compared with other activated carbon adsorbents, thereby having better effect of adsorbing sulfur substances in gas,
the preparation method of the embodiment utilizes the advantages that the activated carbon has high activity, high mechanical strength, strong chemical stability, easy regeneration, recyclability and the like, and the specific surface area and the aperture size of the pores of the activated carbon are better increased by combining the alkali washing and impregnation of the carbonized material with high-temperature roasting; meanwhile, alkaline impregnation can better promote the loading of metal ions, the loaded metal compounds can be better and uniformly loaded in the ultrasonic vibration state, the impregnation is more sufficient by utilizing a rotary evaporator, and the active carbon adsorbent is obtained by loading the metal compounds on the surface of the primary active carbon adsorbent through in-situ synthesis, so that the specific surface area of the active carbon is increased, the surface functional groups and the metal compounds are effectively modified, the adsorption performance of the active carbon adsorbent is enhanced, and the sulfur content in gas can be better reduced.
The above description is only for the purpose of illustrating the present invention, and the scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the technical scope of the present invention.
Claims (7)
1. An activated carbon adsorbent for reducing the sulfur content in polluted gas is characterized in that a primary activated carbon adsorbent is obtained by combining alkaline washing and impregnation with high-temperature roasting, and a metal compound is loaded on the surface of the primary activated carbon adsorbent through in-situ synthesis to obtain the activated carbon adsorbent, and the preparation method specifically comprises the following steps:
1) and (3) a drying stage: preheating and drying the raw material particles, wherein the preheating and drying temperature is set to be 100-200 ℃, the time is set to be 1-3 hours, and the moisture and the internal water in the raw material particles are released;
2) primary carbonization: carrying out primary carbonization on the dried raw material particles, wherein the temperature of the primary carbonization is set to be 300-600 ℃, and the time is set to be 2-4 hours;
3) alkali washing and dipping: and (3) putting the processed primary carbonized material into a rotary evaporator containing an alkaline activating agent and a water vapor activating aid for dipping, wherein the alkali-carbon ratio of alkaline washing dipping is 2-3: 1;
4) and (3) high-temperature roasting: roasting the carbonized material subjected to alkaline washing and impregnation in an environment with the temperature of 600-900 ℃ and the time of 2-3 hours to obtain a primary activated carbon adsorbent;
5) further activation: loading metal ions on the surfaces of active carbon pore channels by dipping with a metal salt solution, namely dipping the primary active carbon in a 10-30% alkaline solution for 4-8 hours; simultaneously adding metal salt into deionized water, heating and stirring for 1-2 hours at the temperature of 60-90 ℃ to obtain a metal ion solution; adding the obtained metal ion solution into a primary activated carbon adsorbent containing an alkaline solution, and mixing in ultrasonic waves for 2-6 hours at the water bath temperature of 40-60 ℃ to obtain an activated carbon adsorbent uniformly loaded with a metal compound;
6) and (3) further drying: the activated carbon adsorbent loaded with the metal compound is dried by high temperature.
2. The activated carbon sorbent for reducing the sulfur content of a contaminated gas according to claim 1, wherein the alkaline activator and alkaline solution comprises at least one of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous ammonia solution.
3. The activated carbon adsorbent for reducing the sulfur content in the polluted gas according to claim 2, wherein in the steam assisted activation, the amount of the steam is 1-2 times of that of the carbonized material, the temperature is set to 300-600 ℃, and the activation time is set to 2-6 hours.
4. The activated carbon sorbent for reducing the sulfur content in the polluted gas according to claim 3, wherein the rotation speed of the rotary evaporator is 50-160 rpm.
5. The activated carbon sorbent for reducing the sulfur content of a contaminated gas according to claim 4, wherein the metal salt comprises at least one of ferric chloride, cupric chloride, calcium chloride, and zinc chloride.
6. The activated carbon sorbent for reducing the sulfur content in the polluted gas according to claim 5, wherein the further drying temperature is 90-180 ℃ and the drying time is 2-8 h.
7. The activated carbon sorbent for reducing the sulfur content in the polluted gas according to claim 6, wherein when the metal salt is ferric chloride, the primary activated carbon is immersed in 10-30% alkaline solution for 4-8 hours in further activation; adding ferric chloride into deionized water, and heating and stirring for 1-2 hours at the temperature of 60-90 ℃ to obtain a solution containing iron ions; and adding the obtained iron ion solution into the primary activated carbon adsorbent dipped in the alkaline solution, and mixing the iron ion solution and the primary activated carbon adsorbent in ultrasonic waves for 2-6 hours at the water bath temperature of 40-60 ℃ to obtain the activated carbon adsorbent uniformly loaded with the ferric hydroxide.
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