CN111821942A - High-efficiency dioxin adsorbent for waste incineration and preparation method and application thereof - Google Patents
High-efficiency dioxin adsorbent for waste incineration and preparation method and application thereof Download PDFInfo
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Abstract
A high-efficiency dioxin adsorbent for waste incineration and a preparation method and application thereof relate to the technical field of waste incineration. The high-efficiency dioxin adsorbent for waste incineration comprises the following raw materials in parts by weight: 30-60 parts of zeolite powder, 10-30 parts of silicon carbide, 5-15 parts of inorganic salt containing sulfur and nitrogen, 10-30 parts of alkali potassium PEG polyurethane resin and 10-30 parts of water. According to the high-efficiency dioxin adsorbent disclosed by the invention, polyethylene glycol and potassium ions are introduced by adding the potassium-base PEG polyurethane resin into the microstructure of the zeolite powder, so that the adsorbent has physical adsorption and chemical adsorption capacities at the same time, and the polyethylene glycol is introduced into the microstructure of the zeolite powder, so that the dioxin in the flue gas is dissolved in the polyethylene glycol by utilizing the good intermiscibility of the polyethylene glycol and organic matters; the chlorine ions have strong attraction capacity to electrons, and potassium ions are added into the polyethylene glycol, so that chlorine-containing organic matters are favorably removed, and dioxin in flue gas is removed.
Description
Technical Field
The invention relates to the technical field of waste incineration, in particular to a high-efficiency dioxin adsorbent for waste incineration and a preparation method thereof.
Background
With the acceleration of the urbanization process in China and the continuous improvement of the living standard of people, the production amount of domestic garbage is increased day by day. The waste incineration treatment not only solves the problem of waste treatment, but also changes waste into valuable, and is widely applied in China. However, the waste generates some secondary pollutants such as hydrogen chloride, heavy metals, dioxin, etc. during incineration, wherein dioxin is considered as the most toxic compound. At present, the tail end control of dioxin in flue gas generally adopts an activated carbon adsorption technology, and in the contact process of the flue gas and activated carbon, the dioxin is adsorbed onto activated carbon particles and finally trapped by a dust remover. However, the activated carbon as a dioxin adsorbing material still has the following defects: 1. the activated carbon can be burnt in the flue gas with over-high temperature, so that accidents such as cloth bag burning and the like are caused; 2. the activated carbon becomes a carbon source for generating dioxin at a certain temperature and under the condition of a catalytic medium; 3. the activated carbon is mainly based on physical adsorption, the chemical adsorption capacity is not obvious, and the physical adsorption can not thoroughly remove dioxin and has reversibility, so that the adsorption of the dioxin by the activated carbon has a memory effect, and a small amount of dioxin can be desorbed when the content of the dioxin in flue gas is reduced.
Disclosure of Invention
In view of the above defects, the present invention aims to provide a high-efficiency dioxin adsorbent, and a preparation method and an application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme: the high-efficiency dioxin adsorbent for waste incineration comprises the following raw materials in parts by weight:
30-60 parts of zeolite powder, 10-30 parts of silicon carbide, 5-15 parts of inorganic salt containing sulfur and nitrogen, 10-30 parts of alkali potassium PEG polyurethane resin and 10-30 parts of water.
The potassium-alkali PEG polyurethane resin comprises the following raw material components in parts by weight:
30% -60% of potassium hydroxide;
PEG400-1000 20％-50％；
10-30% of polyethylene polyamine.
The dioxin efficient adsorbent is a particulate matter with a pore channel, and the average pore diameter of the pore channel is 5-7 nm.
Wherein the pore volume of the high-efficiency dioxin adsorbent ranges from 0.12cm to 0.25cm3/g。
The proportion of mesopores of the high-efficiency dioxin adsorbent is more than 65 percent, wherein the mesopores refer to pores with the pore diameter of 2-50 nm.
The invention also provides a preparation method of the dioxin high-efficiency adsorbent for waste incineration,
the method comprises the following steps: putting 30-60 parts of zeolite powder into a container, adding 10-30 parts of silicon carbide, 5-15 parts of sulfur-nitrogen-containing inorganic salt, 10-30 parts of alkali potassium PEG polyurethane resin and 10-30 parts of water at the same time, stirring, and uniformly stirring to obtain a slurry mixture;
step two: drying the slurry mixture in air at 100-105 ℃ for 2-3 hours to remove water to obtain a dried substance;
step three: and (3) placing the dried material in a calcining furnace, and heating the dried material from the temperature of 110-150 ℃ to the temperature of 350-500 ℃, wherein the heating process comprises the following steps: heating up to 50 ℃ for the first time, preserving heat for 30 minutes, heating up to 50 ℃ for the second time, preserving heat for 2 hours, heating up to 50 ℃ for the third time, preserving heat for 30 minutes, heating up to 50 ℃ for the fourth time, preserving heat for 2 hours, and so on;
step four: and cooling the calcined dried substance to below 80 ℃, and grinding the dried substance to obtain the granular adsorbent.
Wherein, the method also comprises the following steps of:
mixing potassium hydroxide, PEG400-1000 and polyethylene polyamine, and reacting at 100-200 ℃ for 2-4 hours.
Wherein, in the third step, the oxygen content of the air in the calcining furnace is less than 6 percent.
Wherein, in the fourth step, the particle size is controlled to be less than or equal to 200 meshes during grinding.
The invention also provides application of the high-efficiency dioxin adsorbent for waste incineration, and when household garbage doped with industrial waste is incinerated, the high-efficiency dioxin adsorbent is mixed with activated carbon for use, so that the high-efficiency dioxin adsorbent has a remarkable dioxin adsorption effect.
According to the high-efficiency dioxin adsorbent disclosed by the invention, polyethylene glycol and potassium ions are introduced by adding the potassium-base PEG polyurethane resin into the microstructure of the zeolite powder, so that the adsorbent has physical adsorption capacity and chemical adsorption capacity. After the zeolite powder is combined with the above substances, the mixture is calcined and heated at a certain temperature, recrystallization can occur, so that more pore channel structures are formed, and the zeolite composite adsorbing material with a larger porous specific surface is formed after the grinding, so that the adsorption and trapping of dioxin are facilitated;
polyethylene glycol is introduced into the microstructure of the zeolite powder, and the good intermiscibility of the polyethylene glycol and organic matters is utilized, so that dioxin in the flue gas is dissolved in the polyethylene glycol; the chlorine ions have strong attraction capacity to electrons, and potassium ions are added into the polyethylene glycol, so that chlorine-containing organic matters are favorably removed, and dioxin in flue gas is removed.
By adding the component silicon carbide, the high-temperature resistance of the high-efficiency dioxin adsorbent is improved, a carbon source is prevented from being provided for the generation of dioxin, and the high-temperature dioxin adsorbent is favorable for activating and degrading molecular groups in a high-temperature environment, so that the adsorption effect of the dioxin is improved.
By adding the inorganic salt containing sulfur and nitrogen as the component and utilizing the nitrogen base and the sulfur base of the inorganic salt containing sulfur and nitrogen to inhibit the output of dioxin doubly, the emission of dioxin is reduced efficiently.
Detailed Description
A high-efficiency dioxin adsorbent for waste incineration comprises the following raw materials in parts by weight:
30-60 parts of zeolite powder, 10-30 parts of silicon carbide, 5-15 parts of inorganic salt containing sulfur and nitrogen, 10-30 parts of alkali potassium PEG polyurethane resin and 10-30 parts of water. Wherein, the inorganic salt containing sulfur and nitrogen can be one or a plurality of compound of sodium sulfide, urea, thiourea or ammonium sulfate.
According to the high-efficiency dioxin adsorbent disclosed by the invention, polyethylene glycol and potassium ions are introduced by adding the potassium-base PEG polyurethane resin into the microstructure of the zeolite powder, so that the adsorbent has physical adsorption capacity and chemical adsorption capacity. After the zeolite powder is combined with the above substances, the mixture is calcined and heated at a certain temperature, recrystallization can occur, so that more pore channel structures are formed, and the zeolite composite adsorbing material with a larger porous specific surface is formed after the grinding, so that the adsorption and trapping of dioxin are facilitated;
polyethylene glycol is introduced into the microstructure of the zeolite powder, and the good intermiscibility of the polyethylene glycol and organic matters is utilized, so that dioxin in the flue gas is dissolved in the polyethylene glycol; the chlorine ions have strong attraction capacity to electrons, and potassium ions are added into the polyethylene glycol, so that chlorine-containing organic matters are favorably removed, and dioxin in flue gas is removed.
By adding the component silicon carbide, the high-temperature resistance of the high-efficiency dioxin adsorbent is improved, a carbon source is prevented from being provided for the generation of dioxin, and the high-temperature dioxin adsorbent is favorable for activating and degrading molecular groups in a high-temperature environment, so that the adsorption effect of the dioxin is improved.
By adding the inorganic salt containing sulfur and nitrogen as the component and utilizing the nitrogen base and the sulfur base of the inorganic salt containing sulfur and nitrogen to inhibit the output of dioxin doubly, the emission of dioxin is reduced efficiently.
Further, the alkali potassium PEG polyurethane resin comprises the following raw material components in percentage by weight:
30% -60% of potassium hydroxide;
PEG400-1000 20％-50％；
10-30% of polyethylene polyamine.
Specifically, the PEG400-1000 is a mixture of PEG400, PEG600, PEG800, and PEG1000, the mixing ratio is not limited, and manufacturers can mix the PEG400-1000 according to actual conditions. The alkaline potassium PEG polyurethane resin is prepared from potassium hydroxide, PEG400-1000 and polyethylene polyamine, so that the alkaline potassium PEG polyurethane resin can adsorb dioxin in smoke, is favorable for treating acid gas in the smoke and realizes efficient smoke treatment. The polyethylene polyamine can be mixed with PEG400-1000, so that the components can be uniformly distributed, the surface activity is good, the moisture and carbon dioxide in the flue gas can be easily absorbed, the corresponding salt can be generated with acid, and the high-efficiency treatment of the waste incineration flue gas is facilitated.
Further, the high-efficiency dioxin adsorbent is a particulate matter with a pore channel, and the average pore diameter of the pore channel is 5-7 nm.
The pore diameter of the pore channel of the high-efficiency dioxin adsorbent provided by the invention is small, so that the specific surface area of the high-efficiency dioxin adsorbent is increased, and the adsorption effect of dioxin is improved. Specifically, the specific surface area of the high-efficiency dioxin adsorbent provided by the invention is between 300 and 600m2(ii) in terms of/g. If the average pore diameter is larger than 7nm, the specific surface area is reduced, so that the adsorption effect of the dioxin is reduced, and if the average pore diameter is smaller than 5nm, the dioxin is easily caused to stay on the outer surface of the adsorbent and is difficult to enter the pores, the requirement on preparation precision is high, the preparation is complex, and the cost of the high-efficiency dioxin adsorbent is high.
Further, the pore volume of the dioxin high-efficiency adsorbent ranges from 0.12cm to 0.25cm3/g。
The pore volume range of the high-efficiency dioxin adsorbent provided by the invention is 0.12-0.25cm3The adsorption effect on dioxin is good. If the pore volume of the high-efficiency dioxin adsorbent is less than 0.12cm3The effective volume of the dioxin efficient adsorbent is too small, the saturated adsorption amount of the dioxin is small, and the adsorption effect is reduced. If the pore volume of the high-efficiency dioxin adsorbent is more than 0.25cm3The/g has good adsorption effect, but the preparation precision requirement is high, the preparation is complex, and the cost of the high-efficiency dioxin adsorbent is high.
Further, the proportion of mesopores of the high-efficiency dioxin adsorbent is more than 65 percent, wherein the mesopores refer to pores with the pore diameter of 2-50 nm.
The proportion of mesopores of the high-efficiency dioxin adsorbent provided by the invention is more than 65%, and pore channels are uniformly formed, so that the high-efficiency dioxin adsorbent is favorably and uniformly mixed with flue gas, and the required purification efficiency can be achieved after sufficient contact time is reached.
The invention also provides a preparation method of the dioxin high-efficiency adsorbent for waste incineration,
the method comprises the following steps: putting 30-60 parts of zeolite powder into a container, adding 10-30 parts of silicon carbide, 5-15 parts of sulfur-nitrogen-containing inorganic salt, 10-30 parts of alkali potassium PEG polyurethane resin and 10-30 parts of water at the same time, stirring, and uniformly stirring to obtain a slurry mixture;
step two: drying the slurry mixture in air at 100-105 ℃ for 2-3 hours to remove water to obtain a dried substance;
step three: and (3) placing the dried material in a calcining furnace, and heating the dried material from the temperature of 110-150 ℃ to the temperature of 350-500 ℃, wherein the heating process comprises the following steps: heating up to 50 ℃ for the first time, preserving heat for 30 minutes, heating up to 50 ℃ for the second time, preserving heat for 2 hours, heating up to 50 ℃ for the third time, preserving heat for 30 minutes, heating up to 50 ℃ for the fourth time, preserving heat for 2 hours, and so on;
step four: and cooling the calcined dried substance to below 80 ℃, and grinding the dried substance to obtain the granular adsorbent.
In the invention, the slurry mixture formed by fully mixing the raw materials is dried and dewatered, then is heated from 150 ℃ to 500 ℃ in a temperature range of 350 ℃ according to a temperature programming mode, is heated for 30 minutes every time when the temperature is raised to 50 ℃, and is heated for 2 hours every time when the temperature is raised to 100 ℃, so that the pore diameter and the pore volume generated at each stage are ensured to have firm and stable skeleton foundation, the collapse of the pores is prevented, the effective adsorption specific surface is favorably increased, the effective porous channel structure is favorably increased, and finally, the grinding is carried out to prepare the dioxin adsorbent with larger specific surface, so that the adsorption effect of the dioxin is improved.
Further, the method also comprises the step of preparing the alkali potassium PEG polyurethane resin:
mixing potassium hydroxide, PEG400-1000 and polyethylene polyamine, and reacting at 100-200 ℃ for 2-4 hours.
30-60% of potassium hydroxide, 20-50% of PEG400-1000 and 10-30% of polyethylene polyamine are prepared into the alkaline potassium-alkali PEG polyurethane resin according to the proportion, so that the alkaline potassium-alkali PEG polyurethane resin can adsorb dioxin in smoke, is favorable for treating acid gas in the smoke and realizes efficient smoke treatment. The polyethylene polyamine can be mixed with PEG400-1000, so that the components can be uniformly distributed, the surface activity is good, the moisture and carbon dioxide in the flue gas can be easily absorbed, the corresponding salt can be generated with acid, and the high-efficiency treatment of the waste incineration flue gas is facilitated.
Further, in the third step, the oxygen content of the air in the calciner is less than 6%.
The oxygen content of the air in the calcining furnace is controlled to be lower than 6%, so that the oxidation of active ingredients for adsorbing and degrading the dioxin is effectively prevented, and the reduction of the adsorption effect of the high-efficiency dioxin adsorbent is avoided.
Further, in the fourth step, the particle size is controlled to be less than or equal to 200 mesh during grinding.
When the high-efficiency dioxin adsorbent is ground, the particle size of the high-efficiency dioxin adsorbent is controlled to be 200 meshes or below 200 meshes, the high-efficiency dioxin adsorbent has high economic ratio and can be suitable for garbage incinerators of different models. If the particle of the high-efficiency dioxin adsorbent is larger than 200 meshes, the specific surface is reduced, and the adsorption effect of the high-efficiency dioxin adsorbent is reduced. On the contrary, although the fineness of the dioxin efficient adsorbent is finer and the specific surface is larger, the processing fineness is high, the production is time-consuming, and the cost for producing the dioxin efficient adsorbent is high.
The invention also provides application of the high-efficiency dioxin adsorbent for waste incineration, and when household garbage doped with industrial waste is incinerated, the high-efficiency dioxin adsorbent is mixed with activated carbon for use, so that the high-efficiency dioxin adsorbent has a remarkable dioxin adsorption effect. When the household garbage doped with the industrial garbage is incinerated, the amount of generated dioxin can be obviously increased, and the dioxin adsorption efficiency can be reduced by singly using the high-efficiency dioxin adsorbent or the activated carbon. After the two materials are mixed for use, the dioxin adsorption efficiency reaches 98 percent, the adsorption effect is obvious, and the discharge amount of the dioxin during incineration of the household garbage doped with industrial garbage is effectively reduced.
The technical solution of the present invention is further illustrated by the following examples.
The first embodiment is as follows:
the raw materials are proportioned according to parts by weight, 30 parts of zeolite powder is placed in a container, and 10 parts of silicon carbide, 5 parts of ammonium sulfate, 10 parts of alkali potassium PEG polyurethane resin and 10 parts of water are added and stirred at the same time. Specifically, the alkali potassium PEG polyurethane resin comprises the following raw materials in parts by weight: 30% potassium hydroxide, 50% PEG400-1000, and 20% polyethylene polyamine; wherein the ammonium sulfate can be replaced by one of sodium sulfide, urea or thiourea.
Drying in air at 100 deg.C for 2 hr;
placing the mixture in a calcining furnace with the oxygen content of 5 percent in the air, and raising the temperature from 110 ℃ to 350 ℃, wherein the temperature raising process comprises the following steps: heating for the first time to 50 ℃, preserving heat for 30 minutes, heating for the second time to 50 ℃, preserving heat for 2 hours, heating for the third time to 50 ℃, preserving heat for 30 minutes, heating for the fourth time to 50 ℃, preserving heat for 2 hours, and so on;
and cooling the calcined dried substance to below 80 ℃, and grinding the dried substance into a high-efficiency dioxin adsorbent with the particle size of 200 meshes.
Example two:
the preparation method comprises the following steps of proportioning raw materials in parts by weight, putting 38 parts of zeolite powder into a container, adding 16 parts of silicon carbide, 7 parts of ammonium sulfate, 15 parts of alkali potassium PEG polyurethane resin and 15 parts of water, and stirring, wherein specifically, the raw materials of the alkali potassium PEG polyurethane resin are proportioned in parts by weight: 30% potassium hydroxide, 50% PEG400-1000, and 20% polyethylene polyamine; wherein the ammonium sulfate can be replaced by one of sodium sulfide, urea or thiourea.
Drying in air at 105 deg.C for 3 hr;
placing the mixture in a calcining furnace with the oxygen content of 5 percent in the air, raising the temperature from 150 ℃ to 500 ℃, and specifically raising the temperature by the following steps: heating for the first time to 50 ℃, preserving heat for 30 minutes, heating for the second time to 50 ℃, preserving heat for 2 hours, heating for the third time to 50 ℃, preserving heat for 30 minutes, heating for the fourth time to 50 ℃, preserving heat for 2 hours, and so on;
and cooling the calcined dried substance to below 80 ℃, and grinding the dried substance into a high-efficiency dioxin adsorbent with the particle size of 200 meshes.
Example three:
the preparation method comprises the following steps of proportioning raw materials in parts by weight, putting 49 parts of zeolite powder into a container, adding 24 parts of silicon carbide, 11 parts of ammonium sulfate, 23 parts of alkali potassium PEG polyurethane resin and 23 parts of water, and stirring, wherein specifically, the raw materials of the alkali potassium PEG polyurethane resin are proportioned in parts by weight: 30% potassium hydroxide, 50% PEG400-1000, and 20% polyethylene polyamine; wherein the ammonium sulfate can be replaced by one of sodium sulfide, urea or thiourea.
Drying in air at 105 deg.C for 3 hr;
placing the mixture in a calcining furnace with the oxygen content of 5 percent in the air, raising the temperature from 150 ℃ to 500 ℃, and specifically raising the temperature by the following steps: heating for the first time to 50 ℃, preserving heat for 30 minutes, heating for the second time to 50 ℃, preserving heat for 2 hours, heating for the third time to 50 ℃, preserving heat for 30 minutes, heating for the fourth time to 50 ℃, preserving heat for 2 hours, and so on;
and cooling the calcined dried substance to below 80 ℃, and grinding the dried substance into a high-efficiency dioxin adsorbent with the particle size of 200 meshes.
Example four:
the preparation method comprises the following steps of proportioning raw materials in parts by weight, putting 60 parts of zeolite powder into a container, adding 30 parts of silicon carbide, 15 parts of ammonium sulfate, 30 parts of alkali potassium PEG polyurethane resin and 30 parts of water, and stirring, wherein specifically, the raw materials of the alkali potassium PEG polyurethane resin are proportioned in parts by weight: 30% potassium hydroxide, 50% PEG400-1000, and 20% polyethylene polyamine; wherein the ammonium sulfate can be replaced by one of sodium sulfide, urea or thiourea.
Drying in air at 105 deg.C for 3 hr;
placing the mixture in a calcining furnace with the oxygen content of 5 percent in the air, raising the temperature from 150 ℃ to 500 ℃, and specifically raising the temperature by the following steps: heating for the first time to 50 ℃, preserving heat for 30 minutes, heating for the second time to 50 ℃, preserving heat for 2 hours, heating for the third time to 50 ℃, preserving heat for 30 minutes, heating for the fourth time to 50 ℃, preserving heat for 2 hours, and so on;
and cooling the calcined dried substance to below 80 ℃, and grinding the dried substance into a high-efficiency dioxin adsorbent with the particle size of 200 meshes.
Example five:
the preparation method comprises the following steps of proportioning raw materials in parts by weight, putting 49 parts of zeolite powder into a container, adding 24 parts of silicon carbide, 11 parts of ammonium sulfate, 23 parts of alkali potassium PEG polyurethane resin and 23 parts of water, and stirring, wherein specifically, the raw materials of the alkali potassium PEG polyurethane resin are proportioned in parts by weight: 60% potassium hydroxide, 30% PEG400-1000 and 10% polyethylene polyamine; wherein the ammonium sulfate can be replaced by one of sodium sulfide, urea or thiourea.
Drying in air at 105 deg.C for 3 hr;
placing the mixture in a calcining furnace with the oxygen content of 5 percent in the air, raising the temperature from 150 ℃ to 500 ℃, and specifically raising the temperature by the following steps: heating for the first time to 50 ℃, preserving heat for 30 minutes, heating for the second time to 50 ℃, preserving heat for 2 hours, heating for the third time to 50 ℃, preserving heat for 30 minutes, heating for the fourth time to 50 ℃, preserving heat for 2 hours, and so on;
and cooling the calcined dried substance to below 80 ℃, and grinding the dried substance into a high-efficiency dioxin adsorbent with the particle size of 200 meshes.
Example six:
the preparation method comprises the following steps of proportioning raw materials in parts by weight, putting 49 parts of zeolite powder into a container, adding 24 parts of silicon carbide, 11 parts of ammonium sulfate, 23 parts of alkali potassium PEG polyurethane resin and 23 parts of water, and stirring, wherein specifically, the raw materials of the alkali potassium PEG polyurethane resin are proportioned in parts by weight: 50% potassium hydroxide, 20% PEG400-1000 and 30% polyethylene polyamine; wherein the ammonium sulfate can be replaced by one of sodium sulfide, urea or thiourea.
Drying in air at 105 deg.C for 3 hr;
placing the mixture in a calcining furnace with the oxygen content of 5 percent in the air, raising the temperature from 150 ℃ to 500 ℃, and specifically raising the temperature by the following steps: heating for the first time to 50 ℃, preserving heat for 30 minutes, heating for the second time to 50 ℃, preserving heat for 2 hours, heating for the third time to 50 ℃, preserving heat for 30 minutes, heating for the fourth time to 50 ℃, preserving heat for 2 hours, and so on;
and cooling the calcined dried substance to below 80 ℃, and grinding the dried substance into a high-efficiency dioxin adsorbent with the particle size of 200 meshes.
Comparative example 1
The activated carbon with the specific surface area of 900-1100 is selected.
Comparative example two:
the preparation method comprises the following steps of proportioning raw materials in parts by weight, putting 49 parts of zeolite powder into a container, adding 24 parts of silicon carbide, 11 parts of ammonium sulfate, 23 parts of alkali potassium PEG polyurethane resin and 23 parts of water, and stirring, wherein specifically, the raw materials of the alkali potassium PEG polyurethane resin are proportioned in parts by weight: 30% potassium hydroxide, 50% PEG400-1000, and 20% polyethylene polyamine; wherein the ammonium sulfate can be replaced by one of sodium sulfide, urea or thiourea.
Drying in air at 105 deg.C for 3 hr;
placing in a calcining furnace with 5% oxygen content in air, directly and slowly heating from 150 ℃ to 500 ℃, and not setting a heat preservation process;
the calcined dry matter was cooled to 80 ℃ or below and ground into an adsorbent having a particle size of 200 mesh.
Specifically, the component ratio of the above examples and comparative examples is shown in tables 1 and 2:
table 1:
table 2:
specifically, the physical properties of the above examples and comparative examples are shown in table 3:
TABLE 3
As is clear from table 3, from example one to example six, compared with comparative example two, since comparative example two did not follow the temperature rise process during the calcination process: the temperature is raised for 50 ℃ for the first time, the temperature is maintained for 30 minutes, the temperature is raised for 50 ℃ for the second time, the temperature is maintained for 2 hours, the temperature is raised for 50 ℃ for the third time, the temperature is maintained for 30 minutes, the temperature is raised for 50 ℃ for the fourth time, the temperature is maintained for 2 hours, and the like, so that the pore diameter and the pore volume generated in each stage cannot be guaranteed to have firm and stable skeleton foundation, the collapse of pores is caused, the increase of the adsorption effective specific surface and the generation of a porous channel structure are influenced, and the generated dioxin adsorbent has small pore diameter, few pore channels, small specific surface area, small pore volume and.
Further, an experimental group is arranged to test the adsorption efficiency of the dioxin;
experiment group one: putting the dioxin efficient adsorbent prepared in the third embodiment into smoke with dioxin, and testing the adsorption efficiency of the dioxin efficient adsorbent on the dioxin;
experiment group two: putting the activated carbon in the first comparative example into flue gas with dioxin, and testing the adsorption efficiency of the activated carbon on the dioxin;
experiment group three: the dioxin efficient adsorbent prepared in the third example and the activated carbon of the first comparative example were mixed in a certain amount and then put into the flue gas with dioxin, and the adsorption efficiency of the mixture of the two was tested.
In the invention, the dioxin inlet concentration and the dioxin outlet concentration are detected by a dioxin detecting instrument, and the removal rate of the dioxin is calculated, so that the adsorption efficiency of each experimental group is known.
Specifically, the amounts and the test data of the respective experimental groups are shown in tables 4 and 5:
table 4:
table 5:
the usage amounts of the dioxin efficient adsorbents in tables 4 and 5 are described, and since the dioxin efficient adsorbents belong to new products and are known to have an adsorption effect according to physical characteristics, but specific adsorption performance of the dioxin efficient adsorbents is not measured, in order to ensure that the discharge amount of dioxin can meet national standards, the usage amount of the dioxin efficient adsorbents in the experiment group one is larger than that of activated carbon in the experiment group two.
As is clear from tables 4 and 5, in the incineration of household garbage and the incineration of household garbage doped with industrial garbage, the adsorption rates of dioxin in flue gas by using the dioxin efficient adsorbents are both greater than 95%, that is, the removal rates of dioxin in flue gas are both greater than 95%, which meets the national standard, and therefore, the dioxin efficient adsorbents provided by the invention have excellent adsorption performance on dioxin.
Further, referring to table 5, when the household garbage doped with industrial garbage is incinerated, along with the increase of the concentration of dioxin, the adsorption efficiency of the activated carbon and the high-efficiency dioxin adsorbent to dioxin is slightly reduced, and as can be seen from experimental group three, under the condition that the activated carbon and the high-efficiency dioxin adsorbent are used together, 98% removal rate can be maintained for dioxin in flue gas, and a significant dioxin adsorption effect is achieved.
The technical principle of the present invention is described above in connection with specific embodiments. The description is made for the purpose of illustrating the principles of the invention and should not be construed in any way as limiting the scope of the invention. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. The high-efficiency dioxin adsorbent for waste incineration is characterized by comprising the following raw materials in parts by weight:
30-60 parts of zeolite powder, 10-30 parts of silicon carbide, 5-15 parts of inorganic salt containing sulfur and nitrogen, 10-30 parts of alkali potassium PEG polyurethane resin and 10-30 parts of water.
2. The high-efficiency dioxin adsorbent for waste incineration according to claim 1, characterized in that the alkali potassium PEG polyurethane resin comprises the following raw material components in parts by weight:
30% -60% of potassium hydroxide;
PEG400-1000 20％-50％；
10-30% of polyethylene polyamine.
3. The high-efficiency dioxin adsorbent for waste incineration according to claim 1, characterized in that it is a particulate matter having pores with an average pore diameter of 5 to 7 nm.
4. The high-efficiency dioxin adsorbent for waste incineration according to claim 3, characterized in that the pore volume of the high-efficiency dioxin adsorbent ranges from 0.12 to 0.25cm3/g。
5. The high-efficiency dioxin adsorbent for waste incineration according to claim 4, characterized in that the proportion of mesopores of the high-efficiency dioxin adsorbent is more than 65%, wherein the mesopores mean pores with a pore diameter of 2 to 50 nm.
6. The method for preparing the high-efficiency dioxin adsorbent for waste incineration according to any one of claims 1 to 5,
the method comprises the following steps: putting 30-60 parts of zeolite powder into a container, adding 10-30 parts of silicon carbide, 5-15 parts of sulfur-nitrogen-containing inorganic salt, 10-30 parts of alkali potassium PEG polyurethane resin and 10-30 parts of water at the same time, stirring, and uniformly stirring to obtain a slurry mixture;
step two: drying the slurry mixture in air at 100-105 ℃ for 2-3 hours to obtain a dried substance;
step three: and (3) placing the dried material in a calcining furnace, and heating the dried material from the temperature of 110-150 ℃ to the temperature of 350-500 ℃, wherein the heating process comprises the following steps: heating up to 50 ℃ for the first time, preserving heat for 30 minutes, heating up to 50 ℃ for the second time, preserving heat for 2 hours, heating up to 50 ℃ for the third time, preserving heat for 30 minutes, heating up to 50 ℃ for the fourth time, preserving heat for 2 hours, and so on;
step four: and cooling the calcined dried substance to below 80 ℃, and grinding the dried substance to obtain the granular adsorbent.
7. The method for preparing the high-efficiency dioxin adsorbent for waste incineration according to claim 6, further comprising the step of preparing the alkali potassium PEG polyurethane resin:
mixing potassium hydroxide, PEG400-1000 and polyethylene polyamine, and reacting at 100-200 ℃ for 2-4 hours.
8. The method of preparing a high efficiency sorbent for dioxins for waste incineration according to claim 6, wherein in the third step, the oxygen content of the air in the calciner is less than 6%.
9. The method for preparing the high-efficiency dioxin adsorbent for waste incineration according to claim 6, characterized in that in the fourth step, the particle size is controlled to be less than or equal to 200 mesh at the time of grinding.
10. The use of the high-efficiency adsorbent for waste incineration dioxin according to any one of claims 1 to 5, characterized in that: when the domestic garbage doped with industrial garbage is incinerated, the dioxin efficient adsorbent is mixed with activated carbon for use, so that the dioxin adsorption effect is obvious.
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