CN115945182A - Adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas and preparation method thereof - Google Patents
Adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas and preparation method thereof Download PDFInfo
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- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
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Abstract
The invention discloses an adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas and a preparation method thereof, and belongs to the technical field of gas purification in an organic coating pyrolysis process. The preparation method of the adsorbent comprises the following steps: respectively carbonizing and modifying the rod biomass and the shell biomass to obtain modified biochar A and modified biochar B, and granulating and roasting the obtained modified biochar A and modified biochar B and an organic binder to obtain the adsorbent. The adsorbent prepared by the technical scheme of the invention can simultaneously adsorb VOCs and dioxin in organic coating pyrolysis flue gas, has a longer service life, can be repeatedly used for many times, reduces the frequency of replacing the adsorbent by enterprises, and reduces the treatment cost for the enterprises. Meanwhile, the main raw materials of the adsorbent are derived from industrial and agricultural wastes, the source is wide, and the production cost is low.
Description
Technical Field
The invention belongs to the technical field of gas purification in the pyrolysis process of an organic coating, and particularly relates to an adsorbent for treating VOCs and dioxin in pyrolysis flue gas of the organic coating and a preparation method thereof.
Background
Along with the gradual depletion of non-ferrous metal mineral resources, the serious shortage of copper resources in China, the recycling of secondary copper resources becomes effective supplement, the waste electronic-grade copper material is taken as a typical secondary non-ferrous metal resource, the pyrolysis technology is a main recycling mode, but the surface of the waste electronic-grade copper material is provided with an organic coating, so that the waste electronic-grade copper material can generate an organic coating in the pyrolysis processVOCs and dioxins, and the emission concentration of the VOCs and the dioxins is often more than 200mg/m 3 And 5ng TEQ/m 3 Much higher than 30mg/m of the country 3 And 0.5ng TEQ/m 3 The emission standard of (2) is widely concerned at present because of the serious harm of VOCs and dioxin to the ecological environment and human health, and how to effectively reduce the emission of VOCs and dioxin in organic coating pyrolysis flue gas is a difficult problem which needs to be solved urgently.
In the existing technology for treating VOCs and dioxin, an adsorption method is regarded as an efficient and economic treatment means with the advantages of low cost, stable effect, regenerable adsorbent and the like. Biochar is a green, environment-friendly, cheap and readily available carbonaceous adsorption material, and has attracted important attention in recent years.
Through retrieval, the Chinese patent "a preparation method of an ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent and application thereof" (CN 201911293894.7) proposes the following technical scheme: the method comprises the steps of chopping, cleaning and drying banana peel, carbonizing to obtain banana peel biochar, uniformly mixing the banana peel biochar and KOH according to a certain mass ratio, activating at high temperature, washing, filtering and drying to obtain the biochar VOCs adsorbent. For the technical scheme, the applicant prepares the biochar adsorbent in a laboratory and tries to adsorb VOCs generated in the pyrolysis process of the organic coating, and finds that the adsorbent has short service life, and the adsorption effect is seriously reduced after the adsorption lasts for 2 to 3 hours, so that the biochar adsorbent cannot be used continuously. If the adsorbent is used for enterprises, the adsorbent needs to be frequently replaced, and the adsorbent can only adsorb VOCs and cannot adsorb VOCs and dioxin at the same time.
Therefore, the development of a durable adsorbent for reducing the emission of VOCs and dioxin in the organic coating pyrolysis process is of great significance.
Disclosure of Invention
1. Problems to be solved
The invention aims to solve the problem of short service life of the traditional charcoal adsorbent and provides an adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas and a preparation method thereof. The adsorbent can simultaneously adsorb VOCs and dioxin in organic coating pyrolysis flue gas, has a long service life, is simple in preparation process and low in cost, and has excellent economic benefits.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
according to the preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas, rod biomass and shell biomass are carbonized and modified respectively to obtain modified biochar A and modified biochar B, and then the modified biochar A and the modified biochar B are granulated and roasted in cooperation with an organic binder to obtain the adsorbent.
Specifically, the preparation of the adsorbent comprises the following steps:
step one, biomass pretreatment and preparation of biochar A and biochar B;
(1) Treating the rod biomass: mixing and crushing the collected rod biomass into proper size according to a certain mass ratio, and drying at a certain temperature;
(2) Shell biomass treatment: mixing and crushing the collected shell biomass into proper size according to a certain mass ratio, and drying at a certain temperature;
(3) Preparing biochar A: carbonizing the dried rod biomass in a certain temperature range and in an inert atmosphere to obtain biochar A, and grinding the biochar A into a certain particle size;
(4) Preparing biochar B: carbonizing the dried rod biomass in a certain temperature range and in an inert atmosphere to obtain biochar B, and grinding the biochar B into a certain particle size.
Step two, preparing catalyst powder suspension;
crushing the waste catalyst, grinding the waste catalyst into a certain particle size, and then stirring and mixing the waste catalyst with an EDTA aqueous solution according to a certain proportion to obtain a catalyst powder suspension.
Step three, preparing modified biochar A;
mixing the biochar A and the catalyst powder suspension according to a certain proportion, and then evaporating and stirring at a certain temperature to obtain the modified biochar A.
Step four, preparation of modified biochar B
Mixing the biochar B and the modifier according to a certain ratio, fully stirring for a certain time to enable the modifier to fully impregnate the biochar B, and filtering and draining to obtain the modified biochar B.
Step five, granulating and roasting;
(1) Mixing the modified biochar A and an organic binder according to a certain proportion, adding water to prepare particles with a certain size, and then adding a certain mass of modified biochar B to continue granulation.
(2) And roasting the prepared particles at a certain temperature under an inert atmosphere to obtain the adsorbent.
As a further optimization of the invention, the straw biomass is selected from one or a combination of more of corn stalks, straw stalks and wheat stalks; the shell biomass is one or a combination of peanut shells, soybean shells and rice bran shells.
As a further optimization of the invention, when the straw biomass is a combination of corn stalks, straw stalks and wheat stalks, the mass of the corn stalks, the straw stalks and the wheat stalks is 1: (2-4): (2-4); when the shell biomass is a combination of peanut shells, soybean shells and rice bran shells, the mass of the peanut shells, the soybean shells and the rice bran shells is 1:1: (2-4).
As a further optimization of the invention, in the step one, the lengths of the crushed rod biomass and the crushed shell biomass are both less than or equal to 1cm. Drying the crushed stalk biomass and shell biomass at 100 ℃ for not less than 2h.
As a further optimization of the invention, the rod biomass and the shell biomass are both in N 2 Charring under an atmosphere, N 2 The introduction amount of the catalyst is 400-600 mL/min, and the carbonization temperature is 600-700 ℃. Meanwhile, the carbonization time of the rod biomass is 1.5-2.5 h, and the carbonization time of the shell biomass is 1-2 h.
As a further optimization of the invention, in the step one, the particle diameter of the ground biochar A is smaller than 100 microns, and the particle diameter of the ground biochar B is smaller than 150 microns.
As further optimization of the invention, in the second step, the waste catalyst is waste generated in the flue gas SCR denitration system of the coal-fired power plant, and the waste catalyst comprises the following components in percentage by mass: tiO 2 2 ：86.97％，WO 3 ：4.69％，SiO 2 ：3.85％，CaO：1.42％，Al 2 O 3 ：0.89％，V 2 O 5 :0.51%, S:0.45%, P:0.06%, na:0.08%, K:0.06 percent, and the balance of inevitable impurities.
The diameter of the milled catalyst particles is less than 74 μm. In the preparation of the catalyst suspension, an aqueous EDTA solution was used at a concentration of 0.2mol/L.
As a further optimization of the invention, the solid-to-liquid ratio of the catalyst powder to the EDTA aqueous solution is 1: (9-11), adopting an analytical purification reagent for EDTA (ethylene diamine tetraacetic acid), wherein the material purity is more than 99%, and the balance is inevitable impurities; .
As a further optimization of the invention, in the third step, the solid-to-liquid ratio of the biochar a to the catalyst powder suspension is 1: (4-6), the evaporation stirring temperature is 150-250 ℃, and the time is 0.5-1.5 h.
As a further optimization of the invention, in the fourth step, the modifier is 0.3mol/L NH 4 HCO 3 A solution; the solid-liquid ratio of the biochar B to the modifier is 1: (9-11), and the stirring time is not less than 12h to ensure that the modifier is fully impregnated in the biochar B.
In the fifth step, the organic binder is PVA (polyvinyl alcohol), analytical pure reagent is adopted, the purity of the material is more than 99%, and the balance is inevitable impurities. The mass ratio of the modified biochar A to the organic binder is (15-20): 1, and the mixing time of the modified biochar A and the organic binder is 5-30 min. The mass of the added modified biochar B is equal to that of the modified raw carbon A. The diameter of the finally prepared particles is 1-2 mm, the roasting temperature is 550-650 ℃, the temperature is raised along with the furnace at the temperature raising rate of 10 ℃/min during actual roasting, and the temperature is kept for 15-25 min after the roasting temperature is reached.
The adsorbent is obtained by the preparation method, is of a spherical structure as a whole, is composed of a skeleton formed by biochar A with a catalyst attached to the surface, and is also attached with a layer of modified biochar B on the surface.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas provided by the invention not only can adsorb VOCs and dioxin in organic coating pyrolysis flue gas at the same time, but also has a longer service life.
(2) According to the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas, the catalyst is waste generated in a coal-fired power plant flue gas SCR denitration system, so that the waste catalyst can be consumed, and the problem of treatment of the waste catalyst is solved to a certain extent; meanwhile, the adopted biomass mainly takes agricultural wastes as raw materials, so that the production cost is lower.
(3) According to the preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas, disclosed by the invention, the preparation process is optimally designed, particularly the group distribution ratio and the process treatment parameters are controlled, so that the adsorption efficiency and the service life of the obtained adsorbent are effectively improved, and the durable adsorbent is produced and used for reducing the emission of VOCs and dioxin in the organic coating pyrolysis process, the frequency of replacing the adsorbent by enterprises is reduced, and the production cost is reduced for the enterprises.
Drawings
FIG. 1 is a schematic flow diagram of a process for preparing the adsorbent of the present invention;
FIG. 2 is a schematic view of the structure of the adsorbent of the present invention;
in the figure:
1. biochar A; 2. a catalyst; 3. and (4) modifying the biochar B.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration exemplary embodiments in which the invention may be practiced, and in which features of the invention are identified by reference numerals. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded in an illustrative rather than a restrictive sense, and any such modifications and variations, if any, are intended to fall within the scope of the invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
It should be noted that the rod biomass and the shell biomass are both agricultural wastes.
The waste catalyst is waste generated in a flue gas SCR denitration system of a coal-fired power plant, and comprises the following components in percentage by mass: tiO 2 2 ：86.97％，WO 3 ：4.69％，SiO 2 ：3.85％，CaO：1.42％，Al 2 O 3 ：0.89％，V 2 O 5 :0.51%, S:0.45%, P:0.06%, na:0.08%, K:0.06 percent, and the balance of inevitable impurities.
The EDTA (ethylene diamine tetraacetic acid) adopts an analytical reagent, the material purity is more than 99 percent, and the rest is inevitable impurities.
The organic binder (PVA, polyvinyl alcohol) adopts analytical pure reagent, the material purity is more than 99 percent, and the rest is inevitable impurities.
The invention is further described with reference to specific examples.
Example 1
As shown in fig. 1 and fig. 2, the preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas in this embodiment specifically includes the following steps:
step one, biochar preparation
(1) Treating the rod biomass: collecting three straw biomasses of corn stalks, straw stalks and wheat stalks, mixing the three straw biomasses according to a mass ratio of 1;
(2) Shell biomass treatment: collecting three shell biomass including peanut shells, soybean shells and rice chaff shells, mixing the three shell biomass according to a mass ratio of 1;
(3) Preparing biochar A: 500g of dried rod biomass is put into a tube furnace, and N is added 2 Heating to 650 ℃ along with the furnace at a heating rate of 10 ℃/min under the atmosphere for high-temperature carbonization for 2h, and controlling N 2 The flow rate is 500mL/min, after carbonization, the prepared biochar A is taken out after the temperature of the tubular furnace is reduced to room temperature, and the biochar A is ground into particles with the diameter of less than 100 mu m by a ball mill;
(4) Preparing biochar B: 500g of dried shell biomass is put into a tube furnace, and N is added 2 Heating to 650 ℃ along with the furnace at a heating rate of 10 ℃/min under the atmosphere for high-temperature carbonization, wherein the carbonization time is 1.5h, and controlling N 2 The flow rate is 500mL/min, after carbonization, the prepared biochar B is taken out after the temperature of the tubular furnace is reduced to room temperature, and the biochar B is ground into particles with the diameter of less than 150 mu m by adopting a ball mill.
Step two, catalyst powder suspension preparation
(1) Carrying out primary crushing treatment on the waste catalyst by using a jaw crusher, and then carrying out crushing and grinding treatment on the waste catalyst to obtain particles with the diameter of less than 74 microns;
(2) Preparing 0.2mol/mL EDTA aqueous solution at the temperature of 80 ℃, mixing the waste catalyst powder and the EDTA aqueous solution according to the solid-to-liquid ratio of 1.
Step three, preparation of modified biochar A
Mixing the biochar A powder and the catalyst powder suspension for 20min according to the solid-to-liquid ratio of 1:5, putting the mixture into a stirring type evaporator, evaporating and stirring the mixture for 1h at the temperature of 200 ℃, and taking the mixture out to obtain the modified biochar A.
Step four, preparation of modified biochar B
According to the solid-liquid ratio of 1 4 HCO 3 Solution) and the biochar B are placed in a beaker, stirred on a magnetic stirrer for 24 hours to ensure that the modifying agent is fully impregnated into the biochar B, and then the modified biochar B is obtained after filtering and draining.
Step five, granulating and roasting
(1) Mixing the modified biochar A and an organic binder (PVA, polyvinyl alcohol) according to a mass ratio of 20 to 1 by a mixer for 10min, adding water into the mixture by using a disc granulator to prepare particles with the diameter of 0.7-1.4 mm, adding the modified biochar B with the same mass as the modified biochar A, and continuously granulating to prepare particles with the diameter of 1-2 mm, wherein the mass of the water added in the whole granulating process is 7.5-8.0% of the total mass of the modified biochar A, the modified biochar B and the organic binder;
(2) Placing the prepared granules in a tube furnace under N 2 Heating to 600 deg.C with furnace at a heating rate of 10 deg.C/min under atmosphere, and calcining at 600 deg.C for 20min, wherein the temperature is constant 2 The introduction amount of the catalyst is 500mL/min, and after roasting is finished, the particles are taken out after the temperature of the tubular furnace is reduced to room temperature, so that the adsorbent is obtained.
The obtained adsorbent is spherical, biochar A obtained by carbonizing rod-type biomass is used as a framework of the adsorbent, a layer of modified biochar B is attached to the surface of the framework, the structure can support the modified biochar B obtained by carbonizing and modifying shell-type biomass, and compared with a traditional adsorbent such as activated carbon, the structure is more fluffy and more in gaps, and compared with a powdery adsorbent, the spherical adsorbent can effectively reduce the transmission resistance of VOCs and dioxin in flue gas, can promote the diffusion transportation of VOCs and dioxin, and enables the adsorbent to have a better adsorption effect on the VOCs and the dioxin.
The specific surface area and the adsorption effect of the obtained adsorbent sample were measured by first measuring the specific surface area of the adsorbent with a specific surface area analyzer, the measurement results are shown in Table 1, then 200g of the adsorbent was placed in the adsorption apparatus, and the adsorbent having a concentration of 283.16mg/m was continuously introduced from the inlet 3 And a concentration of 5.3ng TEQ/m 3 The concentration of VOCs and dioxin in the outlet of the adsorption device was detected by a 3010MINIFID portable total hydrocarbon analyzer and a high-resolution magnetic mass spectrometer, and the adsorption time of the adsorbent was recorded, with the results shown in table 1.
Comparative example 1
The comparative adsorbent was prepared substantially as in example 1, except that: in the fourth step, no modifier is added. The specific surface area and the adsorption effect of the prepared product were measured by the measurement method in example 1, and the results are shown in table 1.
Comparative example 2
The adsorbent of this comparative example was prepared substantially as in example 1, except that: EDTA was not added in step two. The specific surface area and the adsorption effect of the prepared product were measured by the measurement method in example 1, and the results are shown in table 1.
Comparative example 3
The adsorbent of this comparative example was prepared substantially as in example 1, except that: EDTA is not added in the second step and a modifier is not added in the fourth step. The specific surface area and the adsorption effect of the prepared product were measured by the measurement method of example 1, and the results are shown in table 1.
Comparative example 4
The comparative adsorbent was prepared substantially as in example 1, except that: in the fourth step, the biochar B and the modifier are mixed according to a solid-liquid ratio of 1. The specific surface area and the adsorption effect of the prepared product were measured by the measurement method of example 1, and the results are shown in table 1.
Comparative example 5
The comparative adsorbent was prepared substantially as in example 1, except that: in the fourth step, the biochar B and the modifier are mixed according to the solid-to-liquid ratio of 1:6. The specific surface area and the adsorption effect of the prepared product were measured by the measurement method of example 1, and the results are shown in table 1.
TABLE 1 adsorption efficiency and service life of the adsorbents obtained in example 1 and comparative examples 1 to 5
By analyzing the table 1 index, the following conclusions can be drawn:
(1) Comparative example 1 in comparison with example 1, in step four without the addition of the modifier, the specific surface area of the adsorbent is reduced by 396.08m 2 Per g, the concentration of VOCs after adsorption is increased by 36.93mg/m 3 The concentration of dioxin after adsorption is increased by 0.75ng TEQ/m 3 The service life is reduced by 4 hours;
(2) Comparative example 2 in comparison with example 1, in the second step without EDTA addition, the specific surface area of the adsorbent was reduced by 16.69m 2 The concentration of VOCs after adsorption is increased by 14.81mg/m 3 The adsorbed dioxin concentration was increased by 3.76ng TEQ/m 3 The service life is reduced by 10 hours;
(3) Comparative example 3 in comparison with example 1, no EDTA addition in step two and no modifier addition in step four, the adsorbent has a reduced specific surface area of 402.56m 2 Per g, the concentration of VOCs after adsorption is increased by 88.32mg/m 3 After adsorption, the concentration of dioxin was increased by 4.15ng TEQ/m 3 The service life is reduced by 13h;
(4) Comparative example 4 in comparison with example 1, when the biochar B and the modifier are mixed, the addition amount of the modifier is too high, and the specific surface area of the adsorbent is reduced by 341.87m 2 (g), the concentration of VOCs after adsorption is increased by 41.78mg/m 3 The adsorbed dioxin concentration was increased by 4.65ng TEQ/m 3 The service life is reduced by 11h;
(5) Comparative example 5 in comparison with example 1, when the biochar B and the modifier are mixed, the adding amount of the modifier is too low, and the specific surface area of the adsorbent is reduced by 449.09m 2 The concentration of VOCs after adsorption is increased by 27.45mg/m 3 The concentration of the adsorbed dioxin is increased by 4.08ng TEQ/m < 3 >, and the service life is shortened by 10 hours;
the applicant researches and discovers that the modifier and EDTA are very important for improving the adsorption efficiency and the service life of the adsorbent. The modification of the biochar B by the modifier can increase the specific surface area and the porosity of the adsorbent in a proper range, because the modifier can generate CO by thermal decomposition 2 、H 2 O and NH 3 ，CO 2 And H 2 O attacks the surface and the inside of the adsorbent, thereby improving the specific surface area and the pore structure of the adsorbent, and NH 3 Can form nitrogen-containing functional groups on the surface of the adsorbent, and the introduction of the nitrogen-containing functional groups can enhance the van der Waals interaction between VOCs and dioxin molecules and the surface of the charcoal, thereby improving the combined adsorption of the VOCs and the dioxin.
The applicant proves through a large number of experiments that when the biochar B and the modifier are mixed according to the solid-liquid ratio of 1:9-1, the modification effect is the best. When the addition amount of the modifier is too high, the modifier is heated to decompose to generate more CO 2 、H 2 O and NH 3 The modification is excessive, the framework of the adsorbent is damaged, and the pore structure is deteriorated, so that the adsorption performance of the adsorbent is obviously reduced; when the addition amount of the modifier is too low, incomplete modification can be caused, and CO generated by thermal decomposition of the modifier 2 、H 2 O and NH 3 Less generation of CO 2 And H 2 The degree of corrosion of O to the adsorbent is not sufficient, pores can be formed only on the surface of the adsorbent, and NH is formed 3 Nitrogen-containing functionalities formed on the surface of the adsorbentThe smaller the amount of clusters, the lower the adsorption performance of the adsorbent.
In addition, through utilizing EDTA aqueous solution to prepare catalyst powder suspension, and the preparation process of follow-up modified biological charcoal A, not only can make the catalyst resume 60-70% activity, and can attach the catalyst on biological charcoal A surface effectively, form modified biological charcoal A, exist at last inside the adsorbent, the catalyst can take place catalytic oxidation reaction with the dioxin of adsorbent surface adsorption for the adsorbent can adsorb while reacting in adsorption process, prevent that dioxin from concentrating on the adsorbent surface, thereby further strengthened the adsorption effect of adsorbent, improved the life of adsorbent.
In addition, the adsorbent prepared by the method has a structure shown in fig. 2, the adsorbent is spherical, biochar A obtained by carbonizing the rod-like biomass is used as a framework of the adsorbent, and the modified biochar B obtained by carbonizing and modifying the shell-like biomass plays a supporting role.
Example 2
As shown in fig. 1 and fig. 2, the specific preparation process of the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas in this embodiment is substantially the same as that in embodiment 1, and is different from that in embodiment 1 in that:
(1) The stalk biomass adopts corn stalks, the shell biomass adopts peanut shells, and the stalk biomass and the shell biomass are dried at 100 ℃ for 2 hours;
(2) The carbonization temperature of the rod biomass is 600 ℃, and the carbonization time is 2.5h; the carbonization temperature of the shell biomass is 700 ℃, and the carbonization time is 1h; during carbonization, N 2 The flow rate is 450mL/min;
(3) When catalyst suspension is prepared, mixing the catalyst and EDTA aqueous solution according to the solid-to-liquid ratio of 1:9;
(4) The solid-liquid ratio between the biochar A and the catalyst powder suspension is 1:4, the evaporation stirring temperature is 150 ℃, and the time is 1.5h;
(5) The solid-liquid ratio of the modified biochar B to the modifier is 1;
(6) Mixing the modified biochar A and an organic binder according to a mass ratio of 18; the mixing time is 5-30 min;
(7) When the particles are calcined, at N 2 Heating to 550 ℃ along with the furnace at a heating rate of 10 ℃/min under the atmosphere, roasting, and keeping the temperature for 25min after the temperature is increased to 550 ℃.
The specific surface area and the adsorption effect of the obtained product were measured by the measurement method of example 1, and the measurement results were substantially the same as those of example 1.
Example 3
As shown in fig. 1 and fig. 2, the specific preparation process of the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas in this embodiment is substantially the same as that in embodiment 1, and is different from that in embodiment 1 in that:
(1) Straw is adopted as the straw biomass, rice bran is adopted as the shell biomass, and the straw biomass and the shell biomass are dried at 100 ℃ for not less than 2 hours;
(2) The carbonization temperature of the rod biomass is 660 ℃, and the carbonization time is 1.9h; the carbonization temperature of the shell biomass is 670 ℃, and the carbonization time is 1.3h; during carbonization, N 2 The flow rate is 400mL/min;
(3) When catalyst suspension is prepared, mixing a catalyst and an EDTA aqueous solution according to a solid-to-liquid ratio of 1;
(4) The solid-liquid ratio between the biochar A and the catalyst powder suspension is 1.5, the evaporation stirring temperature is 200 ℃, and the time is 1.0h;
(5) The solid-liquid ratio of the modified biochar B to the modifier is 1;
(6) Mixing the modified biochar A and an organic binder according to a mass ratio of 15; the mixing time is 5-30 min;
(7) When the particles are calcined, at N 2 Heating to 650 ℃ along with the furnace at a heating rate of 10 ℃/min in the atmosphere for roastingThe temperature is raised to 650 ℃ and then the temperature is kept for 20min.
The specific surface area and the adsorption effect of the obtained product were measured by the measurement method of example 1, and the results were substantially the same as those of example 1.
Example 4
As shown in fig. 1 and fig. 2, the specific preparation process of the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas in this embodiment is substantially the same as that in embodiment 1, and is different from that in embodiment 1 in that:
(1) The straw biomass adopts wheat straw, the shell biomass adopts soybean shell, and the straw biomass and the shell biomass are dried at 100 ℃ for 2.5 hours;
(2) The carbonization temperature of the rod biomass is 700 ℃, and the carbonization time is 1.5h; the carbonization temperature of the shell biomass is 600 ℃, and the carbonization time is 2h; during carbonization, N 2 The flow rate is 600mL/min;
(3) When catalyst suspension is prepared, mixing a catalyst and an EDTA aqueous solution according to a solid-to-liquid ratio of 1;
(4) The solid-liquid ratio between the biochar A and the catalyst powder suspension is 1:6, the evaporation stirring temperature is 250 ℃, and the time is 0.5h;
(5) The solid-liquid ratio of the modified biochar B to the modifier is 1:9, and the stirring time is 12 hours;
(6) Mixing the modified biochar A and an organic binder according to a mass ratio of 20; the mixing time is 5-30 min;
(7) When the particles are calcined, at N 2 Heating to 620 ℃ along with the furnace at the heating rate of 10 ℃/min under the atmosphere, roasting, and keeping the temperature for 15min after the temperature is raised to 620 ℃.
The specific surface area and the adsorption effect of the obtained product were measured by the measurement method of example 1, and the results were substantially the same as those of example 1.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded as illustrative rather than restrictive, and any such modifications and variations are intended to be included within the scope of the present invention as described herein. Furthermore, the background is intended to be illustrative of the state of the art as developed and the meaning of the present technology and is not intended to limit the scope of the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. When a rate, pressure, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.
Claims (10)
1. A preparation method of an adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas is characterized by comprising the following steps: respectively carbonizing and modifying the rod biomass and the shell biomass to obtain modified biochar A and modified biochar B, and granulating and roasting the obtained modified biochar A and modified biochar B and an organic binder to obtain the adsorbent.
2. The preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas according to claim 1, characterized by comprising the following steps:
step one, biomass pretreatment and preparation of biochar A and biochar B;
step two, preparing catalyst powder suspension;
step three, preparing modified biochar A;
step four, preparing modified biochar B;
step five, granulating and roasting: firstly, mixing modified biochar A and an organic binder, adding water to prepare granules, then adding modified biochar B to continue granulating, and finally roasting the prepared granules to obtain the adsorbent.
3. The preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas according to claim 2, characterized in that: in the first step of the method,
the preparation method of the biochar A comprises the following steps: firstly, crushing and drying the rod biomass, and then carbonizing and grinding the dried rod biomass to obtain charcoal A; the straw biomass is one or a combination of corn stalks, straw stalks and wheat stalks;
the preparation method of the biochar B comprises the following steps: firstly, crushing and drying shell biomass, and then carbonizing and grinding the dried shell biomass to obtain biochar B, wherein the shell biomass is one or a combination of peanut shells, soybean shells and rice bran shells.
4. The preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas as claimed in claim 3, characterized in that: when combination of corn stalks, straw stalks and wheat stalks is selected for use by straw biomass, the quality of the corn stalks, the straw stalks and the wheat stalks is 1: (2-4): (2-4);
when the shell biomass is a combination of peanut shells, soybean shells and rice bran shells, the mass of the peanut shells, the soybean shells and the rice bran shells is 1:1: (2-4).
5. The preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas according to claim 3, characterized in that: the lengths of the crushed rod biomass and the crushed shell biomass are less than or equal to 1cm, the drying temperature is 100 ℃, and the drying time is not less than 2h; the rod biomass and the shell biomass are carbonized under inert protective atmosphere, and the carbonization temperature is 600-700 ℃.
6. The preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas according to claim 5, characterized in that: when the rod biomass and the shell biomass are carbonized, the introduced inert atmosphere introduction amount is 400-600 mL/min, the carbonization time of the rod biomass is 1.5-2.5 h, and the carbonization time of the shell biomass is 1-2 h; the diameter of the biochar A particles obtained by grinding is less than 100 mu m, and the diameter of the biochar B particles obtained by grinding is less than 150 mu m.
7. The preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas according to any one of claims 2 to 6, characterized by comprising the following steps: in the second step, the waste catalyst adopts waste generated in a flue gas SCR denitration system of a coal-fired power plant, and the preparation method of the catalyst suspension comprises the following steps: crushing the catalyst, grinding the crushed catalyst until the particle diameter is less than 74 mu m, and then mixing the crushed catalyst with an EDTA aqueous solution according to a solid-to-liquid ratio of 1: (9-11) stirring and mixing.
8. The preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas according to claim 7, characterized in that: in the third step, the biochar A and the catalyst powder suspension are mixed according to the solid-to-liquid ratio of 1: (4-6) mixing, evaporating and stirring to obtain modified biochar A; the evaporation and stirring temperature is 150-250 ℃, and the time is 0.5-1.5 h;
in the fourth step, the biochar B and the modifier are mixed according to the solid-to-liquid ratio of 1: (9-11), mixing, stirring to enable the modifier to fully impregnate the biochar B, filtering, and draining to obtain modified biochar B; the modifier adopts NH 4 HCO 3 And mixing the solution, and stirring for not less than 12h.
9. The preparation method of the adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas according to any one of claims 2 to 6, characterized by comprising the following steps: the organic binder adopts PVA; in the fifth step, the mass ratio of the modified biochar A to the organic binder is (15-20): 1, and the mixing time of the modified biochar A and the organic binder is 5-30 min; the addition amount of the modified biochar B is equal to that of the modified biochar A, the diameter of the prepared particles is 1-2 mm, and the roasting temperature is 550-650 ℃.
10. The utility model provides a handle adsorbent of VOCs and dioxin in organic coating pyrolysis flue gas which characterized in that: prepared by the preparation method of any one of claims 1 to 9.
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