CN115945182B - Adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas and preparation method thereof - Google Patents
Adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas and preparation method thereof Download PDFInfo
- Publication number
- CN115945182B CN115945182B CN202211639822.5A CN202211639822A CN115945182B CN 115945182 B CN115945182 B CN 115945182B CN 202211639822 A CN202211639822 A CN 202211639822A CN 115945182 B CN115945182 B CN 115945182B
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- biochar
- biomass
- flue gas
- dioxins
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003463 adsorbent Substances 0.000 title claims abstract description 100
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 51
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 34
- 238000000576 coating method Methods 0.000 title claims abstract description 33
- 150000002013 dioxins Chemical class 0.000 title claims abstract description 33
- 239000011248 coating agent Substances 0.000 title claims abstract description 32
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003546 flue gas Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002028 Biomass Substances 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 238000010000 carbonizing Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 45
- 239000003607 modifier Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 28
- 238000003763 carbonization Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 21
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- 239000002699 waste material Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 9
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 8
- 244000105624 Arachis hypogaea Species 0.000 claims description 8
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 8
- 235000018262 Arachis monticola Nutrition 0.000 claims description 8
- 244000068988 Glycine max Species 0.000 claims description 8
- 235000010469 Glycine max Nutrition 0.000 claims description 8
- 240000007594 Oryza sativa Species 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 8
- 241000209140 Triticum Species 0.000 claims description 8
- 235000021307 Triticum Nutrition 0.000 claims description 8
- 240000008042 Zea mays Species 0.000 claims description 8
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 8
- 235000005822 corn Nutrition 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 235000020232 peanut Nutrition 0.000 claims description 8
- 235000009566 rice Nutrition 0.000 claims description 8
- 239000010902 straw Substances 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims 1
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 11
- 239000002154 agricultural waste Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002440 industrial waste Substances 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 35
- 230000000694 effects Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 9
- 238000005457 optimization Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- 230000000630 rising effect Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 240000008790 Musa x paradisiaca Species 0.000 description 4
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000001354 calcination Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an adsorbent for treating VOCs and dioxins 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: carbonizing and modifying the rod biomass and the shell biomass respectively to obtain modified biochar A and modified biochar B, and granulating and roasting the obtained modified biochar A and modified biochar B with an organic binder to obtain the adsorbent. The adsorbent prepared by the technical scheme of the invention can adsorb VOCs and dioxin in pyrolysis flue gas with organic coatings at the same time, has a longer service life, can be repeatedly used, 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, and are wide in source and low in production cost.
Description
Technical Field
The invention belongs to the technical field of gas purification in an organic coating pyrolysis process, and particularly relates to an adsorbent for treating VOCs and dioxins in organic coating pyrolysis smoke and a preparation method thereof.
Background
With the gradual exhaustion of nonferrous metal mineral resources, copper resources in China are seriously short, secondary copper resources are effectively supplemented by recycling, the waste electronic grade copper material is taken as a typical secondary nonferrous metal resource, and the pyrolysis technology is a main recycling mode, but because the surface of the waste electronic grade copper material is provided with a layer of organic coating, the waste electronic grade copper material can be produced in the pyrolysis processVOCs and dioxins are produced, and the emission concentration of VOCs and dioxins often exceeds 200mg/m 3 And 5ng TEQ/m 3 Far higher than the national 30mg/m 3 And 0.5ng TEQ/m 3 At present, the serious harm of VOCs and dioxins to the ecological environment and human health is received attention, and how to effectively reduce the emission of VOCs and dioxins in organic coating pyrolysis flue gas has become a difficult problem to be solved.
In the prior art for treating VOCs and dioxins, the adsorption method is considered 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, low-cost and easily available carbon adsorption material, and has been paid attention in recent years.
Through retrieval, the technical proposal of the Chinese patent 'a preparation method of an ultra-high performance biomass-based banana peel-oriented activated carbon VOCs adsorbent and application thereof' (CN 201911293894.7) is as follows: cutting banana peel, cleaning, drying and carbonizing to obtain banana peel biochar, uniformly mixing the banana peel biochar with KOH according to a certain mass ratio, activating at a 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 a short service life, and the adsorption effect is seriously reduced after the adsorbent is continuously adsorbed for 2 to 3 hours, so that the adsorbent cannot be continuously used. If the adsorbent is used for enterprises, the adsorbent needs to be replaced frequently, and the adsorbent can only adsorb VOCs and cannot adsorb VOCs and dioxin at the same time.
Therefore, development of a durable adsorbent for reduction of VOCs and dioxins in organic coating pyrolysis processes is of great importance.
Disclosure of Invention
1. Problems to be solved
The invention aims to solve the problem of short service life of the traditional biochar adsorbent, and provides an adsorbent for treating VOCs and dioxin in organic coating pyrolysis flue gas and a preparation method thereof. The adsorbent disclosed by the invention can be used for simultaneously adsorbing VOCs and dioxins in pyrolysis smoke of an organic coating, has a longer service life, and is simple in preparation process, low in cost and good in economic benefit.
2. Technical proposal
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 dioxins in organic coating pyrolysis flue gas, disclosed by the invention, the rod biomass and the shell biomass are carbonized and modified respectively to obtain the modified biochar A and the modified biochar B, and then the modified biochar A and the modified biochar B are granulated and roasted by matching with an organic binder to obtain the adsorbent, and the adsorbent can adsorb VOCs and dioxins in the organic coating pyrolysis flue gas at the same time and has a longer service life compared with the conventional biochar adsorbent.
Specifically, the preparation of the adsorbent of the invention comprises the following steps:
step one, biomass pretreatment and preparation of biochar A and biochar B;
(1) Treatment of biomass in the stems: mixing and crushing the collected rod biomass according to a certain mass ratio to a proper size, and drying at a certain temperature;
(2) Shell biomass treatment: mixing and crushing the collected shell biomass according to a certain mass ratio to a proper size, and drying at a certain temperature;
(3) Preparing biochar A: carbonizing the dried biomass rod under a certain temperature range and inert atmosphere to obtain biochar A, and grinding the biochar A into a certain particle size;
(4) Preparing biochar B: carbonizing the dried biomass rod under a certain temperature range and inert atmosphere to obtain biochar B, and grinding the biochar B into a certain particle size.
Preparing catalyst powder suspension;
crushing the waste catalyst, grinding the crushed waste catalyst into a certain particle size, and stirring and mixing the crushed waste catalyst with EDTA water solution according to a certain proportion to obtain catalyst powder suspension.
Step three, preparing modified biochar A;
and 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, preparing modified biochar B
And mixing the biochar B and the modifier according to a certain proportion, fully stirring for a certain time to fully impregnate the biochar B with the modifier, and filtering and draining water to obtain the modified biochar B.
Step five, granulating and roasting;
(1) Mixing the modified biochar A and the organic binder according to a certain proportion, adding water to prepare particles with a certain size, and adding the modified biochar B with a certain mass to continuously granulate.
(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 stalk biomass is selected from one or more of corn stalks, straw stalks and wheat stalks; the shell biomass is one or a combination of more of peanut shells, soybean shells and rice chaff shells.
As a further optimization of the invention, when the biomass of the stalk class is selected from the combination of corn stalk, straw stalk and wheat stalk, the mass of the corn stalk, straw stalk and wheat stalk is 1: (2-4): (2-4); when the shell biomass is selected from peanut shells, soybean shells and rice chaff shells, the mass ratio of the peanut shells to the soybean shells to the rice chaff shells is 1:1: (2-4).
As further optimization of the invention, in the first step, the length of the crushed rod biomass and the crushed shell biomass is less than or equal to 1cm. Drying the crushed biomass rod and shell at 100 ℃ for not less than 2 hours.
As a further optimization of the invention, both the biomass of the stems and the biomass of the hulls are in N 2 Charring under atmosphere, N 2 The ventilation amount of the catalyst is 400-600 mL/min, and the carbonization temperature is 600-700 ℃. Meanwhile, the carbonization time of the biomass of the stems is 1.5-2.5 h, and the carbonization time of the biomass of the shells is 1-2 h.
As a further optimization of the invention, in the first step, the particle diameter of the ground biochar A is smaller than 100 mu m, and the particle diameter of the ground biochar B is smaller than 150 mu m.
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 waste catalyst comprises the following components in percentage by mass: tiO (titanium dioxide) 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% and the balance of unavoidable impurities.
The particle diameter of the catalyst after grinding is smaller than 74 mu m. The concentration of the aqueous EDTA solution used in the preparation of the catalyst suspension was 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), EDTA (ethylenediamine tetraacetic acid) adopts an analytically pure reagent, the purity of the substance is more than 99%, and the balance is unavoidable impurities; .
As a further optimization of the invention, in the step three, the solid-to-liquid ratio of the biochar a to the catalyst powder suspension is 1: (4-6), the evaporating and 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 NH of 0.3mol/L 4 HCO 3 A solution; the solid-liquid ratio of the biochar B to the modifier is 1: (9-11), stirring for not less than 12 hours to ensure that the modifier fully impregnates the biochar B.
In the fifth step, the organic binder is PVA (polyvinyl alcohol), and the analytically pure reagent is adopted, so that the purity of the substance is more than 99%, and the balance is unavoidable 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 charcoal A. The diameter of the finally prepared particles is 1-2 mm, the roasting temperature is 550-650 ℃, the actual roasting is carried out at the heating rate of 10 ℃/min along with the furnace, and the temperature is kept for 15-25 min after the roasting temperature is reached.
The adsorbent is obtained by adopting the preparation method, has a spherical structure, is composed of a framework with the biochar A with the catalyst attached to the surface, and is also attached with a layer of modified biochar B, the adsorbent with the structure can improve the adsorption effect, is particularly suitable for simultaneously adsorbing VOCs and dioxin in organic coating pyrolysis flue gas, can be reused, and remarkably prolongs the service life of the adsorbent compared with the existing modified biochar adsorbent.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) The adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas can adsorb VOCs and dioxins in organic coating pyrolysis flue gas simultaneously, and has a longer service life.
(2) According to the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas, waste generated in a flue gas SCR denitration system of a coal-fired power plant is adopted as a catalyst, so that the waste catalyst can be consumed, and the treatment problem 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 dioxins in organic coating pyrolysis flue gas, disclosed by the invention, the preparation process is optimally designed, and particularly the component proportion and the process treatment parameters are controlled, so that the adsorption efficiency and the service life of the adsorbent are effectively improved, and the durable adsorbent is produced, is used for reducing the emission of VOCs and dioxins in the organic coating pyrolysis process, reduces the frequency of replacing the adsorbent by enterprises, and reduces the production cost for the enterprises.
Drawings
FIG. 1 is a schematic illustration of a process flow for preparing an adsorbent of the present invention;
FIG. 2 is a schematic structural view of the adsorbent of the present invention;
in the figure:
1. biochar a; 2. a catalyst; 3. modified 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 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 merely illustrative and not limiting of the invention's features and characteristics in order to set forth the best mode of carrying out the invention and to sufficiently enable those skilled in the art to practice the invention. It will be understood that various modifications and changes may be made without departing from the scope of the invention as defined by the appended claims. The detailed description and drawings are to be regarded in an illustrative rather than a restrictive sense, and if any such modifications and variations are desired to be included within the scope of the invention described herein. Furthermore, the background art is intended to illustrate the status and meaning of the development of the technology and is not intended to limit 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The biomass rods and the biomass shells are 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 (titanium dioxide) 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% and the balance of unavoidable impurities.
The EDTA (ethylenediamine tetraacetic acid) adopts an analytically pure reagent, the purity of the substance is more than 99%, and the balance is unavoidable impurities.
The organic binder (PVA, polyvinyl alcohol) adopts an analytically pure reagent, the purity of the substance is more than 99%, and the balance is unavoidable impurities.
The invention is further described below in connection with specific embodiments.
Example 1
As shown in fig. 1 and 2, the preparation method of the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas in this embodiment specifically includes the following steps:
step one, biochar preparation
(1) Treatment of biomass in the stems: collecting three types of biomass of corn stalks, straw stalks and wheat stalks, mixing the three types of biomass according to the mass ratio of 1:2:2, putting the mixture into a crusher for crushing, wherein the length of the crushed mixture is less than or equal to 1cm, and then drying the crushed mixture at the temperature of 100 ℃ for 3 hours;
(2) Shell biomass treatment: collecting three shell biomass of peanut shells, soybean shells and rice chaff shells, mixing the three shell biomass according to the mass ratio of 1:1:2, putting the mixture into a crusher for crushing, wherein the length of the crushed mixture is less than or equal to 1cm, and drying the crushed shell biomass at the temperature of 100 ℃ for 3 hours;
(3) Preparing biochar A: 500g of dried biomass rod is put into a tube furnace and is treated by N 2 Heating to 650 ℃ with a furnace at a heating rate of 10 ℃/min under the atmosphere to carry out high-temperature carbonization, wherein the carbonization time is 2h, and controlling N 2 The flow rate is 500mL/min, after carbonization is completed, the prepared biochar A is taken out after the tube furnace is cooled to room temperature, and is ground into particles with the diameter smaller than 100 mu m by adopting a ball mill;
(4) Preparing biochar B: 500g of dried shell biomass is taken and put into a tube furnace, and the biomass is put into N 2 High-temperature carbonization is carried out in the atmosphere at the heating rate of 10 ℃/min along with the heating of the furnace to 650 ℃, the carbonization time is 1.5h, and N is controlled 2 The flow rate is 500mL/min, after carbonization is completed, the prepared biochar B is taken out after the tube furnace is cooled to room temperature, and the biochar B is ground into particles with the diameter smaller than 150 mu m by adopting a ball mill.
Step two, preparation of catalyst powder suspension
(1) Performing primary crushing treatment on the waste catalyst by adopting a jaw crusher, and then performing crushing and grinding treatment on the waste catalyst to obtain particles with diameters smaller than 74 mu m;
(2) Preparing 0.2mol/mL EDTA aqueous solution at 80 ℃, mixing the waste catalyst powder with the EDTA aqueous solution according to a solid-to-liquid ratio of 1:10, and stirring for 30min to obtain catalyst powder suspension.
Step three, preparation of modified biochar A
Mixing the biochar A powder with the catalyst powder suspension for 20min according to the solid-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 out the mixture to obtain the modified biochar A.
Step four, preparing modified biochar B
The modifier (NH with concentration of 0.3 mol/L) was added at a solid-to-liquid ratio of 1:10 4 HCO 3 Solution) and the biochar B are placed into a beaker, stirred on a magnetic stirrer for 24 hours, so that the modifier fully impregnates the biochar B, and then the modified biochar B is obtained after filtration and water draining.
Step five, granulating and roasting
(1) Mixing modified biochar A and organic binder (PVA, polyvinyl alcohol) according to a mass ratio of 20:1 for 10min by adopting a mixer, adding water into the mixture to prepare particles with the diameter of 0.7-1.4 mm by using a disc granulator, adding modified biochar B with the same mass as the modified biochar A for continuous granulation, and finally preparing particles with the mass of 1-2 mm, wherein the mass of water added in the whole granulation process is 7.5-8.0% of the total mass of the modified biochar A, the modified biochar B and the organic binder;
(2) The prepared granules are put into a tube furnace and are put into N 2 Roasting in atmosphere at the temperature rising rate of 10 ℃/min along with the temperature rising of the furnace to 600 ℃, keeping the temperature constant for 20min after the temperature rises to 600 ℃, and roasting process N 2 The inlet amount of the catalyst is 500mL/min, and after roasting, the particles are taken out after the tube furnace is cooled to room temperature, so as to obtain the adsorbent.
The structural schematic diagram of the obtained adsorbent is shown in fig. 2, the adsorbent is spherical, the biochar A obtained by carbonizing the rod 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 the shell biomass, compared with the structure of the traditional adsorbent such as activated carbon, the structure is fluffier, the gaps are more, and compared with the powdery adsorbent, the spherical adsorbent can effectively reduce the transmission resistance of VOCs and dioxins in flue gas, can promote the diffusion and transportation of the VOCs and the dioxins, and has better adsorption effect on the VOCs and the dioxins.
The specific surface area and adsorption effect of the obtained adsorbent sample were detected, the specific surface area of the adsorbent was first detected by a specific surface area analyzer, the detection results are shown in Table 1, 200g of the adsorbent was then placed in an adsorption apparatus, and the adsorbent was continuously introduced from an inlet at a concentration of 283.16mg/m 3 And a concentration of 5.3ng TEQ/m 3 And the concentration of VOCs and dioxin in the outlet of the adsorption device is detected by 3010MINIFID portable total hydrocarbon analyzer and high-resolution magnetic mass spectrometry system, and the adsorption time of the adsorbent is recorded, and the result is shown in Table 1.
Comparative example 1
The adsorbent of this comparative example was prepared in substantially the same manner as in example 1, except that: and in the fourth step, no modifier is added. The specific surface area and adsorption effect of the prepared product were measured by the measuring method in example 1, and the results are shown in Table 1.
Comparative example 2
The adsorbent of this comparative example was prepared in substantially the same manner as in example 1, except that: EDTA was not added in step two. The specific surface area and adsorption effect of the prepared product were measured by the measuring method in example 1, and the results are shown in Table 1.
Comparative example 3
The adsorbent of this comparative example was prepared in substantially the same manner 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 adsorption effect of the prepared product were measured by the measuring method in example 1, and the results are shown in Table 1.
Comparative example 4
The adsorbent of this comparative example was prepared in substantially the same manner 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 1:13. The specific surface area and adsorption effect of the prepared product were measured by the measuring method in example 1, and the results are shown in Table 1.
Comparative example 5
The adsorbent of this comparative example was prepared in substantially the same manner 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 adsorption effect of the prepared product were measured by the measuring method in example 1, and the results are shown in Table 1.
TABLE 1 adsorption efficiency and service Life of adsorbents obtained in example 1 and comparative examples 1 to 5
By analysing the index of table 1, the following conclusions can be drawn:
(1) Comparative example 1 compared with example 1, no modifier was added in step four, the specific surface area of the adsorbent was reduced by 396.08m 2 Per gram, the concentration of VOCs after adsorption is increased by 36.93mg/m 3 The dioxin concentration after adsorption is increased by 0.75ng TEQ/m 3 The service life is reduced by 4 hours;
(2) Comparative example 2 compared with example 1, no EDTA was added in step two, the specific surface area of the adsorbent was reduced by 16.69m 2 Per gram, the concentration of VOCs after adsorption is increased by 14.81mg/m 3 The concentration of dioxin after adsorption is increased by 3.76ng TEQ/m 3 The service life is reduced by 10 hours;
(3) Comparative example 3 compared with example 1, no EDTA was added in step two and no modifier was added in step four, the specific surface area of the adsorbent was reduced by 402.56m 2 Per g, the concentration of VOCs after adsorption is increased by 88.32mg/m 3 The dioxin concentration after adsorption is increased by 4.15ng TEQ/m 3 The service life is reduced by 13 hours;
(4) Comparative example 4 compared with example 1, when biochar B was mixed with the modifier, the addition amount of the modifier was too high, and the specific surface area of the adsorbent was reduced by 341.87m 2 Per gram, the concentration of VOCs after adsorption increases by 41.78mg/m 3 The concentration of dioxin after adsorption is increased by 4.65ng TEQ/m 3 The service life is reduced by 11 hours;
(5) Comparative example 5 compared with example 1, when biochar B was mixed with the modifier, the amount of the modifier added was too low, and the specific surface area of the adsorbent was reduced by 449.09m 2 Per gram, 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/m3, and the service life is reduced by 10 hours;
applicants' studies have found that modifiers and EDTA are extremely important for improving the adsorption efficiency and service life of the adsorbent. Modifying biochar B with modifier can increase specific surface area and porosity of adsorbent in proper range, due to CO generation caused by thermal decomposition of modifier 2 、H 2 O and NH 3 ，CO 2 And H 2 O attacks the surface and interior of the adsorbent, thereby improving the specific surface area and pore structure of the adsorbent, and NH 3 The nitrogen-containing functional groups can be formed 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 biochar, so that the joint adsorption of the VOCs and the dioxin is improved.
The applicant proves through a large number of experiments that the modification effect is best when the biochar B and the modifier are mixed according to the solid-to-liquid ratio of 1:9-1:11. 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 adsorbent framework is damaged, the pore structure is deteriorated, and the adsorption performance is obviously reduced; when the addition amount of the modifier is too low, incomplete modification is caused, and CO generated by thermal decomposition of the modifier is generated 2 、H 2 O and NH 3 Less CO is caused 2 And H 2 The corrosion degree of O on the adsorbent is insufficient, pores can only be formed on the surface of the adsorbent, and NH 3 Nitrogen-containing formed on the adsorbent surfaceFewer functional groups result in a lower adsorption performance of the adsorbent.
In addition, through utilizing EDTA aqueous solution to prepare catalyst powder suspension and the subsequent preparation process of modified biochar A, not only can the catalyst resume 60-70% activity, but also can effectively attach the catalyst on the surface of biochar A, form modified biochar A, finally exist in the adsorbent, the catalyst can take place catalytic oxidation reaction with the dioxin that the adsorbent surface adsorbed, make the adsorbent can adsorb the while reaction in the adsorption process, prevent the dioxin from enriching on the adsorbent surface, thereby further strengthened the adsorption effect of adsorbent, improved the life of adsorbent.
In addition, the structure of the adsorbent prepared by the method is shown in a figure 2, the adsorbent is spherical, the biochar A obtained by carbonizing the rod biomass is used as a skeleton of the adsorbent, the modified biochar B obtained by carbonizing and modifying the shell biomass has a supporting effect, the structure is more fluffy than that of the traditional adsorbent such as activated carbon, the gaps are more, and compared with the powdery adsorbent, the spherical adsorbent can effectively reduce the transmission resistance of VOCs and dioxin in flue gas, can promote the diffusion and transportation of the VOCs and the dioxin, and has better adsorption effect on the VOCs and the dioxin.
Example 2
As shown in fig. 1 and 2, the specific preparation process of the adsorbent for treating VOCs and dioxins in pyrolysis flue gas with an organic coating in this embodiment is basically the same as that in embodiment 1, and is different from embodiment 1 in that:
(1) The biomass of the stems adopts corn stalks, the biomass of the shells adopts peanut shells, and the biomass of the stems and the biomass of the shells are dried at 100 ℃ for 2 hours;
(2) The carbonization temperature of the biomass is 600 ℃, and the carbonization time is 2.5 hours; the carbonization temperature of the shell biomass is 700 ℃, and the carbonization time is 1h; n during carbonization 2 The flow rate is 450mL/min;
(3) When preparing the catalyst suspension, mixing the catalyst and the EDTA water solution according to a 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 1:11, and the stirring time is 16h;
(6) Mixing the modified biochar A and an organic binder according to the mass ratio of 18:1; the mixing time is 5-30 min;
(7) During the calcination of the granules, the granules are sintered in the presence of N 2 Roasting in the atmosphere at the temperature rising rate of 10 ℃/min along with the temperature rising of the furnace to 550 ℃, and keeping the temperature constant for 25min after the temperature rises to 550 ℃.
The specific surface area and adsorption effect of the obtained product were measured by the measuring method of example 1, and the measuring result was substantially the same as that of example 1.
Example 3
As shown in fig. 1 and 2, the specific preparation process of the adsorbent for treating VOCs and dioxins in pyrolysis flue gas with an organic coating in this embodiment is basically the same as that in embodiment 1, and is different from embodiment 1 in that:
(1) The straw stalk is adopted as the stalk biomass, the rice chaff husk is adopted as the shell biomass, and the stalk biomass and the shell biomass are both dried at 100 ℃ for not less than 2 hours;
(2) The carbonization temperature of the biomass of the stems 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; n during carbonization 2 The flow rate is 400mL/min;
(3) When preparing the catalyst suspension, mixing the catalyst and EDTA water solution according to a solid-to-liquid ratio of 1:9.6;
(4) The solid-to-liquid ratio between the biochar A and the catalyst powder suspension is 1:5.5, 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 1:9.5, and the stirring time is 20h;
(6) Mixing the modified biochar A and an organic binder according to the mass ratio of 15:1; the mixing time is 5-30 min;
(7) During the calcination of the granules, the granules are sintered in the presence of N 2 Baking in atmosphere at a heating rate of 10deg.C/min with furnace heating to 650deg.CBurning, and keeping the temperature at 650 ℃ for 20min.
The specific surface area and adsorption effect of the obtained product were measured by the measuring method of example 1, and the result was substantially the same as in example 1.
Example 4
As shown in fig. 1 and 2, the specific preparation process of the adsorbent for treating VOCs and dioxins in pyrolysis flue gas with an organic coating in this embodiment is basically the same as that in embodiment 1, and is different from embodiment 1 in that:
(1) The biomass of the stalk adopts wheat stalk, the biomass of the shell adopts soybean shell, and the biomass of the stalk and the biomass of the shell are both dried at 100 ℃ for 2.5h;
(2) The carbonization temperature of the biomass of the stems is 700 ℃ and the carbonization time is 1.5h; the carbonization temperature of the shell biomass is 600 ℃, and the carbonization time is 2 hours; n during carbonization 2 The flow rate is 600mL/min;
(3) When preparing catalyst suspension, mixing the catalyst and EDTA water solution according to a solid-to-liquid ratio of 1:11;
(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 the mass ratio of 20:1; the mixing time is 5-30 min;
(7) During the calcination of the granules, the granules are sintered in the presence of N 2 Roasting in the atmosphere at the temperature rising rate of 10 ℃/min along with the temperature rising of the furnace to 620 ℃, and keeping the temperature at the constant temperature of 620 ℃ for 15min.
The specific surface area and adsorption effect of the obtained product were measured by the measuring method of example 1, and the result was substantially the same as in example 1.
The invention has been described in detail hereinabove with reference to specific exemplary embodiments thereof. It will be understood that various modifications and changes may be made without departing from the scope of the invention as defined by the appended claims. The detailed description and drawings are to be regarded in an illustrative rather than a restrictive sense, and if any such modifications and variations are desired to be included within the scope of the invention described herein. Furthermore, the background art is intended to illustrate the status and meaning of the development of the technology and is not intended to limit the invention or the application and field of application of the invention.
More specifically, although exemplary embodiments of the present invention have been described herein, the present invention is not limited to these embodiments, but includes any and all embodiments that have been modified, omitted, e.g., combined, adapted, and/or substituted between the various embodiments, as would be recognized by those skilled in the art in light of the foregoing detailed description. The limitations in the claims are to be interpreted broadly based on 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, definitions, will control. Where a rate, pressure, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range bounded by a list of upper and lower preferred 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 1-50 should be understood to include any number, combination of numbers, or subranges of numbers 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, as well as all fractional values between the integers described above, such as 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. Regarding sub-ranges, specifically considered are "nested sub-ranges" that extend from any end point within the range. For example, the nested subranges of exemplary ranges 1-50 can 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 (8)
1. A preparation method of an adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas is characterized by comprising the following steps: carbonizing and modifying the rod biomass and the shell biomass respectively to obtain modified biochar A and modified biochar B, and granulating and roasting the obtained modified biochar A and modified biochar B with an organic binder to obtain an adsorbent;
the method specifically comprises the following steps:
step one, biomass pretreatment and preparation of biochar A and biochar B;
preparing catalyst powder suspension;
the catalyst adopts 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 (titanium dioxide) 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%, the balance of unavoidable impurities;
step three, preparing modified biochar A;
the solid-to-liquid ratio of biochar A to catalyst powder suspension is 1: (4-6) mixing, and evaporating and stirring to obtain modified biochar A; the evaporation stirring temperature is 150-250 ℃ and the time is 0.5-1.5 h;
step four, preparing modified biochar B;
the solid-liquid ratio of the biochar B to the modifier is 1: (9-11) mixing, stirring to fully impregnate the modified biochar B, filtering and draining to obtain the modified biochar B; the modifier adopts NH 4 HCO 3 The solution is mixed and stirred for not less than 12 hours;
step five, granulating and roasting: firstly, mixing modified biochar A with an organic binder, adding water to prepare particles, then adding modified biochar B to continuously granulate, and finally roasting the prepared particles to obtain the adsorbent.
2. The method for preparing the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas according to claim 1, which is characterized in that: in the first step, the first step is to perform,
the preparation method of the biochar A comprises the following steps: crushing and drying the rod biomass, and carbonizing and grinding the dried rod biomass to obtain biochar A; the stalk biomass is one or a combination of more 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 selected from one or more of peanut shells, soybean shells and rice chaff shells.
3. The method for preparing the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas according to claim 2, which is characterized in that: when the stalk biomass is selected from the combination of corn stalk, straw stalk and wheat stalk, the mass of the corn stalk, straw stalk and wheat stalk is 1: (2-4): (2-4);
when the shell biomass is selected from peanut shells, soybean shells and rice chaff shells, the mass ratio of the peanut shells to the soybean shells to the rice chaff shells is 1:1: (2-4).
4. The method for preparing the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas according to claim 2, which is characterized in that: the length of the crushed rod biomass and the crushed shell biomass is less than or equal to 1cm, the drying temperature is 100 ℃, and the drying time is not less than 2 hours; the stem biomass and the shell biomass are carbonized under inert protective atmosphere, and the carbonization temperature is 600-700 ℃.
5. The method for preparing the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas, as set forth in claim 4, is characterized in that: when the biomass rod and the biomass shell are carbonized, the introduced inert atmosphere has the introduced amount of 400-600 mL/min, the carbonization time of the biomass rod is 1.5-2.5 h, and the carbonization time of the biomass shell is 1-2 h; the particle diameter of the ground biochar A is smaller than 100 mu m, and the particle diameter of the ground biochar B is smaller than 150 mu m.
6. The method for preparing the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas according to any one of claims 2 to 5, which is characterized in that: in the second step, the catalyst suspension is prepared as follows: crushing and grinding the catalyst until the particle diameter is smaller than 74 mu m, and then mixing the catalyst with EDTA water solution according to a solid-liquid ratio of 1: (9-11) stirring and mixing.
7. The method for preparing the adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas according to any one of claims 2 to 5, which is characterized in that: 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 ℃.
8. An adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas, which is characterized in that: prepared by the preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211639822.5A CN115945182B (en) | 2022-12-20 | 2022-12-20 | Adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211639822.5A CN115945182B (en) | 2022-12-20 | 2022-12-20 | Adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115945182A CN115945182A (en) | 2023-04-11 |
| CN115945182B true CN115945182B (en) | 2024-04-16 |
Family
ID=87289035
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211639822.5A Active CN115945182B (en) | 2022-12-20 | 2022-12-20 | Adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115945182B (en) |
Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10249158A (en) * | 1997-03-18 | 1998-09-22 | Hitachi Zosen Corp | Device for removing harmful material in waste incineration gas |
| EP1025894A1 (en) * | 2000-02-21 | 2000-08-09 | Rheinbraun Aktiengesellschaft | Method and adsorbent for dry exhaust gas purification |
| JP2001113125A (en) * | 1999-10-15 | 2001-04-24 | Mitsubishi Heavy Ind Ltd | Device and method for treating waste gas |
| WO2002048032A2 (en) * | 2000-12-11 | 2002-06-20 | United States Filter Corporation | Activated carbon for odor control and method for making same |
| JP2006263587A (en) * | 2005-03-24 | 2006-10-05 | Mizusawa Shoji Kk | Method for treatment of combustion exhaust-gas |
| CN101785969A (en) * | 2010-03-03 | 2010-07-28 | 王向明 | Method of flue gas purification and system thereof |
| CN103657638A (en) * | 2013-12-31 | 2014-03-26 | 重庆远达催化剂制造有限公司 | Integral dioxin removing catalyst and preparation method thereof |
| CN104307303A (en) * | 2014-10-22 | 2015-01-28 | 成都彩星科技实业有限公司 | Volatile pollutant treatment method of solvent type coating preparation workshop |
| CN104474836A (en) * | 2014-10-22 | 2015-04-01 | 成都彩星科技实业有限公司 | A treating method for volatile pollutants of solvent-type paint |
| CN105236405A (en) * | 2015-09-11 | 2016-01-13 | 中国石油大学(华东) | Convenient biomass-based nitrogen-doped active carbon preparation method |
| CN107282003A (en) * | 2017-07-04 | 2017-10-24 | 北京林业大学 | A kind of preparation method of the efficient modified activated carbon for removing formaldehyde in air |
| CN108163853A (en) * | 2018-02-07 | 2018-06-15 | 华中科技大学 | Method, product and its application of high nitrogenous porous carbon material are prepared using biomass |
| CN108745282A (en) * | 2018-05-25 | 2018-11-06 | 武汉钢铁有限公司 | A kind of flue gas desulfurization and denitrification pressed active carbon and preparation method thereof based on metallurgical solid waste |
| CN109569519A (en) * | 2018-10-22 | 2019-04-05 | 江汉大学 | The method for preparing active sludge carbon base formaldehyde adsorbent using municipal sludge |
| CN110745825A (en) * | 2019-12-16 | 2020-02-04 | 江苏科技大学 | Preparation method of high-performance biomass-based shaddock peel oriented activated carbon VOCs adsorbent |
| CN110813240A (en) * | 2019-12-16 | 2020-02-21 | 江苏科技大学 | Preparation method and application of ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent |
| CN111603888A (en) * | 2020-06-22 | 2020-09-01 | 中冶节能环保有限责任公司 | System for utilize modified active carbon alternating temperature to inhale desorption and purify sintering flue gas |
| CN111821945A (en) * | 2020-07-07 | 2020-10-27 | 美埃(中国)环境科技股份有限公司 | Active carbon modification method for removing sulfur dioxide and hydrogen sulfide gas in air |
| CN112044397A (en) * | 2020-09-07 | 2020-12-08 | 福州职业技术学院 | Modified biochar-based adsorbent with core-shell structure and preparation method thereof |
| CN112642496A (en) * | 2020-11-18 | 2021-04-13 | 苏州西热节能环保技术有限公司 | Regenerated catalyst capable of realizing synchronous denitration and VOCs and CO removal and preparation method thereof |
| CN112725616A (en) * | 2020-12-29 | 2021-04-30 | 安徽工业大学 | Method for reducing emission of sintering flue gas pollutants by using pellets containing SCR waste catalyst |
| CN112779418A (en) * | 2020-12-29 | 2021-05-11 | 安徽工业大学 | Preparation method of pellet containing SCR (Selective catalytic reduction) waste catalyst |
| CN112897503A (en) * | 2021-01-25 | 2021-06-04 | 上海应用技术大学 | Acid modification preparation method of biomass charcoal material with toluene adsorption effect |
| CN113620410A (en) * | 2021-08-09 | 2021-11-09 | 佛山市南海区苏科大环境研究院 | Braided fabric framework biomembrane material for targeted wastewater treatment and preparation method thereof |
| CN114797837A (en) * | 2022-03-20 | 2022-07-29 | 浙江大学 | Catalyst capable of removing secondary pollutants in flue gas by concerted catalysis under low-temperature condition |
| CN115301057A (en) * | 2022-09-14 | 2022-11-08 | 河南龙成煤高效技术应用有限公司 | Flue gas desulfurization and denitrification equipment and method |
-
2022
- 2022-12-20 CN CN202211639822.5A patent/CN115945182B/en active Active
Patent Citations (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10249158A (en) * | 1997-03-18 | 1998-09-22 | Hitachi Zosen Corp | Device for removing harmful material in waste incineration gas |
| JP2001113125A (en) * | 1999-10-15 | 2001-04-24 | Mitsubishi Heavy Ind Ltd | Device and method for treating waste gas |
| EP1025894A1 (en) * | 2000-02-21 | 2000-08-09 | Rheinbraun Aktiengesellschaft | Method and adsorbent for dry exhaust gas purification |
| WO2002048032A2 (en) * | 2000-12-11 | 2002-06-20 | United States Filter Corporation | Activated carbon for odor control and method for making same |
| JP2006263587A (en) * | 2005-03-24 | 2006-10-05 | Mizusawa Shoji Kk | Method for treatment of combustion exhaust-gas |
| CN101785969A (en) * | 2010-03-03 | 2010-07-28 | 王向明 | Method of flue gas purification and system thereof |
| CN103657638A (en) * | 2013-12-31 | 2014-03-26 | 重庆远达催化剂制造有限公司 | Integral dioxin removing catalyst and preparation method thereof |
| CN104307303A (en) * | 2014-10-22 | 2015-01-28 | 成都彩星科技实业有限公司 | Volatile pollutant treatment method of solvent type coating preparation workshop |
| CN104474836A (en) * | 2014-10-22 | 2015-04-01 | 成都彩星科技实业有限公司 | A treating method for volatile pollutants of solvent-type paint |
| CN105236405A (en) * | 2015-09-11 | 2016-01-13 | 中国石油大学(华东) | Convenient biomass-based nitrogen-doped active carbon preparation method |
| CN107282003A (en) * | 2017-07-04 | 2017-10-24 | 北京林业大学 | A kind of preparation method of the efficient modified activated carbon for removing formaldehyde in air |
| CN108163853A (en) * | 2018-02-07 | 2018-06-15 | 华中科技大学 | Method, product and its application of high nitrogenous porous carbon material are prepared using biomass |
| CN108745282A (en) * | 2018-05-25 | 2018-11-06 | 武汉钢铁有限公司 | A kind of flue gas desulfurization and denitrification pressed active carbon and preparation method thereof based on metallurgical solid waste |
| CN109569519A (en) * | 2018-10-22 | 2019-04-05 | 江汉大学 | The method for preparing active sludge carbon base formaldehyde adsorbent using municipal sludge |
| CN110745825A (en) * | 2019-12-16 | 2020-02-04 | 江苏科技大学 | Preparation method of high-performance biomass-based shaddock peel oriented activated carbon VOCs adsorbent |
| CN110813240A (en) * | 2019-12-16 | 2020-02-21 | 江苏科技大学 | Preparation method and application of ultrahigh-performance biomass-based banana peel oriented activated carbon VOCs adsorbent |
| CN111603888A (en) * | 2020-06-22 | 2020-09-01 | 中冶节能环保有限责任公司 | System for utilize modified active carbon alternating temperature to inhale desorption and purify sintering flue gas |
| CN111821945A (en) * | 2020-07-07 | 2020-10-27 | 美埃(中国)环境科技股份有限公司 | Active carbon modification method for removing sulfur dioxide and hydrogen sulfide gas in air |
| CN112044397A (en) * | 2020-09-07 | 2020-12-08 | 福州职业技术学院 | Modified biochar-based adsorbent with core-shell structure and preparation method thereof |
| CN112642496A (en) * | 2020-11-18 | 2021-04-13 | 苏州西热节能环保技术有限公司 | Regenerated catalyst capable of realizing synchronous denitration and VOCs and CO removal and preparation method thereof |
| CN112725616A (en) * | 2020-12-29 | 2021-04-30 | 安徽工业大学 | Method for reducing emission of sintering flue gas pollutants by using pellets containing SCR waste catalyst |
| CN112779418A (en) * | 2020-12-29 | 2021-05-11 | 安徽工业大学 | Preparation method of pellet containing SCR (Selective catalytic reduction) waste catalyst |
| CN112897503A (en) * | 2021-01-25 | 2021-06-04 | 上海应用技术大学 | Acid modification preparation method of biomass charcoal material with toluene adsorption effect |
| CN113620410A (en) * | 2021-08-09 | 2021-11-09 | 佛山市南海区苏科大环境研究院 | Braided fabric framework biomembrane material for targeted wastewater treatment and preparation method thereof |
| CN114797837A (en) * | 2022-03-20 | 2022-07-29 | 浙江大学 | Catalyst capable of removing secondary pollutants in flue gas by concerted catalysis under low-temperature condition |
| CN115301057A (en) * | 2022-09-14 | 2022-11-08 | 河南龙成煤高效技术应用有限公司 | Flue gas desulfurization and denitrification equipment and method |
Non-Patent Citations (1)
| Title |
|---|
| Enhanced catalytic activity for simultaneous removal of PCDD/Fs and NO over carbon nanotubes modified MnOx‑CeO2/TiO2 catalystat low temperature;Qiulin Wang;Waste Disposal & Sustainable Energy;20210222;第3卷;第63-71页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115945182A (en) | 2023-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106362690A (en) | Magnetic biochar adsorbing material and preparation method thereof | |
| CN110064367B (en) | Biomass-based activated carbon microsphere and preparation method and application thereof | |
| CN110523373B (en) | Preparation method of oil shale semi-coke adsorbent | |
| CN108311104A (en) | A kind of charcoal preparation method of synchronous pyrolysis load iron | |
| CN110813239A (en) | Preparation method of biochar-loaded lanthanum-doped iron oxide | |
| CN111701568A (en) | Eggshell straw biochar composite microsphere phosphorus removal adsorbent with high adsorption performance and preparation method and application thereof | |
| CN107867688A (en) | A kind of preparation method for the shaddock peel activated carbon for being used for purification of air and sewage disposal | |
| CN109225135A (en) | A kind of modification biological charcoal adsorbent material and preparation method thereof with to Pb in water body2+Removal application | |
| CN111408373B (en) | 3D catalyst for catalytic degradation of organic pollutants and preparation and application thereof | |
| CN109173999A (en) | A kind of preparation method and applications of biology carbon microspheres | |
| CN110142026A (en) | The alkali lignin base charcoal efficient absorption material of cadmium, preparation method and applications in adsorbed water body | |
| CN113003572A (en) | Method for preparing activated carbon from sludge and activated carbon | |
| CN114259984A (en) | Alkali modified charcoal-loaded zero-valent iron composite material and preparation method and application thereof | |
| Gao et al. | Preparation of spiramycin fermentation residue derived biochar for effective adsorption of spiramycin from wastewater | |
| CN107555414B (en) | Garden waste biomass charcoal and preparation method and application thereof | |
| CN113856630B (en) | Straw carbon magnesium lanthanum LDH nano phosphorus adsorption material and preparation method and application thereof | |
| CN104445188B (en) | A kind of solution is utilized to embathe the method that deliming prepares rice husk matrix activated carbon | |
| CN115945182B (en) | Adsorbent for treating VOCs and dioxins in organic coating pyrolysis flue gas and preparation method thereof | |
| CN112121762A (en) | Preparation method of biomass charcoal-based filter material loaded with nano zero-valent iron | |
| CN107226470A (en) | Adjustable macropore biological activated carbon of adhesive-free hole and its preparation method and application | |
| CN107233888A (en) | Biomass prepares gas combustion multifunction catalyst and preparation method | |
| CN101816928A (en) | Method for preparing coke-powder-based carbon adsorbing material by using waste coke powder | |
| CN115974076A (en) | Preparation method and application of hydrothermal nitrogen-doped cork-based activated carbon | |
| TWI772919B (en) | Method of fabricating bio-based activated carbon having high specific area with solid digestate used as precursor | |
| CN114618434A (en) | Method for removing Cd in water body2+Preparation method and application of biochar loaded zero-valent iron material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |