CN117772220A - Porous carbon/ceramic composite functional material for removing site peculiar smell organic pollutants - Google Patents
Porous carbon/ceramic composite functional material for removing site peculiar smell organic pollutants Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 67
- 239000000463 material Substances 0.000 title claims abstract description 65
- 239000000919 ceramic Substances 0.000 title claims abstract description 57
- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002910 solid waste Substances 0.000 claims abstract description 23
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 19
- 239000000440 bentonite Substances 0.000 claims abstract description 19
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 19
- 239000002028 Biomass Substances 0.000 claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 15
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 15
- 239000011572 manganese Substances 0.000 claims abstract description 15
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000007598 dipping method Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 31
- 239000007789 gas Substances 0.000 claims description 26
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 16
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 8
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 claims description 8
- 150000001216 Samarium Chemical class 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 150000002696 manganese Chemical class 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 240000008042 Zea mays Species 0.000 claims description 5
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 5
- 235000005822 corn Nutrition 0.000 claims description 5
- 239000008188 pellet Substances 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012876 carrier material Substances 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 241000209140 Triticum Species 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- 235000013399 edible fruits Nutrition 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- 229940099596 manganese sulfate Drugs 0.000 claims description 2
- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- JPDBEEUPLFWHAJ-UHFFFAOYSA-K samarium(3+);triacetate Chemical compound [Sm+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JPDBEEUPLFWHAJ-UHFFFAOYSA-K 0.000 claims description 2
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 claims description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 2
- 230000001953 sensory effect Effects 0.000 claims 1
- 238000000746 purification Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
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- 230000003197 catalytic effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
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- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
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- 239000008204 material by function Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- WKXHZKXPFJNBIY-UHFFFAOYSA-N titanium tungsten vanadium Chemical compound [Ti][W][V] WKXHZKXPFJNBIY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 238000009412 basement excavation Methods 0.000 description 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention relates to a porous carbon/ceramic composite functional material for removing site peculiar smell organic pollutants. The porous carbon/ceramic composite functional material loaded with manganese and samarium double active components and having higher mechanical strength is prepared by taking industrial solid waste iron tailings, bentonite and agricultural and forestry solid waste source biomass as raw materials through the processes of mixing, granulating, dipping, drying and roasting. The functional material can efficiently remove organic pollutants with site odor at 300-350 ℃, and the purified tail gas has no odor.
Description
Technical field:
the invention belongs to the technical field of field odor organic pollutant treatment, and particularly relates to a porous carbon/ceramic composite functional material for removing field odor organic pollutants, which is used for purifying field odor organic pollutants.
The background technology is as follows:
typical peculiar smell pollution sites generated in industries such as chemical industry, pharmaceutical manufacturing, landfill and the like have environmental hazards due to peculiar smell organic pollutants dissipated in the process of excavation and restoration, and can generate olfactory stimulation at a low concentration (ppb), so that the purification technology of the peculiar smell organic pollutants becomes a research hot spot. At present, peculiar smell organic pollutants dissipated in the field can be collected through a awning, and are conveyed into a purification reactor under negative pressure to be removed, and the key of affecting the removal effect is a purification functional material. Recent researches show that the adsorption and catalytic oxidation functions of the material are coupled, and the material has better purifying effect on organic pollutants with peculiar smell.
The key of the adsorption/catalytic oxidation functional material is the assembly design based on a carrier material with broad-spectrum adsorption performance and an active component of the organic pollutant with high-efficiency catalytic oxidation peculiar smell. Research reports that natural clay such as bentonite and industrial solid waste such as iron tailings can be used as cheap raw materials to prepare a carrier with certain mechanical strength and load active components, and the functional material for catalyzing and oxidizing peculiar smell organic pollutants can be obtained, but the purification efficiency is poor at the temperature lower than 350 ℃, and the purified tail gas still has peculiar smell. Research shows that the carbon-based functional material has larger specific surface area and rich pore canal structure, can improve the purification efficiency of the peculiar smell organic pollutants through adsorption, but the single carbon-based material only has adsorption function and has poor purification performance of the peculiar smell gas.
According to the invention, industrial solid waste iron tailings, bentonite and agricultural and forestry solid waste source biomass are used as raw materials, and manganese and samarium active components are loaded, so that the novel porous carbon/ceramic composite functional material with high mechanical strength, which can purify site odor organic pollutants through adsorption/catalysis, can effectively solve the problem of purified odor, and related researches are not reported.
The invention comprises the following steps:
the invention aims to provide a porous carbon/ceramic composite functional material for removing organic pollutants with peculiar smell in a field. The porous carbon/ceramic composite functional material is prepared by taking industrial solid waste iron tailings as a carrier material, bentonite as a binder, agricultural and forestry solid waste source biomass as a pore-forming agent, carrying manganese/samarium double-active components by an impregnation method after granulation and pore-forming, and drying and baking, wherein the compressive strength is 420-500N, the wear resistance is 90-99%, and the site odor organic pollutants can be removed efficiently at 300-350 ℃.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a porous carbon/ceramic composite functional material for removing site peculiar smell organic pollutants is prepared by taking industrial solid waste iron tailings as a carrier material, bentonite as a binder, agricultural and forestry solid waste source biomass as a pore-forming agent, granulating and roasting in an air atmosphere to obtain a porous carbon/ceramic carrier, immersing porous carbon/Tao Zaiti in a mixed solution containing manganese salt and samarium salt, loading manganese/samarium double-active components by an immersion method, and drying and roasting to obtain the porous carbon/ceramic composite functional material.
The roasting temperature in the air atmosphere is 500-950 ℃, preferably 600-800 ℃, and the roasting time in the air atmosphere is 30-90 min.
The roasting temperature in the drying roasting is 300-500 ℃, preferably 300-450 ℃ and the roasting atmosphere is N 2 。
The porous carbon/ceramic composite functional material comprises the following raw materials in percentage by mass: 30-60 wt% of iron tailings, 30-60 wt% of bentonite, 5-15 wt% of agriculture and forestry solid waste source biomass, and 5-20 wt% of total manganese/samarium loading, wherein the molar ratio of manganese/samarium is 1:1-9:1, and the total manganese/samarium loading refers to the mass of manganese and samarium accounting for the total mass of the functional material.
The agriculture and forestry solid waste source biomass is one or more of corn stalk, wheat stalk, rice stalk, bagasse, cotton stalk, coconut shell, fruit shell and the like; the manganese salt is at least one of manganese chloride, manganese nitrate, manganese sulfate, potassium permanganate and the like; the samarium salt is at least one of samarium chloride, samarium nitrate, samarium sulfate, samarium acetate and the like.
The specific preparation process of the porous carbon/ceramic composite functional material for removing the site peculiar smell organic pollutants comprises the following steps:
step 1, mixing: crushing iron tailings, bentonite and agriculture and forestry solid waste source biomass, sieving with a 80-120 mesh sieve, weighing the iron tailings, the bentonite and the agriculture and forestry solid waste source biomass, uniformly mixing, adding water, uniformly stirring at a speed of 60-120 r/min, and stirring for 2-5 min; the addition amount of the water is 5-20wt% of the total mass of the iron tailings, bentonite and the agriculture and forestry solid waste source biomass;
step 2, granulating: granulating the material obtained in the step 1 in a disc granulator at a rotating speed of 30-80 r/min to obtain balls with a diameter of 5-30 mm; after the pellets are dried, heating to 500-950 ℃ at a speed of 5-10 ℃/min, and roasting for 30-90 min in air atmosphere to obtain porous carbon/Tao Zaiti;
step 3, dipping: soaking the porous carbon/Tao Zaiti obtained in the step 2 in a mixed solution of manganese salt and samarium salt for 30-90 min;
step 4, drying: drying the sample obtained in the step 3 at 60-100 ℃ to constant weight;
step 5, roasting: heating to 300-500 ℃ at a speed of 5-10 ℃/min under nitrogen atmosphere, and roasting for 1-3 h to obtain the porous carbon/ceramic composite functional material.
The application conditions of the porous carbon/ceramic composite functional material for removing the site peculiar smell organic pollutants are as follows: collecting the field peculiar smell gas through a awning, conveying the field peculiar smell gas into a purifying reactor under negative pressure to remove peculiar smell organic pollutants, wherein the reaction temperature is 50-350 ℃, the concentration of the peculiar smell organic pollutants is 50-500 ppm, and O is the same as that of the organic pollutants 2 The content is 5-30%, the mass airspeed is 3600-72000 mL (g) -1 ·h -1 )。
The organic pollutants of the site peculiar smell comprise hydrocarbons and volatile organic matters containing sulfur, nitrogen, chlorine and oxygen elements, and are preferably toluene, methyl mercaptan, methylamine, trichloroethylene and the like.
Compared with the prior art, the invention has the beneficial effects that:
compared with commercial vanadium-tungsten-titanium catalyst, the porous carbon/ceramic functional material prepared by the invention has higher purification efficiency, and the purified tail gas has no peculiar smell, so that the peculiar smell can be effectively prevented from penetrating (see table 1).
TABLE 1 comparison of porous carbon/ceramic functional Material Performance index results
Experimental conditions: reaction temperature is 350 ℃, toluene concentration of a representative compound of peculiar smell organic pollutants in hydrocarbon sites is 60ppm, O 2 10% by volume and 36000mL (g) -1 ·h -1 )。
The balls in the granulation process of the invention need to be roasted for a period of time in air atmosphere, so that porous carbon/ceramic carriers with higher strength can be obtained, and then the valence state of active components on the carriers is effectively regulated by soaking roasting, so that the functional materials achieve excellent peculiar smell purifying effect, and the tail gas has no peculiar smell according to the measurement of the three-point comparison type bad smell bag method (GB/T14675-93).
The specific embodiment is as follows:
for a better understanding of the present invention, the present invention will be further described with reference to the following embodiments, but the examples are not intended to limit the scope of the present invention.
Example 1
(1) The preparation method of the porous carbon/ceramic composite functional material (simply referred to as porous carbon/ceramic composite functional material) for removing the site peculiar smell organic pollutants comprises the following steps:
step 1, mixing: crushing iron tailings, bentonite and corn stalks, sieving with an 80-mesh sieve, weighing 40wt% of iron tailings, 50wt% of bentonite and 10wt% of corn stalks, uniformly mixing, adding 15wt% of water, and stirring at a speed of 100r/min for 3min;
step 2, granulating: granulating the material obtained in the step 1 in a disc granulator at a rotating speed of 50r/min to obtain balls with a diameter of 5 mm; after the pellets are dried, heating to 800 ℃ at a speed of 10 ℃/min, and roasting for 60min in an air atmosphere to obtain porous carbon/Tao Zaiti;
step 3, dipping: impregnating the porous carbon/Tao Zaiti obtained in the step 2 into a manganese/samarium solution with a molar ratio of 3:1, manganese nitrate and samarium nitrate mixed solution for 60min, wherein the total manganese/samarium loading is 15wt%;
step 4, drying: drying the sample prepared in the step 3 to constant weight at 80 ℃;
step 5, roasting: heating to 400 ℃ at the speed of 10 ℃/min, and roasting for 1h in nitrogen atmosphere to obtain the porous carbon/ceramic composite functional material.
(2) Purification performance of porous carbon/ceramic composite functional material on organic pollutants with site peculiar smell
The experimental conditions for evaluating the toluene performance of the porous carbon/ceramic composite functional material for purifying the organic pollutant representative of the peculiar smell of the hydrocarbon field are as follows: collecting off-flavor gas in the field through a awning, conveying the off-flavor gas into a purifying reactor under negative pressure, wherein the reaction temperature is 50-350 ℃, the toluene concentration is 60ppm, and O is 2 The volume content was 10% and the mass space velocity was 36000mL (g) -1 ·h -1 ). Detecting the toluene content in the tail gas after the reaction by adopting gas chromatography, and calculating the toluene removal rate; the compressive strength and the abrasion resistance of the porous carbon/ceramic composite functional material were measured by a compressive strength tester and an abrasion resistance tester, respectively, and the results are shown in table 2. The toluene removal rate is more than 99% at 300-350 ℃, and the purified tail gas is found to have no peculiar smell according to the measurement of the three-point comparison type bad smell bag method (GB/T14675-93).
TABLE 2 removal rate of toluene and compression and wear resistance values of porous carbon/ceramic composite functional material
Example 2
(1) The porous carbon/ceramic composite functional material for removing the site peculiar smell organic pollutants in the embodiment is the same as the embodiment 1 in raw materials and preparation process, and is characterized in that the mixing conditions in the embodiment are as follows: weighing 35wt% of iron tailings, 45wt% of bentonite and 20wt% of corn straw, and uniformly mixing.
(2) Purification performance of porous carbon/ceramic composite functional material on organic pollutants with site peculiar smell
The experimental conditions for evaluating the performance of the porous carbon/ceramic composite functional material for purifying the methyl mercaptan which is a representative compound of peculiar smell organic pollutants in a sulfur-containing field are as follows: site odorCollecting the body by awning, delivering the body into a purifying reactor under negative pressure, reacting at 50-350 ℃ and methyl mercaptan concentration of 60ppm and O 2 The volume content was 10% and the mass space velocity was 36000mL (g) -1 ·h -1 ). Detecting the methyl mercaptan content in the tail gas after the reaction by adopting gas chromatography, and calculating the methyl mercaptan removal rate; the compressive strength and the abrasion resistance of the porous carbon/ceramic composite functional material were measured by a compressive strength tester and an abrasion resistance tester, respectively, and the results are shown in table 3. The removal rate of methyl mercaptan is more than 99 percent at the temperature of 300-350 ℃, and the tail gas is found to have no peculiar smell according to the measurement of the three-point comparison type bad smell bag method (GB/T14675-93).
TABLE 3 removal rate and compression and wear resistance values of porous carbon/ceramic composite functional Material for methyl mercaptan
Example 3
(1) The porous carbon/ceramic composite functional material for removing the site peculiar smell organic pollutants in the embodiment has the raw materials and the preparation process which are the same as those in the embodiment 1, and the granulation conditions in the embodiment are as follows: after the pellets are dried, the temperature is increased to 600 ℃ at the speed of 10 ℃/min, and the pellets are roasted for 40min in air atmosphere, so that the porous carbon/ceramic carrier is obtained.
(2) Purification performance of porous carbon/ceramic composite functional material on organic pollutants with site peculiar smell
The experimental conditions for evaluating the methylamine performance of the porous carbon/ceramic composite functional material for purifying the organic pollutant representative compound of the peculiar smell of the nitrogenous site are set as follows: collecting off-flavor gas in the field through a awning, conveying the off-flavor gas into a purifying reactor under negative pressure, wherein the reaction temperature is 50-350 ℃, the methylamine concentration is 60ppm, and O 2 The volume content was 10% and the mass space velocity was 36000mL (g) -1 ·h -1 ). Detecting the content of methylamine in the tail gas after the reaction by adopting gas chromatography, and calculating the methylamine removal rate; the compressive strength and the abrasion resistance of the porous carbon/ceramic composite functional material were measured by a compressive strength tester and an abrasion resistance tester, respectively, and the results are shown in table 4. The removal rate of methylamine is more than 99 percent under the condition of 300-350 ℃, according to the following three proceduresThe point comparison type bad smell bag method (GB/T14675-93) detects that the tail gas has no peculiar smell.
TABLE 4 removal rate and compression and wear resistance values of porous carbon/ceramic composite functional material for methylamine
Example 4
(1) The porous carbon/ceramic composite functional material for removing the site peculiar smell organic pollutants in the embodiment has the raw materials and the preparation process which are the same as those in the embodiment 1, and the impregnation conditions in the embodiment are as follows: porous carbon/Tao Zaiti was impregnated with manganese/samarium at a molar ratio of 9:1, and the total manganese/samarium loading is 10wt percent in the mixed solution of manganese nitrate and samarium nitrate for 40 min.
(2) Purification performance of porous carbon/ceramic composite functional material on organic pollutants with site peculiar smell
The experimental conditions for evaluating the performance of the porous carbon/ceramic composite functional material for purifying trichloroethylene which is a representative compound of peculiar smell organic pollutants in a chlorine-containing site are as follows: collecting off-flavor gas in the field through a awning, conveying the off-flavor gas into a purifying reactor under negative pressure, wherein the reaction temperature is 50-350 ℃, the concentration of trichloroethylene is 60ppm, and the concentration of O is 60ppm 2 The volume content was 10% and the mass space velocity was 36000mL (g) -1 ·h -1 ). Detecting the content of trichloroethylene in the tail gas after the reaction by adopting gas chromatography, and calculating the removal rate of the trichloroethylene; the compressive strength and the abrasion resistance of the porous carbon/ceramic composite functional material were measured by a compressive strength tester and an abrasion resistance tester, respectively, and the results are shown in table 5. The trichloroethylene removal rate is more than 99% at 350 ℃, and the tail gas has no peculiar smell according to the measurement of three-point comparison type bad smell bag method (GB/T14675-93).
TABLE 5 removal rate and compression and wear resistance values of porous carbon/ceramic composite functional Material for trichloroethylene
Comparative example 1
Only the iron tailings, the agriculture and forestry solid waste source biomass, the manganese salt and the samarium salt described in the example 1 of the present application are added, and the treatment is performed according to the mixing, granulating, drying, impregnating and roasting conditions of the example 1.
Comparative example 2
Only the iron tailings, the solid waste source biomass of agriculture and forestry and bentonite are added, and the treatment is carried out according to the mixing, granulating, drying, impregnating and roasting conditions of the example 1.
Comparative example 3
Only attapulgite was added instead of bentonite, and the treatment was carried out according to the mixing, granulating, drying, impregnating, and roasting conditions of example 1.
Comparative example 4
Only one commercial granular activated carbon was used.
Comparative example 5
Only one commercial vanadium tungsten titanium catalyst was used.
The functional materials of comparative examples 1 to 5 obtained above were all tested under the site odor organic contaminant purification test conditions of example 1, the toluene removal rate results are shown in table 7, and the strength values are shown in table 8. The odor intensity is measured according to the three-point comparison type odor bag method (GB/T14675-93) at 300-350 ℃, and the odor can be smelled in the tail gas purified by the comparison material, so that the tail gas purified by the porous carbon/ceramic composite functional material has no odor.
Table 7 comparative examples and comparative table of example 1 para-toluene removal rate
Table 8 comparison of the intensity values of comparative example and example 1
The comparison of the results of the table shows that the porous carbon/ceramic composite functional material prepared by the invention has excellent removal rate of organic pollutants with site odor, especially the removal rate of the organic pollutants with site odor is more than 99% under the condition of 350 ℃, and the purified tail gas has no odor and has higher mechanical strength.
The invention is applicable to the prior art where it is not described.
Claims (7)
1. A porous carbon/ceramic composite functional material for removing site peculiar smell organic pollutants is characterized in that: the method comprises the steps of taking industrial solid waste iron tailings as a carrier material, taking bentonite as a binder, taking agriculture and forestry solid waste source biomass as a pore-forming agent, granulating and roasting in an air atmosphere to obtain a porous carbon/ceramic carrier, soaking porous carbon/Tao Zaiti in a mixed solution containing manganese salt and samarium salt, loading manganese/samarium double-active components by an soaking method, and drying and roasting to obtain the porous carbon/ceramic composite functional material;
the porous carbon/ceramic composite functional material comprises the following raw materials in percentage by mass: 30-60 wt% of iron tailings, 30-60 wt% of bentonite, 5-15 wt% of agriculture and forestry solid waste source biomass, and 5-20 wt% of total manganese/samarium loading, wherein the molar ratio of manganese/samarium is 1:1-9:1;
the roasting temperature in the air atmosphere is 500-950 ℃, and the roasting time in the air atmosphere is 30-90 min.
2. The porous carbon/ceramic composite functional material for removing organic pollutants of site odor according to claim 1, wherein: the agriculture and forestry solid waste source biomass is one or more of corn stalk, wheat stalk, rice stalk, bagasse, cotton stalk, coconut shell or fruit shell;
the manganese salt is at least one of manganese chloride, manganese nitrate, manganese sulfate or potassium permanganate;
the samarium salt is at least one of samarium chloride, samarium nitrate, samarium sulfate or samarium acetate.
3. The porous carbon/ceramic composite functional material for removing organic pollutants with peculiar smell of field as set forth in claim 1, wherein: the roasting temperature in the drying roasting is 300-500 ℃ and the roasting atmosphere is N 2 。
4. The porous carbon/ceramic composite functional material for removing organic pollutants of site odor according to claim 1, wherein: the preparation method of the porous carbon/ceramic composite functional material comprises the following specific steps:
step 1, mixing: crushing iron tailings, bentonite and agriculture and forestry solid waste source biomass, sieving with a 80-120 mesh sieve, weighing the iron tailings, bentonite and agriculture and forestry solid waste source biomass, uniformly mixing, adding water, and uniformly stirring at a speed of 60-120 r/min; the addition amount of the water is 5-20wt% of the total mass of the iron tailings, bentonite and the agriculture and forestry solid waste source biomass;
step 2, granulating: granulating the material obtained in the step 1 in a disc granulator at a rotating speed of 30-80 r/min to obtain balls with a diameter of 5-30 mm; after the pellets are dried, heating to 500-950 ℃ at a speed of 5-10 ℃/min, and roasting for 30-90 min in air atmosphere to obtain porous carbon/Tao Zaiti;
step 3, dipping: soaking the porous carbon/Tao Zaiti obtained in the step 2 in a mixed solution of manganese salt and samarium salt for 30-90 min;
step 4, drying: drying the sample obtained in the step 3 at 60-100 ℃ to constant weight;
step 5, roasting: heating to 300-500 ℃ at a speed of 5-10 ℃/min under nitrogen atmosphere, and roasting for 1-3 h to obtain the porous carbon/ceramic composite functional material.
5. The porous carbon/ceramic composite functional material for removing organic pollutants of site odor according to claim 1, wherein: t for purifying site odor organic pollutants by using porous carbon/ceramic composite functional material 90％ The temperature is less than 350 ℃, the compressive strength is 420-500N, and the wear resistance is 90-97%.
6. The porous carbon/ceramic composite functional material for removing organic pollutants of site odor according to claim 1, wherein: the porous carbon/ceramic compositeThe functional material is used for removing the peculiar smell organic pollutants in the field, the peculiar smell gas in the field is collected by a awning and conveyed into a purifying reactor under negative pressure to remove the peculiar smell organic pollutants, the reaction temperature is 50-350 ℃, the concentration of the peculiar smell organic pollutants is 50-500 ppm, and the concentration of O is 50-500 ppm 2 The volume content is 5-30%, the mass airspeed is 3600-72000 mL (g) -1 ·h -1 )；
After the reaction is finished, the tail gas odor intensity is evaluated according to the sensory description of three-point comparison type odor bag method, and the purified tail gas has no odor under the condition of 300-350 ℃.
7. The porous carbon/ceramic composite functional material for removing organic pollutants with site odor of claim 6, wherein: the organic pollutant with peculiar smell in the field is at least one of toluene, methyl mercaptan, methylamine or trichloroethylene.
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| CN202410049081.8A CN117772220A (en) | 2024-01-12 | 2024-01-12 | Porous carbon/ceramic composite functional material for removing site peculiar smell organic pollutants |
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