CN113941349A - Bone carbon supported catalyst and preparation method and application thereof - Google Patents
Bone carbon supported catalyst and preparation method and application thereof Download PDFInfo
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- CN113941349A CN113941349A CN202111238370.5A CN202111238370A CN113941349A CN 113941349 A CN113941349 A CN 113941349A CN 202111238370 A CN202111238370 A CN 202111238370A CN 113941349 A CN113941349 A CN 113941349A
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- bone carbon
- bone
- supported catalyst
- manganese
- formaldehyde
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 158
- 239000003054 catalyst Substances 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 189
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 162
- 238000001354 calcination Methods 0.000 claims abstract description 49
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 36
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- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 33
- 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 29
- 239000008367 deionised water Substances 0.000 claims description 23
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000005639 Lauric acid Substances 0.000 claims description 2
- 229940071125 manganese acetate Drugs 0.000 claims description 2
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- 235000007079 manganese sulphate Nutrition 0.000 claims description 2
- 239000011702 manganese sulphate Substances 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 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
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 43
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 34
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- 238000007254 oxidation reaction Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 10
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 9
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
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- Chemical Kinetics & Catalysis (AREA)
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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
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- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention belongs to the technical field of waste gas treatment, and relates to a bone carbon supported catalyst, and a preparation method and application thereof. The preparation method of the bone carbon supported catalyst comprises the following steps: heating the animal bone to 500-550 ℃ at a heating rate of 2-10 ℃/min under the air condition, and calcining for 6h to form bone carbon; then adopting equal-volume impregnation according to the bone carbon: impregnation liquid =1 g: 1.2ml, soaking the bone carbon in a manganese salt/saturated fatty acid solution, stirring for 10-15 min, aging for 4-8 h, drying, heating to 350-400 ℃ at a speed of 2 ℃/min, and calcining for 4-5h to obtain the bone carbon supported catalyst. The bone carbon sample can realize the combined efficient removal of toluene and formaldehyde at 250-310 ℃, has excellent continuous activity and water resistance, can be recycled for multiple times through transient thermal regeneration, and has no safety risk of heat storage and fire.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, relates to purification treatment of VOCs, and particularly relates to a bone carbon supported catalyst for efficiently and jointly removing toluene and formaldehyde, and a preparation method and application thereof.
Background
In recent years, China obtains remarkable results in the aspect of controlling organized waste gas emission, and unorganized waste gas collection and treatment in industrial production become the next important treatment target. In the production process of industries such as furniture production and processing, indoor building material production and the like, a large amount of VOCs exist in workshop air due to the use of solvents and adhesives, and the problem of air pollution to the workshop working environment and the surrounding area environment is not ignored. Among them, toluene and formaldehyde are two types of VOC in which important control is required, whether from the health of plant workers or from the environmental standpoint. The reports show that toluene and formaldehyde are two types of VOC which have the greatest threat to the health of furniture production and storage related personnel, the respiratory function, the neural function and the immune function of a human body can be reduced after long-term exposure, and related chronic diseases and carcinogenesis can be possibly caused; meanwhile, contamination by VOCs is largely related to their formation of secondary organic aerosols in the ambient atmosphere, with toluene and formaldehyde having proven to be the most potential secondary organic aerosol-forming precursors and radical donors. Therefore, effective reduction of the unorganized emissions of toluene and formaldehyde in the related industries has become a very urgent issue.
At present, most of industries mostly adopt single or combined processes of adsorption, photocatalysis or adsorption combined light and thermal catalysis for removing tail gas containing toluene and/or formaldehyde, and the treatment scheme has low pollutant outlet concentration and good safety, but inevitably causes the problems of complex treatment system, huge equipment investment, huge operation and maintenance cost and the like. In order to simplify the system, reduce the cost and improve the efficiency of the thermal catalysis process, the pollution tail gas is treated independently by utilizing thermal catalysis, and the method becomes a breakthrough. Among them, the supported catalyst is favored because it can use a relatively inexpensive carrier, and the use of noble metals and transition metals is greatly reduced. The activated carbon and activated coke supported catalyst is popularized because the cost performance is higher than that of artificial carrier supported catalysts such as molecular sieves, synthetic hydroxyapatite, synthetic montmorillonite and the like. However, in practical application, because the working temperature window of the combined removal of toluene and formaldehyde by the thermal catalytic oxidation method is generally higher than 180 ℃, the risk of heat accumulation and fire ignition is easy to occur when the thermal catalytic oxidation is carried out by using the carbon-based carrier catalyst, and the safety of human life and property can be endangered.
The prior art CN 110841588B discloses that an animal bone without organic matters is calcined for 3-5 hours at 550-650 ℃; as shown in the attached drawing, the crystal form of the XRD pattern is obviously stronger; the crystal form of the hydroxyapatite of the main body is relatively large, which is not beneficial to fully doping the manganese oxide into the hydroxyapatite crystal lattice and promoting the oxygen species activity of the hydroxyapatite; and the method is not beneficial to the dispersion of manganese oxide on the bone carbon carrier, so that the method is not suitable for preparing the bone carbon supported catalyst. The prior art CN 107096492A discloses that animal bones are used as raw materials, and are calcined for 1-2 hours at 600-700 ℃ after being crushed; similarly, the hydroxyapatite crystal form of the bone carbon main body calcined in the patent CN 107096492 a is relatively larger, and therefore, the bone carbon main body is not suitable for the preparation of the bone carbon supported catalyst by the method of the present invention.
Disclosure of Invention
The invention aims to provide a bone carbon supported catalyst for efficiently and jointly removing toluene and formaldehyde, a preparation method and application thereof, which can reduce the temperature window for removing toluene and formaldehyde and simultaneously has good water resistance.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a bone carbon supported catalyst, comprising:
s1, washing the animal bones with deionized water, and drying at 100-110 ℃ for 10-12 h;
s2, heating the dried animal bone in the S1 to 500-550 ℃ at the speed of 2-10 ℃/min under the air condition, and calcining for 5-6 hours to form bone carbon;
s3, grinding, sieving and washing bone carbon, and drying at 100-110 ℃ for 10-12 h; then adopting equal-volume impregnation according to the bone carbon: 1g of impregnation liquid: 1.2ml, soaking the bone carbon in a manganese salt/saturated fatty acid solution, stirring for 10-15 min, aging for 4-8 h, drying, heating to 350-400 ℃ at a speed of 2 ℃/min, and calcining for 4-5h to obtain the bone carbon supported catalyst.
Preferably, the animal bone is degummed defatted bovine bone.
On one hand, the industrial by-product of the degummed and degreased beef bone is stable in components, and can be produced in batches like activated coke. On the other hand, compared with other bones, the ox bone becomes a carrier after calcination and then is loaded with active metal to prepare the catalyst with higher mechanical strength, and the loss caused by friction and insufficient strength among catalyst particles in the transportation process can be avoided.
Preferably, the washing comprises: adding 50-200ml of deionized water into 50 g of animal bones, uniformly mixing, and repeatedly cleaning until the water body is transparent.
Preferably, the temperature rising rate in the step S2 is 2-4 ℃/min.
Different heating rates can affect the residual carbon content of the bone carbon carrier, and the higher the heating rate, the easier the organic matters on the surfaces of the bovine bone particles are carbonized to form carbon shells, so that the residual carbon content is higher. Too much residual carbon masks the sites of hydroxyapatite and forms hydrophobic regions on the surface, which are detrimental to the loading of the active metal. Therefore, the prepared catalyst has different catalytic efficiency, and the catalyst prepared at the temperature rise speed of 2-4 ℃/min has the best catalytic efficiency.
Preferably, the calcination temperature in the step S2 is 530-550 ℃.
The calcination temperature is preferably chosen to keep the crystal lattice of the hydroxyapatite from excessively increasing and to ensure that the carbon content is low, and the calcination temperature is preferably 530 ℃ and 550 ℃.
Preferably, the sieving in the step S3 is to sieve the ground bone carbon with 40-100 meshes.
If the bone charcoal is too large in mesh, the bone charcoal is easy to get out of the air, and if the bone charcoal is too small, the bone charcoal is easy to block.
Preferably, the manganese salt is one or more of manganese sulfate, manganese acetate or manganese nitrate.
Further preferably, the manganese salt is manganese nitrate.
Manganese nitrate at nitrate as an anionic ligand is most beneficial for the dispersion of cations on the hydroxyapatite surface, as it is most easily inserted into the hydroxyapatite lattice; and the decomposition temperature of the manganese nitrate is low, so that the calcination temperature can be low, the weak crystal form of the manganese oxide can be maintained, and the dispersity of the manganese oxide is improved. Thus, the catalyst obtained is most effective.
Preferably, the saturated fatty acid is oleic acid or lauric acid.
Further preferably, the saturated fatty acid is oleic acid.
Oleic acid is cheap and has the best matching effect with manganese nitrate.
Preferably, the manganese salt/saturated fatty acid solution is a manganese nitrate/oleic acid solution.
Preferably, the preparation method of the manganese nitrate/oleic acid solution comprises the following steps: weighing 2.34g of 50% manganese nitrate solution and 1.85g of oleic acid, adding deionized water to a final volume of 3.6ml, and magnetically stirring for 5-8 min to form a uniform emulsion.
Preferably, the calcination temperature in step S4 is 400 ℃.
The calcination at 400 ℃ can ensure that the generated manganese oxide has low crystal lattice while ensuring that the manganese nitrate is fully decomposed.
The invention also claims a bone carbon supported catalyst prepared by the preparation method.
Preferably, the bone carbon supported catalyst takes Mn metal oxide as an active component, bone carbon particles as a carrier and oleic acid as an auxiliary agent, and the diameter of the bone carbon particles is 40-60 meshes.
Preferably, the crystal grain size of the bone carbon supported catalyst is 10-15 nm.
Calcining the bone carbon carrier at 530-550 ℃, wherein the hydroxyapatite in the cattle bone after calcination is in a medium crystal form, and the grain size is 10-15 nm. The weaker crystal form is more beneficial to the interaction of hydroxyapatite and transition metal ions. The invention also claims the application of the bone carbon supported catalyst in the joint removal of toluene and formaldehyde.
The invention also claims the application of the bone carbon supported catalyst in the catalytic oxidation treatment of exhaust gas.
The invention also claims a catalyst comprising a bone carbon supported catalyst.
The invention also claims the application of the catalyst in the joint removal of toluene and formaldehyde.
The invention also claims the application of the catalyst in the catalytic oxidation treatment of exhaust gas.
The invention is further explained below:
the main component of the bone carbon carrier in the method is hydroxyapatite. Calcining the bone carbon carrier at 530-550 ℃, wherein the hydroxyapatite in the cattle bone after calcination is in a medium crystal form, and the grain size is 10-15 nm. The weaker crystal form is more beneficial to the interaction of hydroxyapatite and transition metal ions. The bone carbon particles have a multi-stage pore structure with developed macropores, mesopores and micropores, so that the bone carbon particles have reasonable pore size distribution, are suitable for the growth and dispersion of active metal centers, only contain a small amount of residual high-temperature carbonized substances, and have no risk of heat storage and fire ignition. The method of the bone carbon supported catalyst is mainly realized by loading manganese oxide by an oleic acid-assisted isometric impregnation method. The manganese nitrate serving as a manganese oxide precursor can perform stronger ion exchange with hydroxyapatite in the calcining process with the aid of oleic acid, so that the dispersibility of manganese oxide species and the activity of hydroxyl oxygen in the hydroxyapatite are improved, the surface appearance of the catalyst is changed, the integral specific surface area of the catalyst is improved, and the catalytic oxidation performance of the catalyst is improved integrally. In addition, active oxygen species existing in the hydroxyapatite have a certain catalytic oxidation effect on formaldehyde and formaldehyde, and the invention further improves the integral oxidation capacity of the supported catalyst on formaldehyde and toluene by loading active manganese species on the hydroxyapatite bone carbon carrier on the basis of the catalytic oxidation effect, so that the supported catalyst is suitable for the combined removal of the toluene and the formaldehyde.
The active component Mn oxide is loaded on a bone carbon carrier with higher specific surface area and ion exchange capacity by using oleic acid as an auxiliary agent, the dispersity of the Mn oxide is improved, so that the bone carbon supported catalyst has stronger redox capacity, more adsorption sites and active oxygen are provided for the removal of toluene and formaldehyde, the removal temperature window of the toluene and formaldehyde is reduced, and meanwhile, the catalyst prepared by the process has good water resistance by testing the water resistance of the catalyst through the existence of water vapor with the volume percent of about 3.5 in simulated flue gas, wherein the water vapor value corresponds to the water vapor contained at the temperature of about 40 ℃ and the humidity of 100%. The bone carbon supported catalyst has no heat storage and fire risk, and industrial waste byproducts are used as raw materials, so that the bone carbon supported catalyst is economic and environment-friendly; the preparation method has simple process, can be realized without harsh process conditions, and is suitable for industrial large-scale popularization.
The method is used for calcining degummed and degreased beef bones at the temperature of 530-550 ℃, and comparing the influence of different heating rates on bone carbon calcination, and aims to keep the crystal size of hydroxyapatite in a microcrystalline or medium crystal form in the calcination process, remove enough organic matters, expose hydroxyapatite sites, and enable hydroxyapatite of a lower crystal form to be combined with oleic acid auxiliary energy to perform ion exchange with manganese ions to a deeper degree, so that manganese hydroxyapatite substances are generated, and the performance of a bone carbon supported catalyst is improved.
Compared with the prior art, the invention has the advantages that:
1. the available VOCs adsorbs catalysis equipment, simplifies VOCs processing system, reduces equipment running cost, does not have the heat accumulation risk of starting a fire simultaneously, improves enterprise's operational safety nature.
2. Experiments prove that the bone carbon supported catalyst prepared by the method has high catalytic activity, the high-efficiency combined removal of toluene and formaldehyde in the circulating air of a workshop can be realized at 250-310 ℃, and the removal efficiency of two kinds of VOC is higher than 90%.
3. The catalyst provided by the invention is used in a thermal catalytic oxidation process, the process operation is simple, and the used bone carbon supported catalyst can be recycled through a simple thermal regeneration process, so that the treatment cost of an enterprise is reduced.
Drawings
FIG. 1 is an XRD pattern of calcined bone carbon at two different temperatures; a is a bone carbon sample formed by calcining for 6 hours at 530-550 ℃; b is a bone carbon sample formed by calcining for 6 hours at 730-750 ℃;
FIG. 2 is the toluene removal performance of the supported catalyst prepared with bone carbon at two calcination temperatures;
FIG. 3 is the formaldehyde removal performance of supported catalysts prepared with bone carbon at two calcination temperatures;
FIG. 4 is the toluene removal performance of three different manganese oxide-loaded bone carbon supported catalysts;
FIG. 5 shows the formaldehyde removal performance of three different manganese oxide-loaded bone carbon supported catalysts;
FIG. 6 shows the toluene removal performance of three supported catalysts prepared by calcining bone carbon at 530-550 ℃ at different heating rates;
FIG. 7 shows the formaldehyde removal performance of three supported catalysts prepared by calcining bone carbon at 530-550 ℃ at different heating rates;
FIG. 8 is a thermogravimetric plot of calcined bone carbon at three different ramp rates to 530-550 ℃;
FIG. 9 shows the toluene removal performance of a supported catalyst using bone carbon, synthetic hydroxyapatite and active coke as carriers;
FIG. 10 shows the formaldehyde removal performance of a supported catalyst using bone carbon, synthetic hydroxyapatite and active coke as carriers;
FIG. 11 shows Mn-OA-Hap synthesized in comparative example 2 for 550-OA-BC and 750-OA-BC in example 1
And Mn-OA-AC four catalysts synthesized in comparative example 4, which have gradient water resistance tests of 3 vol.%, 6 vol.% and 9 vol.% for toluene removal, respectively;
FIG. 12 is a 3 vol.%, 6 vol.%, 9 vol.% gradient water resistance test for formaldehyde removal for the four catalysts 550-OA-BC, 750-OA-BC from example 1, Mn-OA-Hap from comparative example 2, and Mn-OA-AC from comparative example 4, respectively;
FIG. 13 is a run-on-regeneration test for toluene removal for the four catalysts 550-OA-BC, 750-OA-BC of example 1, Mn-OA-Hap synthesized in comparative example 2, and Mn-OA-AC synthesized in comparative example 4;
FIG. 14 is a test of the persistence-regeneration of formaldehyde removal for the four catalysts 550-OA-BC, 750-OA-BC of example 1, Mn-OA-Hap synthesized in comparative example 2, and Mn-OA-AC synthesized in comparative example 4;
figure 15 is a prior art bone carbon XRD pattern.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments.
Example 1
The main active component of the bone carbon supported catalyst is Mn metal oxide, the carrier is bone carbon calcined at 530-550 ℃ and 730-750 ℃ respectively, the calcining atmosphere is air, and the mass percentage of the Mn metal oxide in the bone carbon supported catalyst accounts for 12-16% of the bone carbon supported catalyst.
The preparation method of the bone carbon supported catalyst comprises the following steps of oleic acid assisted equivalent-volume impregnation, wherein the oleic acid: 1mol of manganese nitrate, and the preparation process comprises the following steps:
s1, repeatedly washing 10g of degummed and degreased beef bones by using deionized water to remove surface impurities, and then placing the degummed and degreased beef bones in an oven to be heated and dried for 12 hours at the temperature of 100-110 ℃;
s2, respectively heating the dried degummed and degreased beef bones at the speed of 2 ℃/min under the air condition to 530-550 ℃ and 730-750 ℃ and calcining for 6 hours to obtain two kinds of bone carbon; respectively grinding and screening the bone carbon by 40-60 meshes, and repeatedly washing the bone carbon by using deionized water to remove ash on the surface and in pores of the bone carbon;
XRD analysis of the two bone carbons was performed, and the results are shown in FIG. 1. Wherein a is a bone carbon sample formed by calcining for 6 hours at 530-550 ℃; b is a bone carbon sample formed by calcining for 6 hours at 730-750 ℃.
The grain size was calculated from the XRD structure by the Debye-Scherrer formula, and the specific data are shown in table 1.
TABLE 1 grain size of calcined bone carbon at two different temperatures
According to the classification standard provided by Stotzel C, et al [3], qualitative and quantitative analysis is carried out on crystal forms of hydroxyapatite calcined at different temperatures according to figure 1 and table 1, and the crystal grain size of the hydroxyapatite in the bone carbon carrier calcined at 530-550 ℃ is 11.1nm, the hydroxyapatite is in a medium crystal form and has strong interaction performance with transition metal ions.
S3: weighing 2.34g of 50% manganese nitrate solution and 1.85g of oleic acid, adding deionized water to a final volume of 3.6mL, magnetically stirring for 5-8 min to form a uniform emulsion, adding 3g of bone carbon (solid solution ratio bone carbon: maceration extract is 1g/1.2mL) obtained in S2, rotationally stirring for 10-15 min, aging for 4-8 h, and placing in an oven for heating and drying at 100-110 ℃ for 12 h;
and S4, placing the dried sample in the S3 in a tube furnace, introducing 100mL/min of air, carrying out temperature programming at the speed of 2 ℃/min to 350-400 ℃, calcining for 4h, and cooling to room temperature to obtain the bone carbon supported catalyst, wherein the expression of the bone carbon supported catalyst is 550-OA-BC and 750-OA-BC.
Example 2
The bone carbon supported catalyst for efficiently removing toluene and formaldehyde comprises a main active component of Mn metal oxide, a carrier of bone carbon calcined at 530-550 ℃ and 730-750 ℃, wherein the calcining atmosphere is air, and the mass percentage of the Mn metal oxide in the bone carbon supported catalyst is 12-16%.
The preparation method of the bone carbon supported catalyst is equal-volume impregnation, and the preparation process comprises the following steps:
s1, repeatedly washing 10g of degummed and degreased beef bones by using deionized water to remove surface impurities, and then placing the degummed and degreased beef bones in an oven to be heated and dried for 12 hours at the temperature of 100-110 ℃;
s2, heating the dried degummed and degreased beef bones to 530-550 ℃ at a speed of 2 ℃/min under the air condition, and calcining at 730-750 ℃ for 6h to form two kinds of bone carbon; grinding and screening the bone carbon by 40-60 meshes, repeatedly washing the bone carbon by using deionized water to remove ash on the surface and in pores, and then placing the bone carbon in an oven to be heated and dried for 12 hours at the temperature of 100-110 ℃;
s3: weighing 2.34g of 50% manganese nitrate solution, adding deionized water until the final volume is 3.3mL, magnetically stirring for 2-3 min, adding 3g of bone carbon (solid solution ratio bone carbon: maceration extract is 1g/1.1mL) obtained in S2, rotationally stirring for 10-15 min, aging for 4-8 h, and placing in an oven for heating and drying at 100-110 ℃ for 12 h;
s4, placing the dried sample in the S3 in a tube furnace, introducing 100mL/min of air, carrying out temperature programming at the speed of 2 ℃/min to 350-400 ℃, calcining for 4h, and then cooling to room temperature to obtain the bone carbon supported catalysts which are 550-BC and 750-BC;
the four catalysts of examples 1 and 2 are used for jointly removing toluene and formaldehyde in circulating air of a workshop, 0.5g of 550-OA-BC, 750-OA-BC, 550-BC and 750-BC is taken as an experimental object, 500mL/min of simulated circulating gas consisting of 350ppm of toluene, 80ppm of formaldehyde, 20 vol.% of O2, 3.5 vol.% of H2O and balance gas N2 is introduced, detailed catalytic oxidation equipment can see Du, Xueyu, et al [1] and Zhang Y, et al [2], the removal efficiency of toluene and formaldehyde under the temperature window of 130-310 ℃ can be respectively shown in figures 2 and 3, and the reaction time is 180 min. As can be seen from fig. 2 and 3, in the comparison with the calcination temperature of the bone carbon support as a variable, the bone carbon supported catalyst (550-OA-BC) prepared by supporting manganese oxide on the bone carbon support calcined at 530 to 550 ℃ by an oleic acid assisted equivalent-volume impregnation method in experimental example 1 is an optimal sample for toluene and formaldehyde removal under the condition of simulated circulating gas, and it is confirmed that the calcination temperature and the preparation method of the bone carbon support in experimental example 1 can promote the removal activity of the catalyst on toluene and formaldehyde.
Meanwhile, as described above, the XRD patterns of the bone carbon in the two prior art in the background art are shown in fig. 15, which are closer to the crystal form of the bone carbon carrier calcined at 730-750 ℃ in fig. 1, and the results of fig. 2 and 3 show that the bone carbon in the prior art may not be suitable for use as the carrier of the present invention.
Example 3
The bone carbon supported catalyst for efficiently removing toluene and formaldehyde comprises a main active component of Mn metal oxide, a carrier of calcined bone carbon at 530-550 ℃, and a calcining atmosphere of air, wherein the mass percentages of the Mn metal oxide in the bone carbon supported catalyst and the mass percentages of the Mn metal oxide in the bone carbon supported catalyst are respectively 8-12% and 16-20%.
The preparation method of the bone carbon supported catalyst comprises the following steps of oleic acid assisted equivalent-volume impregnation, wherein the oleic acid: 1mol of manganese nitrate, and the preparation process comprises the following steps:
s1, repeatedly washing 10g of degummed and degreased beef bones by using deionized water to remove surface impurities, and then placing the degummed and degreased beef bones in an oven to be heated and dried for 12 hours at the temperature of 100-110 ℃;
s2, heating the dried degummed and degreased beef bones to 530-550 ℃ at the speed of 2 ℃/min under the air condition, and calcining for 6h to form bone carbon; grinding and screening the bone carbon by 40-60 meshes, and repeatedly washing the bone carbon by using deionized water to remove ash on the surface and in pores of the bone carbon;
s3: 1.64g of a 50% manganese nitrate solution and 1.30g of oleic acid are weighed out and deionized water is added to a final volume of
3.6mL (or weighing 3.04g of 50% manganese nitrate solution and 2.41g of oleic acid, adding deionized water to a final volume of 3.6 mL), magnetically stirring for 5-8 min to form uniform emulsion, adding 3g of bone carbon (solid solution ratio bone carbon: impregnating solution is 1g/1.2mL) obtained in S2, rotationally stirring for 10-15 min, aging for 4-8 h, and placing in an oven for heating and drying at 100-110 ℃ for 12 h;
s4, placing the dried sample in the S3 in a tube furnace, introducing 100mL/min of air, carrying out temperature programming at the speed of 2 ℃/min to 350-400 ℃, calcining for 4h, and then cooling to room temperature, wherein the expressions of the obtained bone carbon supported catalysts are 550-OA-BC-0.7 and 550-OA-BC-1.3 respectively;
the two catalysts and 550-OA-BC are respectively used for jointly removing toluene and formaldehyde in circulating air of a workshop, 0.5g of catalyst is taken as an experimental object, 500mL/min of simulated circulating gas consisting of 350ppm of toluene, 80ppm of formaldehyde, 20 vol.% of O2, 3.5 vol.% of H2O and balance gas N2 is introduced, detailed catalytic oxidation equipment can be seen in Du, Xueyu, et al [1] and Zhang Y, et al [2], the removal efficiency of toluene and formaldehyde can be seen in figure 4 and figure 5 respectively under the temperature window of 130-310 ℃, and the reaction time is 180 min.
As can be seen from fig. 4 and 5, in comparison with different manganese oxide loading amounts as variables, the bone carbon supported catalyst (550-OA-BC) prepared by loading manganese oxide with a mass fraction of 12-16% on a bone carbon support calcined at 530-550 ℃ by an oleic acid assisted equivalent-volume impregnation method in experimental example 1 is an optimal sample for simulating the removal of toluene and formaldehyde under the condition of circulating gas, and the temperature required for 90% of the removal rate of toluene is reduced by at least 20 ℃. It was confirmed that the manganese oxide loading in experimental example 1 can promote the activity of the catalyst for removing toluene and formaldehyde.
Example 4
The bone carbon supported catalyst for efficiently removing toluene and formaldehyde comprises a main active component of Mn metal oxide, a carrier of calcined bone carbon at 530-550 ℃, and a calcining atmosphere of air, wherein the Mn metal oxide in the bone carbon supported catalyst accounts for 12-16% of the mass of the bone carbon supported catalyst.
The preparation method of the bone carbon supported catalyst comprises the following steps of oleic acid assisted equivalent-volume impregnation, wherein the oleic acid: 1mol of manganese nitrate, and the preparation process comprises the following steps:
s1, repeatedly washing 10g of degummed and degreased beef bones by using deionized water to remove surface impurities, and then placing the degummed and degreased beef bones in an oven to be heated and dried for 12 hours at the temperature of 100-110 ℃;
s2, heating the dried degummed and degreased beef bones to 530-550 ℃ at the heating rate of 5 ℃/min and 10 ℃/min respectively under the air condition, and calcining for 6 hours to form two kinds of bone carbon; respectively grinding and screening the bone carbon by 40-60 meshes, and repeatedly washing the bone carbon by using deionized water to remove ash on the surface and in pores of the bone carbon;
thermogravimetric analysis was performed on the two kinds of bone carbons after washing and the bone carbon obtained at the temperature increase rate of 2 ℃/min in example 1, respectively, as shown in fig. 8. The results show that the temperature increase rate during the calcination of the bone carbon carrier affects the residual carbon content of the bone carbon carrier, and the higher the temperature increase rate, the more easily the organic matter on the surface of the bovine bone particles is carbonized to form a carbon shell, thereby the higher the residual carbon content. Too much residual carbon masks the sites of hydroxyapatite and forms hydrophobic regions on the surface, which are detrimental to the loading of the active metal.
S3: weighing 2.34g of 50% manganese nitrate solution and 1.85g of oleic acid, adding deionized water until the final volume is 3.6mL, magnetically stirring for 5-8 min to form uniform emulsion, adding 3g of bone carbon (solid solution ratio bone carbon: maceration extract is 1g/1.2mL) obtained in S2, rotationally stirring for 10-15 min, aging for 4-8 h, and placing in an oven for heating and drying at 100-110 ℃ for 12 h;
s4, placing the dried sample in the S3 in a tube furnace, introducing 100mL/min of air, carrying out temperature programming at the speed of 2 ℃/min to 350-400 ℃, calcining for 4h, and then cooling to room temperature to obtain the bone carbon supported catalyst expressed as 550-OA-BC-C and 550-OA-BC-CC;
the two catalysts and 550-OA-BC are respectively used for jointly removing toluene and formaldehyde in circulating air of a workshop, 0.5g of catalyst is taken as an experimental object, 500mL/min of simulated circulating gas consisting of 350ppm of toluene, 80ppm of formaldehyde, 20 vol.% of O2, 3.5 vol.% of H2O and balance gas N2 is introduced, detailed catalytic oxidation equipment can be seen in Du, Xueyu, et al [1] and Zhang Y, et al [2], the removal efficiency of toluene and formaldehyde can be seen in figures 6 and 7 respectively under the temperature window of 130-310 ℃, and the reaction time is 180 min.
In comparison with different temperature rise rates as variables, the bone carbon supported catalyst (550-OA-BC) prepared by loading manganese oxide on a bone carbon carrier calcined at a temperature of 530 to 550 ℃ at a rate of 2 ℃/min by an oleic acid-assisted equivalent volume impregnation method in experimental example 1 is an optimal sample for toluene and formaldehyde removal under simulated circulating gas conditions, and the temperature required for achieving 90% toluene and formaldehyde removal rate is reduced by at least 20 ℃. It was confirmed that the temperature increase rate in experimental example 1 can promote the removal activity of the catalyst for toluene and formaldehyde.
Comparative example 1
A hydroxyapatite supported catalyst for removing toluene and formaldehyde is commercially available hydroxyapatite synthesized by a precipitation method, and the main active component of the hydroxyapatite supported catalyst is a Mn metal oxide which accounts for 12-16% of the catalyst by mass percent.
The preparation method of the hydroxyapatite supported catalyst is equal-volume impregnation, and the preparation process comprises the following steps:
s1: weighing 2.34g of 50% manganese nitrate solution, adding deionized water until the final volume is 3.3mL, magnetically stirring for 2-3 min, adding 3g of hydroxyapatite (solid solution ratio hydroxyapatite: impregnating solution is 1g/1.1mL), rotationally stirring for 10-15 min, aging for 4-8 h, and placing in an oven for heating and drying at 100-110 ℃ for 12 h;
s2, placing the dried sample in the S1 in a tube furnace, introducing 100mL/min of air, carrying out temperature programming at the speed of 2 ℃/min to 350-400 ℃, calcining for 4h, and then cooling to room temperature, wherein the obtained hydroxyapatite supported catalyst is represented as Mn-Hap.
Comparative example 2
A hydroxyapatite supported catalyst for removing toluene and formaldehyde is commercially available hydroxyapatite synthesized by a precipitation method, and the main active component of the hydroxyapatite supported catalyst is a Mn metal oxide which accounts for 12-16% of the catalyst by mass percent.
The preparation method of the hydroxyapatite supported catalyst comprises the following steps of oleic acid assisted equivalent-volume impregnation, wherein the oleic acid: 1mol of manganese nitrate, and the preparation process comprises the following steps:
s1: weighing 2.34g of 50% manganese nitrate solution and 1.85g of oleic acid, adding deionized water until the final volume is 3.3mL, magnetically stirring for 5-8 min to form uniform emulsion, adding 3g of hydroxyapatite (solid solution ratio hydroxyapatite: maceration extract: 1g/1.1mL), rotationally stirring for 10-15 min, aging for 4-8 h, and placing in an oven for heating and drying at 100-110 ℃ for 12 h;
and S2, placing the dried sample in the S1 in a tube furnace, introducing 100mL/min of air, carrying out temperature programming at the speed of 2 ℃/min to 350-400 ℃, calcining for 4h, and cooling to room temperature to obtain the hydroxyapatite supported catalyst expressed as Mn-OA-Hap.
Comparative example 3
An active coke supported catalyst for removing toluene and formaldehyde is provided, wherein the active coke is commercially available active coke, and the main active component of the active coke supported catalyst is Mn metal oxide which accounts for 12-16% of the catalyst by mass.
The preparation method of the active coke supported catalyst is equal-volume impregnation, and the preparation process comprises the following steps:
s1: weighing 2.34g of 50% manganese nitrate solution, adding deionized water until the final volume is 3.3mL, magnetically stirring for 2-3 min, adding 3g of active coke (solid solution active coke: impregnation liquid is 1g/1.1mL), rotationally stirring for 10-15 min, aging for 4-8 h, and placing in an oven for heating and drying at 100-110 ℃ for 12 h;
s2, placing the dried sample in the S1 into a tube furnace, and introducing 100mL/min of air at the speed of 2 ℃/min
And (3) carrying out rate programmed heating to 350-400 ℃, calcining for 4h, cooling to room temperature, and expressing the obtained active coke supported catalyst as Mn-AC.
Comparative example 4
The active coke supported catalyst for removing toluene and formaldehyde is commercially available active coke synthesized by a precipitation method, and the main active component of the active coke supported catalyst is Mn metal oxide which accounts for 12-16% of the catalyst by mass.
The preparation method of the active coke-supported catalyst comprises the steps of oleic acid assisted equivalent-volume impregnation, wherein the oleic acid: 1mol of manganese nitrate, and the preparation process comprises the following steps:
s1: weighing 2.34g of 50% manganese nitrate solution and 1.85g of oleic acid, adding deionized water until the final volume is 3.3mL, magnetically stirring for 5-8 min to form uniform emulsion, adding 3g of active coke (solid solution active coke: impregnation solution is 1g/1.1mL), rotationally stirring for 10-15 min, aging for 4-8 h, and placing in an oven for heating and drying at 100-110 ℃ for 12 h;
s2, placing the dried sample in the S1 in a tubular furnace, introducing 100mL/min of air, carrying out temperature programming at the speed of 2 ℃/min to 350-400 ℃, calcining for 4h, cooling to room temperature, and expressing the obtained active coke supported catalyst as Mn-OA-AC;
550-OA-BC prepared in the example and the catalysts prepared in the comparative examples 1 to 4 are respectively used for jointly removing toluene and formaldehyde in the circulating air of a workshop, 0.5g of the catalyst is taken as an experimental object, 500mL/min of simulated circulating gas consisting of 350ppm of toluene, 80ppm of formaldehyde, 20 vol.% of O2, 3.5 vol.% of H2O and balance gas N2 is introduced, detailed equipment of catalytic oxidation can be seen in Du, Xueyu, et al [1] and Zhang Y, et al [2], the removal efficiency of toluene and formaldehyde under the temperature window of 130-310 ℃ can be respectively seen in figures 9 and 10, and the reaction time is 180 min.
As can be seen from fig. 9 and 10, the bone carbon supported catalyst (550-OA-BC) prepared by supporting manganese oxide on a bone carbon support by an oleic acid-assisted equivalent-volume impregnation method in experimental example 1 was the best sample for simulating the removal of toluene and formaldehyde under the conditions of circulating gas, compared to the catalysts prepared by supporting manganese oxide on other supports. It follows that the sample of experimental example 1 has better combined toluene and formaldehyde removal activity in the presence of 3.5 vol.% water vapor compared to the same type of supported catalyst. The bone carbon supported catalyst (550-OA-BC) prepared by the method in the experimental example 1 can ensure that the removal efficiency of toluene and formaldehyde is higher than 95% at 250-310 ℃, and is beneficial to operation and application in actual production.
The durability-regenerability tests for toluene and formaldehyde removal at an operating temperature of 260 deg.C for the four catalysts 550-OA-BC, 750-OA-BC of example 1, Mn-OA-Hap synthesized in comparative example 2, and Mn-OA-AC synthesized in comparative example 4 are shown in FIGS. 13 and 14. As can be seen from FIGS. 13 and 14, the same preparation was carried out
In the method, the catalyst taking the calcined bone carbon at 530-550 ℃ as the carrier has obviously higher persistence. The removal efficiency of toluene and formaldehyde from 99% and 98% slowly dropped to 83% and 92%, respectively, after operating the bone carbon supported catalyst (550-OA-BC) prepared in example 1 at a catalytic temperature of 260 ℃ for 36 hours. In addition, after 36 hours of operation, the catalyst in the experiment was thermally regenerated under the condition of keeping at 300 ℃ for 30 minutes under the air condition, and the removal efficiency of toluene and formaldehyde of the bone carbon supported catalyst (550-OA-BC) prepared in example 1 was respectively increased to 99% and 98% after thermal regeneration, which is obviously higher than that of the catalyst of other carriers. Compared with other supported catalysts, the bone carbon supported catalyst (550-OA-BC) prepared in example 1 has no phenomenon of accelerated deactivation in use after two thermal cycles, and the bone carbon supported catalyst (550-OA-BC) can be used by simple multiple-cycle thermal regeneration at 300 ℃ for 30 minutes.
Gradient water resistance tests of 3 vol.%, 6 vol.%, 9 vol.% for toluene and formaldehyde removal for the four catalysts 550-OA-BC, 750-OA-BC of example 1, Mn-OA-Hap of comparative example 2 and Mn-OA-AC of comparative example 4, respectively, at an operating temperature of 260 ℃ are shown in fig. 11 and fig. 12. As can be seen from fig. 13 and 14, in the same preparation method, the water resistance of the catalyst using bone carbon calcined at 530 to 550 ℃ as a carrier is significantly higher in the catalysts of other carriers. The removal efficiency of toluene and formaldehyde did not change significantly after the bone carbon supported catalyst prepared in example 1 (550-OA-BC) was run at a catalytic temperature of 260 ℃ for 120 minutes at a water vapor concentration of 3 vol.%; after 120 minutes of operation at a catalytic temperature of 260 ℃ with a water vapor concentration of 6 vol.%, the removal efficiency of toluene and formaldehyde slowly dropped from 99% and 98% to 91% and 86%, respectively; after 120 minutes of operation at a catalytic temperature of 260 ℃ with a moisture concentration of 9 vol.%, the removal efficiency of toluene and formaldehyde slowly dropped from 93% and 86% to 87% and 80%, respectively. Considering that the maximum possible moisture content in the plant circulating air is about 3.5 vol.% H2O (corresponding to moisture contained at 100% humidity around 40 ℃), the water resistance exhibited by the bone carbon supported catalyst (550-OA-BC) prepared in example 1 is considered sufficient to accomplish efficient removal of VOCs from the plant circulating air atmosphere.
In conclusion, the bone carbon supported catalyst can well realize the efficient combined removal of toluene and formaldehyde under the condition of simulating the atmosphere of circulating gas. The preparation process of the sample is simple, the raw materials are low in price, the regeneration and the utilization are easy, and the application prospect is good.
Reference documents:
[1]Du,Xueyu,Li,Caiting,Zhao,&Lingkui,et al.(2018).Promotional removal of hcho from simulated flue gas over mn-fe oxides modified activated coke.Applied Catalysis BEnvironmental An International Journal Devoted to Catalytic Science&Its Applications.
[2]Zhang Y,Li C,Zhu Y,et al.Insight into the enhanced performance of toluene removal from simulated flue gas over Mn-Cu oxides modified activated coke[J].Fuel,2020,276:118099.
[3]StotzelC,FA Müller,Reinert F,et al.Ion adsorption behaviour of hydroxyapatite with different crystallinities[J].Colloids&Surfaces B Biointerfaces,2009,74(1):91-95.
while the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A preparation method of a bone carbon supported catalyst is characterized by comprising the following steps:
s1, washing the animal bones with deionized water, and drying at 100-110 ℃ for 10-12 h;
s2, heating the dried animal bone in the S1 to 500-550 ℃ at a heating rate of 2-10 ℃/min under the air condition, and calcining for 5-6 hours to form bone carbon;
s3, grinding, sieving and cleaning bone charcoal, and drying at 100-110 ℃ for 10-12 h; then adopting equal-volume impregnation according to the bone carbon: impregnation liquid =1 g: 1.2ml, soaking the bone carbon in a manganese salt/saturated fatty acid solution, stirring for 10-15 min, aging for 4-8 h, drying, heating to 350-400 ℃ at a speed of 2 ℃/min, and calcining for 4-5h to obtain the bone carbon supported catalyst.
2. The method of claim 1, wherein the washing comprises: adding 50-200ml of deionized water into 50 g of animal bones, uniformly mixing, and repeatedly cleaning until the water body is transparent.
3. The production method according to claim 1, wherein the temperature increase rate in step S2 is 2 ℃/min.
4. The method according to claim 1, wherein the calcination temperature in step S2 is 530 to 550 ℃.
5. The preparation method according to claim 1, wherein the manganese salt is one or more of manganese sulfate, manganese acetate or manganese nitrate; preferably, the manganese salt is manganese nitrate.
6. The production method according to claim 1, wherein the saturated fatty acid is oleic acid or lauric acid; preferably, the saturated fatty acid is oleic acid.
7. The method of claim 1, wherein the manganese salt/saturated fatty acid solution is a manganese nitrate/oleic acid solution; preferably, the preparation method of the manganese nitrate/oleic acid solution comprises the following steps: weighing 2.34g of 50% manganese nitrate solution and 1.85g of oleic acid, adding deionized water to a final volume of 3.6ml, and magnetically stirring for 5-8 min to form a uniform emulsion.
8. A bone carbon-supported catalyst prepared by the preparation method according to any one of claims 1 to 7.
9. The bone carbon supported catalyst of claim 8, wherein the bone carbon supported catalyst has a grain size of 10-15 nm; preferably, the diameter of the bone carbon particles is 40-60 meshes.
10. Use of a bone carbon supported catalyst according to claim 8 or 9 or a catalyst composition comprising a bone carbon supported catalyst according to claim 8 or 9 as an active ingredient for the combined removal of toluene and formaldehyde.
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Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4003854A (en) * | 1974-06-03 | 1977-01-18 | Gennady Alexeevich Skvortsov | Catalyst of supported vanadium oxide and manganese oxide and method of producing same |
| JP2004313858A (en) * | 2003-04-14 | 2004-11-11 | Toshiaki Aranaka | Treatment method and treatment apparatus for waste bone and meat |
| JP2006116421A (en) * | 2004-10-21 | 2006-05-11 | Aisin Takaoka Ltd | Deodorizing material, manufacturing method therefor and deodorizing method |
| DE102006018529A1 (en) * | 2006-04-21 | 2007-11-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Preparing Hopcalite-catalyst, useful e.g. to oxidize carbon monoxide in fuel cells, comprises coprecipitating oxides of copper and manganese, calcinating, treating the coprecipitate with nitric acid and copper salt containing solution |
| CN102202761A (en) * | 2008-09-30 | 2011-09-28 | 苏德-化学股份公司 | Recovery and purification process for organic molecules |
| WO2012107022A2 (en) * | 2011-02-08 | 2012-08-16 | Universität Rostock | Method for purifying biogas, flue gas or liquids, adsorbent therefor, filters, and use of the adsorbent |
| CN103962163A (en) * | 2014-04-22 | 2014-08-06 | 大连理工大学 | Transition metal-doped hydroxyapatite preparation method and application of transition metal-doped hydroxyapatite for catalytic oxidation of formaldehyde |
| CN106622186A (en) * | 2015-11-04 | 2017-05-10 | 朱秀琴 | Preparation method of adsorbent based on sulfur hexafluoride decomposers in electric equipment |
| CN107159202A (en) * | 2017-04-01 | 2017-09-15 | 浙江工业大学 | A kind of supported palladium catalyst of additive Mn and preparation method and application |
| CN109012753A (en) * | 2018-09-17 | 2018-12-18 | 佛山市森昂生物科技有限公司 | A kind of preparation method of denitration catalyst carrier |
| CN110841588A (en) * | 2019-10-31 | 2020-02-28 | 西安交通大学 | Adsorption type bone apatite and preparation method and application thereof |
| CN113144894A (en) * | 2021-06-02 | 2021-07-23 | 南京风清扬健康科技有限公司 | Functional material for visually degrading formaldehyde and VOCs at normal temperature and pressure and preparation method thereof |
-
2021
- 2021-10-25 CN CN202111238370.5A patent/CN113941349B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4003854A (en) * | 1974-06-03 | 1977-01-18 | Gennady Alexeevich Skvortsov | Catalyst of supported vanadium oxide and manganese oxide and method of producing same |
| JP2004313858A (en) * | 2003-04-14 | 2004-11-11 | Toshiaki Aranaka | Treatment method and treatment apparatus for waste bone and meat |
| JP2006116421A (en) * | 2004-10-21 | 2006-05-11 | Aisin Takaoka Ltd | Deodorizing material, manufacturing method therefor and deodorizing method |
| DE102006018529A1 (en) * | 2006-04-21 | 2007-11-08 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Preparing Hopcalite-catalyst, useful e.g. to oxidize carbon monoxide in fuel cells, comprises coprecipitating oxides of copper and manganese, calcinating, treating the coprecipitate with nitric acid and copper salt containing solution |
| CN102202761A (en) * | 2008-09-30 | 2011-09-28 | 苏德-化学股份公司 | Recovery and purification process for organic molecules |
| WO2012107022A2 (en) * | 2011-02-08 | 2012-08-16 | Universität Rostock | Method for purifying biogas, flue gas or liquids, adsorbent therefor, filters, and use of the adsorbent |
| CN103962163A (en) * | 2014-04-22 | 2014-08-06 | 大连理工大学 | Transition metal-doped hydroxyapatite preparation method and application of transition metal-doped hydroxyapatite for catalytic oxidation of formaldehyde |
| CN106622186A (en) * | 2015-11-04 | 2017-05-10 | 朱秀琴 | Preparation method of adsorbent based on sulfur hexafluoride decomposers in electric equipment |
| CN107159202A (en) * | 2017-04-01 | 2017-09-15 | 浙江工业大学 | A kind of supported palladium catalyst of additive Mn and preparation method and application |
| CN109012753A (en) * | 2018-09-17 | 2018-12-18 | 佛山市森昂生物科技有限公司 | A kind of preparation method of denitration catalyst carrier |
| CN110841588A (en) * | 2019-10-31 | 2020-02-28 | 西安交通大学 | Adsorption type bone apatite and preparation method and application thereof |
| CN113144894A (en) * | 2021-06-02 | 2021-07-23 | 南京风清扬健康科技有限公司 | Functional material for visually degrading formaldehyde and VOCs at normal temperature and pressure and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| YINDI ZHANG ET AL: "Insight into the enhanced performance of toluene removal from simulated flue gas over Mn-Cu oxides modified activated coke", 《FUEL》 * |
| 喻明俄等: "以改性TiO2 -SnO2 为载体的 SCＲ 脱硝催化剂性能", 《环境工程学报》 * |
| 张安超;郑雯雯;孙志君;胡松;朱建安;向军;: "负载型MnO_x/Al_2O_3催化剂低温下脱除烟气中单质汞特性", 煤炭学报 * |
| 王帅;赵朝成;王永强;: "La_xCe_(1-x)MnO/γ-Al_2O_3催化剂的制备及其催化燃烧甲苯的性能", 环境工程学报 * |
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