CN113941349B - 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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- CN113941349B CN113941349B CN202111238370.5A CN202111238370A CN113941349B CN 113941349 B CN113941349 B CN 113941349B CN 202111238370 A CN202111238370 A CN 202111238370A CN 113941349 B CN113941349 B CN 113941349B
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 188
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 155
- 239000003054 catalyst Substances 0.000 title claims abstract description 138
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 167
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 150
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- 238000001354 calcination Methods 0.000 claims abstract description 41
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- 238000000034 method Methods 0.000 claims description 37
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- 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
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 4
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- 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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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
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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
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- 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
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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
- 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
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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
- 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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- General Chemical & Material Sciences (AREA)
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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 6 hours to form bone carbon; then adopting isovolumetric impregnation according to the bone carbon: impregnating solution = 1g:1.2ml of the bone carbon is immersed in a manganese salt/saturated fatty acid solution, stirred for 10-15 min, aged for 4-8 hours, dried, heated to 350-400 ℃ at a speed of 2 ℃/min, and calcined 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 the temperature of 250-310 ℃, has excellent continuous activity and water resistance, can be recycled for multiple times through short-term heat regeneration, and has no safety risk of heat accumulation and fire.
Description
Technical Field
The invention belongs to the technical field of waste gas treatment, relates to purification treatment of VOCs, and in particular 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 has achieved remarkable results in controlling organized waste gas emission, and the collection and treatment of the unorganized waste gas in industrial production becomes the next important treatment target. In the industries of furniture production and processing, indoor building material production and the like, due to the use of solvents and adhesives, a large amount of VOCs exist in workshop air, and the problem of air pollution caused by workshop working environment and surrounding area environment cannot be ignored. Toluene and formaldehyde are two types of VOCs in which important control is required, both from the health of shop workers and from the environmental point of view. Toluene and formaldehyde are reported to be two types of VOCs which have the greatest threat to the health of furniture production and storage related personnel, and long-term exposure can reduce the respiratory function, the nerve function and the immune function of a human body and possibly cause related chronic diseases and cause cancer teratogenesis; at the same time, VOCs are responsible to a large extent for their formation of secondary organic aerosols in the surrounding atmospheric environment, with toluene and formaldehyde proven to be the most potential secondary organic aerosol forming precursors and radical donors. Therefore, effective reduction of the emissions of toluene and formaldehyde from the related industries has become a very urgent issue.
At present, most industries adopt single or combined technologies such as adsorption, photocatalysis or adsorption combined photocatalysis and thermocatalysis to remove tail gas containing toluene and/or formaldehyde, and the treatment scheme has the problems of low pollutant outlet concentration and good safety, but inevitably causes complicated treatment system, huge equipment investment, huge operation and maintenance cost and the like. In order to simplify the system and reduce the cost, the efficiency of the thermocatalysis process is improved, so that the polluted tail gas is singly treated by thermocatalysis to form a break. Among them, the supported catalyst is favored because it can utilize a relatively inexpensive carrier, and greatly reduces the use of noble metals and transition metals. Wherein, the cost performance of the active carbon and active coke supported catalyst is higher than that of the artificial carrier supported catalyst such as molecular sieve, synthetic hydroxyapatite, synthetic montmorillonite and the like. However, in practical application, the working temperature window for the combined removal of toluene and formaldehyde by using the thermocatalytic oxidation method is generally higher than 180 ℃, so that the risk of heat accumulation and ignition easily occurs when the thermocatalytic oxidation is performed by using the carbon-based carrier catalyst, and the life and property safety of personnel can be endangered.
The prior art CN 110841588B discloses an animal bone from which organic matters are removed, which is calcined for 3 to 5 hours at 550 to 650 ℃; as shown in the attached drawing, the XRD pattern crystal form is obviously stronger; the main body of the hydroxyapatite has relatively large crystal form, namely, the manganese oxide is unfavorable for fully doping the crystal lattice of the hydroxyapatite, so that the activity of oxygen species of the hydroxyapatite is promoted; meanwhile, the method is not suitable for preparing the bone carbon supported catalyst because the dispersion of manganese oxide on the bone carbon carrier is not facilitated. The prior art CN 107096492A discloses that animal bones are taken as raw materials, crushed and calcined for 1 to 2 hours at 600 to 700 ℃; similarly, the hydroxyapatite crystal form of the bone carbon body calcined in patent CN 107096492A is relatively larger and thus is also unsuitable for use in the process of the present invention for preparing bone carbon supported catalysts.
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 removal temperature window of toluene and formaldehyde and has good water resistance.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a bone carbon supported catalyst, comprising:
s1, washing animal bones by using deionized water, and then drying at 100-110 ℃ for 10-12h;
s2, heating the animal bone dried in the step S1 to 500-550 ℃ at a speed of 2-10 ℃/min under the air condition, and calcining for 5-6h to form bone carbon;
s3, grinding, sieving and washing bone carbon, and drying at 100-110 ℃ for 10-12h; then adopting isovolumetric impregnation according to the bone carbon: impregnating solution = 1g:1.2ml of the bone carbon is immersed in manganese salt/saturated fatty acid solution, stirred for 10-15 min, aged for 4-8 h, dried, heated to 350-400 ℃ at the speed of 2 ℃/min, and calcined for 4-5h, thus obtaining the bone carbon supported catalyst.
Preferably, the animal bone is degummed defatted bovine bone.
On the one hand, the degummed and defatted bovine bone is a definite industrial byproduct, has relatively stable components, and can be produced in batches like active coke. On the other hand, compared with other bones, the bovine bones become carriers after calcination, and the catalyst prepared by loading active metals is higher in mechanical strength, so that the loss caused by insufficient friction and strength among catalyst particles in transportation can be avoided.
Preferably, the washing comprises: adding 50-200ml deionized water into 50 g animal bone, mixing, repeatedly cleaning, and making water transparent.
Preferably, the temperature rising speed 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 is, the more organic matters on the surface of the bovine bone particles are carbonized to form a carbon shell, so that the higher the residual carbon content is. Excessive residual carbon masks the sites of hydroxyapatite and forms hydrophobic regions on the surface, which is detrimental to the loading of active metals. The catalyst thus prepared also has different catalytic efficiency, and the catalyst prepared at a heating rate of 2-4 deg.c/min has the best catalytic efficiency.
Preferably, the calcination temperature in the step S2 is 530-550 ℃.
The calcination temperature is preferably chosen in order to keep the hydroxyapatite lattice excessively large and to ensure a low carbon content, and the calcination temperature is optimal at 530-550 ℃.
Preferably, the sieving in the step S3 is to screen the ground bone carbon with 40-100 meshes.
The bone charcoal has the advantages of large mesh number, easy aeration, small mesh size and easy blockage.
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 as an anionic ligand is most beneficial for the dispersion of cations on the surface of hydroxyapatite as it is most easily intercalated into the hydroxyapatite lattice; and the decomposition temperature of the manganese nitrate is low, the calcination temperature can be low, the weak crystal form of the manganese oxide is maintained, and the dispersibility of the manganese oxide is improved. Therefore, the effect of the obtained catalyst is optimal.
Preferably, the saturated fatty acid is oleic acid or lauric acid.
Further preferably, the saturated fatty acid is oleic acid.
Oleic acid is low in price 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: 2.34g of 50% manganese nitrate solution and 1.85g of oleic acid are weighed, deionized water is added to a final volume of 3.6ml, and magnetic stirring is carried out for 5-8 min, so that a uniform emulsion is formed.
Preferably, the calcination temperature in the step S4 is 400 ℃.
Calcination at 400 ℃ can ensure that manganese nitrate is fully decomposed and the generated manganese oxide crystal lattice is low.
The invention also discloses the 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, oleic acid as an auxiliary agent, and the diameter of the bone carbon particles is 40-60 meshes.
Preferably, the grain size of the bone carbon supported catalyst is 10-15nm.
The bone carbon carrier is calcined at 530-550 ℃, and the hydroxyapatite in the bovine bone after calcination presents a medium crystal form, and the grain size is 10-15nm. The weaker crystal form is more favorable for the interaction of the hydroxyapatite and the transition metal ions. The invention also claims the application of the bone carbon supported catalyst in the combined removal of toluene and formaldehyde.
The invention also claims the application of the bone carbon supported catalyst in the catalytic oxidation treatment of waste gas.
The invention also claims a catalyst comprising a bone carbon supported catalyst.
The invention also claims the application of the catalyst in the combined removal of toluene and formaldehyde.
The invention also claims the application of the catalyst in catalytic oxidation treatment of waste gas.
The invention is further explained below:
the main component of the bone carbon carrier in the method is hydroxyapatite. The bone carbon carrier is calcined at 530-550 ℃, and the hydroxyapatite in the bovine bone after calcination presents a medium crystal form, and the grain size is 10-15nm. The weaker crystal form is more favorable for the interaction of the hydroxyapatite and the 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 more reasonable pore size distribution, are suitable for the growth and dispersion of active metal centers, contain only a small amount of residual high-temperature carbonized substances, and have no heat accumulation and fire risk. The method for loading the bone carbon supported catalyst is mainly realized by loading manganese oxide by an oleic acid auxiliary isovolumetric impregnation method. The manganese nitrate is used as a manganese oxide precursor substance and can be subjected to stronger ion exchange with the hydroxyapatite in the calcining process under the assistance of oleic acid, so that the dispersibility of the manganese oxide species and the activity of hydroxyl oxygen in the hydroxyapatite are improved, the surface morphology of the catalyst is changed, the specific surface area of the catalyst is improved, and the catalytic oxidation performance of the catalyst is improved as a whole. In addition, the active oxygen species existing in the hydroxyapatite has a certain catalytic oxidation effect on formaldehyde and formaldehyde, and the active manganese species are loaded on the hydroxyapatite bone carbon carrier on the basis of the catalytic oxidation method, so that the overall oxidation capability of the supported catalyst on formaldehyde and toluene is further improved, and the supported catalyst is suitable for the combined removal of the toluene and the formaldehyde.
The active component Mn oxide is supported on a bone carbon carrier with higher specific surface area and ion exchange capacity by using oleic acid as an auxiliary agent, so that the dispersibility of the Mn oxide is improved, the bone carbon supported catalyst has stronger oxidation-reduction capacity, more adsorption sites and active oxygen are provided for removing toluene and formaldehyde, the removal temperature window of the toluene and the formaldehyde is reduced, and meanwhile, by simulating about 3.5vol% of water vapor in flue gas, the water vapor value corresponds to the water vapor contained in 100% of humidity at about 40 ℃ of air temperature, and the water resistance of the catalyst is tested, so that the catalyst prepared by the process has good water resistance. The bone carbon supported catalyst has no heat accumulation and fire risk, and uses industrial waste byproducts as raw materials, so that the catalyst is economical and environment-friendly; the preparation method has simple process, can be realized without harsh process conditions, and is suitable for industrialized large-scale popularization.
The degummed and defatted bovine bone is calcined at the temperature of 530-550 ℃, and the influences of different heating speeds on bone carbon calcination are compared, so that the size of hydroxyapatite crystals is kept in a microcrystalline or medium crystal form in the calcination process, enough organic matters are removed, hydroxyapatite sites are exposed, the hydroxyapatite with a lower crystal form can be combined with oleic acid to assist in carrying out ion exchange with manganese ions to a deeper degree, and therefore manganese hydroxyapatite substances are generated, and the performance of the bone carbon supported catalyst is improved.
Compared with the prior art, the invention has the beneficial effects that:
1. the existing VOCs adsorption/catalysis equipment can be utilized, the VOCs treatment system is simplified, the equipment operation cost is reduced, the heat accumulation and fire risk is avoided, and the operation safety of enterprises is improved.
2. Experiments prove that the bone carbon supported catalyst prepared by the method has higher catalytic activity, can realize the efficient combined removal of toluene and formaldehyde in the circulating air of a workshop at the temperature of 250-310 ℃, and has the removal efficiency of the two VOCs 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 enterprises is reduced.
Drawings
FIG. 1 is an XRD pattern of two different temperature calcined bone carbons; a is a bone carbon sample formed by calcining for 6 hours at 530-550 ℃; b is a bone carbon sample formed by calcining at 730-750 ℃ for 6 hours;
FIG. 2 is a graph showing the para-toluene removal performance of supported catalysts prepared from two calcined temperature bone carbons;
FIG. 3 is a graph showing formaldehyde removal performance of supported catalysts prepared from two calcined temperature bone carbons;
FIG. 4 is a graph of the para-toluene removal performance of three different manganese oxide loaded bone carbon supported catalysts;
FIG. 5 is a graph of formaldehyde removal performance of three different manganese oxide loaded bone carbon supported catalysts;
FIG. 6 is a graph showing the para-toluene removal performance of three supported catalysts prepared by calcining bone carbon at different ramp rates to 530-550 ℃;
FIG. 7 is a graph showing formaldehyde removal performance of three supported catalysts prepared by calcining bone carbon at different ramp rates to 530-550 ℃;
FIG. 8 is a thermogravimetric plot of calcined bone carbon at three different ramp rates to 530-550 ℃;
FIG. 9 shows the removal performance of supported catalyst p-toluene with bone carbon, synthetic hydroxyapatite and activated coke as carriers;
FIG. 10 shows formaldehyde removal performance of supported catalysts with bone carbon, synthetic hydroxyapatite and activated coke as supports;
FIG. 11 shows the Mn-OA-Hap synthesized for 550-OA-BC, 750-OA-BC and comparative example 2 in example 1
And 3vol.%, 6vol.%, 9vol.% gradient water resistance test for toluene removal of the four Mn-OA-AC catalysts synthesized in comparative example 4, respectively;
FIG. 12 is a 3vol.%, 6vol.%, 9vol.% gradient water resistance test for the four catalysts of 550-OA-BC, 750-OA-BC, mn-OA-Hap synthesized in comparative example 2, and Mn-OA-AC synthesized in comparative example 4, respectively, for formaldehyde removal in example 1;
FIG. 13 is a continuous-regeneration test of toluene removal for four catalysts of 550-OA-BC, 750-OA-BC, mn-OA-Hap synthesized in comparative example 2, and Mn-OA-AC synthesized in comparative example 4 in example 1;
FIG. 14 is a sustainability-regenerability test of four catalysts of 550-OA-BC, 750-OA-BC, mn-OA-Hap synthesized in comparative example 2, and Mn-OA-AC synthesized in comparative example 4 in example 1 for formaldehyde removal;
fig. 15 is a prior art bone carbon XRD pattern.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
Example 1
The main active component of the bone carbon supported catalyst is Mn metal oxide, the carriers are bone carbon calcined at the temperature of 530-550 ℃ and the temperature of 730-750 ℃ respectively, the calcining atmosphere is air, and the mass percentage of Mn metal oxide in the bone carbon supported catalyst is 12-16% of the bone carbon supported catalyst.
The preparation method of the bone carbon supported catalyst comprises the steps of oleic acid auxiliary isovolumetric impregnation, and oleic acid: manganese nitrate=1 mol:1mol, the preparation process comprises the following steps:
s1, repeatedly washing 10g of degummed and defatted beef bones by using deionized water to remove impurities on the surfaces of the degummed and defatted beef bones, and then placing the degummed and defatted beef bones in an oven for heating and drying at 100-110 ℃ for 12h;
s2, respectively heating the dried degummed and defatted bovine bone to 530-550 ℃ at a speed of 2 ℃/min under the air condition, and calcining at 730-750 ℃ for 6 hours to obtain two bone carbons; grinding and screening the bone carbon to 40-60 meshes respectively, 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 was performed on both bone carbons, 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 at 730-750 ℃ for 6 h.
The grain size was calculated from the XRD structure by the Debye-Scherrer formula, and specific data were obtained as shown in Table 1.
TABLE 1 grain size of calcined bone carbon at two different temperatures
According to the classification standard proposed by Stotzel C, et al [3], qualitative and quantitative analysis of crystal forms of hydroxyapatite calcined at different temperatures according to FIG. 1 and Table 1 shows that the crystal grain size of hydroxyapatite in a bone carbon carrier calcined at 530-550 ℃ is 11.1nm, and the bone carbon carrier presents 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 obtained in S2 (solid solution ratio bone carbon: impregnating solution=1 g/1.2 mL), rotationally stirring for 10-15 min, aging for 4-8 h, and heating and drying for 12h at 100-110 ℃ in an oven;
s4, placing the dried sample in the S3 in a tube furnace, introducing 100mL/min of air, programming to be at a temperature of 350-400 ℃ at a speed of 2 ℃/min, calcining for 4 hours, and cooling to room temperature to obtain the bone carbon supported catalyst expressed as 550-OA-BC and 750-OA-BC.
Example 2
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 ℃, the calcining atmosphere is air, and the mass percentage of Mn metal oxide in the bone carbon supported catalyst is 12-16% of the bone carbon supported catalyst.
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 defatted beef bones by using deionized water to remove impurities on the surfaces of the degummed and defatted beef bones, and then placing the degummed and defatted beef bones in an oven for heating and drying at 100-110 ℃ for 12h;
s2, heating the dried degummed and defatted bovine bones to 530-550 ℃ respectively at 2 ℃/min under the air condition, and calcining for 6 hours at 730-750 ℃ to form two kinds of bone carbon; grinding and screening the bone carbon to 40-60 meshes, repeatedly washing the bone carbon by using deionized water to remove ash on the surface and in pores of the bone carbon, and then placing the bone carbon in an oven to heat and dry for 12 hours at 100-110 ℃;
s3: weighing 2.34g of 50% manganese nitrate solution, adding deionized water to a final volume of 3.3mL, magnetically stirring for 2-3 min, adding 3g of bone carbon obtained in S2 (solid solution ratio bone carbon: impregnating solution=1 g/1.1 mL), rotationally stirring for 10-15 min, aging for 4-8 h, and heating and drying for 12h at 100-110 ℃ in an oven;
s4, placing the dried sample in the S3 in a tube furnace, introducing 100mL/min of air, programming to be at a temperature of 350-400 ℃ at a speed of 2 ℃/min, calcining for 4 hours, and cooling to room temperature, wherein the obtained bone carbon supported catalyst is expressed as 550-BC and 750-BC;
the four catalysts of examples 1 and 2 were used for combined removal of toluene and formaldehyde in the circulating air of the plant, 0.5g of 550-OA-BC, 750-OA-BC, 550-BC, 750-BC were taken as experimental objects, 500mL/min of simulated circulating gas consisting of 350ppm toluene, 80ppm formaldehyde, 20vol.% O2, 3.5vol.% H2O and balance gas N2 was introduced, catalytic oxidation detailed equipment was visible Du, xueyu, et al. [1] and Zhang Y, et al. [2], and the removal efficiencies of toluene and formaldehyde were visible respectively in FIGS. 2 and 3 at a temperature window of 130 to 310℃for a reaction time of 180min. As can be seen from fig. 2 and 3, in comparison with the calcination temperature of the bone carbon support as a variable, the bone carbon supported catalyst (550-OA-BC) prepared by loading manganese oxide on the bone carbon support calcined at 530-550 ℃ in experimental example 1 by the oleic acid-assisted isovolumetric impregnation method was the best sample for toluene and formaldehyde removal under simulated recycle gas conditions, and it was confirmed that the calcination temperature and preparation method of the bone carbon support in experimental example 1 were capable of promoting the activity of the catalyst for toluene and formaldehyde removal.
Meanwhile, as described previously, the XRD patterns of the bone carbon of the two prior art in the background art are shown in fig. 15, which is 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 are combined, so that it is confirmed that the bone carbon of the prior art may not be suitable for use as the carrier of the present invention.
Example 3
The main active component of the bone carbon supported catalyst is Mn metal oxide, the carrier is bone carbon calcined at 530-550 ℃, the calcining atmosphere is air, and the mass percentage of Mn metal oxide in the bone carbon supported catalyst is 8-12% and 16-20% of the bone carbon supported catalyst respectively.
The preparation method of the bone carbon supported catalyst comprises the steps of oleic acid auxiliary isovolumetric impregnation, and oleic acid: manganese nitrate=1 mol:1mol, the preparation process comprises the following steps:
s1, repeatedly washing 10g of degummed and defatted beef bones by using deionized water to remove impurities on the surfaces of the degummed and defatted beef bones, and then placing the degummed and defatted beef bones in an oven for heating and drying at 100-110 ℃ for 12h;
s2, heating the dried degummed and defatted bovine bone to 530-550 ℃ at 2 ℃/min under the air condition, and calcining for 6 hours to form bone carbon; grinding and screening the bone carbon to 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 50% manganese nitrate solution and 1.30g of oleic acid were weighed out and deionized water was added to a final volume
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 a uniform emulsion, adding 3g of bone carbon obtained in S2 (solid solution ratio bone carbon: impregnating solution=1 g/1.2 mL), rotationally stirring for 10-15 min, aging for 4-8 h, and heating and drying for 12h at 100-110 ℃ in an oven;
s4, placing the dried sample in the S3 in a tube furnace, introducing 100mL/min of air, programming to be at a temperature of 350-400 ℃ at a speed of 2 ℃/min, calcining for 4 hours, and cooling to room temperature, wherein the expression of the obtained bone carbon supported catalyst is 550-OA-BC-0.7 and 550-OA-BC-1.3 respectively;
the two catalysts and 550-OA-BC are respectively used for the combined removal of toluene and formaldehyde in the circulating air of a workshop, 0.5g of the catalyst is respectively taken as an experimental object, 500mL/min of simulated circulating gas consisting of 350ppm of toluene, 80ppm of formaldehyde, 20vol.% of O2, 3.5vol.% of H2O and balance gas N2 is introduced, the detailed catalytic oxidation equipment is shown as Du, xueyu, et al [1] and Zhang Y, et al [2], the removal efficiency of the toluene and the formaldehyde is shown as figure 4 and figure 5 respectively under the temperature window of 130-310 ℃, and the reaction time is 180min.
As can be seen from fig. 4 and 5, in comparison with different manganese oxide loadings as variables, the bone carbon supported catalyst (550-OA-BC) prepared by loading 12 to 16% by mass of manganese oxide on the bone carbon support calcined at 530 to 550 ℃ in experimental example 1 by the oleic acid-assisted isovolumetric impregnation method was the best sample for toluene and formaldehyde removal under simulated recycle gas conditions, and the temperature required for 90% toluene removal was reduced by at least 20 ℃. The manganese oxide loading in experimental example 1 was confirmed to promote the catalyst activity for toluene and formaldehyde removal.
Example 4
The main active component of the bone carbon supported catalyst is Mn metal oxide, the carrier is bone carbon calcined at 530-550 ℃, the calcining atmosphere is air, and the mass percentage of Mn metal oxide in the bone carbon supported catalyst is 12-16% of the bone carbon supported catalyst.
The preparation method of the bone carbon supported catalyst comprises the steps of oleic acid auxiliary isovolumetric impregnation, and oleic acid: manganese nitrate=1 mol:1mol, the preparation process comprises the following steps:
s1, repeatedly washing 10g of degummed and defatted beef bones by using deionized water to remove impurities on the surfaces of the degummed and defatted beef bones, and then placing the degummed and defatted beef bones in an oven for heating and drying at 100-110 ℃ for 12h;
s2, heating the dried degummed and defatted bovine bone to 530-550 ℃ under the air condition at the heating rates of 5 ℃/min and 10 ℃/min respectively, and calcining for 6 hours to form two bone carbons; grinding and screening the bone carbon to 40-60 meshes respectively, 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 bone carbons after washing and the bone carbon obtained at a heating rate of 2 ℃/min in example 1, respectively, as shown in fig. 8. The results show that the rate of temperature rise during calcination of the bone carbon support affects the residual carbonaceous content of the bone carbon support, with higher temperature rise rates resulting in easier carbonization of organic matter on the surface of the bovine bone particles to form a carbon shell and thus higher residual carbonaceous content. Excessive residual carbon masks the sites of hydroxyapatite and forms hydrophobic regions on the surface, which is detrimental to the loading of active metals.
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 uniform emulsion, adding 3g of bone carbon obtained in S2 (solid solution ratio bone carbon: impregnating solution=1 g/1.2 mL), rotationally stirring for 10-15 min, aging for 4-8 h, and heating and drying for 12h at 100-110 ℃ in a baking oven;
s4, placing the dried sample in the S3 in a tube furnace, introducing 100mL/min of air, programming to be at a temperature of 350-400 ℃ at a speed of 2 ℃/min, calcining for 4 hours, and cooling to room temperature to obtain bone carbon supported catalysts expressed as 550-OA-BC-C and 550-OA-BC-CC;
the two catalysts and 550-OA-BC are respectively used for the combined removal of 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 toluene, 80ppm formaldehyde, 20vol.% O2, 3.5vol.% H2O and balance gas N2 is introduced, the detailed catalytic oxidation equipment is shown as Du, xueyu, et al [1] and Zhang Y, et al [2], the removal efficiency of the toluene and the formaldehyde is shown as figure 6 and figure 7 respectively at the temperature window of 130-310 ℃, and the reaction time is 180min.
In comparison with different heating rates as variables, the bone carbon supported catalyst (550-OA-BC) prepared by loading manganese oxide on the calcined bone carbon support heated to 530-550 ℃ by 2 ℃/min through the oleic acid-assisted isovolumetric impregnation method in experimental example 1 was the best sample for toluene and formaldehyde removal under simulated recycle gas conditions, and the temperature required for achieving 90% toluene and formaldehyde removal was reduced by at least 20 ℃. It was confirmed that the rate of temperature increase in experimental example 1 was able to promote the activity of the catalyst for toluene and formaldehyde removal.
Comparative example 1
A hydroxyapatite supported catalyst for removing toluene and formaldehyde is prepared from the hydroxyapatite synthesized by a precipitation method, wherein the main active component of the hydroxyapatite supported catalyst is Mn metal oxide, and the mass percentage of the hydroxyapatite supported catalyst is 12-16%.
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 to a final volume of 3.3mL, magnetically stirring for 2-3 min, adding 3g of hydroxyapatite (the ratio of solid solution to hydroxyapatite: impregnating solution=1 g/1.1 mL), rotationally stirring for 10-15 min, ageing for 4-8 h, and heating and drying for 12h at 100-110 ℃ in an oven;
s2, placing the dried sample in the S1 in a tube furnace, introducing 100mL/min of air, programming to be at a temperature of 350-400 ℃ at a speed of 2 ℃/min, calcining for 4 hours, and cooling to room temperature to obtain the hydroxyapatite supported catalyst expressed as Mn-Hap.
Comparative example 2
A hydroxyapatite supported catalyst for removing toluene and formaldehyde is prepared from the hydroxyapatite synthesized by a precipitation method, wherein the main active component of the hydroxyapatite supported catalyst is Mn metal oxide, and the mass percentage of the hydroxyapatite supported catalyst is 12-16%.
The preparation method of the hydroxyapatite supported catalyst comprises the steps of oleic acid auxiliary isovolumetric impregnation, and oleic acid: manganese nitrate=1 mol:1mol, 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 to a final volume of 3.3mL, magnetically stirring for 5-8 min to form uniform emulsion, adding 3g of hydroxyapatite (the solid solution ratio of the hydroxyapatite is that of the impregnating solution=1 g/1.1 mL), rotationally stirring for 10-15 min, aging for 4-8 h, and heating and drying for 12h at 100-110 ℃ in an oven;
s2, placing the dried sample in the S1 in a tube furnace, introducing 100mL/min of air, programming to be heated to 350-400 ℃ at a speed of 2 ℃/min, calcining for 4 hours, and cooling to room temperature to obtain the hydroxyapatite supported catalyst expressed as Mn-OA-Hap.
Comparative example 3
The active coke supported catalyst for removing toluene and formaldehyde is commercial active coke, and the active coke supported catalyst mainly comprises Mn metal oxide accounting 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 to a final volume of 3.3mL, magnetically stirring for 2-3 min, adding 3g of active coke (solid solution ratio active coke: impregnating solution=1 g/1.1 mL), rotationally stirring for 10-15 min, aging for 4-8 h, and heating and drying for 12h at 100-110 ℃ in an oven;
s2, placing the dried sample in the S1 into a tube furnace, and introducing 100mL/min of air at a speed of 2 ℃/min
The temperature is programmed to 350-400 ℃ for calcination for 4 hours, and then the catalyst is cooled to room temperature, and the obtained active coke supported catalyst is expressed 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 active coke supported catalyst mainly comprises Mn metal oxide accounting for 12-16% of the catalyst by mass.
The preparation method of the active coke supported catalyst comprises the steps of oleic acid auxiliary isovolumetric impregnation, and oleic acid: manganese nitrate=1 mol:1mol, 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 to a final volume of 3.3mL, magnetically stirring for 5-8 min to form uniform emulsion, adding 3g of active coke (solid solution ratio active coke: impregnating solution=1 g/1.1 mL), rotationally stirring for 10-15 min, aging for 4-8 h, and heating and drying for 12h at 100-110 ℃ in an oven;
s2, placing the dried sample in the S1 in a tube furnace, introducing 100mL/min of air, programming to be at a temperature of 350-400 ℃ at a speed of 2 ℃/min, calcining for 4 hours, and cooling to room temperature to obtain an active coke supported catalyst expressed as Mn-OA-AC;
the catalysts prepared in examples 550-OA-BC and comparative examples 1-4 were used for combined removal of toluene and formaldehyde in the circulating air of a workshop, 0.5g of the catalyst was taken as an experimental object, 500mL/min of simulated circulating gas consisting of 350ppm toluene, 80ppm formaldehyde, 20vol.% O2, 3.5vol.% H2O and balance gas N2 was introduced, catalytic oxidation details were visible Du, xueyu, et al [1] and Zhang Y, et al [2], the removal efficiency of p-toluene and formaldehyde at a temperature window of 130-310℃was visible respectively, and the reaction time was 180min.
As can be seen from fig. 9 and 10, the bone carbon supported catalyst (550-OA-BC) prepared by loading the manganese oxide on the bone carbon support by the oleic acid-assisted isovolumetric impregnation method in experimental example 1 was the best sample for toluene and formaldehyde removal under simulated recycle gas conditions, compared with the catalysts prepared by loading the manganese oxide on other supports. Thus, the sample of experimental example 1 has better combined toluene and formaldehyde removal activity in the presence of 3.5vol.% water vapor than the same type of supported catalyst. The bone carbon supported catalyst (550-OA-BC) prepared by the method described 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 continuous-regeneration tests for toluene and formaldehyde removal at 260℃for the four catalysts 550-OA-BC, 750-OA-BC, mn-OA-Hap synthesized in comparative example 2, and Mn-OA-AC synthesized in comparative example 4, respectively, are shown in FIGS. 13 and 14. As can be seen from FIGS. 13 and 14, in the same preparation
Under the method, the catalyst taking the calcined bone carbon at 530-550 ℃ as the carrier has obviously higher persistence. The bone carbon supported catalyst (550-OA-BC) prepared in example 1 was slowly decreased in toluene and formaldehyde removal efficiency from 99% and 98% to 83% and 92%, respectively, after 36 hours of operation at 260 ℃. In addition, after 36 hours of operation, each catalyst in the experiment was thermally regenerated under air conditions at 300 ℃ for 30 minutes as a thermal regeneration condition, and the removal efficiency of the bone carbon supported catalyst (550-OA-BC) prepared in example 1, after thermal regeneration, was raised to 99% and 98% respectively, which was significantly higher than that of the other supported catalysts. And compared with other supported catalysts, the bone carbon supported catalyst (550-OA-BC) prepared in the example 1 has no phenomenon of accelerated deactivation in use after two times of thermal cycles, which shows that the bone carbon supported catalyst (550-OA-BC) can be used by performing multiple times of cyclic thermal regeneration at a simple temperature of 300 ℃ for 30 minutes.
The 3vol.%, 6vol.%, 9vol.% gradient water resistance tests for the four catalysts 550-OA-BC, 750-OA-BC, mn-OA-Hap synthesized in comparative example 2 and Mn-OA-AC synthesized in comparative example 4 in example 1 are shown in FIGS. 11 and 12, respectively, for toluene and formaldehyde removal at an operating temperature of 260 ℃. As can be seen from fig. 13 and 14, the water resistance of the catalyst using the calcined bone carbon at 530 to 550 ℃ as a carrier of the catalyst of other carriers was significantly higher under the same preparation method. The bone carbon supported catalyst (550-OA-BC) prepared in example 1 did not significantly change the toluene and formaldehyde removal efficiency after 120 minutes of operation at a catalytic temperature of 260 ℃ and a water vapor concentration of 3 vol%; after 120 minutes of operation at 260 ℃ catalytic temperature and 6vol.% water vapor concentration, the toluene and formaldehyde removal efficiency slowly decreased from 99% and 98% to 91% and 86%, respectively; after 120 minutes of operation at 260 ℃ catalytic temperature and 9vol.% water vapor concentration, the toluene and formaldehyde removal efficiency slowly decreased from 93% and 86% to 87% and 80%, respectively. Considering that the maximum possible moisture content in the shop circulating air is about 3.5vol.% H2O (corresponding to moisture contained at 100% humidity around 40 c), the water resistance exhibited by the bone carbon supported catalyst (550-OA-BC) prepared in example 1 may be considered to be sufficient to achieve efficient removal of VOCs in the shop 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 sample preparation process is simple, the raw materials are low in price and easy to recycle, and the method has good application prospect.
Reference is made to:
[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 embodiments of the present invention, it will be appreciated by those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the present invention.
Claims (14)
1. A method for preparing a bone carbon supported catalyst, comprising:
s1, washing animal bones by using deionized water, and then drying at 100-110 ℃ for 10-12 hours;
s2, heating the animal bone dried 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 carbon, and drying at 100-110 ℃ for 10-12h; then adopting isovolumetric impregnation according to the bone carbon: impregnating solution = 1g:1.2ml of the bone carbon is immersed in a manganese salt/saturated fatty acid solution, stirred for 10-15 min, aged for 4-8 hours, dried, heated to 350-400 ℃ at a speed of 2 ℃/min, and calcined for 4-5h to obtain the bone carbon supported catalyst.
2. The method of preparation according to claim 1, wherein the washing comprises: adding 50-200-ml deionized water into 50 g animal bone, mixing, and repeatedly cleaning until the water body is transparent.
3. The method according to claim 1, wherein the heating rate in the step S2 is 2 ℃/min.
4. The method according to claim 1, wherein the calcination temperature in the step S2 is 530-550 ℃.
5. The preparation method according to claim 1, wherein the manganese salt is one or more of manganese sulfate, manganese acetate and manganese nitrate.
6. The method of claim 5, wherein the manganese salt is manganese nitrate.
7. The method of claim 1, wherein the saturated fatty acid is oleic acid or lauric acid.
8. The method of claim 7, wherein the saturated fatty acid is oleic acid.
9. The method of claim 1, wherein the manganese salt/saturated fatty acid solution is a manganese nitrate/oleic acid solution.
10. The method of claim 9, wherein the method of preparing the manganese nitrate/oleic acid solution comprises: 2.34g of 50% manganese nitrate solution and 1.85g of oleic acid are weighed, deionized water is added to a final volume of 3.6ml, and magnetic stirring is carried out for 5-8 min, so that a uniform emulsion is formed.
11. A bone carbon supported catalyst prepared by the preparation method according to any one of claims 1 to 10.
12. The bone carbon supported catalyst according to claim 11, wherein the bone carbon supported catalyst has a grain size of 10-15nm.
13. The bone carbon supported catalyst according to claim 12, wherein the bone carbon particles have a diameter of 40 to 60 mesh.
14. Use of a bone carbon supported catalyst according to any one of claims 11 to 13 or a catalyst composition comprising the bone carbon supported catalyst according to any one of claims 11 to 13 as active ingredient for the combined removal of toluene and formaldehyde.
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