CN107185581A - A kind of SBA15 catalyst for loading cobalt-based - Google Patents
A kind of SBA15 catalyst for loading cobalt-based Download PDFInfo
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- CN107185581A CN107185581A CN201710180985.4A CN201710180985A CN107185581A CN 107185581 A CN107185581 A CN 107185581A CN 201710180985 A CN201710180985 A CN 201710180985A CN 107185581 A CN107185581 A CN 107185581A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0333—Iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Abstract
The invention discloses a kind of SBA15 catalyst for loading cobalt-based, the load capacity of the cobalt-based is 2%wt, and cobalt-based is highly dispersed in inside SBA15 ducts；Its preparation method, it is as follows：First, the SBA15 of 2 parts by weight solid powder is weighed, both are dissolved in the absolute ethyl alcohol of 100 parts by weight, are placed in magnetic agitation 5h in beaker by the nitric acid cobalt granule of 0.1973 parts by weight；Secondly, standing, crystallization 24h；Then, vacuum rotary evaporator evaporation drying 2h is placed in, temperature is 60 DEG C；Finally, 450 DEG C of roasting 5h in Muffle furnace.The SBA15 catalyst of the load cobalt-based of the present invention, for promoting the magnesium sulfite during magnesia FGD to aoxidize, catalytic efficiency is improved while reducing cost.
Description
Technical field
The present invention is applied to magnesia FGD technical field, more particularly, to a kind of SBA15 catalyst for loading cobalt-based, uses
Magnesium sulfite oxidation during magnesia FGD is promoted.
Background technology
In recent years, SBA-15 turns into research pair with catalyst carrier more because of strong and high-specific surface area the advantage of its stability
As the solid phase Co-SBA-15 that Hassan et al. is prepared for different loads amount using dual infusion process (double-solvent) is urged
Agent, applied to the oxidation reaction of carbon, propylene and toluene, as a result shows, the catalyst that load capacity is less than or equal to 12wt% can
Reaction temperature is reduced, there is higher selective catalysis activity to the reaction.Franken is prepared for using die version method
Cu0.25Co2.75O4-SBA-15, and have studied its catalytic action to N2O reduction reactions.Garg utilizes equi-volume impregnating
(incipient wetness impregnation), using ZrSBA-15 as carrier, is prepared for 8wt%Mo promoter
Catalyst of the loading between 1-5wt%, 3wt% catalyst is in thiophene HDS and cyclohexene HYD
Show highest catalytic activity.Hassan is prepared for height point using dual infusion process (two-solvent technique)
The catalyst of scattered different cobalt loadings, have studied its catalytic action to carbon black oxidation reaction, as a result shows, the load of low cobalt base
The catalyst of amount shows optimal catalytic effect.Osakoo has synthesized Pd-Co-SBA-15 using co-impregnation, and have studied it
Catalytic performance in Fischer-Tropsch Synthesis (FTS).Rodrigues is closed using microwave and conventional hydrothermal method
Into two kinds of SBA-15, Co-SBA-15 is prepared for by humidity infusion process, applied to Fischer-Tropsch (FT)
Reaction evaluates its catalytic performance, as a result shows that the Co-SBA-15 that two ways is obtained has compared to other mesoporous materials to C5+
Higher selection activity.Taghavimoghaddam is respectively with Co (NO3)2·6H2O and CoCl2·6H2O is active component, is passed through
Double solvent method and infusion process (" two-solvent " method and impregnation) are prepared for the support type SBA- of cobalt
15, and have studied catalytic action of two kinds of samples to cyclohexanol liquid phase oxidation reactions.Tsoncheva is impregnated using tradition
Method is prepared for the SBA-15 of cobalt support type, and have studied it to the total oxidation reaction of ethyl acetate (ethyl acetate total
Oxidation catalytic action).Zhao is prepared for the Cu-Co-SBA-15 of different content with isometric co-impregnation, have studied
Its effect to toluene catalytic combustion.Prieto is prepared for 1wt%Ru -20wt%Co support type SBA-15 catalyst, and grinds
Influence of the pore size to metal dispersity and catalyst catalytic performance is studied carefully.In a word, the studies above using the compound of cobalt as
Active component is carried on SBA-15 applied to various catalytic reactions, but Co-SBA-15 is applied into the reaction that magnesium sulfite is aoxidized
It yet there are no exploration.
Chinese magnesium ore deposit is enriched, and magnesium oxide method sulfur removal technology is because having few absorbent consumption, accessory substance reusable edible, investment
With the low advantage of operating cost, easily led using more and more extensively, desulfurization side product magnesium sulfite oxidation is insufficient in the industry
Cause accessory substance hardly possible to recycle and secondary pollution etc., thus magnesium sulfite oxidation progressively by many focus of attention.
The content of the invention
The purpose of the present invention is to improve a kind of SBA15 catalyst for loading cobalt-based, for promoting magnesia FGD during
Magnesium sulfite oxidation, improve catalytic efficiency while reducing cost.
In order to solve the above technical problems, the present invention is adopted the following technical scheme that：
A kind of SBA15 catalyst for loading cobalt-based of the present invention, the load capacity of the cobalt-based is 1-10%wt, and cobalt-based is highly
It is scattered in inside SBA15 ducts.
Further, the load capacity of the cobalt-based is 2%wt.
The preparation method of SBA15 catalyst, first, weighs the SBA15 of 2 parts by weight solid powder, 0.1973 parts by weight
Nitric acid cobalt granule, both are dissolved in the absolute ethyl alcohol of 100 parts by weight, magnetic agitation 5h in beaker is placed in；Secondly, standing, crystalline substance
Change 24h；Then, vacuum rotary evaporator evaporation drying 2h is placed in, temperature is 60 DEG C；Finally, 450 DEG C of roastings in Muffle furnace
5h。
Load the application of magnesium sulfite oxidation of the SBA15 catalyst of cobalt-based during magnesia FGD is promoted.With showing
There is technology to compare, advantageous effects of the invention：In catalyst Co-SBA-15 the existence form of cobalt element be Co (III) and
Co (II), metal ion Co (III) reactivity are not as good as Co (II).In cobalt/cobalt oxide crystal the Co (II) of low-oxidation-state from
Son forms cavitation damage easily by Co (III) ionic compartmentation of high oxidation state, and the polymolecularity of cobalt/cobalt oxide in the catalyst
Contribute to metalepsis of the Co (III) to Co (II), and then improve catalyst activity；Co-SBA-15 has high efficiente callback performance,
The catalytic performance that reclaiming is more than 4 times is approximate with the Co2+ of ionic state catalytic effect consistent；It is green, stable recovery
Type catalyst, has remarkable effect to the oxidation and reduction absorption tower size for promoting desulfuration byproduct magnesium sulfite；Cobalt loading
In 2wt%, the dispersiveness of cobalt/cobalt oxide is higher, and specific surface area of catalyst and pore volume are larger, maintain unsupported SBA15 hole
Obvious clogging, magnesium sulfite oxidation rate highest, up to 0.0780mmolL-1, up to on-catalytic do not occur for road structure, duct
Under the conditions of more than 8 times of oxidation rate；Low-load amount, high oxidization rate can greatly reduce absorption tower size, reduction reaction solution poison
Property.
Brief description of the drawings
The invention will be further described for explanation below in conjunction with the accompanying drawings.
Fig. 1 is influence of the cobalt load to catalyst performance；
Fig. 2 is influence of the cobalt content to catalytic performance
Fig. 3 tests design sketch for the recyclability of Co-SBA-15 catalyst；
Fig. 4 is isothermal adsorption desorption curve before and after SBA-15 loads；
Fig. 5 is different loads amount Co-SBA-15 graph of pore diameter distribution；
Fig. 6 is SBA-15 XRD characterization result figures
Fig. 7 is Co-SBA-15 XRD characterization result figures；
Fig. 8 is different loads amount Co-SBA-15 XPS collection of illustrative plates；
Fig. 9 schemes for pure SBA-15 SEM
Figure 10 schemes for 1wt%Co-SBA-15 SEM；
Figure 11 schemes for 2wt%Co-SBA-15 SEM；
Figure 12 schemes for 5wt%Co-SBA-15 SEM；
Figure 13 schemes for 10wt%Co-SBA-15 SEM；
Figure 14 is Co-SBA-15 EDX characterization result figures；
Figure 15 is TEM phenograms；
Figure 16 is that cobalt-based is highly dispersed in SBA15 ducts schematic internal view；
Figure 17 is the oxidation effectiveness schematic diagram of magnesium sulfite under different Co load capacity.
Embodiment
A kind of SBA15 catalyst for loading cobalt-based, the load capacity of the cobalt-based is 2%wt, and cobalt-based is highly dispersed in
Inside SBA15 ducts.
Its preparation method, it is as follows：
First, 2g SBA15 solid powder is weighed, both are dissolved in 100ml nothing by 0.1973g nitric acid cobalt granule
Water-ethanol, is placed in magnetic agitation 5h in beaker；Secondly, standing, crystallization 24h；Then, it is placed in vacuum rotary evaporator evaporation drying
2h, temperature is 60 DEG C；Finally, 450 DEG C of roasting 5h in Muffle furnace.
The catalyst is primarily to facilitate the magnesium sulfite oxidation during magnesia FGD.
As illustrated in fig. 1 and 2, it is the influence of cobalt load and load capacity to catalytic performance.Cobalt-based load capacity is to catalyst performance
There is considerable influence, as load capacity is raised, the oxidation rate of magnesium sulfite increases rapidly, and cobalt loading is in 2wt%, sulfurous acid
Magnesium oxidation rate highest, up to 0.0780mmolL-1, up to on-catalytic under the conditions of more than 8 times of oxidation rate, cobalt loading continues
Increase, oxidation rate is gradually reduced and tended towards stability.Cobalt loading is in 2wt%, dispersed higher, the catalyst of cobalt/cobalt oxide
Specific surface area and pore volume are larger, and obvious clogging does not occur for duct, therefore its catalytic performance is optimal.Increase with load capacity, sample
Product structural order is reduced, and cobalt active sites are reduced, and cobalt/cobalt oxide dispersiveness is substantially reduced, and catalyst is easily aoxidized in magnesium sulfite
During block, reduce reaction rate.TOF values are higher when load factor is 1wt% and 2wt%, continue to rise with load factor
Height, TOF values are reduced rapidly, illustrate that low cobalt base load capacity catalyst effect is best.With Co-CNTs catalyst in research before
Compare, Co-SBA-15 TOF values are far above Co-CNTs catalyst.Co-CNTs catalyst reaches most when load factor is 30%
Big catalysis oxidation 6.94 × 10-5molL-1s-1 of speed, and Co-SBA-15 optimal cobalt loading is compared with Co-CNTs
Reduce 14 times, and improve reaction rate, this is probably that interaction between active component and carrier is caused, Co-
SBA-15 catalyst greatly reduces cobalt nitrate consumption, reduces preparation cost.
As shown in figure 3, being Co-SBA-15 catalyst recyclability test results, 4 catalyst have been carried out successively and have reclaimed real
Test, catalyst concn is fixed value 1.000gL-1 under the conditions of the recovery used every time.Experimental result such as Fig. 3, has found sub-
The oxidation rate of magnesium sulfate reduces with recovered frequency increase and tends to definite value, from 0.076mmolL-1Gradually reduce to
0.041mmol·L-1, but still 4 times of reaction rate during up to on-catalytic.According to middle cobalt ions of having published an article to magnesium sulfite
The influence of oxidation, it is 0.0456mmolL that can obtain the reaction rate under the concentration of cobalt ions-1·s-1, not recovered Co-
The homogeneous catalytic oxidation speed of the equal concentration of cobalt ions of catalysis oxidation speed ratio of SBA-15 catalyst is higher by 70%.Even if repeating
Using the Co-SBA-15 catalyst of 4 times, its reaction rate still improves more than 3.4 times compared with on-catalytic, close to fresh
Co2+The homogeneous catalysis performance of catalyst.
Catalyst characterization
1st, BET characterization results
As Fig. 4 be SBA-15 and different loads amount Co-SBA-15 N2 absorption/desorption isotherm, SBA-15 with difference bear
The adsorption isothermal curve of the cobalt-base catalyst of carrying capacity is Langmiur IV type thermoisopleths, and relative partial pressure (P/P0) is in 0.6-
Occur H1 hysteresis loops in the range of 0.9, this be on uniform outer surface multilayer absorption, mesoporous material internal capillaries cohesion and
What internal structure was determined.The result verification is meso-hole structure material SBA-15 used in invention, also illustrate that its two dimension
Column pore passage structure and homogeneous pore distribution, average pore size about 7.41nm.Fig. 5 shows that load capacity is at 1%, cobalt-base catalyst
With unsupported SBA-15 specific surface area, pore volume, aperture without bigger difference；When continuing to increase to 10% with load capacity, hole
Footpath is still maintained between 5-10nm, belongs to meso-hole structure, but specific surface area, pore volume and aperture are respectively from 603m2·g-1、
1.17cm3·g-1, 7.52nm gradually reduced to 533m2·g-1、0.81cm3·g-1, 5.61nm, this phenomenon with
Taghavimoghaddam result is consistent.This is probably the impregnation concentrations increase due to cobalt nitrate, fired to be fixed on SBA-
Cobalt/cobalt oxide inside 15 increases, while cobalt oxide particles are nanoscale, easily occupies the active site inside SBA-15 ducts,
Therefore there is reduction trend in its specific surface area, aperture and pore volume.In a word, understand Co-SBA-15 through catalyst from BET analysis results
Preparation technology still remains complete meso-hole structure and internal gutter structure is relatively stablized, is difficult to cave in.
2nd, XRD characterization results
As shown in Figures 6 and 7, SBA-15 and Co-SBA-15 XRD spectra diffraction maximum trend is substantially the same, while all considerable
Observe (100) that three diffraction maximums are respectively belonging to ordered mesoporous material, (110) and (200) crystal face.This result and Fig. 4 phases
It coincide, demonstrates load capacity the meso-hole structure of catalyst is not produced and significantly affect.However as load capacity increase, peak intensity
Gradually reduce, this is probably, because the cobalt nitrate of load is scattered in inside SBA-15 so as to occupy its cell channels, to cause catalysis
The order reduction of agent structure.There is wider strong peak at 20 ° -25 ° in the wide-angle XRD of different loads amount, illustrates Jie in order
Significant change does not occur for undefined structure before and after Porous materials SBA-15 loads.There are the weaker spike of intensity, peak between 35 ° -40 °
Strong to increase and increase with cobalt loading, the intensity decreases in 10wt% may be relevant with the content and decentralization of cobalt in catalyst,
Easily there is agglomeration in cobalt loading active component cobalt in 10wt%, and decentralization declines.When cobalt load factor is more than 5wt%,
The weaker peak of intensity can be observed at 37 °, 58 ° and 65 °, Co is respectively belonging to3O4(311), (511) and (440) are brilliant
Face but these characteristic peaks are not observed under 1wt% and 2wt% load capacity, illustrates that cobalt divides in SBA-15 ducts and surface
Dissipate good, its main cause is there is hydrophilic radical in SBA-15, and cabaltous nitrate hexahydrate is easier to evenly spread to SBA-15 tables
Face and internal gutter, this is also to reduce to improve strong foundation with load capacity hole diameter enlargement.As seen from the figure, cobalt loading is 2%
When, catalyst structure order and cobalt decentralization are good, and the catalytic action for demonstrating its oxidation to magnesium sulfite is optimal.
3rd, XPS characterization results
The Co-SBA-15 of different cobalt loadings Co 2p collection of illustrative plates is as shown in figure 8, the Co 2p collection of illustrative plates substantially phase of each load capacity
Together, occur two obvious peaks at 780.8eV and 796.8eV, only less offset occurs in peak position in 5wt% collection of illustrative plates.
The spin separation that Co-SBA-15 can be obtained by figure can be 16eV, illustrate that Co's in the catalyst of different loads amount is primarily present form
It is Co2+.Meanwhile, obvious satellite peak can be observed in figure near 786.8eV and 805eV, and due to general Co2+Compound
Satellite peak position is than Co 2p3/2 main peaks high 5~6eV, Co3+The satellite peak position 10~11eV higher than main peak of compound, and compared with
It is weak, therefore contain Co simultaneously in the catalyst2+And Co3+, but the Co form that is primarily present is Co2+.(swarming 783.4) is in addition, mistake
Cross the chemical shift of metallic element reduces with the rise of chemical valence, therefore can determine whether out the chemical valence state of cobalt such as according to peak position
Shown in Fig. 7, higher chemical shift correspondence Co2+Compound and relatively low chemical shift correspondence Co3+Compound.Therefore catalyst is speculated
In cobalt with CoO and Co3O4Mixed form exist.According to the Co fitted under different loads amount2+And Co3+Knowable to peak area,
With the rise of cobalt loading in catalyst, cobaltⅡ content is first raised to be reduced afterwards and content is most in 2wt%Co-SBA-15
It is high；The change of trivalent cobalt content is little, and only in 5wt%Co-SBA-15, content is higher.Load capacity is sub- at 2% as shown in Figure 2
Magnesium sulfate oxidation rate highest, therefore can speculate that divalence cobalt its major catalytic in magnesium sulfite oxidation is acted on.
Table 1 shows catalyst surface each element atom number accounting, as follows,
Each element atomic ratio and different valence state cobalt ratio
According to divalence cobalt and trivalent in each element atom number accounting, total cobalt in the full spectrograms of XPS of each load capacity catalyst
Cobalt content can be tried to achieve by its correspondence peak area respectively.
As shown in Table 1, the cobalt content of catalyst external surface is raised with cobalt loading and gradually increased, but much smaller than the name of cobalt
Cobalt in adopted load capacity, this explanation catalyst is largely distributed in catalytic inner duct.And the nominal load capacity of cobalt exists
During 10wt%, its surface cobalt content is only 0.6%, and this is probably the further increase due to cobalt loading, causes cobalt activearm
Distribution is raw to reunite, and bulky grain cobalt easily comes off from catalyst external surface, causes catalyst external surface cobalt content relatively low.With name
The rise of adopted load capacity, Co2+ contents are first raised and reduced afterwards, and this is consistent with catalyst catalytic performance in Fig. 1, and this explanation is in sulfurous
That play major catalytic in sour magnesia is Co2+ rather than Co3+.
4th, SEM characterization results
As described and depicted in figs. 9-13, SBA-15 and each load capacity Co-SBA-15 are amplified into 1 μm and 100nm to be observed, such as
It is micron-sized uniform club shaped structure to scheme SBA-15 and Co-SBA-15, and surface is more smooth, and length and width is respectively 1-2 μm and 0.5-
1 μm, the Co-SBA-15 catalyst that size and Osakoo et al. are prepared using Fischer-Tropsch Synthesis method
It is identical.As schemed, after fired load cobalt-based, significant change does not occur for SBA-15 granular sizes, structure and pattern, with BET above
It is consistent with XRD characterization result, it was demonstrated that SBA-15 structural stability.Such as Figure 10, after cobalt/cobalt oxide load, SBA-15 particles
There is tiny circular protrusions particle in surface, and as load capacity gradually increases, circular protrusions particle progressively becomes big and increased, can
Speculate the cluster body that the circular granular is cobalt/cobalt oxide, cobalt easily produces reunion as magnetisable material with the increase of load capacity.With
When in Figure 11-13 between 2wt%~10wt% load capacity, the result that magnesium sulfite oxidation rate increases and reduced with load capacity
Unanimously.
SBA-15 has two-dimentional hexagonal hole road, and aperture does not occur substantially in 9nm or so, and with load capacity rise pore passage structure
Change.Cobalt oxide is dispersed in SBA-15 surfaces and its inside.
As shown in figure 14, such as the EDX spectrograms that figure is sample, SBA-15 is made up of tri- kinds of elements of O, Si, Cu during unsupported cobalt,
After load, the presence at cobalt peak can be clearly observable at tri- positions of 0.75keV, 6.9keV, 7.55keV, and with Co loads
That measures is gradually risen, and Co peaks, O peaks, Si peaks, the intensity at Cu peaks are stepped up, and this has absolutely proved that cobalt is highly dispersed in SBA-
Inside 15.And for different loads amount sample, Co peak intensities gradually rise with load capacity under equal micro- detection area, i.e., cobalt contains
Amount rise, demonstrates cobalt oxide particles and agglomeration easily occurs under high capacity amount.Therefore in Co-SBA-15 catalysis oxidations
In the reaction of magnesium sulfite, the oxidation rate of magnesium sulfite is begun to decline when cobalt loading is continued to raise by 2wt%.
Raised with load capacity, reduction temperature is gradually reduced, i.e. the more big easier reduction of load capacity, this explanation is with cobalt loading
Increase, the adhesion between Co and carrier gradually weakens, and Co degree of scatter gradually weakens.1wt% and two catalyst of 2wt%
The degree of scatter of cobalt is higher, but because the relative amount of cobalt in 2wt%Co-SBA-15 is higher, with higher catalytic activity,
Therefore 2wt%Co-SBA-15 has optimal catalytic effect in magnesium sulfite oxidation.
When the nominal load capacity of cobalt continues to raise from 2wt%, the cobalt active component in SBA-15 ducts easily occur accumulation and
Agglomeration, causes hexagonal hole road by Partial Blocking, in some instances it may even be possible to destroy 10% load in SBA-15 meso-hole structure, XRD
The small-angle diffraction peak of amount, which substantially weakens, has turned out this possibility.Simultaneously by BET measurement result it can also be seen that catalyst
Pore volume and aperture be all remarkably decreased, thus cause catalytic activity gradually to reduce, and then cause the oxidation rate of magnesium sulfite fast
Prompt drop is low.Therefore, the catalytic process is main is controlled by catalyst duct interior catalyst.
5th, TEM characterization results
As shown in figure 15, (a-1, a-2) is SBA-15 phenograms；(b-1, b-2) is 1wt%Co-SBA-15 phenograms；
(c-1, c-2) is 2wt%Co-SBA-15 phenograms；(d-1, d-2) is 5wt%Co-SBA-15 phenograms；(e-1, e-2) is
10wt%Co-SBA-15 phenograms.It can be clearly observable from figure, SBA-15 has two-dimentional hexagonal hole road, aperture is left in 9nm
The right side, and significant change does not occur with load capacity rise pore passage structure.Cobalt oxide is dispersed in SBA-15 surfaces and its inside, with
XRD results match, and when load capacity is 1wt% and 2wt%, cobalt/cobalt oxide cluster body particle is smaller and is uniformly dispersed, cobalt oxidation
Composition granule size is between 5-9nm, and the particle of cobalt oxide is between 2-4nm in Escalera [18] researchs, and this difference may
It is due to that cobalt active component is different with preparation method to cause.Obvious blocking does not occur for duct.Continue to raise with load capacity, cobalt oxidation
Thing is become larger by small cluster body, and presentation banding is uniformly distributed.Because Cluster Phenomenon, large area easily occur for cobalt/cobalt oxide
Duct is blocked, causes load capacity oxidation rate of magnesium sulfite in the range of 2wt%~10wt% to gradually reduce.
As shown in figure 16, cobalt-based is highly dispersed in inside SBA15 ducts.
As shown in figure 17, cobalt loading is at 2%, and there is Co-SBA-15 optimal catalysis to imitate to magnesium sulfite oxidation reaction
Really.Cobalt loading is in 1% and 2%, as illustrated, Co is distributed mainly on the inside of duct, and Co dispersivenesses are preferably.And with negative
Carrying capacity continues to raise cobalt oxide particles on the inside of duct and easily occurs agglomeration, blocks duct, makes cobalt/cobalt oxide dispersiveness big
Reduce greatly, therefore its catalytic effect aoxidized to magnesium sulfite is also greatly reduced.
Co-SBA-15 in the present invention significantly reduces cobalt loading, and greatly improved compared with Co-CNTs
The oxidation rate of magnesium sulfite.SBA-15 has more avtive spots, bigger aperture compared to CNTs, more stable urged
Agent structure.Meanwhile, the cobalt loaded in Co-SBA-15 largely enters inside duct, forms activated centre, therefore in sulfurous acid
It is mainly endoporus catalysis in magnesium oxidation reaction to work, and the cobalt loaded in Co-CNTs is largely attached on the outside of carbon pipe, hole
Footpath is smaller, and clogging is serious in pipe.Therefore, Co-SBA-15 (only accounts for cobalt loading in Co-CNTs by low cobalt load capacity
6.7%), you can reach 1.12 times of Co-CNTs catalytic effect.
Using alcohol dipping method prepare high degree of dispersion Co-SBA-15 catalyst in magnesium sulfite oxidation reaction have compared with
High activity, high catalytic effect is reached using low cobalt load level.The preparation technology can keep the original two dimensions of SBA-15
Hexagonal hole road, high-specific surface area and ordered mesopore structure.Characterized, obtained by BET, XRD, XPS, EDS, SEM, TEM and TPR
Going out 2wt%Co-SBA-15 samples, there is high-specific surface area, large aperture, structurally ordered, high cobalt decentralization and cobalt oxide not to roll into a ball
It is poly-, therefore it has higher catalytic performance to magnesium sulfite oxidation.Sulfite oxidation is by being the Co-SBA-15 by high degree of dispersion
Interior catalyst control.Magnesium sulfite oxidation rate can be improved more than 6 times by 2wt%Co-SBA-15 compared with pure SBA-15.
Continue to raise with load capacity, make effective avtive spot less because reunion occurs for cobalt oxide, so as to cause magnesium sulfite to aoxidize
Rate reduction.Co-SBA-15 catalyst is in addition to high TOF values, also with good regenerability, therefore the green ring
Protect, the heterogeneous catalysis that stability is strong has broad application prospects.In addition, the reproducibility composition in carrier helps to pass through
Lattice defect is formed to improve the catalytic performance of catalyst.Acquired results help to develop new catalyst, promote wet desulphurization
The oxidation of sulfite salt.
Embodiment described above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is carried out
Limit, on the premise of design spirit of the present invention is not departed from, those of ordinary skill in the art make to technical scheme
Various modifications and improvement, all should fall into claims of the present invention determination protection domain in.
Claims (4)
1. a kind of SBA15 catalyst for loading cobalt-based, it is characterised in that：The load capacity of the cobalt-based is 1-10%wt, and cobalt-based
It is highly dispersed in inside SBA15 ducts.
2. a kind of SBA15 catalyst for loading cobalt-based, it is characterised in that：The load capacity of the cobalt-based is 2%wt.
3. the preparation method of the SBA15 catalyst of load cobalt-based according to claim 1, it is characterised in that：First, weigh
Both are dissolved in the anhydrous second of 100 parts by weight by the SBA15 of 2 parts by weight solid powder, the nitric acid cobalt granule of 0.1973 parts by weight
Alcohol, is placed in magnetic agitation 5h in beaker；Secondly, standing, crystallization 24h；Then, vacuum rotary evaporator evaporation drying 2h is placed in,
Temperature is 60 DEG C；Finally, 450 DEG C of roasting 5h in Muffle furnace.
4. the SBA15 catalyst of load cobalt-based according to claim 1, it is characterised in that：It is promoting magnesia FGD
During magnesium sulfite oxidation application.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109364708A (en) * | 2018-11-20 | 2019-02-22 | 华北电力大学（保定） | A kind of promotion ammonia process of desulfurization by-product recovery inhibits SO2And NH3The catalyst discharged again |
| CN109772427A (en) * | 2019-02-22 | 2019-05-21 | 浙江大学 | It is a kind of for the catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid and its preparation and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109364708A (en) * | 2018-11-20 | 2019-02-22 | 华北电力大学（保定） | A kind of promotion ammonia process of desulfurization by-product recovery inhibits SO2And NH3The catalyst discharged again |
| CN109772427A (en) * | 2019-02-22 | 2019-05-21 | 浙江大学 | It is a kind of for the catalyst of sulphur nitrogen recycling in magnesium processes simultaneous SO_2 and NO removal technique absorbing liquid and its preparation and application |
| CN110116019A (en) * | 2019-04-28 | 2019-08-13 | 太原理工大学 | A kind of nano-cobaltic-cobaltous oxide/aluminium oxide@carried catalyst and its preparation method and application |
| CN110116019B (en) * | 2019-04-28 | 2022-02-25 | 太原理工大学 | Nano cobaltosic oxide/alumina @ carrier catalyst and preparation method and application thereof |
| CN110201710A (en) * | 2019-07-09 | 2019-09-06 | 华北电力大学（保定） | A kind of cobalt-based mesoporous material Co-TUD-1 catalyst and its preparation method and application |
| CN113336310A (en) * | 2021-06-10 | 2021-09-03 | 南开大学 | Catalytic ozone water treatment method using cobalt-containing nitrogen-doped ordered mesoporous carbon as catalyst |
| CN113336310B (en) * | 2021-06-10 | 2022-08-05 | 南开大学 | Catalytic ozone water treatment method using cobalt-containing nitrogen-doped ordered mesoporous carbon as catalyst |
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