CN109225251B - Hierarchical porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst and preparation method thereof - Google Patents
Hierarchical porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst and preparation method thereof Download PDFInfo
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- CN109225251B CN109225251B CN201811141785.9A CN201811141785A CN109225251B CN 109225251 B CN109225251 B CN 109225251B CN 201811141785 A CN201811141785 A CN 201811141785A CN 109225251 B CN109225251 B CN 109225251B
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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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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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
- B01D53/8603—Removing sulfur compounds
- B01D53/8609—Sulfur oxides
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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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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Abstract
The invention provides a preparation method of a hierarchical porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst, which comprises the following steps: (1) soaking the waste leather scraps in water, adding plant polyphenol for reaction, adding the obtained product into an aldehyde cross-linking agent solution, adjusting the pH value, reacting to graft the plant polyphenol onto amino groups on the surfaces of the waste leather scraps, separating a reaction product, washing and drying; (2) soaking the plant polyphenol grafted waste leather scraps obtained in the step (1) in water, adjusting the pH value, reacting, and adding Ti (SO)4)2Aqueous solution and composition containing metal ions Mn+Reacting the aqueous solution of (A) with Ti, adjusting the pH value of the aqueous solution, and reacting the aqueous solution of (A) with Ti4+And metal ion Mn+Loading the plant polyphenol grafted waste leather scraps, separating a reaction product, washing and drying to obtain a precursor; (3) and calcining the precursor at 600-800 ℃ in a nitrogen atmosphere to obtain the catalyst. The composite carbon fiber low-temperature sulfur dioxide adsorption catalyst prepared by the method has excellent recycling performance.
Description
Technical Field
The invention belongs to the field of low-temperature desulfurization adsorption catalysts, relates to a low-temperature sulfur dioxide adsorption catalyst for hierarchical porous composite carbon fibers and a preparation method thereof, and particularly relates to a method for preparing hierarchical porous Ti-M/C composite carbon fibers based on waste dander modified by plant polyphenol, the hierarchical porous Ti-M/C composite carbon fibers prepared by the method, and application of the hierarchical porous Ti-M/C composite carbon fibers in low-temperature sulfur dioxide adsorption catalysis.
Background
With the development of industry and the improvement of environmental protection requirements, steel and nonferrous metal are smelted,The purification of flue gas in building materials and chemical industry has been proposed. SO of China2The pollution control and treatment starts late, the technology is relatively laggard, and the large-scale flue gas desulfurization device in China at present basically depends on a wet limestone-gypsum method which takes limestone as a desulfurizing agent and produces a large amount of carbon dioxide and gypsum as byproducts. The method has the advantages of complex flow, high consumption of the desulfurizer, difficult outlet of byproducts and new pollution problem. The method not only leads to high desulfurization cost, but also does not accord with the concept of circular economy, and is difficult to adapt to the increasingly high environmental protection and technical requirements of the current country. Therefore, the activated carbon method with low consumption of the purifying agent and low operation cost becomes the most promising method which is recognized by experts at home and abroad, can be recycled and can simultaneously realize desulfurization and denitrification. However, the traditional carbon-method desulfurization technology has the problems of limited desulfurization capacity, difficult engineering amplification, frequent regeneration times and the like, which greatly hinders the industrial popularization and application of the technology. Therefore, renewable, cheap and rich-source raw materials are searched, a recyclable desulfurization and denitrification catalyst is developed, sulfur resources are recycled, and a flue gas desulfurization and denitrification technology with high production added value is the key for realizing the conversion of a flue gas desulfurization and denitrification mode from a traditional pollution treatment mode to a circular economy mode.
Traditionally, activated carbon is selected as a carrier of a desulfurization catalyst, and the low operation cost and the abundant microporous structure of the activated carbon enable the activated carbon to have larger physical adsorption capacity and conveniently adsorb one or more impregnated metal ions. However, the activated carbon carrier lacks the dispersing and anchoring ability to the nanoparticles, and during the use process, the active components loaded by the activated carbon are easy to migrate, agglomerate and fall off, and are further inactivated, and need to be frequently regenerated.
The leather industry inevitably produces a large amount of waste leather scraps due to raw leather trimming, grey leather chipping and the like, and it is reported that about 140 tons of leather leftover wastes are produced every year in China, and the solid wastes are one of the important factors causing serious pollution of the leather industry. At present, the research on the resource utilization and high-value utilization of the tanning solid waste has important strategic significance on solving the tanning pollution and promoting the sustainable development of the leather industry and related industries in China. The waste leather scraps have wide sources and low cost, are used as a natural biological polymer material and mainly come from skins of livestock such as pigs, cattle, sheep and the like, and account for 95-98 percent of the total fiber mass of the dermis. Animal skins produced by livestock such as pigs, cattle, sheep and the like are byproducts of animal husbandry, the content of collagen of the animal skins reaches more than 90 percent, the animal skins are one of renewable animal biomass resources with the largest resource quantity in the world, and the resource of the animal skins is increasing along with the improvement of the living standard of human beings. The waste leather scraps have higher chemical reaction activity, if a novel desulfurization catalyst and a preparation technology thereof can be developed on the basis of the waste leather scraps, the technical problems of uneven distribution of active ingredients, easy migration, easy agglomeration and frequent regeneration and the like of the conventional desulfurization catalyst prepared by taking activated carbon as a carrier by adopting an impregnation method are solved, and the method not only has positive significance for resource utilization of the waste leather scraps, but also has immeasurable value for developing a more efficient and environment-friendly desulfurization technology in the future.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a graded porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst and a preparation method thereof, solves the problem of uneven distribution of active ingredients of the existing desulfurization catalyst prepared by taking active carbon as a carrier and adopting an impregnation method, and provides a new way for resource utilization of waste leather scraps.
The preparation method of the graded porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst provided by the invention comprises the following steps:
(1) preparation of plant polyphenol grafted waste dander
Soaking 3-8 parts by mass of waste leather scraps in 100 parts by mass of water to enable the water to fully soak the waste leather scraps, then adding 2-6 parts by mass of plant polyphenol to react for at least 0.5h, separating out a reaction product, adding 30-100 parts by mass of an aldehyde cross-linking agent solution with the concentration of 1-10 wt%, adjusting the pH value to 6.0-6.5, then reacting to enable the plant polyphenol to be grafted to amino groups on the surfaces of the waste leather scraps, then separating out the reaction product, washing and drying to obtain the plant polyphenol grafted waste leather scraps;
(2) carrying Ti4+And Mn+Preparation of the precursor
Soaking 3-10 parts by mass of plant polyphenol grafted waste leather scraps in 300-500 parts by mass of water to enable the water to fully soak plant polyphenol grafted collagen fibers, and using H to2SO4Adjusting the pH value to 1.8-2.0 by HCOOH buffer solution, reacting for at least 1h, adding Ti (SO)4)2Aqueous solution and composition containing metal ions Mn+Reacting the aqueous solution for at least 1h, then adjusting the pH value of the obtained reaction solution to 3.8-4.0, reacting for 10-14 h at the temperature of 30-50 ℃, and adding Ti4+And metal ion Mn+Loading the plant polyphenol grafted waste leather scraps, separating a reaction product, washing and drying to obtain a precursor; the metal ion Mn+Is Co2+、Ni2+、V3+Or Cu2+；
(3) Calcination of
And heating the precursor to 600-800 ℃ at a heating rate of 1-5 ℃/min in a nitrogen atmosphere, keeping the temperature, and calcining for 4-10 hours to obtain the hierarchical porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst.
In the above technical scheme, the plant polyphenol is a molecule conforming to the definition of White-Bate-Smith-Swain-Haslam, and preferably, the plant polyphenol is condensed tannin. The condensed tannin has a general structural formula shown in formula (I), wherein R is1And R2The selection principle of (A) is only to make the condensed tannin conform to the definition of White-Bate-Smith-Swain-Haslam, and the structure of the typical condensed tannin is shown as the formula (II). Further preferably, the plant polyphenol comprises bayberry polyphenol, larch polyphenol, oak cup polyphenol, black wattle polyphenol, grape polyphenol and the like.
In the technical scheme, in the step (2), 0.005-0.008 mol of Ti is added into each 1g of plant polyphenol grafted waste scurf4+And metal ion Mn+Adding Ti (SO) in a proportion4)2Aqueous solution and metal ion-containing aqueous solutionMn+An aqueous solution of (a). Preferably, Ti (SO) is controlled in step (2)4)2Aqueous solution and composition containing metal ions Mn+The aqueous solution of (2) is added in an amount such that Ti is present4+And Mn+The molar ratio of (1-2) to (1-2). More preferably, Ti (SO) is controlled in step (2)4)2Aqueous solution and composition containing metal ions Mn+The aqueous solution of (2) is added in an amount such that Ti is present4+And Mn+The molar ratio of (1-2) to (1). Further preferably, Ti (SO) is controlled in the step (2)4)2Aqueous solution and composition containing metal ions Mn+The aqueous solution of (2) is added in an amount such that Ti is present4+And Mn+The molar ratio of (1.5-2) to (1).
In the above technical solution, the aldehyde crosslinking agent is preferably an aldehyde group-containing crosslinking agent having no more than 5 carbon atoms, and typically formaldehyde, acetaldehyde, butyraldehyde and glutaraldehyde.
In the technical scheme, because the waste leather scraps can not resist high temperature, the thermal shrinkage temperature Ts is about 100 ℃, in order to avoid the deformation of the structures of the waste leather scraps grafted by the plant polyphenol and the precursor caused by overhigh temperature during drying, the temperature of the drying operation in the steps (1) and (2) is controlled not to exceed 80 ℃.
In the above technical scheme, the step (1) is preferably carried out under stirring.
In the technical scheme, the step (1) preferably comprises the steps of adding plant polyphenol, reacting for 1-3 hours, adjusting the pH value to 6.0-6.5, and reacting for 4-7 hours at 30-50 ℃ to graft the plant polyphenol onto amino groups on the surface of the collagen fibers.
In step (2) of the above technical scheme, H is adopted2SO4The pH value of the-HCOOH buffer solution is adjusted to 1.8-2.0, SO as to better control Ti (SO)4)2Preferably, the hydrolysis speed is adjusted to 1.8-2.0, the reaction is carried out for 2-6 h, the pH value is adjusted to 3.8-4.0, and Ti (SO) is added4)2Aqueous solution and composition containing metal ions Mn+Reacting the aqueous solution for 2-5 hours, and adjusting the pH value of the obtained reaction solution to 3.8-4.0 within 1-4 hours by adding alkali liquor in a manner of adding alkali liquor in a fractional manner.
In the above technical scheme, the reason why the temperature rise rate is controlled to be 1-5 ℃/min in the step (3) is that the temperature rise rate is too fast, and the structure collapse is easily caused when the template is removed by calcination.
In the technical scheme, the soaking time of the waste scurf in water in the step (1) is preferably 2-6 h, and the soaking time of the plant polyphenol grafted waste scurf in water in the step (2) is preferably 1-2 h.
The invention also provides a low-temperature sulfur dioxide adsorption catalyst for the graded porous composite carbon fiber prepared by the method, which specifically comprises a low-temperature sulfur dioxide adsorption catalyst for Ti-Co/C, Ti-Ni/C, Ti-V/C and Ti-Cu/C composite carbon fiber. The composite carbon fiber low-temperature sulfur dioxide adsorption catalyst provided by the invention better keeps the natural fiber appearance of the waste scurf template, and has a micropore-mesopore hierarchical pore structure.
The following provides a brief description of the principles of the present invention:
the molecular structure of the waste scurf contains-COOH, -OH and-NH2、-CONH2and-CONH-, etc., which can bind metal ions through coordination bonds, but the sweeps cannot coordinate all metal ions, and only metal ions having empty d orbitals (for example, Ti)4+) Can be combined with the waste shavings, and Co2+、Ni2+、V3+And Cu2+These metal ions cannot be directly bound to the waste. To realize Co2+、Ni2+、V3+、Cu2+The invention carries out grafting through proper bridge molecules, and the metal ions are loaded on the waste leather scraps through the bridge molecules. On one hand, the bridge molecules are required to be loaded on the waste leather scraps template, and on the other hand, the other end of the bridge molecules must have double capabilities of anchoring metal ions and dispersing nano particles, so that the catalyst with high activity and high reusability can be prepared.
As shown in the formula (III), hydroxyl on the B ring of the condensed tannin can be complexed with metal ions to form a five-membered chelate ring, so that the grafting of the metal ions on the condensed tannin is realized.
The direct combination of plant polyphenol and waste scurf is hydrophobic bond-hydrogen bond combination, which is easily destroyed under the action of hydrogen bond reagent, and as a result, plant polyphenol molecules are dissolved out from waste scurf by water or organic solvent. The method aims to solve the problem of the solidification degree of plant polyphenol on waste leather scraps and simultaneously ensures that the polyphenol solidified on the waste leather scraps still has the capacity of combining with metal ions. The invention utilizes the fact that aldehyde substances can generate addition reaction with amino acid residues on the side chain of the waste scurf, and simultaneously utilizes the point that nucleophilic reaction sites at C6 and C8 sites on the A ring of the structure of the cerobenzene polyphenol in the condensed tannin can generate cross-linking reaction with the aldehyde substances, and the plant polyphenol and-NH on the surface of the waste scurf under the action of the aldehyde cross-linking agent2A Mannich reaction takes place to graft onto the surface of the crumb. Meanwhile, non-covalent crosslinking can be formed between the benzene rings of the plant polyphenol and the waste scurf molecules. Therefore, the plant polyphenol is firmly grafted on the waste scurf, and the complexing ability of the plant polyphenol and metal ions is kept.
Taking bayberry polyphenol as an example, the structural formula of the bayberry polyphenol is shown as a formula (IV), the bayberry polyphenol contains a pyrogallol structure shown as a formula (V), two dissociated hydroxyl groups in the pyrogallol structure can be complexed with metal ions to form a five-membered chelate ring, the rest one phenolic hydroxyl group does not enter the inner boundary of a complex, but the dissociation of the former two phenolic hydroxyl groups can be promoted to make the complex more stable, and therefore, the effect that the plant polyphenol has the effect of stabilizing the metal ions Co2+、Ni2+、V3+、Cu2+Grafting of (3). Taking the case of glutaraldehyde as an example, the structural formula of the waxberry polyphenol grafted waste leather scraps formed after the waxberry polyphenol is grafted on the waste leather scraps is shown as a formula (VI).
On the basis, firstly, plant polyphenol molecules are grafted on the surface of the waste leather scraps through covalent bonds under the action of a cross-linking agent; subsequently, Ti4+/Mn+Precursor and plant polyphenolAbundant ortho-position phenolic hydroxyl groups are subjected to coordination chelation and loaded on the waste leather scrap template; then, the intermediate product is in N2High temperature calcination in a gas stream, in which the scrap template is carbonized with Ti loaded4+/Mn+The precursor is converted into an oxide or an atomic state with desulfurization catalytic activity, and the migration and agglomeration of nano metal particles can be effectively inhibited by the template domain limiting effect of the waste scurf and the anchoring and dispersing effect of the plant polyphenol, so that the Ti-M/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst with excellent catalytic performance and good recycling performance is prepared. The reaction principle of the plant polyphenol anchored metal ions dispersed on the waste leather scraps is schematically shown in figure 1.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention successfully prepares the graded porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst by using the waste leather scraps as a carbon source and plant polyphenol as bridge molecules, the catalyst completely keeps the natural fiber morphology of a waste leather scraps template, avoids the structural collapse in the high-temperature calcination process, and the framework of the catalyst is formed by partially crystallized pure anatase nano TiO2The crystal grains are assembled, and the imperfect crystal structure provides more active sites, so that the desulfurization activity of the material is improved; meanwhile, the catalyst has a micropore-mesopore hierarchical pore structure and larger specific surface area and pore volume, which is very beneficial to the SO by Ti-M/C2Adsorption and catalytic removal; in addition, the catalytic desulfurization performance of the catalyst is further improved due to the synergistic effect of the Ti-M (M ═ Co, Ni, V and Cu) bimetal. The template confinement effect of the waste scurf and the anchoring and dispersing effect of the plant polyphenol on the active ingredients greatly improve the activity and stability of the catalyst. Compared with the active-based desulfurization catalyst modified by the traditional impregnation method, the catalyst provided by the invention has obviously improved catalytic activity and recycling performance, and solves the problem of uneven distribution of active ingredients in the existing desulfurization catalyst prepared by taking activated carbon as a carrier by an impregnation method. The invention also provides a new way for the resource utilization of the waste dander.
2. Experiments show that the reaction temperature is 80 ℃, and the humidity is increasedUnder the conditions that the temperature is 80 ℃, the total airflow amount is 120mL/min and the mass of the catalyst is 1g, when the Ti-Co/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst prepared by the method is used for the first time, the accumulated sulfur capacity is up to 677.55mg/g when the desulfurization time is 1200min, when the catalyst is used in the 4 th cycle regeneration, the accumulated sulfur capacity of the same desulfurization time is 656.08mg/g, which is reduced by about 2.5-3.1%, under the same test conditions, when the Ti-Ni/C, Ti-V/C and Ti-Cu/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst is regenerated and used in the 4 th cycle, the cumulative sulfur capacity was reduced by only about 9.8%, about 13.5% and about 16.9% relative to the 1 st use, while under the same test conditions, activated carbon was the Ti catalyst prepared on the support.2-Co1The cumulative sulfur capacity of ACF at 1200min of desulfurization was nearly 450mg/g for the 1 st use and about 35% less for the same desulfurization time for the 4 th regeneration. Therefore, the template confinement effect of the waste leather scraps and the dispersion and anchoring effect of the ortho-position phenolic hydroxyl rich in plant polyphenol on the nano metal particles are demonstrated, the agglomeration and the falling off of the nano metal particles in the catalytic reaction process are effectively inhibited, and the recycling performance of the catalyst is effectively improved.
Drawings
FIG. 1 is a schematic view showing the reaction principle of plant polyphenol anchored metal ions dispersed on waste dander.
FIG. 2 shows CF, CF-BT-C, Co3C and Ti2-Co1In the scanning electron micrograph of/C, the scale bar in the graphs (a) to (d) is 100. mu.m, (e) is 10. mu.m, and (f) is 1. mu.m.
FIG. 3 is Ti2-Co1EDX elemental distribution of/C, where the scale bar of the (a) diagram is 6 μm.
FIG. 4 is a graph of the full pore size distribution of Ti-Co/C.
FIG. 5 is CF-C, CF-BT-C, Ti2-Co1/C、Ti1-Co1/C、Ti1-Co2C and Co3X-ray diffraction pattern of/C.
FIG. 6 is Ti2-Co1XPS energy spectrum of/C.
FIG. 7 is a schematic diagram of a simulated flue gas desulfurization unit.
FIG. 8 is Co3C and Ti2-Co1Cumulative sulfur capacity curve of ACF.
FIG. 9 is Ti2-Co1/C、Ti1-Co1/C、Ti1-Co2C and Co3Cumulative sulfur capacity curve for/C.
FIG. 10 is Ti2-Co1The recycling performance of the/C can be tested.
Detailed Description
The invention provides a graded porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst and a preparation method thereof, which are further described by the following examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can implement the present invention with some insubstantial modifications and adaptations according to the above disclosure.
Example 1
In the embodiment, the preparation of the hierarchical porous Ti-Co/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst comprises the following steps:
(1) preparation of waxberry polyphenol grafted waste scurf
Placing 5.0g of waste dandruff (CF) in a 250mL three-necked flask, adding 100mL of deionized water, soaking for 4H to make the deionized water fully infiltrate the waste dandruff, adding 3.0g of bayberry polyphenol (BT), stirring at room temperature for reaction for 2H, filtering to separate out a reaction product, adding 50mL of 2.0 wt% glutaraldehyde aqueous solution, and adding 0.1mol/L of H2SO4And (3) adjusting the pH value of the solution to 6.0-6.5, stirring and reacting for 6h at 30 ℃, filtering and separating out a reaction product, washing the reaction product with deionized water, and drying the reaction product overnight at 35 ℃ in vacuum to obtain the bayberry polyphenol grafted waste scurf (CF-BT).
(2) Carrying Ti4+And Co2+Preparation of the precursor
Placing 5g CF-BT in a 500mL three-necked flask, adding 400mL deionized water, and soaking at room temperature for 1h under stirringFully soaking CF-BT in ionized water and using H2SO4HCOOH buffer (H)2SO4HCOOH is 10, v/v, 97 wt% concentrated sulfuric acid and 98 wt% concentrated formic acid), the pH value is adjusted to be 1.8-2.0, the reaction is carried out for 3h at room temperature, and then Ti (SO) is added4)2Aqueous solution and CoCl2Reacting the aqueous solution for 4 hours, then adjusting the pH value of the obtained reaction solution to 3.8-4.0 within 2 hours by using saturated sodium bicarbonate solution, reacting for 12 hours at 40 ℃, and adding Ti4+And Co2+Loading the reaction product on CF-BT, filtering and separating the reaction product, washing the reaction product with deionized water, and drying the reaction product overnight in vacuum at 45 ℃ to obtain the precursor.
In this example, Ti (SO) was controlled4)2Aqueous solution and CoCl2The aqueous solution is added in such an amount that Ti is present4+And Co2+Is 0.03mol in total, and Ti4+And Co2+The molar ratio of the Ti to the Ti is 2:1, 1:1 and 1:2 respectively, and three Ti are prepared4+And Co2+Different loading amounts of precursors.
(3) Calcination of
And (3) placing the precursor prepared in the step (2) in a tubular furnace, heating to 600 ℃ at a heating rate of 5 ℃/min under the atmosphere of 99.99% high-purity flowing nitrogen, keeping the temperature, and calcining for 4 hours to obtain the hierarchical porous Ti-Co/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst. Ti when preparing the precursor according to the step (2)4+And Co2+In the same ratio, the catalysts obtained by calcination are respectively denoted as Ti2-Co1/C，Ti1-Co1C and Ti1-Co2/C。
Comparative example 1
In the comparative example, a Co/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst was prepared.
The operation of this comparative example was substantially the same as that of example 1 except that only CoCl was added in step (2)2Aqueous solution without addition of Ti (SO)4)2Aqueous solution, control of Co2+The total amount of addition of (1) is 0.03 mol. The Co/C composite carbon fiber low-temperature desulfurization catalyst obtained after calcination is recorded as Co3/C。
Comparative example 2
In this comparative example, Ti was prepared by a conventional impregnation method using Activated Carbon Fiber (ACF) as a carrier2-Co1/ACF。
Adding 5.0g ACF into Ti (SO) at 30 deg.C4)2Aqueous solution and CoCl2In a mixed solution of aqueous solutions, Ti in the mixed solution4+And Co2+In a molar ratio of 2:1, Ti4+And Co2+The total mole amount of the Ti is 0.03mol, the Ti is kept stable at 30 ℃, the mixture is stirred for 24 hours, the product obtained by dipping is washed, then dried for 1 day at 100 ℃, then placed in a tubular furnace, heated to 600 ℃ at the heating rate of 5 ℃/min under the atmosphere of 99.99 percent high-purity flowing nitrogen, and calcined for 4 hours at the temperature, and the Ti is obtained2-Co1/ACF。
Comparative example 3
In this comparative example, CF-BT was prepared by the procedure of step (1) of example 1, and then CF-TA was calcined by the procedure of step (3) of example 1 to obtain carbonized CF-BT, denoted CF-BT-C, which did not support any metal.
Example 2: characterization of the catalyst
1. Scanning electron microscope and energy dispersive X-ray spectroscopy
For CF, CF-BT-C, Co in example 1 and comparative examples 1 and 33C and Ti2-Co1The results of the scanning electron microscope test are shown in FIG. 2. FIG. 2(a) (b) are the scanning electron micrographs of CF and CF-BT-C, respectively, and it can be seen from FIG. 2(b) that the product after carbonization of CF-BT is massive and has no fiber morphology. FIG. 2(c) shows Co3The shape of the scanning electron microscope image of/C does not retain the structural characteristics of the waste leather scraps, and the carbonized product is in a sheet shape. The reason is probably that cobalt particles are relatively dispersed due to the steric hindrance effect of the bayberry polyphenol, nano particles cannot be adjacently bonded and assembled, and a fiber framework collapses when the waste scurf template is removed at high temperature. FIGS. 2(d) to (f) are Ti2-Co1Scanning electron micrographs of/C at different magnifications, as can be seen, Ti2-Co1the/C has clear and regular fiber morphology, and well retains the structural characteristics of ordered layering of the waste scurf. This is because of Ti4+The method has high reactivity, can be fully combined with the waste leather scraps, and can assemble a nano metal layer on the surface of the fiber in the calcining process, thereby avoiding the collapse of the waste leather scrap template during the calcining process and well keeping the morphology of the fiber. The fibrous shape is beneficial to promoting mass and heat transfer of gas-phase catalytic reaction, and can also effectively solve the problems of large resistance of a fixed reaction bed and gas resistance of gas blockage.
FIG. 3 is Ti2-Co1EDX element distribution diagram of/C, and FIGS. 3(b) to (e) are EDX element distribution diagrams at the box frame in FIG. 3(a), and it is understood from these diagrams that Ti, O, C and Co are uniformly distributed on the composite carbon fiber.
2.N2Isothermal adsorption desorption test
For Ti2-Co1/C、Ti1-Co1C and Ti1-Co2C carrying out N2In the isothermal adsorption and desorption experiment, fig. 4 is a full pore size distribution diagram of Ti-Co/C, wherein in fig. 4, the ordinate represents the pore volume increment and the abscissa represents the pore size. It can be seen from FIG. 4 that the micropores of Ti-Co/C are concentrated around 1.7 nm; simultaneously has a mesoporous structure, in the mesoporous range, Ti2-Co1C to Ti1-Co1C and Ti1-Co2the/C has narrower pore distribution and larger pore volume. The micropores and the mesopores coexist to form a hierarchical pore structure with developed Ti-Co/C and larger specific surface area and pore volume, which is very beneficial to the SO of the Ti-Co/C2Adsorption and catalytic removal.
Table 1 shows the pore structure parameters of Ti-Co/C. The total pore volume in the table is determined by the relative pressure P/P0The liquid nitrogen partial pressure at 0.95 is calculated, the micropore surface area SBET is obtained by a t-plot method, and the micropore volume Vs is relative pressure P/P0The amount of liquid nitrogen adsorbed at 0.1 was converted into a volume.
TABLE 1 pore Structure parameters of Ti-Co/C
[a]Brunauer-Emmett-Teller；[b]Mesopore ratio＝Mesopore surface area/BET surface area
As can be seen from Table 1, as the ratio of titanium in the sample decreases, the number of Ti-Co/C micropores increases, and the specific surface area, the total pore volume, the porosity and the average pore diameter decrease. This is because of Ti4+The metal oxide fiber is easy to be coordinated and combined with rich active groups on the surface of the waste scurf, is used as a main component of a metal oxide fiber framework, and can better copy the fiber morphology and the natural mesoscopic structure of a waste scurf template in the heat treatment process. Therefore, Ti4+The higher the content is, the more developed the formed mesoporous structure is, and the larger the mesoporous rate is; ti is also endowed with a developed fibrous multi-stage pore structure2-Co1A large specific surface area of/C; the large specific surface area is beneficial to the uniform distribution of active sites, and diffusion areas near the active sites are difficult to overlap and can be used as SO3/H2SO4The pore volume of the storage space increases accordingly.
XRD analysis
For CF-C, CF-BT-C, Ti2-Co1/C、Ti1-Co1/C、Ti1-Co2C and Co3The results of X-ray diffraction measurements are shown in FIG. 5. The curves in FIG. 5 are, from top to bottom, CF-C, CF-BT-C, Co3/C、Ti2-Co1/C、Ti1-Co1C and Ti1-Co2XRD profile of/C. CF-C, CF-BT-C, Co3Broad peaks of the curve of/C at 2 theta, 26 degrees and 43 degrees respectively correspond to carbon (002) crystal faces and (100) crystal faces, and the product after carbonization has low crystallization degree and mainly consists of amorphous carbon; the diffraction peak at 26 ° 2 θ indicates the formation of the graphitized structure of the carbon. For Ti1-Co2C and Ti1-Co1The characteristic peak in the graph shows that the TiO is2Exists in basically amorphous structure and has only weak anatase characteristic peak. From Ti2-Co1Obvious anatase TiO observed in the spectrum of the/C2Diffraction peaks. I.e. with Ti4+The content is increased, and the anatase content and the crystallization degree in the sample are gradually increased.
TiO as building fibrous skeleton2On one hand, a protective layer can be formed to ensure that the catalyst material is more acid-resistant, and has better thermal stability and reusability; on the other hand, partially crystalline TiO2Oxygen vacancy exists to make it to O2Has strong dissociation and adsorption capacity, and can form active lattice oxygen after adsorbing oxygen, thereby being capable of reacting on SO2Has high oxidative desulfurization activity. At the same time, the nano TiO with better crystallization2The catalyst also changes the void structure of the catalyst to a certain extent, is beneficial to the gas-solid reaction and plays a role in loosening and dispersing the active component, thereby leading the catalyst to have better catalytic desulfurization activity. In addition, the Ti-Co/C only contains pure anatase phase TiO2This is advantageous for further improvement of desulfurization catalytic activity. In general, anatase TiO2The reason for the higher catalytic activity of (a) than that of the rutile type is that: (1) rutile type TiO2The forbidden band width is small, and the positive conduction band of the forbidden band hinders the reduction reaction of oxygen; (2) anatase type TiO2The crystal lattice contains more defects and dislocations, SO that more oxygen vacancies are generated to capture electrons, and the oxygen vacancies on the surface can be used as oxidized SO2Thereby enlarging anatase TiO2Desulfurization activity of (2). Nano TiO 22The crystal structure has many defects which are active sites of the catalyst in different reactions, namely nano TiO2Small size, high surface energy, and high reactivity of these surface atoms. Visible, nano TiO2The catalyst carrier has good sulfur fixation and stability, and can be used as a cocatalyst to act synergistically with active components, thereby greatly improving the catalytic desulfurization activity of Ti-Co/C.
From fig. 5, no characteristic peaks for any cobalt species could be found, probably due to: firstly, the cobalt oxide is amorphous and cannot be observed due to low content; secondly, the cobalt element can be completely introduced into TiO2In the structure of (1), is uniformly dispersed in TiO2In the crystal lattice, a solid solution is formed therewith. Since in the case of 6 coordination, Ti4+And Co2+Have relatively similar ionic radii and can occupy each other in a condensed stateAccording to the corresponding lattice position, a solid solution is formed, so that the XRD characteristic peak of the cobalt element forming a crystal structure can not be detected in the nano composite particles. Indicating that the cobalt element may be CoTiO3The existence of the form explains the reason that the 2p3/2 peak of the cobalt element in the sample has a larger difference with the 2p3/2 standard peak position of CoO in the XPS test. The high dispersion of the cobalt as the main catalyst and the nanometer scale exceeding the lower limit of XRD detection are favorable to raising the desulfurizing catalytic activity.
XPS analysis
For Ti2-Co1X-ray photoelectron spectroscopy was performed on/C, and FIG. 6 shows Ti2-Co1XPS spectrum of/C, wherein (a) is full spectrum, (b) is Ti2p, (C) is O1 s, and (d) is Co2 p. As can be seen, the chemical composition is C (68.9%), O (20.91%), Ti (3.94%), Co (2.38%), N (3.88%). From FIG. 6(b), it can be seen that the peak of Ti2p is symmetrically distributed in 458.7eV (2p3/2) and 464.3eV (2p1/2), the former corresponds to Ti2p 3/2, the latter corresponds to Ti2p 1/2, and no other peaks appear in the figure, indicating that the Ti element exists mainly in +4 valence.
The XPS spectrum of the cobalt element is subjected to peak separation treatment to obtain 4 peaks, the peaks at 782.411 and 797.422eV correspond to 2P3/2 and 2P1/2 of the cobalt element, although the 2P3/2 peak is closest to the Co2P3/2 standard peak position (780.0eV) and the 2P1/2 standard peak position (795.5eV) of CoO, the difference of binding energy is larger (1.3eV), and cobalt is seen not to exist in the form of CoO but possibly exists in the form of composite oxide CoOx in the form of TiO2In crystalline grains, TiO2The Co on the surface of the fiber exists in the form of complex oxide with a more complex composition.
Example 3: evaluation of flue gas desulfurization Performance of catalyst
1. Desulfurization device and method
FIG. 7 is a schematic diagram of a simulated flue gas desulfurization device for evaluating the flue gas desulfurization performance of a sulfur dioxide adsorbing catalyst. The flue gas desulfurization performance of Ti-Co/C is carried out in a fixed bed desulfurization reactor, the inner diameter of the reactor is 10mm, a sieve plate is arranged in the middle part to support a catalyst bed layer, a layer of glass wool is firstly filled at the upper part of the sieve plate, the weighed catalyst is filled in the reactor, and then a layer of glass wool is continuously filled on the sieve plateSo that the reaction gas is sufficiently preheated. The reaction gas is uniformly mixed by the mixer and then enters the fixed bed desulfurization reactor. The catalyst loading was 100mm and the loading was 1.0 g. The simulated flue gas proportion is (V/V): SO (SO)2，2000ppm；O2，10％；N2Balancing; the total gas flow is 120mL/min, and the desulfurization and humidification temperatures are both 80 ℃.
The desulfurization performance of the catalyst was tested in the desulfurization apparatus shown in FIG. 7 by the following procedure:
(1) the pressure bottle of nitrogen gas, oxygen and sulfur dioxide of opening experimental apparatus, adjust the air velocity respectively and be: 50mL/min of nitrogen, 60mL/min of oxygen and 10mL/min of sulfur dioxide.
(2) Sample loading: and drying the catalyst to be tested in a drying box, weighing about 1g of the catalyst to be tested, filling the catalyst into a fixed bed desulfurization reactor, and connecting all pipelines and a testing system to ensure that no gas is leaked. After the sample is filled, all the laboratory instruments are connected.
(3) Measuring the concentration of the raw gas: adjusting an instrument switch valve to make the gas flow directly flow into the flue gas analyzer without passing through the reactor, and waiting for the computer display of SO on the flue gas analyzer2After the concentration has substantially stabilized (usually no more than 30ppm change in the index within 30min is considered stable).
(4) And (3) starting detection: after all experimental devices are connected, the air flow is controlled at 120mL/min, the humidification temperature is kept at 80 ℃ (controlled by a super constant temperature water bath), and the reaction temperature is kept at 80 ℃ (controlled by a constant temperature water bath). Computer set for recording SO once per minute2The sampling was continued until the experiment was stopped.
(5) And (3) recovering a sample: and (4) arranging the serial numbers of the catalysts subjected to the desulfurization performance test, and putting the serial numbers into a sample bag for analysis.
2. Cumulative sulfur capacity comparison of catalysts
Under the conditions that the reaction temperature is 80 ℃, the humidifying temperature is 80 ℃, the total amount of air flow is 120mL/min and the mass of the catalyst is 1g, the Co/ACF immobilized by the control sample activated carbon fiber and the Co prepared by using the waste leather scraps as templates are respectively compared3/C、Ti2-Co1/C、Ti1-Co1/C、Ti1-Co2Cumulative sulfur capacity of/C.
FIG. 8 is Co3C and Ti2-Co1Cumulative sulfur capacity curve of/ACF, Ti can be seen from FIG. 82-Co1ACF having a cumulative sulfur capacity higher than Co for an initial period of time3C; after 480min of desulfurization, Co3The sulfur capacity of the/C is higher than that of Ti2-Co1ACF, and remains advanced for a longer period of time thereafter, and both begin to lose desulfurization activity at 1000 min. Ti2-Co1The initial desulfurization performance of ACF is obviously superior, which is probably due to the rich microporous structure and larger pore volume of the active carbon carrier to SO2Stronger physical adsorption. Co3The accumulated sulfur capacity of the/C at a later stage for a longer time is higher than that of Ti2-Co1the/ACF, which is probably due to the anchoring and dispersing effect of the bayberry polyphenol on the active ingredients, improves the activity and the continuous desulfurization capability of the catalyst to a certain extent.
FIG. 9 is Ti2-Co1/C、Ti1-Co1/C、Ti1-Co2C and Co3The cumulative sulfur capacity curve of/C, as can be seen from FIG. 9, the cumulative sulfur capacity of the catalyst at 1200min of desulfurization is in the following order: ti2-Co1/C>Ti1-Co1/C>Ti1-Co2/C>Co3It can be seen that as the Ti content decreases, the sulfur capacity also decreases due to the Ti metal energy being the catalyst fiber framework and pore structure, which is responsible for SO2The adsorption and mass transfer of the adsorbent have good promotion effect; simultaneous TiO 22The introduction of crystallites has a good promoter for desulfurization, which is described above by XRD in relation to TiO2The relationship between the crystal form and the desulfurization performance has been elucidated. On the other hand, the accumulated sulfur capacity of Ti-Co/C increases linearly with time due to the synergistic effect of Ti-Co bimetal; and for single metal Co3catalyst/C, cumulative sulfur capacity ratio Ti in initial stage1-Co1C and Ti1-Co2the/C is slightly dominant, but the cumulative sulfur capacity does not increase after 900min, losing desulfurization activity. Co3Desulfurization Performance ratio of/C before deactivation of Ti1-Co1/C、Ti1-Co2high/C, probably because of the active metal component Co supported by it2+More active sites are abundant; and its limitation may be Co3the/C can not form a fiber shape with a developed and communicated mesoporous structure in the carbonization process, so that H accumulated in catalyst micropores can not be discharged in time2SO4(ii) a Meanwhile, the flaky shape is not beneficial to mass and heat transfer, and finally the desulfurization capability of the catalyst is lost after the catalyst reacts for a period of time.
It can also be found from FIG. 9 that Co supporting cobalt as a single metal3The cumulative sulfur capacity at 1200min for the/C catalyst was significantly less than that of the supported bimetallic Ti-Co/C catalyst. The reason that the accumulated sulfur capacity of the bimetal is linearly increased all the time compared with that of the single metal is probably that a certain synergistic effect is generated between the Ti-Co bimetal, the electron exchange rate is promoted, the catalytic efficiency and the catalyst poisoning resistance of a system are improved, the particle size and the dispersion degree of an active metal component Co are improved, and a new cocatalyst site is formed, SO that SO is more effectively catalytically oxidized2The sulfur capacity can be continuously and linearly increased.
3.Ti2-Co1Cyclic use performance of/C catalyst
Ti2-Co1The Ti is examined by repeating the catalytic desulfurization test under the same condition after the heat treatment and the regeneration after the use of the catalyst2-Co1The recycling performance of the/C. FIG. 10 is Ti2-Co1The recycling performance of the/C catalyst can be tested. As can be seen from FIG. 9, Ti2-Co1The cumulative sulfur capacity at 1200min of desulfurization was 677.55mg/g for the 1 st use, while the cumulative sulfur capacity at the same desulfurization time was 656.08mg/g, a reduction of only about 3.1% for the 4 th regeneration use.
4.Ti2-Co1Cyclic use performance of ACF catalyst
Examination of Ti according to the method described above2-Co1The result of the recycling performance of the ACF shows that: ti2-Co1The cumulative sulfur capacity of ACF is close to 450mg/g when the desulfurization time is 1200min during the 1 st use, and the ACF is regenerated and used in the 4 th cycleThe cumulative sulfur capacity for the same desulfurization time was reduced by about 35%.
According to Ti2-Co1C and Ti2-Co1The test result of the recycling performance of the ACF shows that the template confinement effect of the waste scurf and the dispersion and anchoring effect of the ortho-position phenolic hydroxyl rich in plant polyphenol on the nano cobalt particles effectively inhibit the agglomeration and the falling off of nano metal particles in the catalytic reaction process, so that the recycling performance of the catalyst can be effectively improved.
Example 4
In the embodiment, the preparation of the hierarchical porous Ti-Co/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst comprises the following steps:
(1) preparation of graft scrap of Hendersia plant
Placing 6.0g of waste leather scraps into a 250mL three-necked bottle, adding 100mL of deionized water, soaking for 5H to enable the deionized water to fully soak the waste leather scraps, then adding 4.0g of black wattle polyphenol, stirring at room temperature for reaction for 2.5H, filtering and separating out a reaction product, adding 40mL of 2.5 wt% glutaraldehyde aqueous solution, and adding 0.1mol/L H2SO4And (3) adjusting the pH value of the solution to 6.0-6.5, stirring and reacting for 5h at 40 ℃, filtering and separating out a reaction product, washing with deionized water, and vacuum drying for 12h at 35 ℃ to obtain black wattle polyphenol grafted waste leather scraps.
(2) Carrying Ti4+And Co2+Preparation of the precursor
Placing 6g of black wattle polyphenol grafted waste bark scraps into a 500mL three-necked bottle, adding 400mL of deionized water, soaking at room temperature for 1.5H under stirring to enable the deionized water to fully infiltrate the black wattle polyphenol grafted waste bark scraps, and using H2SO4HCOOH buffer (H)2SO4HCOOH is 10, v/v, 97 wt% concentrated sulfuric acid and 98 wt% concentrated formic acid), the pH value is adjusted to be 1.8-2.0, the reaction is carried out for 4h at room temperature, and then Ti (SO) is added4)2Aqueous solution and CoCl2Aqueous solution of Ti4+And Co2+Is 0.03mol in total, and Ti4+And Co2+Is 1.5:1, reacting for 4h, and then adjusting the pH value of the obtained reaction solution within 3h by using saturated sodium bicarbonate solutionAdjusting the temperature to 3.8-4.0, reacting for 11h at 45 ℃, and adding Ti4+And Co2+Loading the waste bark chip grafted by the black wattle polyphenol, finally filtering and separating out a reaction product, washing the reaction product by deionized water, and carrying out vacuum drying overnight at the temperature of 45 ℃ to obtain a precursor.
(3) Calcination of
And (3) placing the precursor prepared in the step (2) in a tubular furnace, heating to 600 ℃ at the heating rate of 4 ℃/min under the atmosphere of 99.99% high-purity flowing nitrogen, keeping the temperature, and calcining for 5 hours to obtain the hierarchical porous Ti-Co/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst, which is recorded as Ti-Co/C.
The Ti-Co/C prepared in this example was tested for its cycling performance by the method of example 3 at a reaction temperature of 80 deg.C, a humidification temperature of 80 deg.C, a total gas flow of 120mL/min, a catalyst mass of 1g, and a desulfurization time per cycle of 1200 min. The results show that the Ti-Co/C at the 4 th cycle regeneration application has only about a 2.5% reduction in cumulative sulfur capacity relative to the 1 st application.
Example 5
In the embodiment, the preparation of the hierarchical porous Ti-Ni/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst comprises the following steps:
(1) preparation of grape polyphenol grafted waste dander
Placing 3.0g of waste dandruff into a 250mL three-necked bottle, adding 100mL of deionized water, soaking for 2H to make the deionized water fully soak the waste dandruff, then adding 2.0g of grape polyphenol, stirring at room temperature for reaction for 0.5H, filtering to separate out reaction products, adding 40mL of 1 wt% acetaldehyde solution, and adding 0.1mol/L of H2SO4And adjusting the pH value of the solution to 6.0-6.5, stirring and reacting for 4 hours at 50 ℃, filtering and separating out a reaction product, washing the reaction product with deionized water, and performing vacuum drying overnight at 45 ℃ to obtain the grape polyphenol grafted waste scurf.
(2) Carrying Ti4+And Ni2+Preparation of the precursor
Placing 3g of grape polyphenol grafted waste scurf into a 500mL three-necked bottle, adding 300mL of deionized water, soaking at room temperature for 1h under the condition of stirring to enable the deionized water to fully soak the grape polyphenol grafted waste scurf,by H2SO4HCOOH buffer (H)2SO4 HCOOH 10, v/v, 97 wt% concentrated sulfuric acid and 98 wt% concentrated formic acid) to adjust pH value to 1.8-2.0, reacting at room temperature for 1h, and adding Ti (SO)4)2Aqueous solution and NiSO4Aqueous solution of Ti4+And Ni2+Is 0.015mol in total and Ti4+And Ni2+The molar ratio of the Ti to the sodium bicarbonate is 2:1, the reaction is carried out for 1 hour, then the pH value of the obtained reaction solution is adjusted to be between 3.8 and 4.0 within 1 hour by using a saturated sodium bicarbonate solution, the reaction is carried out for 10 hours at the temperature of 50 ℃, and the Ti is added4+And Ni2+Loading the waste skin scraps grafted by the grape polyphenol, finally filtering and separating out a reaction product, washing the reaction product by deionized water, and carrying out vacuum drying at 40 ℃ overnight to obtain a precursor.
(3) Calcination of
And (3) placing the precursor prepared in the step (2) into a tube furnace, heating to 650 ℃ at a heating rate of 3 ℃/min under the atmosphere of 99.99% high-purity flowing nitrogen, keeping the temperature for calcining for 10 hours, and using the graded porous Ti-Ni/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst, namely Ti-Ni/C.
The Ti-Ni/C prepared in this example was tested for its cycling performance by the method of example 3 at a reaction temperature of 80 deg.C, a humidification temperature of 80 deg.C, a total gas flow of 120mL/min, a catalyst mass of 1g, and a desulfurization time per cycle of 1200 min. The results show that the Ti-Ni/C in the 4 th cycle regeneration only reduces the cumulative sulfur capacity by about 9.8% relative to the 1 st use.
Example 6
In the embodiment, the preparation of the hierarchical porous Ti-V/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst comprises the following steps:
(1) preparation of larch polyphenol grafted waste dander
Putting 8.0g of waste scurf into a 250mL three-necked bottle, adding 100mL of deionized water, soaking for 6H to enable the deionized water to fully soak the waste scurf, then adding 6.0g of larch polyphenol, stirring at room temperature for reaction for 1H, filtering and separating out a reaction product, adding 100mL of butyraldehyde solution with the concentration of 3 wt%, and adding 0.1mol/L of H2SO4Adjusting the pH of the solution to 6.0-6.5And (3) stirring and reacting for 7h at 40 ℃, filtering and separating out a reaction product, washing the reaction product by using deionized water, and performing vacuum drying overnight at 40 ℃ to obtain the larch polyphenol grafted waste scurf.
(2) Carrying Ti4+And V3+Preparation of the precursor
Placing 10g of larch polyphenol grafted waste leather scraps into a 1000mL three-necked bottle, adding 500mL of deionized water, soaking at room temperature for 2H under stirring to fully soak the larch polyphenol grafted waste leather scraps with the deionized water, and using H2SO4HCOOH buffer (H)2SO4HCOOH is 10, v/v, 97 wt% concentrated sulfuric acid and 98 wt% concentrated formic acid), the pH value is adjusted to be 1.8-2.0, the reaction is carried out for 6h at room temperature, and then Ti (SO) is added4)2Aqueous solutions and VCl3Aqueous solution of Ti4+And V3+Is 0.08mol in total and Ti4+And V3+The molar ratio of the Ti to the organic solvent is 1.2:1, the reaction is carried out for 5 hours, then the pH value of the obtained reaction solution is adjusted to 3.8-4.0 within 4 hours by using saturated sodium bicarbonate solution, the reaction is carried out for 14 hours at the temperature of 30 ℃, and the Ti is added4+And V3+Loading the obtained product on larch polyphenol grafted waste leather scraps, filtering and separating a reaction product, washing the reaction product by deionized water, and carrying out vacuum drying at 50 ℃ overnight to obtain a precursor.
(3) Calcination of
And (3) placing the precursor prepared in the step (2) in a tubular furnace, heating to 700 ℃ at a heating rate of 2 ℃/min under the atmosphere of 99.99% high-purity flowing nitrogen, keeping the temperature, and calcining for 5 hours to obtain the hierarchical porous Ti-V/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst, which is recorded as Ti-V/C.
The Ti-V/C prepared in this example was tested for its cycling performance by the method of example 3 at a reaction temperature of 80 deg.C, a humidification temperature of 80 deg.C, a total gas flow of 120mL/min, a catalyst mass of 1g, and a desulfurization time per cycle of 1200 min. The results show that the Ti-V/C at the 4 th cycle regeneration application has only about 13.5% reduction in cumulative sulfur capacity relative to the 1 st application.
Example 7
In the embodiment, the preparation of the hierarchical porous Ti-Cu/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst comprises the following steps:
(1) preparation of acorn polyphenol grafted waste leather scraps
Placing 6.0g of waste leather scraps into a 250mL three-necked bottle, adding 100mL of deionized water, soaking for 4H to enable the deionized water to fully soak the waste leather scraps, then adding 5.0g of acorn polyphenol, stirring at room temperature for reaction for 3H, filtering to separate out a reaction product, adding 30mL of 10 wt% formaldehyde solution, and adding 0.1mol/L of H2SO4And (3) adjusting the pH value of the solution to 6.0-6.5, stirring and reacting for 4 hours at 45 ℃, filtering and separating out a reaction product, washing the reaction product with deionized water, and drying the reaction product overnight at 40 ℃ in vacuum to obtain the oak cup polyphenol grafted waste leather scraps.
(2) Carrying Ti4+And Cu2+Preparation of the precursor
Placing 4g of waste crumb grafted by acorn polyphenol in a 500mL three-necked bottle, adding 350mL of deionized water, soaking at room temperature for 2H under the condition of stirring to enable the deionized water to fully soak the waste crumb grafted by the acorn polyphenol, and using H2SO4HCOOH buffer (H)2SO4HCOOH is 10, v/v, 97 wt% concentrated sulfuric acid and 98 wt% concentrated formic acid), the pH value is adjusted to be 1.8-2.0, the reaction is carried out for 2h at room temperature, and then Ti (SO) is added4)2Aqueous solution and CuSO4Aqueous solution of Ti4+And Cu2+Is 0.03mol in total, and Ti4+And Cu2+The molar ratio of the Ti to the sodium bicarbonate is 2:1, the reaction is carried out for 2 hours, then the pH value of the obtained reaction solution is adjusted to be between 3.8 and 4.0 within 3 hours by using saturated sodium bicarbonate solution, the reaction is carried out for 12 hours at the temperature of 40 ℃, and the Ti is added4+And Cu2+Loading the obtained product on waste leather scraps grafted by the acorn polyphenol, finally filtering and separating out a reaction product, washing the reaction product by using deionized water, and carrying out vacuum drying at 40 ℃ overnight to obtain a precursor.
(3) Calcination of
And (3) placing the precursor prepared in the step (2) in a tube furnace, heating to 800 ℃ at a heating rate of 1 ℃/min under a flowing nitrogen atmosphere with high purity of 99.99%, keeping the temperature, and calcining for 4 hours to obtain the hierarchical porous Ti-Cu/C composite carbon fiber low-temperature sulfur dioxide adsorption catalyst, which is recorded as Ti-Cu/C.
The Ti-Cu/C prepared in this example was tested for its cycling performance by the method of example 3 at a reaction temperature of 80 deg.C, a humidification temperature of 80 deg.C, a total gas flow of 120mL/min, a catalyst mass of 1g, and a desulfurization time per cycle of 1200 min. The results show that the Ti-Cu/C at the 4 th cycle regeneration application has only about a 16.9% reduction in cumulative sulfur capacity relative to the 1 st application.
Claims (6)
1. A preparation method of a hierarchical porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst is characterized by comprising the following steps:
(1) preparation of plant polyphenol grafted waste dander
Soaking 3-8 parts by mass of waste leather scraps in 100 parts by mass of water to enable the water to fully soak the waste leather scraps, then adding 2-6 parts by mass of plant polyphenol to react for at least 0.5h, separating out a reaction product, adding 30-100 parts by mass of an aldehyde cross-linking agent solution with the concentration of 1-10 wt%, adjusting the pH value to 6.0-6.5, then reacting to enable the plant polyphenol to be grafted to amino groups on the surfaces of the waste leather scraps, then separating out the reaction product, washing and drying to obtain the plant polyphenol grafted waste leather scraps; the plant polyphenol is bayberry polyphenol, larch polyphenol, oak cup polyphenol, black wattle polyphenol or grape polyphenol;
(2) carrying Ti4+And Mn+Preparation of the precursor
Soaking 3-10 parts by mass of plant polyphenol grafted waste leather scraps in 300-500 parts by mass of water to enable the water to fully soak the plant polyphenol grafted waste leather scraps, and using H to2SO4Adjusting the pH value to 1.8-2.0 by HCOOH buffer solution, reacting for at least 1h, adding Ti (SO)4)2Aqueous solution and composition containing metal ions Mn+Reacting for at least 1h, and then adjusting the pH value of the obtained reaction liquid to 3.8-4.0 at 30-50oC, reacting for 10-14 h to obtain Ti4+And metal ion Mn+Loading the plant polyphenol grafted waste leather scraps, separating a reaction product, washing and drying to obtain a precursor; the metal ion Mn+Is Co2+、Ni2+、V3+Or Cu2+；
In this step, per 1g plant polyphenolAdding Ti with the total amount of 0.005-0.008 mol into the grafted waste leather scraps4+And metal ion Mn+Adding Ti (SO) in a proportion4)2Aqueous solution and composition containing metal ions Mn+Controlling Ti (SO) in an aqueous solution of4)2Aqueous solution and composition containing metal ions Mn+The aqueous solution of (2) is added in an amount such that Ti is present4+And Mn+The molar ratio of (1-2) to (1-2);
(3) calcination of
And heating the precursor to 600-800 ℃ at a heating rate of 1-5 ℃/min in a nitrogen atmosphere, keeping the temperature, and calcining for 4-10 h to obtain the hierarchical porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst.
2. The method for preparing the hierarchical porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst according to claim 1, wherein the aldehyde crosslinking agent is a crosslinking agent containing aldehyde groups and having no more than 5 carbon atoms.
3. The method for preparing the hierarchical porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst according to claim 1, wherein the drying temperature in steps (1) and (2) is controlled not to exceed 80 ℃oC。
4. The preparation method of the graded porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst according to claim 1, wherein the step (1) is carried out for 1-3 hours after plant polyphenol is added, the pH value is adjusted to 6.0-6.5, and the pH value is 30-50oC, reacting for 4-7 h to graft the plant polyphenol onto amino groups on the surfaces of the waste leather scraps.
5. The preparation method of the graded porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst according to claim 1, characterized in that in the step (2), the pH value is adjusted to 1.8-2.0, then the reaction is carried out for 2-6 h, the pH value is adjusted to 3.8-4.0, and Ti (SO) is added4)2Aqueous solution and composition containing metal ions Mn+Reacting the aqueous solution for 2 to 5 hours, and then adding alkali liquor in a manner of adding alkali liquor in portions 1Adjusting the pH value of the obtained reaction liquid to 3.8-4.0 within 4 h.
6. The graded porous composite carbon fiber low-temperature sulfur dioxide adsorption catalyst prepared by the method of any one of claims 1 to 5.
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