CN112169798A - Catalyst with collagen-based carbon material loaded with metal cobalt and preparation method and application thereof - Google Patents
Catalyst with collagen-based carbon material loaded with metal cobalt and preparation method and application thereof Download PDFInfo
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- CN112169798A CN112169798A CN202011100276.9A CN202011100276A CN112169798A CN 112169798 A CN112169798 A CN 112169798A CN 202011100276 A CN202011100276 A CN 202011100276A CN 112169798 A CN112169798 A CN 112169798A
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- 102000008186 Collagen Human genes 0.000 title claims abstract description 66
- 108010035532 Collagen Proteins 0.000 title claims abstract description 66
- 229920001436 collagen Polymers 0.000 title claims abstract description 66
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 55
- 239000010941 cobalt Substances 0.000 title claims abstract description 55
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 49
- 239000002184 metal Substances 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 29
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002351 wastewater Substances 0.000 claims abstract description 14
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
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- 238000000034 method Methods 0.000 claims description 18
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- 229910052724 xenon Inorganic materials 0.000 claims description 10
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 239000012425 OXONE® Substances 0.000 claims description 7
- HJKYXKSLRZKNSI-UHFFFAOYSA-I pentapotassium;hydrogen sulfate;oxido sulfate;sulfuric acid Chemical compound [K+].[K+].[K+].[K+].[K+].OS([O-])(=O)=O.[O-]S([O-])(=O)=O.OS(=O)(=O)O[O-].OS(=O)(=O)O[O-] HJKYXKSLRZKNSI-UHFFFAOYSA-I 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 10
- 230000015556 catabolic process Effects 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 238000006731 degradation reaction Methods 0.000 abstract description 9
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 8
- 229910001868 water Inorganic materials 0.000 abstract description 8
- 238000003763 carbonization Methods 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 abstract 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 26
- -1 hydroxyl radicals Chemical class 0.000 description 10
- 210000003491 skin Anatomy 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000002957 persistent organic pollutant Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
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- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 241001494479 Pecora Species 0.000 description 2
- RZUBARUFLYGOGC-MTHOTQAESA-L acid fuchsin Chemical compound [Na+].[Na+].[O-]S(=O)(=O)C1=C(N)C(C)=CC(C(=C\2C=C(C(=[NH2+])C=C/2)S([O-])(=O)=O)\C=2C=C(C(N)=CC=2)S([O-])(=O)=O)=C1 RZUBARUFLYGOGC-MTHOTQAESA-L 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010035664 Pneumonia Diseases 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 240000008866 Ziziphus nummularia Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
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- 238000004043 dyeing Methods 0.000 description 1
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- 230000003100 immobilizing effect Effects 0.000 description 1
- 239000000991 leather dye Substances 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
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- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 235000001459 whitebark Nutrition 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
The invention belongs to the technical field of biomass material resource utilization and composite oxidation catalysis material preparation, and particularly relates to preparation of a collagen-based carbon material loaded metal cobalt catalyst and application of the catalyst in dye degradation. Firstly, adjusting the surface charge of amphoteric electrolyte of hide powder collagen molecules, secondly adding a cobalt salt solution to coordinate with active groups of hide powder collagen to prepare a collagen loaded metal cobalt material, secondly carrying out anoxic carbonization to generate a collagen bio-based carbon material loaded with metal cobalt, and finally combining with potassium persulfate to carry out heterogeneous Co/PMS system photo-assisted catalytic oxidation degradation leather making dye. The collagen-based carbon material loaded metal cobalt catalyst prepared by the invention is used for treating tanning dye wastewater, can realize high-efficiency degradation of dye, can firmly adsorb and immobilize cobalt ions on the collagen-based carbon material, has less cobalt dissolution, has high recovery rate of the catalyst, and does not cause secondary pollution to water.
Description
Technical Field
The invention belongs to the technical field of biomass material resource utilization and composite oxidation catalysis material preparation, and particularly relates to preparation of a collagen-based carbon material loaded metal cobalt catalyst and application of the catalyst in dye degradation.
Background
The leather industry is the top of the light industry in China, and makes great contribution to the economic development of China, and simultaneously faces a series of environmental pollution problems. For example, due to the limited binding sites of the hide fibers and the obstruction of the three-dimensional space network of the hide collagen, dyes cannot completely permeate and absorb in the process of dyeing the blue hide, so that a great amount of dyes still remain in the wastewater. Most dyes have complex aromatic ring structures, so that the dyes in the wastewater have considerable stability to light, common chemical reagents and common microorganisms, and if the dyes are not treated, the dyes in the wastewater can be enriched in organisms through water circulation or food chains to generate toxic action, so that the problem of decolorization of the dye wastewater is always the focus of attention in the chemical industry and the environmental protection industry.
The traditional treatment methods of the dye wastewater at present comprise physical treatment, biological treatment, chemical treatment and combined technical treatment. Compared with the traditional treatment method, the advanced oxidation technology treatment method has the advantages of simple operation, quick reaction, little or no secondary pollution, wide application range, capability of efficiently treating refractory organic pollutants and the like.
The principle of treating waste water by advanced oxidation method is that under the action of light, heat, electricity and catalyst, the oxidant can produce active free radical (such as. OH,. O) with strong oxidizing property in the reaction system2-、·OOH、SO4 -Etc.) under appropriate conditions, these radicals attack organic contaminants in the water and undergo electron transfer with most of the organic matter in the wastewaterAddition, substitution and other reactions to break the chemical bonds of the organic molecules, so as to decompose the organic pollutants difficult to degrade into low-toxic or non-toxic small molecular substances, even more completely degrade, and directly degrade into CO by complete mineralization2And H2O。
The traditional advanced oxidation technology is a treatment means for degrading organic pollutants by taking hydroxyl radicals (. OH) as active substances, but the method is difficult to operate, inconvenient in raw material transportation and difficult to treat sludge generated by reaction, SO that the method is based on sulfate radicals (SO)4 -The advanced oxidation technology of (a) comes into force as a novel advanced oxidation technology. In recent years, with the progress and development of research on related aspects, SO has been discovered4 -There are two main ways of generation: one is obtained by acting on persulfate through pyrolysis, photolysis, radiolysis and the like; the other is obtained by catalyzing and decomposing persulfate by using transition metal (such as cobalt, iron, silver, copper and the like) and derivatives thereof as catalysts. Under the condition of normal temperature, the persulfate degrades organic pollutants in the wastewater, has slow degradation rate, long required reaction time, low degradation rate and unobvious effect, but can generate sulfate radicals with strong oxidizing property in the solution under the excitation of heating, illumination (ultraviolet, natural light and the like), ultrasound, microwaves, transition metal ions and the like.
The Co/PMS (cobalt/peroxymonosulfate) system is a 'transition metal + peroxide' system, and the catalytic oxidation system can generate free radical SO with strong oxidation property through certain reaction4 -To prepare the compound. Organic pollutant molecules in wastewater can be treated by SO4 -Decomposed into small-molecule organic matter, some of which can even be mineralized into small-molecule species. The Co/PMS system of the advanced oxidation method is divided into a homogeneous Co/PMS system and a heterogeneous Co/PMS system, wherein the homogeneous Co/PMS system mainly refers to a catalytic system formed by Co formed by a cobalt salt solution acting on PMS; the heterogeneous Co/PMS system comprises: co oxide catalyst/PMS, supported heterogeneous Co/PMS system, etc.
However, the transition metal cobalt, a toxic heavy metal, appears in the water in the form of ions as Co2+、Co3+And respiratory diseases such as asthma, pneumonia and the like can be caused after people drink the tea. The homogeneous Co/PMS system treats organic waste water, the solution contains a certain amount of cobalt ions after reaction, the heavy metal ions are difficult to recover, and the treated solution has certain harm to the environment (cobalt ions are dissolved), so that the development of an effective heterogeneous Co/PMS catalytic oxidation system has profound significance for treating organic waste water difficult to degrade. The heterogeneous Co/PMS system can catalyze and degrade dye wastewater, has strong oxidation performance, has good catalyst recycling performance, and cannot cause secondary pollution.
On the other hand, collagen is one of the most abundant renewable biomass resources in the world, is mainly stored in the dermis layer of animals, and is generally used for producing leather products, medical wound accessories, cosmetics, beauty and skin care products and other related industries. The molecular chain of the collagen contains a large number of hydrophilic active groups, such as carboxyl, amino, hydroxyl and the like, and can generate coordination with various metal ions, such as bivalent iron ions, trivalent chromium ions, trivalent aluminum ions, trivalent titanium ions, zirconium ions and the like. The tanning process of leather in the leather industry changes leather, and the effective crosslinking between collagen fibers is realized by utilizing the coordination effect of trivalent chromium salt or other metal salt and collagen active groups, so that the service performances of heat resistance, enzyme resistance, microorganism resistance and the like of the leather are improved. However, the leather is made of raw leather with different sizes and thicknesses, and trimming, shaving and the like are required in the production process so as to obtain leather products with better uniformity, which also results in a large amount of waste leftovers containing collagen every year.
Disclosure of Invention
In order to improve a homogeneous Co/PMS system, Co ions are difficult to recover and cause certain damage to the environment, and waste collagen resources are utilized at a high value, white leather powder prepared from leather-making leftover waste is used as a base material, Co ions are immobilized on leather powder collagen fibers through coordination and combination based on a complex reaction principle of leather collagen and metal ions in leather-making chemistry, the leather powder loaded with metal cobalt is calcined at high temperature by using the collagen fibers as a template, a metal Co catalyst loaded on a collagen-based carbon material is prepared, then PMS is activated, a loaded heterogeneous Co/PMS system is formed, and leather-making dye wastewater is catalytically degraded.
The technical scheme of the invention is as follows:
the catalyst is prepared by fixing Co ions through the complexing coordination of collagen and metal ions in leather-making leftover waste white leather powder.
The white skin powder is any one of pigskin powder, sheep skin powder and cowhide powder.
The particle size of the white peel powder is below 20 meshes, the ash content is not more than 0.5%, and the pH value is 5.0-5.5.
The preparation method of the catalyst with the collagen-based carbon material loaded with the metal cobalt comprises the following steps:
(1) balance adjustment: adding cortex moutan powder into deionized water, stirring, adding swelling inhibitor, stirring, adjusting pH to 2.5-3.0 with acid solution, and standing;
(2) preparing a collagen-loaded metal cobalt material: adding cobalt salt into the aqueous solution obtained in the step (1) and stirring for reaction; adjusting the pH value of the system to 3.0-4.0 by adopting an alkaline solution, reacting, filtering, washing, drying and grinding to obtain the collagen-loaded metal cobalt material;
(3) preparing a collagen-based carbon material loaded metal cobalt catalyst: and (3) heating and firing the collagen loaded metal cobalt material prepared in the step (2) in a nitrogen atmosphere, slowly cooling to room temperature, and taking out to obtain the carbonized collagen fiber loaded metal cobalt catalyst.
Preferably, in the step (1), the swelling inhibitor is any one of sodium chloride and sodium sulfate; in the step (1), deionized water: white peel powder: the mass ratio of the swelling inhibitor is 100:4-5: 5-8.
Preferably, in the step (1), the acid is any one of sulfuric acid, hydrochloric acid, formic acid and benzenesulfonic acid; the mass fraction of the acid solution is in the range of 10% to 5%.
Preferably, in the step (2), the cobalt salt is Co (NO)3)2·6H2O、CoSO4·7H2O、CoCl2·6H2And O is any one of the above. The dosage of the cobalt salt is 1-2.5 times of the weight of the hide powder; the alkaline solution is any one of ammonium bicarbonate, sodium bicarbonate and sodium acetate solution; the mass fraction of the alkaline solution is 5-10%.
Preferably, the temperature-rising firing process in step (3) is as follows: heating to 300 ℃ for firing for 2 hours, then gradually heating to 600 ℃ for firing for 2 hours, and then preserving heat at 800 ℃ for 1 hour.
The collagen-based carbon material loaded metal cobalt catalyst prepared by the preparation method is applied to degradation of leather dye wastewater.
The application comprises the following steps:
s1 adding potassium monopersulfate into the dye solution for tanning, shaking up to dissolve, adding the catalyst of the collagen-based carbon material loaded with metal cobalt as the material in claim 1 or the material in claim 4, and placing the mixed solution in a photochemical reactor for dark reaction with the assistance of ultrasound; so that the adsorption-desorption balance is achieved;
s2, installing a xenon lamp into the photochemical reaction instrument, opening a xenon lamp switch, pulling a lampshade open, and carrying out photocatalytic degradation on the mixed solution under the irradiation of visible light;
the mass volume ratio of the catalyst to the tanning dye solution is 1-0.5 mg: 1 mL; the mass fraction of the potassium monopersulfate is 0.05-0.15 g/mL.
The invention has the beneficial effects that:
(1) the homogeneous Co/PMS system has high catalytic efficiency and strong oxidizing capacity, but has inherent defects. Such as the difficulty in recycling the catalyst, and is mostly limited to Co2+Is not environmentally friendly. Although the amount of Co used is small, it still causes potential secondary pollution and biological toxicity. The collagen-based carbon material loaded metal cobalt catalyst prepared by the invention can firmly adsorb and load cobalt ions on the collagen-based carbon material due to the coordination effect of collagen and cobalt metal and the characteristics of large specific surface area and porosity of biochar, and canTo reduce its dissolution and facilitate the recycling of the support.
(2) At present, people usually remove dyes in wastewater by means of physical adsorption of activated carbon and resin, but the dyes enriched on the activated carbon and the resin are difficult to biodegrade, the adsorbent is regenerated by methods such as high-temperature pyrolysis, solvent dissolution and ultrasonic decomposition, the problems of difficult elution, adsorbent loss, high energy consumption and the like exist to different degrees, and the problem of how to treat elution waste liquid in which the dyes are concentrated and ineffective adsorbent residues is to be solved. The collagen-based carbon material loaded metal cobalt catalyst prepared by the invention is used for treating water dye, belongs to a heterogeneous Co/PMS catalytic oxidation system, can efficiently oxidize and decompose organic wastes such as dye and the like, and can decompose the organic wastes into low-toxicity or non-toxic micromolecular substances, and even finally can be completely mineralized and degraded into CO2And H2And O, the dye is degraded thoroughly, pollution is not transferred, and new pollution is not caused.
(3) According to the invention, after the skin powder material for adsorbing cobalt ions is carbonized, the adsorption performance of the collagen base material for immobilizing metal cobalt is enhanced, the dosage of the metal cobalt ions is reduced to a certain extent, and the method is simple to operate, simple in condition and easy to control in process. The loaded heterogeneous Co/PMS system after the potassium hydrogen persulfate combined treatment is used for catalyzing to generate SO with strong oxidizing property4 -Has strong effect on the degradation of the dye and does not produce sludge.
Drawings
FIG. 1 is an SEM scanning electron micrograph of Kraft white skin powder;
FIG. 2 is an SEM scanning electron micrograph and an EDS energy spectrum analysis chart of a cowhide white skin powder loaded with metal cobalt ions;
FIG. 3 is SEM scanning electron micrograph and EDS energy spectrum analysis of the metallic cobalt catalyst loaded on the collagen carbon-based material.
Detailed Description
The following description is only a preferred embodiment of the present invention, and is only for the purpose of describing the present invention, and should not be construed as limiting the scope of the present invention.
Example 1
(1) Balance adjustment: adding 10g of sheep skin white skin powder into 250g of deionized water, stirring at room temperature for 4h, adding 20g of sodium sulfate, fully stirring for 0.5h, adjusting the pH value to about 2.5 by using a sulfuric acid solution with the mass fraction of 5%, and standing for 0.5 h.
(2) Preparing a collagen-loaded metal cobalt material: to the aqueous solution of step (1), 10g of CoCl was added2·6H2O and the reaction is stirred for 4 h. Slowly raising the pH value of the system to 3 within 2h by using an ammonium bicarbonate solution with the mass fraction of 5%, raising the temperature to 45 ℃, reacting for 4h again, filtering, fully washing the product for multiple times by using deionized water and ethanol in sequence, drying for 12h at 50 ℃, and grinding to obtain the collagen-loaded metal cobalt material.
(3) Preparing a collagen-based carbon material loaded metal cobalt catalyst: and (3) putting the collagen loaded metal cobalt material prepared in the step (2) into a tubular furnace, introducing nitrogen, heating to 300 ℃, firing for 2 hours, gradually heating to 600 ℃, firing for 2 hours, keeping the temperature at 800 ℃ for 1 hour, slowly cooling the tubular furnace to room temperature, and taking out to obtain the carbonized collagen fiber loaded metal cobalt catalyst.
(4) Catalytic oxidative degradation of dyes
And (3) putting 50mL of acid fuchsin solution with the concentration of 50mg/L into a quartz tube, adding 2.5g of potassium monopersulfate, shaking up to dissolve, adding 25mg of the catalyst prepared in the step (3), shaking up to dissolve, placing into an ultrasonic cleaner for ultrasonic treatment for 1min, and placing the mixed solution into a photochemical reactor for dark reaction for 30min to enable the mixed solution to reach adsorption-desorption balance. And then installing a 500W xenon lamp in the photochemical reaction instrument, opening a xenon lamp switch, pulling a lampshade open, and carrying out a photocatalytic degradation experiment on the mixed solution under the irradiation of visible light for 2.5 h.
Example 2
(1) Balance adjustment: adding 9g of cow leather bark powder into 200mL of deionized water, stirring at room temperature for 4h, adding 14g of sodium chloride, fully stirring for 0.5h, adjusting the pH value to be about 3.0 by adding 10% by mass of formic acid solution, and standing for 0.5 h.
(2) Preparing a collagen-loaded metal cobalt material: adding 20g Co (NO) into the aqueous solution of the step (1)3)2·6H2O and stirring the mixture to react for 5 hours. Using small particles with mass fraction of 8%Slowly raising the pH value of the system to 4 within 2h by using a soda solution, raising the temperature to 45 ℃, reacting for 4h again, filtering, fully washing the product for multiple times by using deionized water and ethanol in sequence, drying for 12h at 50 ℃, and grinding to obtain the collagen-loaded metal cobalt material.
(3) Preparing a collagen-based carbon material loaded metal cobalt catalyst: and (3) putting the collagen loaded metal cobalt material prepared in the step (2) into a tubular furnace, introducing nitrogen, heating to 300 ℃, firing for 2 hours, gradually heating to 600 ℃, firing for 2 hours, keeping the temperature at 800 ℃ for 1 hour, slowly cooling the tubular furnace to room temperature, and taking out to obtain the carbonized collagen fiber loaded metal cobalt catalyst.
(4) Catalytic oxidative degradation of dyes
And (3) putting 50mL of alkaline brown solution with the concentration of 50mg/L into a quartz tube, adding 5g of potassium monopersulfate, shaking up to dissolve, adding 50mg of the catalyst prepared in the step (3), shaking up to dissolve, placing in an ultrasonic cleaner for ultrasonic treatment, and placing the mixed solution in a photochemical reactor for dark reaction for 30min to ensure that the mixed solution reaches adsorption-desorption balance. And then installing a 500W xenon lamp in the photochemical reaction instrument, opening a xenon lamp switch, pulling a lampshade open, and carrying out a photocatalytic degradation experiment on the mixed solution under the irradiation of visible light for 2.5 h.
Example 3
(1) Balance adjustment: adding 10g of pigskin white skin powder into 200ml of deionized water, stirring at room temperature for 4h, adding 10g of sodium chloride, fully stirring for 0.5h, adjusting the pH value to about 2.5 by using a benzenesulfonic acid solution with the mass fraction of 10%, and standing for 0.5 h.
(2) Preparing a collagen-loaded metal cobalt material: adding 25g of CoSO into the aqueous solution in the step (1)4·7H2O and stirring the mixture to react for 6 hours. And slowly raising the pH value of the system to 4.0 within 2h by using a sodium acetate solution with the mass fraction of 10%, raising the temperature to 45 ℃, reacting for 4h, filtering, fully washing the product for multiple times by using deionized water and ethanol in sequence, drying for 12h at 50 ℃, and grinding to obtain the collagen-loaded metal cobalt material.
(3) Preparing a collagen-based carbon material loaded metal cobalt catalyst: and (3) putting the collagen loaded metal cobalt material prepared in the step (2) into a tubular furnace, introducing nitrogen, heating to 300 ℃, firing for 2 hours, gradually heating to 600 ℃, firing for 2 hours, keeping the temperature at 800 ℃ for 1 hour, slowly cooling the tubular furnace to room temperature, and taking out to obtain the carbonized collagen fiber loaded metal cobalt catalyst.
(4) Catalytic oxidative degradation of dyes
Putting 50mL of direct acid-resistant jujube red solution with the concentration of 50mg/L into a quartz tube, adding 7.5g of potassium monopersulfate, shaking up to dissolve, adding 40mg of the catalyst prepared in the step (3), shaking up, placing in an ultrasonic cleaner for ultrasonic treatment, and placing the mixed solution in a photochemical reactor for dark reaction for 30min to ensure that the mixed solution reaches adsorption-desorption balance. And then installing a 500W xenon lamp in the photochemical reaction instrument, opening a xenon lamp switch, pulling a lampshade open, and carrying out a photocatalytic degradation experiment on the mixed solution under the irradiation of visible light for 2.5 h.
In order to illustrate the effective benefits of the present invention, the results of scanning electron microscopy and surface energy spectroscopy analysis of the kraft white leather powder, the cobalt-loaded kraft white leather powder, and the carbonized collagen-based cobalt metal catalyst of example 2 are shown in fig. 1-3. As can be seen from fig. 1, the unmodified white bark powder has a structural form of mixing long fibers and short fibers, and the loaded cobalt ions and the carbonized bark powder (fig. 2 and 3) have an obvious short fiber form, because the modified material is subjected to grinding treatment after the cobalt metal is loaded, and longer collagen fibers are ground into short fibers. In addition, from the energy spectrum analysis of fig. 2 and 3, it is easily found that the energy spectrum of Co element appears in the skin powder, which indicates that metallic cobalt is loaded on the collagen fiber, and the content of C in the base material after carbonization is 37.68 (wt.%), which is much higher than the content of C in the fiber before carbonization, which is 4.19 (wt.%), showing significant carbonization.
In order to further illustrate the effective benefits of the invention, the concentration of the dye after the light treatment in examples 1-3 is measured by spectrophotometry at the maximum absorption wavelength of the dye, the concentrations of acid fuchsin, alkali brown and direct acid-resistant purplish red are respectively 8.5mg/L, 3.2mg/L and 6.7mg/L, the degradation rates reach 91.5%, 96.8% and 93.3%, which shows that the collagen-based carbon material loaded metal cobalt catalyst prepared by the invention can well degrade tanning dye based on a heterogeneous Co/PMS system.
Claims (10)
1. The catalyst is characterized in that the catalyst is prepared by fixing Co ions through the complexing coordination of collagen and metal ions in leather-making leftover waste white leather powder.
2. The catalyst with metallic cobalt supported by collagen-based carbon material according to claim 1, wherein the white hide powder is any one of pigskin powder, sheepskin powder and cowhide powder.
3. The collagen-based carbon material supported metal cobalt catalyst as claimed in claim 1 or 2, wherein the particle size of the parchment powder is less than 20 meshes, the ash content is not more than 0.5%, and the pH value is 5.0-5.5.
4. The method for preparing a catalyst with metallic cobalt loaded on collagen-based carbon material according to claim 1, comprising the following steps:
(1) balance adjustment: adding cortex moutan powder into deionized water, stirring, adding swelling inhibitor, stirring again, adjusting pH to 2.5-3.0 with acid solution, and standing;
(2) preparing a collagen-loaded metal cobalt material: adding cobalt salt into the aqueous solution obtained in the step (1) and stirring for reaction; adjusting the pH value of the system to 3.0-4.0 by adopting an alkaline solution, reacting, filtering, washing, drying and grinding to obtain the collagen-loaded metal cobalt material;
(3) preparing a collagen-based carbon material loaded metal cobalt catalyst: and (3) heating and firing the collagen loaded metal cobalt material prepared in the step (2) in a nitrogen atmosphere, slowly cooling to room temperature, and taking out to obtain the carbonized collagen fiber loaded metal cobalt catalyst.
5. The method for preparing the catalyst according to claim 4, wherein in the step (1), the swelling inhibitor is any one of sodium chloride and sodium sulfate; in the step (1), deionized water: white peel powder: the mass ratio of the swelling inhibitor is 100:4-5: 5-8.
6. The method for preparing the catalyst according to claim 4, wherein in the step (1), the acid is any one of sulfuric acid, hydrochloric acid, formic acid and benzenesulfonic acid; the mass fraction of the acid solution is in the range of 10% to 5%.
7. The method of claim 4, wherein in the step (2), the cobalt salt is Co (NO)3)2·6H2O、CoSO4·7H2O、CoCl2·6H2Any one of O; the dosage of the cobalt salt is 1-2.5 times of the weight of the hide powder; the alkaline solution is any one of ammonium bicarbonate, sodium bicarbonate and sodium acetate solution; the mass fraction of the alkaline solution is 5-10%.
8. The method for preparing the catalyst according to claim 4, wherein the step (3) of firing at elevated temperature comprises: heating to 300 ℃ for firing for 2 hours, then gradually heating to 600 ℃ for firing for 2 hours, and then preserving heat at 800 ℃ for 1 hour.
9. Use of a catalyst comprising metallic cobalt supported on a collagen-based carbon material according to claim 1 or prepared according to claim 4 for degrading tannery dye wastewater.
10. Use according to claim 9, characterized in that it comprises the following steps:
s1 adding potassium monopersulfate into the dye solution for tanning, shaking up to dissolve, adding the catalyst of the collagen-based carbon material loaded with metal cobalt as the material in claim 1 or the material in claim 4, and placing the mixed solution in a photochemical reactor for dark reaction with the assistance of ultrasound; so that the adsorption-desorption balance is achieved;
s2, installing a xenon lamp into the photochemical reaction instrument, opening a xenon lamp switch, pulling a lampshade open, and carrying out photocatalytic degradation on the mixed solution under the irradiation of visible light;
the mass volume ratio of the catalyst to the tanning dye solution is 1-0.5 mg: 1 mL; the mass fraction of the potassium monopersulfate is 0.05-0.15 g/mL.
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